Patent Application
20230345751
Organic electroluminescent devices containing one or more light-emitting layers based on organics such as, e.g., organic light-emitting diodes (OLEDs), light-emitting electrochemical cells (LECs) and light-emitting transistors gain increasing importance. In particular, OLEDs are promising devices for electronic products such as e.g., screens, displays and illumination devices. In contrast to most electroluminescent devices essentially based on inorganics, organic electroluminescent devices based on organics are often rather flexible and producible in particularly thin layers. The OLED-based screens and displays already available today bear either good efficiencies and long lifetimes or good color purity and long lifetimes, but do not combine all three properties, i.e., good efficiency, long lifetime, and good color purity.
The color purity or color point of an OLED is typically provided by CIEx and CIEy coordinates, whereas the color gamut for the next display generation is provided by so-called BT-2020 and DCPI3 values. Generally, in order to achieve these color coordinates, top emitting devices are needed to adjust the color coordinate by changing the cavity. In order to achieve high efficiency in top emitting devices while targeting these color gamut, a narrow emission spectrum in bottom emitting devices is needed.
State-of-the-art phosphorescence emitters exhibit a rather broad emission, which is reflected in a broad emission of phosphorescence-based OLEDs (PHOLEDs) with a full-width-half-maximum (FWHM) of the emission spectrum, which is typically larger than 0.25 eV. The broad emission spectrum of PHOLEDs in bottom devices, leads to high losses in out-coupling efficiency for top emitting device structure while targeting BT-2020 and DCPI3 color gamut.
Additionally, phosphorescence materials are typically based on transition metals, e.g., iridium, which are quite expensive materials within the OLED stack due to their typically low abundance. Thus, transition metal based materials have the most potential for cost reduction of OLEDs. Lowering of the content of transition metals within the OLED stack thus is a key performance indicator for pricing of OLED applications.
Recently, some fluorescence or thermally-activated-delayed-fluorescence (TADF) emitters have been developed that display a rather narrow emission spectrum, which exhibits an FWHM of the emission spectrum, which is typically smaller than or equal to 0.25 eV, and therefore more suitable to achieve BT-2020 and DCPI3 color gamut. However, such fluorescence and TADF emitters typically suffer from low efficiency due to decreasing efficiencies at higher luminance (i.e., the roll-off behaviour of an OLED) as well as low lifetimes due to for example the exciton-polaron annihilation or exciton-exciton annihilation.
These disadvantages may be overcome to some extend by applying so-called hyper approaches. The latter rely on the use of an energy pump which transfers energy to a fluorescent emitter preferably displaying a narrow emission spectrum as stated above. The energy pump may for example be a TADF material displaying reversed-intersystem crossing (RISC) or a transition metal complex displaying efficient intersystem crossing (ISC). However, these approaches still do not provide organic electroluminescent devices combining all of the aforementioned desirable features, namely: good efficiency, long lifetime, and good color purity.
A central element of an organic electroluminescent device for generating light typically is the at least one light-emitting layer placed between an anode and a cathode. When a voltage (and electrical current) is applied to an organic electroluminescent device, holes and electrons are injected from an anode and a cathode, respectively.
Typically, a hole transport layer is(typically) located between a light-emitting layer and an anode, and an electron transport layer is typically located between a light-emitting layer and a cathode. The different layers are sequentially disposed. Excitons of high energy are then generated by recombination of the holes and the electrons in a light-emitting layer. The decay of such excited states (e.g., singlet states such as S1 and/or triplet states such as T1 to the ground state (S0) desirably leads to the emission of light.
Surprisingly, it has been found that an organic electroluminescent device's light-emitting layer consisting of one or more layers including a phosphorescence material, a small full width at half maximum (FWHM) emitter, a host material, and optionally a TADF material, provides an organic electroluminescent device having a long lifetime, a high quantum yield and exhibiting narrow emission, ideally suitable to achieve the BT-2020 and DCPI3 color gamut.
Herein, a phosphorescence material and/or an optional TADF material might transfer energy to a small full width at half maximum (FWHM) emitter displaying emission of light.
The present invention relates to an organic electroluminescent device including at least one light-emitting layer B which is composed of one or more sublayers, wherein the one or more sublayers are adjacent to each other and as a whole contain:
One aspect of the present invention relates to an organic electroluminescent device which includes at least one light-emitting layer B including one or more sublayers, wherein the one or more sublayers are adjacent to each other and as a whole contain:
(iv) a thermally activated delayed fluorescence (TADF) material EB, which has a lowermost excited singlet state energy level E(S1E) and a lowermost excited triplet state energy level E(T1E),
In one embodiment of the invention, at least one of the one or more sublayers of the at least one light-emitting layer B includes:
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B composed of one or more sublayers, wherein the one or more sublayers of the light-emitting layer B include:
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B composed of one or more sublayers, wherein the one or more sublayers of the light-emitting layer B include:
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B composed of one or more sublayers, wherein the one or more sublayers of the light-emitting layer B include:
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B including:
In one embodiment of the invention, the organic electroluminescent device includes a light-emitting layer B composed of exactly one layer including:
In a preferred embodiment, the organic electroluminescent device includes a light-emitting layer B composed of exactly one layer including:
In a preferred embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B consisting of exactly one (sub)layer. In a preferred embodiment of the invention, each light-emitting layer B included in the electroluminescent device according to the invention consists of exactly one (sub)layer. In a preferred embodiment of the invention, the electroluminescent device according to the invention includes exactly one light-emitting layer B consisting of exactly one (sub)layer.
In another embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of more than one sublayer. In another embodiment of the invention, each light-emitting layer B included in the electroluminescent device according to the invention includes more than one sublayer. In another embodiment of the invention, each light-emitting layer B included in the electroluminescent device according to the invention consists of more than one sublayer.
In another embodiment of the invention, the electroluminescent device according to the invention includes exactly one light-emitting layer B composed of more than one sublayer. In another embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of exactly two sublayers.
In another embodiment of the invention, each light-emitting layer B included in the electroluminescent device according to the invention is composed of exactly two sublayers. In another embodiment of the invention, the electroluminescent device according to the invention includes exactly one light-emitting layer B composed of exactly two sublayers.
In another embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of more than two sublayers. In another embodiment of the invention, each light-emitting layer B included in the electroluminescent device according to the invention is composed of more than two sublayers.
In another embodiment of the invention, the electroluminescent device according to the invention includes exactly one light-emitting layer B composed of more than two sublayers.
In one embodiment of the invention, each light-emitting layer B of the organic electroluminescent device according to the invention includes exactly one, exactly two, or exactly three sublayers.
It is understood that different sublayers of a light-emitting layer B do not necessarily all include the same materials or even the same materials in the same ratios.
It is understood that different sublayers of a light-emitting layer B are adjacent to each other.
In one embodiment of the invention, at least one sublayer includes exactly one TADF material EB and exactly one phosphorescence material PB.
In one embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of more than one sublayers, wherein at least one sublayer does not include a TADF material EB, a phosphorescence material PB, or a small FWHM emitter SB.
In one embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes at least one host material HB, exactly one phosphorescence material PB, and exactly one small FWHM emitter SB.
In one embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes at least one host material HB, exactly one TADF material EB, exactly one phosphorescence material PB, and exactly one small FWHM emitter SB.
In one embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one TADF material EB, exactly one phosphorescence material PB, and exactly one small FWHM emitter SB.
In one embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one phosphorescence material PB, and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one TADF material EB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one phosphorescence material PB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB and exactly one TADF material EB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB and exactly one phosphorescence material PB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one TADF material EB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one TADF material EB and exactly one phosphorescence material PB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one phosphorescence material PB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one TADF material EB, and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one TADF material EB, and exactly one phosphorescence material PB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one phosphorescence material PB, and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one phosphorescence material PB, exactly one TADF material EB, and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayers, wherein at least one sublayer includes exactly one host material HB, exactly one TADF material EB, exactly one phosphorescence material PB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, a sublayer includes exactly one TADF material EB and a sublayer (preferably another sublayer) includes exactly one phosphorescence material PB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B including (or consisting of) three or more than three sublayers, wherein the first sublayer B1 includes exactly one TADF material EB, the second sublayer B2 exactly one phosphorescence material PB, and the third sublayer B3 includes exactly one small FWHM emitter SB.
It is understood that the sublayers of a light-emitting layer B can be fabricated in different orders, e.g., B1-B2-B3, B1-B3-B2, B2-B1-B3, B2-B3-B1, B3-B2-B1, B3-B1-B2, and with one or more different sublayers in between.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B including (or consisting of) two or more than two sublayers, wherein the first sublayer B1 includes exactly one TADF material EB and exactly one phosphorescence material PB, and the second sublayer B2 includes exactly one small FWHM emitter SB. In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B including (or consisting of) two or more than two sublayers, wherein the first sublayer B1 includes exactly one TADF material EB and the second sublayer B2 includes exactly one phosphorescence material PB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B including (or consisting of) two or more than two sublayers, wherein the first sublayer B1 includes exactly one phosphorescence material PB, and the second sublayer B2 includes exactly one TADF material EB and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, an electroluminescent device according to the invention includes at least one light-emitting layer B including (or consisting of) two or more than two sublayers, wherein the first sublayer B1 includes exactly one small FWHM emitter SB, and the second sublayer B2 includes exactly one TADF material EB and exactly one phosphorescence material PB. In a preferred embodiment, sublayers B1 and B2 are (directly) adjacent to each other, in other words, are in (direct) contact with each other.
It is understood that an organic electroluminescent device according to the invention may optionally also include one or more light-emitting layers which do not fulfill the requirements given for a light-emitting layer B in the context of the present invention. In other words: An organic electroluminescent device according to the present invention includes at least one light-emitting layer B as defined herein and may optionally include one or more additional light-emitting layers for which the requirements given herein for a light-emitting layer B do not necessarily apply. In another embodiment of the invention, at least one, but not all light-emitting layers included in an organic electroluminescent device according to the invention are light-emitting layers B as defined within the specific embodiments of the invention.
In a preferred embodiment of the invention, each light-emitting layer included in an organic electroluminescent device according to the invention is a light-emitting layer B as defined within the specific embodiments of the invention.
The (at least one) host material HB, (at least one) phosphorescence material PB, and the (at least one) small FWHM emitter SB may be included in the organic electroluminescent device in any amount and any ratio.
In a preferred embodiment, the (at least one) host material HB, (at least one) phosphorescence material PB, (at least one) thermally activated delayed fluorescence (TADF) material EB, and the (at least one) small FWHM emitter SB may be included in the organic electroluminescent device in any amount and any ratio.
In a preferred embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayer, wherein each of the at least one sublayer includes more of the (at least one) host material HB (more specific: HP and/or HN and/or HBP), than of the (at least one) small FWHM emitter SB, according to the weight.
In a preferred embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayer, wherein each of the at least one sublayer includes more of the (at least one) host material HB (more specific: HP and/or HN and/or HBP), than of the (at least one) phosphorescence material PB, according to the weight.
In a preferred embodiment of the invention, the electroluminescent device according to the invention includes at least one light-emitting layer B composed of one or more than one sublayer, wherein each of the at least one sublayer includes more of the (at least one) host material HB (more specific: HP and/or HN and/or HBP), than of the (at least one) TADF material EB, according to the weight.
In a preferred embodiment of the invention, each of the at least one light-emitting layer B in an organic electroluminescent device according to the present invention includes more of the at least one TADF material EB than of the at least one small FWHM emitter SB, according to the weight.
In a preferred embodiment, in the organic electroluminescent device according to the present invention, the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, in the organic electroluminescent device according to the present invention, the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, in the organic electroluminescent device according to the present invention, the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, in the organic electroluminescent device according to the present invention, the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, wherein EB is optional, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, wherein EB is optional, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, wherein EB is optional, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In a preferred embodiment, wherein EB is optional, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In an even more preferred embodiment, wherein EB is necessary, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In an even more preferred embodiment, wherein EB is necessary, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In an even more preferred embodiment, wherein EB is necessary, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In an even more preferred embodiment, wherein EB is necessary, in an organic electroluminescent device according to the present invention, the (at least one) light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes (or consists of):
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes less than or equal to 5% by weight of one or more phosphorescence material PB.
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B including:
E(T1H)>E(T1P) (1)
E(T1P)>E(S1S) (2), and
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In a particularly preferred embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In a particularly preferred embodiment of the invention, the at least one, preferably each, light-emitting layer B includes or consists of:
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes less than or equal to 3% by weight, of phosphorescence material PB.
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes less than or equal to 1% by weight, of phosphorescence material PB.
In one embodiment of the invention, the at least one, preferably each, light-emitting layer B includes 10-40% by weight of one or more TADF material EB.
In one embodiment of the invention, the mass ratio of the (at least one) small full width at half maximum (FWHM) emitter SB to the (at least one) phosphorescence material PB (SB:PB) is ≥1.
In one embodiment of the invention, in at least one light-emitting layer B, the mass ratio of the at least one small full width at half maximum (FWHM) emitter SB to the at least one phosphorescence material PB (SB:PB) is ≥1. In one embodiment of the invention, in each light-emitting layer B, the mass ratio of the at least one small full width at half maximum (FWHM) emitter SB to the at least one phosphorescence material PB (SB:PB) is ≥1.
In one embodiment of the invention, the mass ratio of the (at least one) small full width at half maximum (FWHM) emitter SB to the (at least one) phosphorescence material PB (SB:PB) is <1.
In one embodiment of the invention, in at least one light-emitting layer B, the mass ratio of the at least one small full width at half maximum (FWHM) emitter SB to the at least one phosphorescence material PB (SB:PB) is <1. In one embodiment of the invention, in each light-emitting layer B, the mass ratio of the at least one small full width at half maximum (FWHM) emitter SB to the at least one phosphorescence material PB (SB:PB) is <1.
In one embodiment of the invention, the mass ratio SB:PB is in the range of from 1:1 to 30:1, in the range of from 1.5:1 to 25:1, in the range from 2:1 to 20:1, in the range of from 4:1 to 15:1, in the range of from 5:1 to 12:1, or in the range of from 10:1 to 11:1. For example, the mass ratio SB:PB is in the range of (approximately) 20:1, 15:1, 12:1, 10:1, 8:1, 5:1, 4:1, 2:1, 1.5:1 or 1:1.
In one embodiment of the invention, the mass ratio of the (at least one) small full width at half maximum (FWHM) emitter SB to the (at least one) phosphorescence material PB (SB:PB) is <1.
In one embodiment of the invention, the mass ratio PB:SB is in the range of from 1:1 to 30:1, in the range of from 1.5:1 to 25:1, in the range from 2:1 to 20:1, in the range of from 4:1 to 15:1, in the range of from 5:1 to 12:1, or in the range of from 10:1 to 11:1. For example, the mass ratio SB:PB is in the range of (approximately) 20:1, 15:1, 12:1, 10:1, 8:1, 5:1, 4:1, 2:1, 1.5:1 or 1:1.
As stated previously, it is understood that different sublayers of a light-emitting layer B do not necessarily all include the same materials or even the same materials in the same ratios.
In one embodiment of the invention, the relations expressed by the following formulas (1) and (2) apply:
E(T1H)>E(T1P) (1)
E(T1P)>E(S1S) (2),
In one embodiment, the aforementioned relations expressed by formulas (1) and (2) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
An organic electroluminescent device including at least one light-emitting layer B including:
E(T1H)>E(T1P) (1)
E(T1P)>E(S1S) (2).
In one embodiment, the aforementioned relations expressed by formulas (1) and (2) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, the relations expressed by the following formulas (3) and (4) apply.
E(T1H)>E(T1E) (3)
E(T1E)>E(T1P) (4),
In one embodiment, the aforementioned relations expressed by formulas (3) and (4) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (3) and (4) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In an alternative embodiment of the invention, the relations expressed by the following formulas (5) and (6) apply.
E(T1P)>E(T1E) (5)
E(S1E)>E(S1S) (6),
In one embodiment, the aforementioned relations expressed by formulas (5) and (6) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (5) and (6) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, the relations expressed by the following formulas (1) to (4) apply:
E(T1H)>E(T1P) (1)
E(T1P)>E(S1S) (2)
E(T1H)>E(S1E) (3)
E(T1E)>E(T1P) (4).
In one embodiment, the aforementioned relations expressed by formulas (1) to (4) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (1) to (4) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the difference (in energy) between the lowermost excited triplet state T1P of each phosphorescence material PB and the lowermost excited triplet state T1E of each TADF material EB is smaller than 0.3 eV: E(T1P)−E(T1E)<0.3 eV, and E(T1E)−E(T1P)<0.3 eV, respectively.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and the lowermost excited triplet state T1E of the at least one, preferably each, TADF material EB is smaller than 0.3 eV: E(T1P)−E(T1E)<0.3 eV, and E(T1E)−E(T1P)<0.3 eV, respectively.
In one embodiment of the invention, in each of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and the lowermost excited triplet state T1E of the at least one, preferably each, TADF material EB is smaller than 0.3 eV: E(T1P)−E(T1E)<0.3 eV, and E(T1E)−E(T1P)<0.3 eV, respectively.
In one embodiment of the invention, the relation expressed by the following formula (4) applies:
E(T1E)>E(T1P) (4).
In one embodiment, the aforementioned relation expressed by formula (4) applies to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relation expressed by formula (4) applies to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, the difference in energy between the lowermost excited triplet state T1E of the at least one, preferably each, TADF material EB and the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB is smaller than 0.2 eV: E(T1E)−E(T1P)<0.2 eV.
In a preferred embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1E of the at least one, preferably each, TADF material EB and the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB is smaller than 0.2 eV: E(T1E)−E(T1P)<0.2 eV.
In a preferred embodiment of the invention, in each of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1E of the at least one, preferably each, TADF material EB and the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB is smaller than 0.2 eV: E(T1E)−E(T1P)<0.2 eV.
In a preferred embodiment of the invention, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and lowermost excited singlet state S1S (energy level E(S1S)) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB is smaller than 0.3 eV: E(T1P)−E(S1S)<0.3 eV.
In a preferred embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and lowermost excited singlet state S1S of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB is smaller than 0.3 eV: E(T1P)−E(S1)<0.3 eV.
In a preferred embodiment of the invention, in each of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of at least one, preferably each phosphorescence material pB and lowermost excited singlet state S1S of at least one, preferably each small full width at half maximum (FWHM) emitter SB is smaller than 0.3 eV: E(T1P)−E(S1)<0.3 eV.
In a preferred embodiment of the invention, the difference in energy between the lowermost excited triplet state T1P of each phosphorescence material PB and lowermost excited singlet state S1S (energy level E(S1)) of each small full width at half maximum (FWHM) emitter SB is smaller than 0.2 eV: E(T1P)−E(S1)<0.2 eV.
In a preferred embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and lowermost excited singlet state S1S of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB is smaller than 0.2 eV: E(T1P)−E(S1)<0.2 eV.
In a preferred embodiment of the invention, in each of the one or more light-emitting layers B, the difference in energy between the lowermost excited triplet state T1P of the at least one, preferably each, phosphorescence material PB and lowermost excited singlet state S1S of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB is smaller than 0.2 eV: E(T1P)−E(S1S)<0.2 eV.
In a preferred embodiment of the invention, the following requirements are fulfilled:
E
HOMO(PB)>EHOMO(HB) (10)
E
HOMO(PB)>EHOMO(SB) (11).
In one embodiment, the aforementioned relations expressed by formulas (10) and (11) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (10) and (11) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the highest occupied molecular orbital HOMO(SB) of each small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of each host material HB having an energy EHOMO(HB):
E
HOMO(SB)>EHOMO(HB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of the at least one, preferably each, host material HB having an energy EHOMO(HB):
E
HOMO(SB)>EHOMO(HB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of the at least one, preferably each, host material HB having an energy EHOMO(HB):
E
HOMO(SB)>EHOMO(HB)
In one embodiment of the invention, the highest occupied molecular orbital HOMO(SB) of each small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of each TADF material EB having an energy EHOMO(EB):
E
HOMO(SB)>EHOMO(EB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of the at least one, preferably each, TADF material EB having an energy EHOMO(EB):
E
HOMO(SB)>EHOMO(EB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of the at least one, preferably each, TADF material EB having an energy EHOMO(EB):
E
HOMO(SB)>EHOMO(EB).
In one embodiment of the invention, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of the at least one, preferably each, TADF material EB having an energy EHOMO(EB).
E
HOMO(PB)>EHOMO(EB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of the at least one, preferably each, TADF material EB having an energy EHOMO(EB):
E
HOMO(PB)>EHOMO(EB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(EB) of the at least one, preferably each, TADF material EB having an energy EHOMO(EB):
E
HOMO(PB)>EHOMO(EB).
In one embodiment of the invention, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of the at least one, preferably each, host material HB having an energy EHOMO(HB).
E
HOMO(PB)>EHOMO(HB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of the at least one, preferably each, host material HB having an energy EHOMO(HB):
E
HOMO(PB)>EHOMO(HB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(HB) of the at least one, preferably each, host material HB having an energy EHOMO(HB):
E
HOMO(PB)>EHOMO(HB).
In one embodiment of the invention, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB):
E
HOMO(PB)>EHOMO(SB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB).
E
HOMO(PB)>EHOMO(SB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) is higher in energy than the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB).
E
HOMO(PB)>EHOMO(SB).
In one embodiment of the invention, the difference (in energy) between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.3 eV:
E
HOMO(PB)−EHOMO(SB)<0.3 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.3 eV:
E
HOMO(PB)−EHOMO(SB)<0.3 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.3 eV:
E
HOMO(PB)−EHOMO(SB)<0.3 eV.
In one embodiment of the invention, the difference (in energy) between the highest occupied molecular orbital HOMO(PB) of each phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of each small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.2 eV: EHOMO(PB)−EHOMO(SB)<0.2 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.2 eV:
E
HOMO(PB)−EHOMO(SB)<0.2 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is smaller than 0.2 eV:
E
HOMO(PB)−EHOMO(SB)<0.2 eV.
In a preferred embodiment of the invention, the difference (in energy) between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<EHOMO(PB)−EHOMO(SB)<0.3 eV.
In a preferred embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<EHOMO(PB)−EHOMO(SB)<0.3 eV.
In a preferred embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<EHOMO(PB)−EHOMO(SB)<0.3 eV.
In one embodiment of the invention, the difference (in energy) between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than or equal to 0.1 eV and smaller than or equal to 0.8 eV:
0.1 eV≤EHOMO(PB)−EHOMO(SB)≤0.8 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than or equal to 0.1 eV and smaller than or equal to 0.8 eV:
0.1 eV≤EHOMO(PB)−EHOMO(SB)≤0.8 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the highest occupied molecular orbital HOMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy EHOMO(PB) and the highest occupied molecular orbital HOMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy EHOMO(SB) is larger than or equal to 0.1 eV and smaller than or equal to 0.8 eV:
0.1 eV≤EHOMO(PB)−EHOMO(SB)≤0.8 eV.
In a preferred embodiment of the invention, the following requirements are fulfilled:
E
LUMO(EB)<ELUMO(HB) (12)
E
LUMO(EB)<ELUMO(PB) (13).
In one embodiment, the aforementioned relations expressed by formulas (12) and (13) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (12) and (13) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the electroluminescent device including a light-emitting layer B composed of one or more sublayers, wherein the one or more sublayers of the light-emitting layer B include:
E
LUMO(EB)<ELUMO(HB) (12)
E
LUMO(EB)<ELUMO(PB) (13)
E
LUMO(EB)<ELUMO(SB) (14).
In one embodiment, the aforementioned relations expressed by formulas (12) to (14) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (12) to (14) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the relations expressed by the following formulas (10) to (13) apply:
E
HOMO(PB)>EHOMO(HB) (10)
E
HOMO(PB)>EHOMO(SB) (11)
E
LUMO(EB)<ELUMO(HB) (12)
E
LUMO(EB)<ELUMO(PB) (13).
In one embodiment, the aforementioned relations expressed by formulas (10) to (13) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (10) to (13) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the relations expressed by the following formulas (10) to (14) apply:
E
HOMO(PB)>EHOMO(HB) (10)
E
HOMO(PB)>EHOMO(SB) (11)
E
LUMO(EB)<ELUMO(HB) (12)
E
LUMO(EB)<ELUMO(PB) (13)
E
LUMO(EB)<ELUMO(SB) (14).
In one embodiment, the aforementioned relations expressed by formulas (10) to (14) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (10) to (14) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(SB)>ELUMO(EB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB).
E
LUMO(SB)>ELUMO(EB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(SB)>ELUMO(EB).
In one embodiment of the invention, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.3 eV:
E
LUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.3 eV:
E
LUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.3 eV:
E
LUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, the difference (in energy) between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.2 eV:
E
LUMO(SB)−ELUMO(EB)<0.2 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.2 eV:
E
LUMO(SB)−ELUMO(EB)<0.2 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is smaller than 0.2 eV:
E
LUMO(SB)−ELUMO(EB)<0.2 eV.
In one embodiment of the invention, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<ELUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<ELUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, in each of the at least one light-emitting layers B, the difference in energy between the lowest unoccupied molecular orbital LUMO(SB) of the at least one, preferably each, small full width at half maximum (FWHM) emitter SB having an energy ELUMO(SB) and the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB) is larger than 0.0 eV and smaller than 0.3 eV:
0.0 eV<ELUMO(SB)−ELUMO(EB)<0.3 eV.
In one embodiment of the invention, the lowest unoccupied molecular orbital LUMO(PB) of each phosphorescence material PB having an energy ELUMO(PB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of each TADF material EB having an energy ELUMO(EB):
E
LUMO(PB)>ELUMO(EB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the lowest unoccupied molecular orbital LUMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy ELUMO(PB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(PB)>ELUMO(EB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the lowest unoccupied molecular orbital LUMO(PB) of the at least one, preferably each, phosphorescence material PB having an energy ELUMO(PB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(PB)>ELUMO(EB).
In one embodiment of the invention, the lowest unoccupied molecular orbital LUMO(HB) of the at least one, preferably each, host material HB having an energy ELUMO(HB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(HB)>ELUMO(EB).
In one embodiment of the invention, in at least one of the one or more light-emitting layers B, the lowest unoccupied molecular orbital LUMO(HB) of the at least one, preferably each, host material HB having an energy ELUMO(HB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(HB)>ELUMO(EB).
In one embodiment of the invention, in each of the at least one light-emitting layers B, the lowest unoccupied molecular orbital LUMO(HB) of the at least one, preferably each, host material HB having an energy ELUMO(HB) is higher in energy than the lowest unoccupied molecular orbital LUMO(EB) of the at least one, preferably each, TADF material EB having an energy ELUMO(EB):
E
LUMO(HB)>ELUMO(EB).
In one embodiment of the invention, the relations expressed by formulas (16) and (17) apply:
|Eλmax(PB)−Eλmax(SB)|<0.30 eV (16),
|Eλmax(EB)−Eλmax(SB)|<0.30 eV (17),
which means: The difference in energy between the energy of the emission maximum Eλmax(PB) of a phosphorescence material PB in the context of the present invention given in electron volt (eV) and the energy of the emission maximum Eλmax(SB) of a small FWHM emitter SB in the context of the present invention given in electron volt (eV) is smaller than 0.30 eV. And: The difference in energy between the energy of the emission maximum Eλmax(EB) of a TADF material EB in the context of the present invention given in electron volt (eV) and the energy of the emission maximum Eλmax(SB) of a small FWHM emitter SB in the context of the present invention given in electron volt (eV) is smaller than 0.30 eV.
In one embodiment, the aforementioned relations expressed by formulas (16) and (17) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (16) and (17) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
An organic electroluminescent device including at least one light-emitting layer B which is composed of one or more sublayers, wherein the one or more sublayers are adjacent to each other and as a whole contain:
|Eλmax(PB)−Eλmax(SB)|<0.30 eV (16),
|Eλmax(EB)−Eλmax(SB)|<0.30 eV (17).
In a preferred embodiment of the invention, the relations expressed by formulas (18) and (19) apply:
|Eλmax(PB)−Eλmax(SB)|<0.20 eV (18),
|Eλmax(EB)−Eλmax(SB)|<0.20 eV (19),
In one embodiment, the aforementioned relations expressed by formulas (18) and (19) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (18) and (19) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
One embodiment of the invention refers to an organic electroluminescent device, wherein
|Eλmax(PB)−Eλmax(SB)|<0.20 eV (18),
|Eλmax(EB)−Eλmax(SB)|<0.20 eV (19).
In an even more preferred embodiment of the invention, the relations expressed by formulas (20) and (21) apply:
|Eλmax(PB)−Eλmax(SB)|<0.1 eV (20),
|Eλmax(EB)−Eλmax(SB)|<0.10 eV (21),
In one embodiment, the aforementioned relations expressed by formulas (20) and (21) apply to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (20) and (21) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the relation expressed by formula (22) applies:
E
λmax(PB)>Eλmax(SB) (22),
In one embodiment, the aforementioned relation expressed by formula (22) applies to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relation expressed by formula (22) applies to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In one embodiment of the invention, the relation expressed by formula (22-a) applies:
E
λmax(EB)>Eλmax(SB) (22-a),
In one embodiment, the aforementioned relation expressed by formula (22-a) applies to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relation expressed by formula (22-a) applies to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which emits light at a distinct color point. According to the present invention, the electroluminescent device (e.g., OLED) emits light with a narrow emission band (small full width at half maximum (FWHM)). In a preferred embodiment, the electroluminescent device (e.g., OLED) according to the invention emits light with a FWHM of the main emission peak of below 0.25 eV, more preferably of below 0.20 eV, even more preferably of below 0.15 eV or even below 0.13 eV.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 (nits) of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 500 nm and 560 nm.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 510 nm and 550 nm.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED) which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 515 nm and 540 nm.
In a preferred embodiment, the electroluminescent device (e.g., an OLED) exhibits a LT95 value at constant current density J0=15 mA/cm2 of more than 100 h, preferably more than 200 h, more preferably more than 400 h, even more preferably more than 750 h or even more than 1000 h.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which emits light at a distinct color point. According to the present invention, the electroluminescent device (e.g., OLED) emits light with a narrow emission band (small full width at half maximum (FWHM)). In a preferred embodiment, the electroluminescent device (e.g., OLED) according to the invention emits light with a FWHM of the main emission peak of below 0.25 eV, more preferably of below 0.20 eV, even more preferably of below 0.15 eV or even below 0.13 eV.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.170) and CIEy (=0.797) color coordinates of the primary color green (CIEx=0.170 and CIEy=0.797) as defined by ITU-R Recommendation BT.2020 (Rec. 2020) and thus may be suited for the use in Ultra High Definition (UHD) displays, e.g., UHD-TVs. In this context, the term “close to” refers to the ranges of CIEx and CIEy coordinates provided at the end of this paragraph. In commercial applications, typically top-emitting (top-electrode is typically transparent) devices are used, whereas test devices as used throughout the present application represent bottom-emitting devices (bottom-electrode and substrate are transparent). Accordingly, a further aspect of the present invention relates to an electroluminescent device (e.g., an OLED), whose emission exhibits a CIEx color coordinate of between 0.15 and 0.45 preferably between 0.15 and 0.35, more preferably between 0.15 and 0.30 or even more preferably between 0.15 and 0.25 or even between 0.15 and 0.20 and/or a CIEy color coordinate of between 0.60 and 0.92, preferably between 0.65 and 0.90, more preferably between 0.70 and 0.88 or even more preferably between 0.75 and 0.86 or even between 0.79 and 0.84.
A further embodiment of the present invention relates to an OLED, which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.265) and CIEy (=0.65) color coordinates of the primary color green (CIEx=0.265 and CIEy=0.65) as defined by DCIP3. In this context, the term “close to” refers to the ranges of CIEx and CIEy coordinates provided at the end of this paragraph. In commercial applications, typically top-emitting (top-electrode is typically transparent) devices are used, whereas test devices as used throughout the present application represent bottom-emitting devices (bottom-electrode and substrate are transparent). Accordingly, a further aspect of the present invention relates to an OLED, whose bottom emission exhibits a CIEx color coordinate of between 0.2 and 0.45 preferably between 0.2 and 0.35 or more preferably between 0.2 and 0.30 or even more preferably between 0.24 and 0.28 or even between 0.25 and 0.27 and/or a CIEy color coordinate of between 0.60 and 0.9, preferably between 0.6 and 0.8, more preferably between 0.60 and 0.70 or even more preferably between 0.62 and 0.68 or even between 0.64 and 0.66.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 420 nm and 500 nm.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 440 nm and 480 nm.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and exhibits an emission maximum between 450 nm and 470 nm.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 18% or even more than 20% and/or exhibits an emission maximum between 420 nm and 500 nm, preferably between 430 nm and 490 nm, more preferably between 440 nm and 480 nm, even more preferably between 450 nm and 470 nm and/or exhibits a LT80 value at 500 cd/m2 of more than 100 h, preferably more than 200 h, more preferably more than 400 h, even more preferably more than 750 h or even more than 1000 h.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which emits light at a distinct color point. According to the present invention, the electroluminescent device (e.g., OLED) emits light with a narrow emission band (small full width at half maximum (FWHM)). In a preferred embodiment, the electroluminescent device (e.g., OLED) according to the invention emits light with a FWHM of the main emission peak of below 0.25 eV, more preferably of below 0.20 eV, even more preferably of below 0.15 eV or even below 0.13 eV.
A further aspect of the present invention relates to an OLED, which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.131) and CIEy (=0.046) color coordinates of the primary color blue (CIEx=0.131 and CIEy=0.046) as defined by ITU-R Recommendation BT.2020 (Rec. 2020) and thus is suited for the use in Ultra High Definition (UHD) displays, e.g., UHD-TVs. In commercial applications, typically top-emitting (top-electrode is transparent) devices are used, whereas test devices as used throughout the present application represent bottom-emitting devices (bottom-electrode and substrate are transparent). The CIEy color coordinate of a blue device can be reduced by up to a factor of two, when changing from a bottom- to a top-emitting device, while the CIEx remains nearly unchanged (Okinaka et al., Society for Information Display International Symposium Digest of Technical Papers, 2015, 46(1):312-313, DOI:10.1002/sdtp.10480). Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEx color coordinate of between 0.02 and 0.30, preferably between 0.03 and 0.25, more preferably between 0.05 and 0.20 or even more preferably between 0.08 and 0.18 or even between 0.10 and 0.15 and/or a CIEy color coordinate of between 0.00 and 0.45, preferably between 0.01 and 0.30, more preferably between 0.02 and 0.20 or even more preferably between 0.03 and 0.15 or even between 0.04 and 0.10.
A further aspect of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 1000 cd/m2 of more than 8%, more preferably of more than 10%, more preferably of more than 13%, even more preferably of more than 15% or even more than 20% and/or exhibits an emission maximum between 590 nm and 690 nm, preferably between 610 nm and 665 nm, even more preferably between 620 nm and 640 nm and/or exhibits a LT80 value at 500 cd/m2 of more than 100 h, preferably more than 200 h, more preferably more than 400 h, even more preferably more than 750 h or even more than 1000 h. Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEy color coordinate of more than 0.25, preferably more than 0.27, more preferably more than 0.29 or even more preferably more than 0.30.
A further embodiment of the present invention relates to an electroluminescent device (e.g., an OLED), which emits light with CIEx and CIEy color coordinates close to the CIEx (=0.708) and CIEy (=0.292) color coordinates of the primary color red (CIEx=0.708 and CIEy=0.292) as defined by ITU-R Recommendation BT.2020 (Rec. 2020) and thus is suited for the use in Ultra High Definition (UHD) displays, e.g., UHD-TVs. In this context, the term “close to” refers to the ranges of CIEx and CIEy coordinates provided at the end of this paragraph. In commercial applications, typically top-emitting (top-electrode is transparent) devices are used, whereas test devices as used throughout the present application represent bottom-emitting devices (bottom-electrode and substrate are transparent). Accordingly, a further aspect of the present invention relates to an OLED, whose emission exhibits a CIEx color coordinate of between 0.60 and 0.88, preferably between 0.61 and 0.83, more preferably between 0.63 and 0.78 or even more preferably between 0.66 and 0.76 or even between 0.68 and 0.73 and/or a CIEy color coordinate of between 0.25 and 0.70, preferably between 0.26 and 0.55, more preferably between 0.27 and 0.45 or even more preferably between 0.28 and 0.40 or even between 0.29 and 0.35.
Accordingly, a further aspect of the present invention relates to an electroluminescent device (e.g., an OLED), which exhibits an external quantum efficiency at 14500 cd/m2 of more than 10%, more preferably of more than 13%, more preferably of more than 15%, even more preferably of more than 17% or even more than 20% and/or exhibits an emission maximum between 590 nm and 690 nm, preferably between 610 nm and 665 nm, even more preferably between 620 nm and 640 nm.
One of the purposes of interest of an organic electroluminescent device may be the generation of light. Thus, the present invention further relates to a method for generating light of a desired wavelength range, including the step of providing an organic electroluminescent device according to any the present invention.
Accordingly, a further aspect of the present invention relates to a method for generating light of a desired wavelength range, including the steps of
A further aspect of the present invention relates to a process of making the organic electroluminescent devices by assembling the elements described above. The present invention also relates to a method for generating green light, in particular by using said organic electroluminescent device.
A further aspect of the invention relates to an organic electroluminescent device, wherein (at least) one, preferably exactly one, of the relations expressed by the following formulas (23) to (25) applies to materials included in the same light-emitting layer B:
440 nm<λmax(SB)<470 nm (23)
510 nm<λmax(SB)<550 nm (24)
610 nm<λmax(SB)<665 nm (25),
wherein λmax(SB) is the emission maximum of the at least one, preferably each, small FWHM emitter SB and is given in nanometers (nm).
In one embodiment of the invention at least one, preferably exactly one, of the relations expressed by the following formulas (23) to (25) applies to materials included in any of the at least one light-emitting layers B of the organic electroluminescent device according to the invention.
A further aspect of the invention relates to a method for generating light, including the steps of:
A further aspect of the invention relates to a method for generating light, including the steps of:
The skilled artisan understands that the at least one TADF material EB and the at least one phosphorescence material PB (vide infra) may be used as emitters in organic electroluminescent devices. However, preferably, in the organic electroluminescent device according to the present invention, the main function of the at least one TADF material EB and the at least one phosphorescence material PB is not emitting light. In a preferred embodiment, upon applying a voltage (and electrical current), the organic electroluminescent device according to the invention emits light, wherein this emission is mainly (i.e., to an extent of more than 50%, preferably of more than 60%, more preferably of more than 70%, even more preferably of more than 80% or even of more than 90%) attributed to fluorescent light emitted by the at least one small FWHM emitter SB. In consequence, the organic electroluminescent device according to the present invention preferably also displays a narrow emission, which is expressed by a small FWHM of the main emission peak of below 0.25 eV, more preferably of below 0.20 eV, even more preferably of below 0.15 eV or even below 0.13 eV.
In a preferred embodiment of the invention, the relation expressed by the following formula (26) applies:
If, for example, the light-emitting layer B includes two small FWHM emitters SB with a concentration of 1% by weight each, the spin coated film preferably also includes 1% by weight of each of the two small FWHM emitters SB. In this exemplary case, the matrix material of the spin coated film would amount to 98% by weight of the spin coated film. This matrix material of the spin coated film may be selected to reflect the weight-ratio of the host materials HB included in the light-emitting layer B of the organic electroluminescent device. If, in the aforementioned example, the light-emitting layer B includes a single host material HB, this host material would preferably be the sole matrix material of the spin coated film. If, however, in the aforementioned example, the light-emitting layer B includes two host materials HB, one with a content of 60% by weight and the other with a content of 20% by weight (i.e., in a ratio of 3:1), the aforementioned matrix material of the spin coated film (including 1% by weight of each of the two small FWHM emitters SB) would preferably be a 3:1-mixture of the two host materials HB as present in the EML.
If more than one light-emitting layer B is contained in an organic electroluminescent device according to the present invention, the relation expressed by the aforementioned formula (26) preferably applies to all light-emitting layers B included in the device.
In one embodiment, for at least one light-emitting layer B of the organic electroluminescent device according to the present invention, the aforementioned ratio FWHMD:FWHMSB is equal to or smaller than 1.50, preferably 1.40, even more preferably 1.30, still even more preferably 1.20, or even 1.10.
In one embodiment, for each light-emitting layer B of the organic electroluminescent device according to the present invention, the aforementioned ratio FWHMD:FWHMSB is equal to or smaller than 1.50, preferably 1.40, even more preferably 1.30, still even more preferably 1.20, or even 1.10.
It should be noted that for the selection of fluorescent emitters for the use as small FWHM emitters SB in the context of the present invention, the FWHM value may be determined as described in a later subchapter of this text (briefly: preferably from a spin coated film of the respective emitter in poly(methyl methacrylate) PMMA with a concentration of 1-5% by weight, in particular 2% by weight, or from a solution, vide infra). This is to say that the FWHM values of the exemplary small FWHM emitters SB listed in Table 1S may not be understood as FWHMSB values in the context of equation (26) and the associated preferred embodiments of the present invention.
The examples and claims further illustrate the invention.
According to the invention, any of the one or more host materials HB included in any of the at least one light-emitting layer B may be a p-host HP exhibiting high hole mobility, an n-host HN exhibiting high electron mobility, or a bipolar host material HBP exhibiting both, high hole mobility and high electron mobility.
An n-host exhibiting high electron mobility in the context of the present invention preferably has a LUMO energy ELUMO(HN) equal to or smaller than −2.50 eV (ELUMO(HN)≤−2.50 eV). Preferably, ELUMO(HN)≤−2.60 eV, more preferably ELUMO(HN)≤−2.65 eV, and even more preferably, ELUMO(HN)≤−2.70 eV. The LUMO is the lowest unoccupied molecular orbital. The energy of the LUMO is determined as described in a later subchapter of this text.
A p-host exhibiting high hole mobility in the context of the present invention preferably has a HOMO energy EHOMO(HP) equal to or higher than −6.30 eV (EHOMO(HP)≥−6.30 eV), preferably EHOMO(HP)≥−5.90 eV, more preferably EHOMO(HP)≥−5.70 eV and even more preferably EHOMO(HP)≥−5.40 eV or even EHOMO(HP)≥−2.60 eV. The HOMO is the highest occupied molecular orbital. The energy of the HOMO is determined as described in a later subchapter of this text.
In one embodiment of the invention, each host material HB is a p-host HP which has a HOMO energy EHOMO(HP) equal to or higher than −6.30 eV (EHOMO(HP)≥−6.30 eV), preferably EHOMO(HP)≥−5.90 eV, more preferably EHOMO(HP)≥−5.70 eV, and even more preferably EHOMO(HP)≥−5.40 eV. The HOMO is the highest occupied molecular orbital. The energy of the HOMO is determined as described in a later subchapter of this text.
In one embodiment of the invention, the at least one, preferably each p-host HP has a HOMO energy EHOMO(HP) smaller than −5.60 eV.
In one embodiment of the invention, the organic electroluminescent device including at least one light-emitting layer B which is composed of one or more sublayers, wherein the one or more sublayers are adjacent to each other and as a whole contain:
(iv) at least one thermally activated delayed fluorescence (TADF) material EB, which has a lowermost excited singlet state energy level E(S1E) and a lowermost excited triplet state energy level E(T1E)
A bipolar host exhibiting high electron mobility in the context of the present invention preferably has a LUMO energy ELUMO(HBP) equal to or smaller than −2.50 eV (ELUMO(HBP)≤−2.50 eV). Preferably, ELUMO(HBP)≤−2.60 eV, more preferably ELUMO(HBP)≤−2.65 eV, and even more preferably, ELUMO(HBP)≤−2.70 eV. The LUMO is the lowest unoccupied molecular orbital. The energy of the LUMO is determined as described in a later subchapter of this text.
A bipolar host exhibiting high hole mobility in the context of the present invention preferably has a HOMO energy EHOMO(HBP) equal to or higher than −6.30 eV (EHOMO(HBP)≥−6.30 eV), preferably EHOMO(HBP)≥−5.90 eV. More, preferably, EHOMO(HBP)≥−5.70 eV and still even more preferably EHOMO(HBP)≥−5.40 eV. The HOMO is the highest occupied molecular orbital. The energy of the HOMO is determined as described in a later subchapter of this text.
In one embodiment of the invention, a bipolar host material HBP, preferably each bipolar host material HBP fulfills both of the following requirements:
The person skilled in the art knows which materials are suitable host materials for use in organic electroluminescent devices such as those of the present invention. See for example: Y. Tao, C. Yang, J. Quin, Chemical Society Reviews 2011, 40, 2943, DOI: 10.1039/C0CS00160K; K. S. Yook, J. Y. Lee, The Chemical Record 2015, 16(1), 159, DOI: 10.1002/tcr.201500221; T. Chatterjee, K.-T. Wong, Advanced Optical Materials 2018, 7(1), 1800565, DOI: 10.1002/adom.201800565;
Q. Wang, Q.-S. Tian, Y.-L. Zhang, X. Tang, L.-S. Liao, Journal of Materials Chemistry C 2019, 7, 11329, DOI: 10.1039/C9TC03092A.
Furthermore, for example, US2006006365 (A1), US2006208221 (A1), US2005069729 (A1), EP1205527 (A1), US2009302752 (A1), US20090134784 (A1), US2009302742 (A1), US2010187977 (A1), US2010187977 (A1), US2012068170 (A1), US2012097899 (A1), US2006121308 (A1), US2006121308 (A1), US2009167166 (A1), US2007176147 (A1), US2015322091 (A1), US2011105778 (A1), US2011201778 (A1), US2011121274 (A1), US2009302742 (A1), US2010187977 (A1), US2010244009 (A1), US2009136779 (A1), EP2182040 (A2), US2012202997 (A1), US2019393424 (A1), US2019393425 (A1), US2020168819 (A1), US2020079762 (A1), and US2012292576 (A1) disclose host materials that may be used in organic electroluminescent devices according to the present invention. It is understood that this does not imply that the present invention is limited to organic electroluminescent devices including host materials disclosed in the cited references. It is also understood that any host materials used in the state of the art may also be suitable host materials HB in the context of the present invention.
In one embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes one or more p-hosts HP. In one embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes only a single host material and this host material is a p-host HP.
In one embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes one or more n-hosts HN. In another embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes only a single host material and this host material is an n-host HN.
In one embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes one or more bipolar hosts HBP. In one embodiment of the invention, each light-emitting layer B of an organic electroluminescent device according to the invention includes only a single host material and this host material is a bipolar host HBP.
In another embodiment of the invention, at least one light-emitting layer B of an organic electroluminescent device according to the invention includes at least two different host materials HB. In this case, the more than one host materials HB present in the respective light-emitting layer B may either all be p-hosts HP or all be n-hosts HN, or all be bipolar hosts HBP, but may also be a combination thereof.
It is understood that, if an organic electroluminescent device according to the invention includes more than one light-emitting layer B, any of them may, independently of the one or more other light-emitting layers B, include either one host material HB or more than one host materials HB for which the above-mentioned definitions apply. It is further understood that different light-emitting layers B included in an organic electroluminescent device according to the invention do not necessarily all include the same materials or even the same materials in the same concentrations.
It is understood that, if a light-emitting layer B of an organic electroluminescent device according to the invention is composed of more than one sublayer, any of them may, independently of the one or more other sublayers, include either one host material HB or more than one host materials HB for which the above-mentioned definitions apply. It is further understood that different sublayers of a light-emitting layer B included in an organic electroluminescent device according to the invention do not necessarily all include the same materials or even the same materials in the same concentrations.
If included in the same light-emitting layer B of an organic electroluminescent device according to the invention, at least one p-host HP and at least one n-host HN may optionally form an exciplex. The person skilled in the art knows how to choose pairs of HP and HN, which form an exciplex and the selection criteria, including HOMO- and/or LUMO-energy level requirements of HP and HN. This is to say that, in case exciplex formation may be aspired, the highest occupied molecular orbital (HOMO) of the p-host material HP may be at least 0.20 eV higher in energy than the HOMO of the n-host material HN and the lowest unoccupied molecular orbital (LUMO) of the p-host material HP may be at least 0.20 eV higher in energy than the LUMO of the n-host material HN.
In a preferred embodiment of the invention, at least one host material HB(e.g., HP, HN, and/or HBP) is an organic host material, which, in the context of the invention, means that it does not contain any transition metals. In a preferred embodiment of the invention, all host materials HB (HP, HN, and/or HBP) in the electroluminescent device of the present invention are organic host materials, which, in the context of the invention, means that they do not contain any transition metals. Preferably, at least one host material HB, more preferably all host materials HB (HP, HN and/or HBP) predominantly consist of the elements hydrogen (H), carbon (C), and nitrogen (N), but may for example also include oxygen (O), boron (B), silicon (Si), fluorine (F), and bromine (Br).
In one embodiment of the invention, each host material HB is a p-host HP.
In a preferred embodiment of the invention, a p-host HP, optionally included in any of the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers), includes or consists of:
In an even more preferred embodiment of the invention, Z1 is at each occurrence a direct bond and adjacent substituents RII do not combine to form an additional ring system.
In a still even more preferred embodiment of the invention, a p-host HP optionally included in an organic electroluminescent device according to the invention is selected from the group consisting of the following structures:
In a preferred embodiment of the invention, an n-host HN optionally included in any of the at least one light-emitting layer B as a whole (consisting of one (sub)layer or including more than one sublayers) includes or consists of a structure according to any of the Formulas HN-I, HN-II, and HN-II
In an even more preferred embodiment of the invention, an n-host HN optionally included in an organic electroluminescent device according to the invention is selected from the group consisting of the following structures:
In one embodiment of the invention, no n-host HN included in any light-emitting layer B of an organic electroluminescent device according to the invention contains any phosphine oxide groups and, in particular, no n-host HN is bis[2-(diphenylphosphino)phenyl] ether oxide (DPEPO).
According to the invention, a thermally activated delayed fluorescence (TADF) material EB is characterized by exhibiting a ΔEST value, which corresponds to the energy difference between the lowermost excited singlet state energy level E(S1E) and the lowermost excited triplet state energy level E(T1E), of less than 0.4 eV, preferably of less than 0.3 eV, more preferably of less than 0.2 eV, even more preferably of less than 0.1 eV, or even of less than 0.05 eV. Thus, ΔEST of a TADF material EB according to the invention is sufficiently small to allow for thermal repopulation of the lowermost excited singlet state S1E from the lowermost excited triplet state T1E (also referred to as up-intersystem crossing or reverse intersystem crossing, RISC) at room temperature (RT, i.e., (approximately) 20° C.).
Preferably, in the context of the present invention, TADF materials display both, prompt fluorescence when the emissive S1E state is reached in the cause of the charge carrier (hole and electron) recombination and delayed fluorescence when the emissive S1E state is reached via thermally activated RISC from the T1E state.
It is understood that a small FWHM emitter SB included in a light-emitting layer B of an organic electroluminescent device according to the invention may optionally also have a ΔEST value of less than 0.4 eV and exhibit thermally activated delayed fluorescence (TADF). However, for any small FWHM emitter SB in the context of the invention, this is only an optional feature.
In a preferred embodiment of the invention, there is spectral overlap between the emission spectrum of at least one TADF material EB and the absorption spectrum of at least one small FWHM emitter SB (when both spectra are measured under comparable conditions). In this case, the at least one TADF material EB may transfer energy to the at least one small FWHM emitter SB.
According to the invention, a TADF material EB has an emission maximum in the visible wavelength range of from 380 nm to 800 nm, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, each TADF material EB has an emission maximum in the deep blue wavelength range of from 380 nm to 470 nm, preferably 400 nm to 470 nm, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, each TADF material EB has an emission maximum in the green wavelength range of from 480 nm to 560 nm, preferably 500 nm to 560 nm, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, each TADF material EB has an emission maximum in the red wavelength range of from 600 nm to 665 nm, preferably 610 nm to 665 nm, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In a preferred embodiment of the invention, the emission maximum (peak emission) of a TADF material EB is at a shorter wavelength than the emission maximum (peak emission) of a small FWHM emitter SB in the context of the present invention.
In a preferred embodiment of the invention, each TADF material EB is an organic TADF material, which, in the context of the invention, means that it does not contain any transition metals. Preferably, each TADF material EB according to the invention predominantly consists of the elements hydrogen (H), carbon (C), and nitrogen (N), but may for example also include oxygen (O), boron (B), silicon (Si), fluorine (F), and bromine (Br).
In a preferred embodiment of the invention, each TADF material EB has a molecular weight equal to or smaller than 800 g/mol.
In one embodiment of the invention, a TADF emitter EB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 30%, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In a preferred embodiment of the invention, a TADF emitter EB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 50%, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In an even more preferred embodiment of the invention, a TADF emitter EB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 70%, typically measured with 10% by weight of the TADF material EB in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, the at least one, preferably each TADF material EB
In one embodiment of the invention, the energy ELUMO(EB) of the lowest unoccupied molecular orbital LUMO(EB) of each TADF material EB is smaller than −2.6 eV.
The person skilled in the art knows how to design TADF molecules EB according to the invention and the structural features that such molecules typically display. Briefly, to facilitate the reverse intersystem crossing (RISC), ΔEST is usually decreased and, in the context of the present invention, ΔEST is smaller than 0.4 eV, as stated above. This is oftentimes achieved by designing TADF molecules EB so that the HOMO and LUMO are spatially largely separated on (electron-) donor and (electron-) acceptor groups, respectively. These groups are usually bulky or connected via spiro-junctions so that they are twisted and the spatial overlap of the HOMO and the LUMO is reduced. However, minimizing the spatial overlap of the HOMO and the LUMO also results in a reduction of the photoluminescence quantum yield (PLQY) of the TADF material, which is unfavorable. Therefore, in practice, these two effects are both taken into account to achieve a reduction of ΔEST as well as a high PLQY.
One common approach for the design of TADF materials is to covalently attach one or more (electron-) donor moieties on which the HOMO is distributed and one or more (electron-) acceptor moieties on which the LUMO is distributed to the same bridge, herein referred to as linker group. A TADF material EB may for example also include two or three linker groups which are bonded to the same acceptor moiety and additional donor and acceptor moieties may be bonded to each of these two or three linker groups.
One or more donor moieties and one or more acceptor moieties may also be bonded directly to each other (without the presence of a linker group).
Typical donor moieties are derivatives of diphenyl amine, carbazole, acridine, phenoxazine, and related structures.
Benzene-, biphenyl-, and to some extend also terphenyl-derivatives are common linker groups.
Nitrile groups are very common acceptor moieties in TADF molecules and known examples thereof include:
Nitrogen-heterocycles such as triazine-, pyrimidine-, triazole-, oxadiazole-, thiadiazole-, heptazine-, 1,4-diazatriphenylene-, benzothiazole-, benzoxazole-, quinoxaline-, and diazafluorene-derivatives are also well-known acceptor moieties used for the construction of TADF molecules. Known examples of TADF molecules including for example a triazine acceptor include PIC-TRZ (7,7′-(6-([1,1′-biphenyl]-4-yl)-1,3,5-triazine-2,4-diyl)bis(5-phenyl-5,7-dihydroindolo[2,3-b]carbazole)), mBFCzTrz (5-(3-(4,6-diphenyl-1,3,5-triazin-2-yl)phenyl)-5H-benzofuro[3,2-c]carbazole), and DCzTrz (9,9′-(5-(4,6-diphenyl-1,3,5-triazin-2-yl)-1,3-phenylene)bis(9H-carbazole)).
Another group of TADF materials includes diaryl ketones such as benzophenone or (heteroaryl)aryl ketones such as 4-benzoylpyridine, 9,10-anthraquinone, 9H-xanthen-9-one, and derivatives thereof as acceptor moieties to which the donor moieties (usually carbazolyl substituents) are bonded. Examples of such TADF molecules include BPBCz (bis(4-(9′-phenyl-9H,9′H-[3,3′-bicarbazol]-9-yl)phenyl)methanone), mDCBP ((3,5-di(9H-carbazol-9-yl)phenyl)(pyridin-4-yl)methanone), AQ-DTBu-Cz (2,6-bis(4-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)anthracene-9,10-dione), and MCz-XT (3-(1,3,6,8-tetramethyl-9H-carbazol-9-yl)-9H-xanthen-9-one), respectively.
Sulfoxides, in particular diphenyl sulfoxides, are also commonly used as acceptor moieties for the construction of TADF materials and known examples include 4-PC-DPS (9-phenyl-3-(4-(phenylsulfonyl)phenyl)-9H-carbazole), DitBu-DPS (9,9′-(sulfonylbis(4,1-phenylene))bis(9H-carbazole)), and TXO-PhCz (2-(9-phenyl-9H-carbazol-3-yl)-9H-thioxanthen-9-one 10,10-dioxide).
Exemplarily, all groups of TADF molecules mentioned above may provide suitable TADF materials EB for use according to the present invention, given that the specific materials fulfills the aforementioned basic requirement, namely the ΔEST value being smaller than 0.4 eV.
The person skilled in the art knows that not only the structures named above, but many more materials may be suitable TADF materials EB in the context of the present invention. The skilled artisan is familiar with the design principles of such molecules and also knows how to design such molecules with a certain emission color (e.g., blue, green or red emission).
See for example: H. Tanaka, K. Shizu, H. Nakanotani, C. Adachi, Chemistry of Materials 2013, 25(18), 3766, DOI: 10.1021/cm402428a; J. Li, T. Nakagawa, J. MacDonald, Q. Zhang, H. Nomura, H. Miyazaki, C. Adachi, Advanced Materials 2013, 25(24), 3319, DOI: 10.1002/adma.201300575; K. Nasu, T. Nakagawa, H. Nomura, C.-J. Lin, C.-H. Cheng, M.-R. Tseng, T. Yasudaad, C. Adachi, Chemical Communications 2013, 49(88), 10385, DOI: 10.1039/c3cc44179b; Q. Zhang, B. Li1, S. Huang, H. Nomura, H. Tanaka, C. Adachi, Nature Photonics 2014, 8(4), 326, DOI: 10.1038/nphoton.2014.12; B. Wex, B. R. Kaafarani, Journal of Materials Chemistry C 2017, 5, 8622, DOI: 10.1039/c7tc02156a; Y. Im, M. Kim, Y. J. Cho, J.-A. Seo, K. S. Yook, J. Y. Lee, Chemistry of Materials 2017, 29(5), 1946, DOI: 10.1021/acs.chemmater.6b05324; T.-T. Bui, F. Goubard, M. Ibrahim-Ouali, D. Gigmes, F. Dumur, Beilstein Journal of Organic Chemistry 2018, 14, 282, DOI: 10.3762/bjoc.14.18; X. Liang, Z.-L. Tu, Y.-X. Zheng, Chemistry—A European Journal 2019, 25(22), 5623, DOI: 10.1002/chem.201805952.
Furthermore, for example, US2015105564 (A1), US2015048338 (A1), US2015141642 (A1), US2014336379 (A1), US2014138670 (A1), US2012241732 (A1), EP3315581 (A1), EP3483156 (A1), and US2018053901 (A1) disclose TADF materials EB that may be used in organic electroluminescent devices according to the present invention. It is understood that this does not imply that the present invention is limited to organic electroluminescent devices including TADF materials disclosed in the cited references. It is also understood that any TADF materials used in the state of the art may also be suitable TADF materials EB in the context of the present invention.
In one embodiment of the invention, each TADF material EB includes one or more chemical moieties independently of each other selected from the group consisting of CN, CF3, and an optionally substituted 1,3,5-triazinyl group.
In one embodiment of the invention, each TADF material EB includes one or more chemical moieties independently of each other selected from the group consisting of CN and an optionally substituted 1,3,5-triazinyl group.
In one embodiment of the invention, each TADF material EB includes one or more optionally substituted 1,3,5-triazinyl group.
In one embodiment of the invention, each TADF material EB includes one or more chemical moieties independently of each other selected from an amino group, indolyl, carbazolyl, and derivatives thereof, all of which may be optionally substituted, wherein these groups may be bonded to the core structure of the respective TADF molecule via a nitrogen (N) or via a carbon (C) atom, and wherein substituents bonded to these groups may form mono- or polycyclic, aliphatic or aromatic, carbo- or heterocyclic ring systems.
In a preferred embodiment of the invention, the at least one, preferably each TADF material EB includes:
one or more first chemical moieties, independently of each other selected from an amino group, indolyl, carbazolyl, and derivatives thereof, all of which may be optionally substituted, wherein these groups may be bonded to the core structure of the respective TADF molecule via a nitrogen (N) or via a carbon (C) atom, and wherein substituents bonded to these groups may form mono- or polycyclic, aliphatic or aromatic, carbo- or heterocyclic ring systems;
In an even more preferred embodiment of the invention, the at least one, preferably each TADF material EB includes:
In a still even more preferred embodiment of the invention, the at least one, preferably each TADF material EB includes:
The person skilled in the art knows that the expression “derivatives thereof” means that the respective parent structure may be optionally substituted or any atom within the respective parent structure may be replaced by an atom of another element for example.
In one embodiment of the invention, the organic electroluminescent device including at least one light-emitting layer B including:
E(T1H)>E(T1P) (1)
E(T1H)>E(T1E) (2),
In one embodiment of the invention, each TADF material EB includes:
In a preferred embodiment of the invention,
In an even more preferred embodiment of the invention,
In a still even more preferred embodiment of the invention,
In a still even more preferred embodiment of the invention,
In a still even more preferred embodiment of the invention,
In a still even more preferred embodiment of the invention,
In a particularly preferred embodiment of the invention,
In a preferred embodiment of the invention, a is always 1 and b is always 0.
In a preferred embodiment of the invention, Z2 is at each occurrence a direct bond.
In a preferred embodiment of the invention, Ra is at each occurrence hydrogen.
In a preferred embodiment of the invention, Ra and Rd are at each occurrence hydrogen.
In a preferred embodiment of the invention, Q3 is at each occurrence nitrogen (N).
In one embodiment of the invention, at least one group RX in Formula EWG-I is CN.
In a preferred embodiment of the invention, exactly one group RX in Formula EWG-I is CN.
In a preferred embodiment of the invention, exactly one group RX in Formula EWG-I is CN and no group RX in Formula EWG-I is CF3.
Examples of first chemical moieties according to the present invention are shown below, which does of course not imply that the present invention is limited to these examples:
Examples of second chemical moieties according to the present invention are shown below, which does of course not imply that the present invention is limited to these examples:
In a preferred embodiment of the invention, each TADF material EB has a structure represented by any of Formulas EB-I, EB-II, EB-III, EB-IV, EB-V, EB-VI, EB-VII, EB-VIII, EB-IX, EB-X, and EB-XI;
In a preferred embodiment of the invention, R13 is at each occurrence hydrogen.
In one embodiment of the invention, RY is at each occurrence CN.
In one embodiment of the invention, RY is at each occurrence CF3.
In one embodiment of the invention, RY is at each occurrence a structure represented by Formula BN-I.
In a preferred embodiment of the invention, RY is at each occurrence independently of each other selected from CN and a structure represented by Formula BN-I.
In a preferred embodiment of the invention, each TADF material EB has a structure represented by any of Formulas EB-I, EB-II, EB-III, EB-IV, EB-V, EB-VI, EB-VII, and EB-X, wherein the aforementioned definitions apply.
In a preferred embodiment of the invention, each TADF material EB has a structure represented by any of Formulas EB-I, EB-III, EB-V, EB-VI, and EB-X, wherein the aforementioned definitions apply.
Examples of TADF materials EB for use in organic electroluminescent devices according to the invention are listed in the following, whereat this does not imply that only the shown examples are suitable TADF materials EB in the context of the present invention.
Non-limiting examples of TADF materials EB according Formula EB-I are shown below:
Non-limiting examples of TADF materials EB according Formula EB-II are shown below:
Non-limiting examples of TADF materials EB according Formula EB-III are shown below:
Non-limiting examples of TADF materials EB according Formula EB-IV are shown below:
Non-limiting examples of TADF materials EB according Formula EB-V are shown below:
Non-limiting examples of TADF materials EB according Formula EB-VI are shown below:
Non-limiting examples of TADF materials EB according Formula EB-VII are shown below:
Non-limiting examples of TADF materials EB according Formula EB-VIII are shown below:
Non-limiting examples of TADF materials EB according Formula EB-IX are shown below:
Non-limiting examples of TADF materials EB according Formula EB-X are shown below:
Non-limiting examples of TADF materials EB according Formula EB-XI are shown below:
The synthesis of TADF materials EB can be accomplished via standard reactions and reaction conditions known to the skilled artisan. Typically, in a first step, a coupling reaction, preferably a palladium-catalyzed coupling reaction, may be performed, which is exemplarily shown below for the synthesis of TADF materials EB according to any of Formulas EB-III, EB-IV, and EB-V.
E1 can be any boronic acid (RB═H) or an equivalent boronic acid ester (RB=alkyl or aryl), in particular two RB may form a ring to give e.g., boronic acid pinacol esters. As second reactant E2 is used, wherein Hal refers to halogen and may be I, Br or Cl, but preferably is Br. Reaction conditions of such palladium-catalyzed coupling reactions are known the person skilled in the art, e.g., from WO 2017/005699, and it is known that the reacting groups of E1 and E2 can be interchanged as shown below to optimize the reaction yields:
In a second step, the TADF molecules are obtained via the reaction of a nitrogen heterocycle in a nucleophilic aromatic substitution with the aryl halide, preferably aryl fluoride E3. Typical conditions include the use of a base, such as tribasic potassium phosphate or sodium hydride, for example, in an aprotic polar solvent, such as dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF), for example.
In particular, the donor molecule E4 is a 3,6-substituted carbazole (e.g., 3,6-dimethylcarbazole, 3,6-diphenylcarbazole, 3,6-di-tert-butylcarbazole), a 2,7-substituted carbazole (e.g., 2,7-dimethylcarbazole, 2,7-diphenylcarbazole, 2,7-di-tert-butylcarbazole), a 1,8-substituted carbazole (e.g., 1,8-dimethylcarbazole, 1,8-diphenylcarbazole, 1,8-di-tert-butylcarbazole), a 1-substituted carbazole (e.g., 1-methylcarbazole, 1-phenylcarbazole, 1-tert-butylcarbazole), a 2-substituted carbazole (e.g., 2-methylcarbazole, 2-phenylcarbazole, 2-tert-butylcarbazole), or a 3-substituted carbazole (e.g., 3-methylcarbazole, 3-phenylcarbazole, 3-tert-butylcarbazole).
Alternatively, a halogen-substituted carbazole, particularly 3-bromocarbazole, can be used as E4.
In a subsequent reaction, a boronic acid ester functional group or boronic acid functional group may be exemplarily introduced at the position of the one or more halogen substituents, which was introduced via E4, to yield the corresponding carbazol-3-yl-boronic acid ester or carbazol-3-yl-boronic acid, e.g., via the reaction with bis(pinacolato)diboron (CAS No. 73183-34-3). Subsequently, one or more substituents Ra, Rb or Rd may be introduced in place of the boronic acid ester group or the boronic acid group via a coupling reaction with the corresponding halogenated reactant, e.g., Ra-Hal, preferably Ra—Cl and Ra-Br.
Alternatively, one or more substituents Ra, Rb or Rd may be introduced at the position of the one or more halogen substituents, which was introduced via D-H, via the reaction with a boronic acid of the substituent Ra [Ra—B(OH)2], Rb [Rb—B(OH)2] or Rd[Rd—B(OH)2] or a corresponding boronic acid ester.
Further TADF materials EB may be obtained analogously. A TADF material EB may also be obtained by any alternative synthesis route suitable for this purpose.
An alternative synthesis route may include the introduction of a nitrogen heterocycle via copper- or palladium-catalyzed coupling to an aryl halide or aryl pseudohalide, preferably an aryl bromide, an aryl iodide, aryl triflate or an aryl tosylate.
The phosphorescence materials PB in the context of the present invention utilize the intramolecular spin-orbit interaction (heavy atom effect) caused by metal atoms to obtain light emission from triplets.
Generally, it is understood, that all phosphorescent complexes that are used in organic electroluminescent devices in the state of the art may also be used in an organic electroluminescent device according to the present invention.
It is common knowledge to those skilled in the art that phosphorescence materials PB used in organic electroluminescent devices are oftentimes complexes of Ir, Pt, Pd, Au, Os, Eu, Ru, Re, Ag and Cu, in the context of this invention preferably of Ir, Pt, and Pd, more preferably of Ir and Pt. The skilled artisan knows which materials are suitable as phosphorescence materials in organic electroluminescent devices and how to synthesize them. Furthermore, the skilled artisan is familiar with the design principles of phosphorescent complexes for use in organic electroluminescent devices and knows how to tune the emission of the complexes by means of structural variations.
See for example: C.-L. Ho, H. Li, W.-Y. Wong, Journal of Organometallic Chemistry 2014, 751, 261, DOI: 10.1016/j.jorganchem.2013.09.035; T. Fleetham, G. Li, J. Li, Advanced Science News 2017, 29, 1601861, DOI: 10.1002/adma.201601861; A. R. B. M. Yusoff, A. J. Huckaba, M. K. Nazeeruddin, Topics in Current Chemistry (Z) 2017, 375:39, 1, DOI: 10.1007/s41061-017-0126-7; T.-Y. Li, J. Wuc, Z.-G. Wua, Y.-X. Zheng, J.-L. Zuo, Y. Pan, Coordination Chemistry Reviews 2018, 374, 55, DOI: 10.1016/j.ccr.2018.06.014.
For example, US2020274081 (A1), US20010019782 (A1), US20020034656 (A1), US20030138657 (A1), US2005123791 (A1), US20060065890 (A1), US20060134462 (A1), US20070034863 (A1), US20070111026 (A1), US2007034863 (A1), US2007138437 (A1), US20080020237 (A1), US20080297033 (A1), US2008210930 (A1), US20090115322 (A1), US2009104472 (A1), US20100244004 (A1), US2010105902 (A1), US20110057559 (A1), US2011215710 (A1), US2012292601 (A1), US2013165653 (A1), US20140246656 (A1), US20030068526 (A1), US20050123788 (A1), US2005260449 (A1), US20060127696 (A1), US20060202194 (A1), US20070087321 (A1), US20070190359 (A1), US2007104979 (A1), US2007224450 (A1), US20080233410 (A1), US200805851 (A1), US20090039776 (A1), US20090179555 (A1), US20100090591 (A1), US20100295032 (A1), US20030072964 (A1), US20050244673 (A1), US20060008670 (A1), US20060134459 (A1), US20060251923 (A1), US20070103060 (A1), US20070231600 (A1), US2007104980 (A1), US2007278936 (A1), US20080261076 (A1), US2008161567 (A1), US20090108737 (A1), US2009085476 (A1), US20100148663 (A1), US2010102716 (A1), US2010270916 (A1), US20110204333 (A1), US2011285275 (A1), US2013033172 (A1), US2013334521 (A1), US2014103305 (A1), US2003068536 (A1), US2003085646 (A1), US2006228581 (A1), US2006197077 (A1), US2011114922 (A1), US2011114922 (A1), US2003054198 (A1), and EP2730583 (A1) disclose phosphorescence materials that may be used as phosphorescence materials PB in the context of the present invention. It is understood that this does not imply that the present invention is limited to organic electroluminescent devices including a phosphorescence materials described in one of the named references.
As laid out in US2020274081 (A1), examples of phosphorescent complexes for use in organic electroluminescent devices such as those of the present invention include the complexes shown below. Again, it is understood that the present invention is not limited to these examples.
As stated above, the skilled artisan will realize that any phosphorescent complexes used in the state of the art may be suitable as phosphorescence materials PB in the context of the present invention.
In one embodiment of the invention, each phosphorescence material PB includes Iridium (Ir).
In one embodiment of the invention, the at least one phosphorescence material PB, preferably each phosphorescence material PB, is an organometallic complex including either iridium (Ir) or platinum (Pt).
In one embodiment of the invention, the at least one phosphorescence material PB, preferably each phosphorescence material PB, is an organometallic complex including iridium (Ir).
In one embodiment of the invention, the at least one phosphorescence material PB, preferably each phosphorescence material PB, is an organometallic complex including platinum (Pt).
Non-limiting examples of phosphorescence materials PB also include compounds represented by the following general Formula PB-I,
In Formula PB-I, M is selected from the group consisting of Ir, Pt, Au, Eu, Ru, Re, Ag and Cu;
In one embodiment of the invention, each phosphorescence materials PB includes or consists of a structure according to Formula PB-I,
Examples of the compounds represented by the Formula PB-I include compounds represented by the following general Formula PB-II or general Formula PB-III:
In Formulas PB-II and PB-III, X′ is an aromatic ring which is carbon(C)-bonded to M and Y′ is a ring, which is nitrogen(N)-coordinated to M to form a ring.
X′ and Y′ are bonded, and X′ and Y′ may form a new ring. In Formula PB-III, Z3 is a bidentate ligand having two oxygens(O). In the Formulas PB-II and PB-III, M is preferably Ir from the viewpoint of high efficiency and long lifetime.
In the Formulas PB-II and PB-III, the aromatic ring X′ is for example a C6-C30-aryl, preferably a C6-C16-aryl, even more preferably a C6-C12-aryl, and particularly preferably a C6-C10-aryl, wherein X′ at each occurrence is optionally substituted with one or more substituents RE.
In the Formulas PB-II and PB-III, Y′ is for example a C2-C30-heteroaryl, preferably a C2-C25-heteroaryl, more preferably a C2-C20-heteroaryl, even more preferably a C2-C15-heteroaryl, and particularly preferably a C2-C10-heteroaryl, wherein Y′ at each occurrence is optionally substituted with one or more substituents RE. Furthermore, Y′ may be, for example, a C1-C5-heteroaryl, which is optionally substituted with one or more substituents RE.
In the Formulas PB-II and PB-III, the bidentate ligand having two oxygens(O) Z3 is for example a C2-C30-bidentate ligand having two oxygens, a C2-C25-bidentate ligand having two oxygens, more preferably a C2-C20-bidentate ligand having two oxygens, even more preferably a C2-C15-bidentate ligand having two oxygens, and particularly preferably a C2-C10-bidentate ligand having two oxygens, wherein Z3 at each occurrence is optionally substituted with one or more substituents RE. Furthermore, Z3 may be, for example, a C2-C5-bidentate ligand having two oxygens, which is optionally substituted with one or more substituents RE.
The substituents RE, R5E, or R6E independently from each other optionally may form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents RE, R5E, R6E, and/or with X′, Y′ and Z3.
Examples of the compound represented by Formula PB-II include Ir(ppy)3, Ir(ppy)2(acac), Ir(mppy)3, Ir(PPy)2(m-bppy), and BtpIr(acac), Ir(btp)2(acac), Ir(2-phq)3, Hex-Ir(phq)3, Ir(fbi)2(acac), fac-Tris(2-(3-p-xylyl)phenyl)pyridine iridium(III), Eu(dbm)3(Phen), Ir(piq)3, Ir(piq)2(acac), Ir(Fiq)2(acac), Ir(Flq)2(acac), Ru(dtb-bpy)3·2(PF6), Ir(2-phq)3, Ir(BT)2(acac), Ir(DMP)3, Ir(Mpq)3, Ir(phq)2tpy, fac-Ir(ppy)2Pc, Ir(dp)PQ2, Ir(Dpm)(Piq)2, Hex-Ir(piq)2(acac), Hex-Ir(piq)3, Ir(dmpq)3, Ir(dmpq)2(acac), FPQIrpic and the like.
Other examples of the compound represented by Formula PB-II include compounds represented by the following Formulas PB-II-1 to PB-II-11. In the structural formula, “Me” represents a methyl group.
Other examples of the compound represented by the Formula PB-III include compounds represented by the following Formulas PB-III-1 to PB-III-6. In the structural formula, “Me” represents a methyl group.
Furthermore, the iridium complexes described in US2003017361 (A1), US2004262576 (A1), WO2010027583 (A1), US2019245153 (A1), US2013119354 (A1), US2019233451 (A1), may be used. From the viewpoint of high efficiency in phosphorescence materials, Ir(ppy)3 and Hex-Ir(ppy)3 are often used for green light emission.
A small full width at half maximum (FWHM) emitter SB in the context of the present invention is any emitter that has an emission spectrum, which exhibits an FWHM of less than or equal to 0.25 eV (≤0.25 eV), typically measured from a spin-coated film with 1 to 5% by weight, in particular with 2% by weight of emitter in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.). Alternatively, emission spectra of small FWHM emitters SB may be measured in a solution, typically with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In a preferred embodiment of the invention, a small FWHM emitter SB is any emitter that has an emission spectrum, which exhibits an FWHM of ≤0.24 eV, more preferably of ≤0.23 eV, even more preferably of ≤0.22 eV, of ≤0.21 eV or of ≤0.20 eV, measured from a spin-coated film with 1 to 5% by weight, in particular with 2% by weight of emitter SB in PMMA at room temperature. Alternatively, emission spectra of small FWHM emitters SB may be measured in a solution, typically with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.). In other embodiments of the present invention, each small FWHM emitter SB exhibits an FWHM of ≤0.19 eV, of <0.18 eV, of ≤0.17 eV, of <0.16 eV, of ≤0.15 eV, of <0.14 eV, of ≤0.13 eV, of <0.12 eV, or of ≤0.11 eV.
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 400 nm to 470 nm, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 500 nm to 560 nm, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 610 nm to 665 nm, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 400 nm to 470 nm, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 500 nm to 560 nm, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In one embodiment of the invention, each small FWHM emitter SB emits light with an emission maximum in the wavelength range of from 610 nm to 665 nm, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
It is understood that a TADF material EB included in a light-emitting layer B of an organic electroluminescent device according to the invention may optionally also be an emitter with an emission spectrum which exhibits an FWHM of less than or equal to 0.25 eV (≤0.25 eV). Optionally, a TADF material EB included in a light-emitting layer B of an organic electroluminescent device according to the invention may also exhibit an emission maximum within the wavelength ranges specified above (namely: 400 nm to 470 nm, 500 nm to 560 nm, 610 nm to 665 nm).
In one embodiment of the invention, one of the relations expressed by the following formulas (23) to (25) applies:
440 nm<λmax(SB)<470 nm (23)
510 nm<λmax(SB)<550 nm (24)
610 nm<λmax(SB)<665 nm (25),
In one embodiment, the aforementioned relations expressed by formulas (23) to (25) apply to materials included in any of the at least one light-emitting layer B of the organic electroluminescent device according to the invention. In one embodiment, the aforementioned relations expressed by formulas (23) to (25) apply to materials included in the same light-emitting layer B of the organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, each small FWHM emitter SB is an organic emitter, which, in the context of the invention, means that it does not contain any transition metals. Preferably, each small FWHM emitter SB according to the invention predominantly consists of the elements hydrogen (H), carbon (C), nitrogen (N), and boron (B), but may for example also include oxygen (O), silicon (Si), fluorine (F), and bromine (Br).
In a preferred embodiment of the invention, each small FWHM emitter SB is a fluorescent emitter, which in the context of the present invention means that, upon electronic excitation (for example in an optoelectronic device according to the invention), the emitter is capable of emitting light at room temperature, wherein the emissive excited state is a singlet state.
In one embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 50%, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In a preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 60%, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In an even more preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 70%, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In a still even more preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 80%, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In a particularly preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 90%, measured (with 1 to 5% by weight, in particular with 2% by weight of the emitter SB) in PMMA at room temperature.
In one embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 50%, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In a preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 60%, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In an even more preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 70%, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In a still even more preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 80%, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
In a particularly preferred embodiment of the invention, a small FWHM emitter SB exhibits a photoluminescence quantum yield (PLQY) equal to or higher than 90%, measured with 0.001-0.2 mg/mL of the emitter SB in dichloromethane or toluene at room temperature (i.e., (approximately) 20° C.).
The person skilled in the art knows how to design small FWHM emitters SB which fulfill the above-mentioned requirements or preferred features.
A class of molecules suitable to provide small FWHM emitters SB in the context of the present invention are the well-known 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based materials, whose structural features and application in organic electroluminescent devices have been reviewed in detail and are common knowledge to those skilled in the art. The state of the art also reveals how such materials may be synthesized and how to arrive at an emitter with a certain emission color.
See for example: J. Liao, Y. Wang, Y. Xu, H. Zhao, X. Xiao, X. Yang, Tetrahedron 2015, 71(31), 5078, DOI: 10.1016/j.tet.2015.05.054; B. M Squeo, M. Pasini, Supramolecular Chemistry 2020, 32(1), 56-70, DOI: 10.1080/10610278.2019.1691727; M. Poddar, R. Misra, Coordination Chemistry Reviews 2020, 421, 213462-213483; DOI: 10.1016/j.ccr.2020.213462.
The skilled artisan is also familiar with the fact that the BODIPY base structure shown below
It is common knowledge to those skilled in the art that one may arrive at more suitable emitter molecules for organic electroluminescent devices by attaching bulky groups as substituents to the BODIPY core structure shown above. These bulky groups may for example (among many others) be aryl, heteroaryl, alkyl or alkoxy substituents or condensed polycyclic aromatics, or heteroaromatics, all of which may optionally be substituted. The choice of suitable substituents at the BODIPY core is obvious for the skilled artisan and can easily be derived from the state of the art. The same holds true for the multitude of synthetic pathways which have been established for the synthesis and subsequent modification of such molecules.
See for example: B. M Squeo, M. Pasini, Supramolecular Chemistry 2020, 32(1), 56-70, DOI: 10.1080/10610278.2019.1691727; M. Poddar, R. Misra, Coordination Chemistry Reviews 2020, 421, 213462-213483; DOI: 10.1016/j.ccr.2020.213462.
Examples of BODIPY-based emitters that may be suitable as small FWHM emitters SB in the context of the present invention are shown below:
It is understood that this does not imply that BODIPY-derivatives with other structural features than those shown above are not suited as small FWHM emitters SB in the context of the present invention.
For example, the BODIPY-derived structures disclosed in US2020251663 (A1), EP3671884 (A1), US20160230960 (A1), US20150303378 (A1) or derivatives thereof may be suitable small FWHM emitters SB for use according to the present invention.
Furthermore, it is known to those skilled in the art, that one may also arrive at emitters for organic electroluminescent devices by replacing one or both of the fluorine substituents attached to the central boron atom of the BODIPY core structure by alkoxy or aryloxy groups which are attached via the oxygen atom and may optionally be substituted, preferably with electron-withdrawing substituents such as fluorine (F) or trifluoromethyl (CF3). Such molecules are for example disclosed in US2012037890 (A1) and the person skilled in the art understands that these BODIPY-related compounds may also be suitable small FWHM emitters SB in the context of the present invention. Examples of such emitter molecules are shown below, which does not imply that only the shown structures may be suitable small FWHM emitters SB in the context of the present invention:
Additionally, the BODIPY-related boron-containing emitters disclosed in US20190288221 (A1) constitute a group of emitters that may provide suitable small FWHM emitters SB for use according to the present invention.
Another class of molecules suitable to provide small FWHM emitters SB in the context of the invention are near-range-charge-transfer (NRCT) emitters.
Typical NRCT emitters are described in the literature to show a delayed component in the time-resolved photoluminescence spectrum and exhibit a near-range HOMO-LUMO separation. See for example: T. Hatakeyama, K. Shiren, K. Nakajima, S. Nomura, S. Nakatsuka, K. Kinoshita, J. Ni, Y. Ono, and T. Ikuta, Advanced Materials 2016, 28(14), 2777, DOI: 10.1002/adma.201505491.
Typical NRCT emitters only show one emission band in the emission spectrum, wherein typical fluorescence emitters display several distinct emission bands due to vibrational progression.
The skilled artisan knows how to design and synthesize NRCT emitters that may be suitable as small FWHM emitters SB in the context of the present invention. For example, the emitters disclosed in EP3109253 (A1) may be used as small FWHM emitters SB in the context of the present invention.
Furthermore, for example, US2014058099 (A1), US2009295275 (A1), US2012319052 (A1), EP2182040 (A2), US2018069182 (A1), US2019393419 (A1), US2020006671 (A1), US2020098991 (A1), US2020176684 (A1), US2020161552 (A1), US2020227639 (A1), US2020185635 (A1), EP3686206 (A1), EP3686206 (A1), WO2020217229 (A1), WO2020208051 (A1), and US2020328351 (A1) disclose emitter materials that may be suitable as small FWHM emitters SB for use according to the present invention.
A group of emitters that may be used as small FWHM emitters SB in the context of the present invention are the boron (B)-containing emitters including or consisting of a structure according to the following Formula DABNA-I:
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, at least one of the one or more small FWHM emitters SB includes a structure according to Formula DABNA-I.
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, each small FWHM emitter SB includes a structure according to Formula DABNA-I.
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, at least one of the one or more small FWHM emitters SB consists of a structure according to Formula DABNA-I.
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, each small FWHM emitter SB consists of a structure according to Formula DABNA-I.
In a preferred embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, A′, B′, and C′ are all aromatic rings with 6 ring atoms each (i.e., they are all benzene rings).
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, Ya and Yb are independently of each other selected from NRDABNA-3, O, C(RDABNA-3)2, and Si(RDABNA-3)2.
In a preferred embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, Ya and Yb are independently of each other selected from NRDABNA-3, O, and S.
In an even more preferred embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, Ya and Yb are independently of each other selected from NRDABNA-3, and O.
In a particularly preferred embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, Ya and Yb are both NRDABNA-3.
In a particularly preferred embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, Ya and Yb are identical and are both NRDABNA-3.
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
RDABNA-1, is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(RDABNA-2)2, ORDABNA-2, SRDABNA-2, Si(RDABNA-2)3,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
RDABNA-1, is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(RDABNA-2)2, ORDABNA-2, SRDABNA-2,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
RDABNA-1, is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(Ph)2, OPh, Me, iPr, tBu, Si(Me)3,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, adjacent substituents selected from RDABNA-1 and RDABNA-2 do not form a mono- or polycyclic, aliphatic or aromatic or heteroaromatic, carbocyclic or heterocyclic ring system which is fused to the adjacent ring A′, B′ or C′.
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I,
In one embodiment of the invention, in which in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula DABNA-I, when Ya and/or Yb is/are NRDABNA-3, C(RDABNA-3)2, Si(RDABNA-3)2, or BRDABNA-3, the one or the two substituents RDABNA-3 do not bond to one or both of the adjacent rings A′ and B′ (for Ya═NRDABNA-3, C(RDABNA-3)2, Si(RDABNA-3)2, or BRDABNA-3) or A′ and C′ (for Yb═NRDABNA-3, C(RDABNA-3)2, Si(RDABNA-3)2, or BRDABNA-3).
In one embodiment, small FWHM emitters SB in the context of the present invention may optionally also be multimers (e.g., dimers) of the aforementioned Formula DABNA-I, which means that their structure includes more than one subunits, each of which has a structure according to Formula DABNA-I. In this case, the skilled artisan will understand that the two or more subunits according to Formula DABNA-I may for example be conjugated, preferably fused to each other (i.e., sharing at least one bond, wherein the respective substituents attached to the atoms forming that bond may no longer be present). The two or more subunits may also share at least one, preferably exactly one, aromatic or heteroaromatic ring. This means that, for example, a small FWHM emitter SB may include two or more subunits each having a structure of Formula DABNA-I, wherein these two subunits share one aromatic or heteroaromatic ring (i.e., the respective ring is part of both subunits). As a result, the respective multimeric (e.g., dimeric) emitter SB may not contain two whole subunits according to Formula DABNA-I as the shared ring is only present once. Nevertheless, the skilled artisan will understand that herein, such an emitter is still considered a multimer (for example a dimer if two subunits having a structure of Formula DABNA-I are included) of Formula DABNA-I. The same holds true for multimers sharing more than one ring. It is preferred that the multimers are dimers including two subunits, each having a structure of Formula DABNA-I.
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, at least one, preferably each small FWHM emitter SB, is a dimer of Formula DABNA-I as described above, which means that the emitter includes two subunits, each having a structure according to Formula DABNA-I.
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of two or more, preferably of exactly two, structures according to Formula DABNA-I (i.e., subunits),
In one embodiment of the invention, in at least one, preferably each, light-emitting layer B, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of two or more, preferably of exactly two, structures according to Formula DABNA-I (i.e., subunits),
Non-limiting examples of emitters including or consisting of a structure according to Formula DABNA-I that may be used as small FWHM emitters SB according to the present invention are listed below.
A group of emitters that may be used as small FWHM emitters SB in the context of the present invention are emitters including or consisting of a structure according to the following Formula BNE-1 or a multimer thereof:
N(C2-C17-heteroaryl)(C6-C18-aryl);
In one embodiment of the invention, at least one of the one or more small FWHM emitters SB includes a structure according to Formula BNE-1.
In one embodiment of the invention, each small FWHM emitter SB includes a structure according to Formula BNE-1.
In one embodiment of the invention, at least one of the one or more small FWHM emitters SB consists of a structure according to Formula BNE-1.
In one embodiment of the invention, each small FWHM emitter SB consists of a structure according to Formula BNE-1.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, V1 is CRBNE-V and V2 is CRBNE-I.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, V1 and V2 are both nitrogen (N).
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, V1 is nitrogen (N) and V2 is CRBNE-I.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, V1 is CRBNE-V and V2 is nitrogen (N).
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, c and d are both 0.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, c is 0 and d is 1.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, c is 1 and d is 0.
In a preferred embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, c and d are both 1.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1,
RBNE-d, RBNE-d′, and RBNE-e are independently of each other selected from the group consisting of: hydrogen, deuterium,
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, RBNE-III and RBNE-e combine to form a direct single bond.
In one embodiment of the invention, in which at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1, RBNE-III and RBNE-e do not combine to form a direct single bond.
In one embodiment, fluorescent emitters suitable as small FWHM emitters SB in the context of the present invention may optionally also be multimers (e.g., dimers) of the aforementioned Formula BNE-1, which means that their structure includes more than one subunits, each of which has a structure according to Formula BNE-1. In this case, the skilled artisan will understand that the two or more subunits according to Formula BNE-1 may for example be conjugated, preferably fused to each other (i.e., sharing at least one bond, wherein the respective substituents attached to the atoms forming that bond may no longer be present). The two or more subunits may also share at least one, preferably exactly one, aromatic or heteroaromatic ring. This means that, for example, a small FWHM emitter SB may include two or more subunits each having a structure of Formula BNE-1, wherein these two subunits share one aromatic or heteroaromatic ring (i.e., the respective ring is part of both subunits). As a result, the respective multimeric (e.g., dimeric) emitter SB may not contain two whole subunits according to Formula BNE-1 as the shared ring is only present once. Nevertheless, the skilled artisan will understand that herein, such an emitter is still considered a multimer (for example a dimer if two subunits having a structure of Formula BNE-1 are included) of Formula BNE-1. The same holds true for multimers sharing more than one ring. It is preferred that the multimers are dimers including two subunits, each having a structure of Formula BNE-1.
In one embodiment of the invention, at least one small FWHM emitter SB, preferably each small FWHM emitter SB, is a dimer of Formula BNE-1 as described above, which means that the emitter includes two subunits, each having a structure according to Formula BNE-1.
In one embodiment of the invention, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of two or more, preferably of exactly two, structures according to Formula BNE-1 (i.e., subunits),
In one embodiment of the invention, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of two or more, preferably of exactly two, structures according to Formula BNE-1 (i.e., subunits),
In one embodiment of the invention, at least one, preferably each, of the one or more small FWHM emitters SB includes or consists of a structure according to Formula BNE-1 (i.e., subunits),
Non-limiting examples of fluorescent emitters including or consisting of a structure according to the aforementioned Formula BNE-1 that may be used as small FWHM emitters in the context of the present invention are shown below:
The synthesis of small FWHM emitters SB including or consisting of a structure according to Formula BNE-1 can be accomplished via standard reactions and reaction conditions known to the skilled artisan.
Typically, the synthesis includes transition-metal catalyzed cross coupling reactions and a borylation reaction, all of which are known to the skilled artisan.
For example, WO2020135953 (A1) teaches how to synthesize small FWHM emitters SB including or consisting of a structure according to Formula BNE-1. Furthermore, US2018047912 (A1) teaches how to synthesize small FWHM emitters SB including or consisting of a structure according to Formula BNE-1, in particular with c and d being 0.
It is understood that the emitters disclosed in US2018047912 (A1) and WO2020135953 (A1) may also be used as small FWHM emitters SB in the context of the present invention.
One approach to design fluorescent emitters relies on the use of fluorescent polycyclic aromatic or heteroaromatic core structures. The latter are, in the context of the present invention, any structures including more than one aromatic or heteroaromatic ring, preferably more than two such rings, which are, even more preferably, fused to each other or linked via more than one direct bond or linking atom. In other words, the fluorescent core structures include at least one, preferably only one, rigid conjugated π-system.
The skilled artisan knows how to select a core structure for a fluorescent emitter, for example from US2017077418 (A1). Examples of common core structures of fluorescent emitters are listed below, wherein this does not imply that only these cores may provide small FWHM emitters SB suitable for the use according to the present invention:
The term fluorescent core structure in this context indicates that any molecule including the core may potentially be used as fluorescent emitter. The person skilled in the art knows that the core structure of such a fluorescent emitter may be optionally substituted and which substituents are suitable in this regard, for example from: US2017077418 (A1), M. Zhu. C. Yang, Chemical Society Reviews 2013, 42, 4963, DOI: 10.1039/c3cs35440g; S. Kima, B. Kimb, J. Leea, H. Shina, Y.-II Parkb, J. Park, Materials Science and Engineering R: Reports 2016, 99, 1, DOI: 10.1016/j.mser.2015.11.001; K. R. J. Thomas, N. Kapoor, M. N. K. P. Bolisetty, J.-H. Jou, Y.-L. Chen, Y.-C. Jou, The Journal of Organic Chemistry 2012, 77(8), 3921, DOI: 10.1021/jo300285v; M. Vanga, R. A. Lalancette, F. Jäkle, Chemistry—A European Journal 2019, 25(43), 10133, DOI: 10.1002/chem.201901231.
Small FWHM emitters SB for use according to the present invention may be obtained from the aforementioned fluorescent core structures, for example, by attaching sterically demanding substituents to the core that hinder the contact between the fluorescent core and adjacent molecules in the respective layer of an organic electroluminescent device.
In the context of the present invention, a compound, for example a fluorescent emitter is considered to be sterically shielded, when a subsequently defined shielding parameter is equal to or below a certain limit which is also defined in a later subchapter of this text.
It is preferred that the substituents used to sterically shield a fluorescent emitter are not just bulky (i.e., sterically demanding), but also electronically inert, which in the context of the present invention means, that these substituents do not include an active atom as defined in a later subchapter of this text. It is understood that this does not imply that only electronically inert (in other words: not active) substituents may be attached to a fluorescent core structure such as the ones shown above. Active substituents may also be attached to the core structure and may be introduced on purpose to tune the photophysical properties of a fluorescent core structure. In this case, it is preferred, that the active atoms introduced via one or more substituents are again shielded by electronically inert (i.e., not active) substituents.
Based on the aforementioned information and common knowledge from the state of the art, the skilled artisan understands how to choose substituents for a fluorescent core structure that may induce steric shielding of the latter and that are electronically inert as stated above. In particular, US2017077418 (A1) discloses substituents suitable as electronically inert (in other words: not active) shielding substituents. Examples of such substituents include linear, branched or cyclic alkyl groups with 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably with 4 to 10 carbon atoms, wherein one or more hydrogen atoms may be replaced by a substituent, preferably by deuterium or fluorine. Other examples include alkoxy groups with 3 to 40 carbon atoms, preferably 3 to 20 carbon atoms, more preferably with 4 to 10 carbon atoms, wherein one or more hydrogen atoms may be replaced by a substituent, preferably by deuterium or fluorine. It is understood that these alkyl and alkoxy substituents may be substituted by substituents other than deuterium and fluorine, for example by aryl groups. In this case, it is preferred that the aryl group as substituent includes 6 to 30 aromatic ring atoms, more preferably 6 to 18 aromatic ring atoms, most preferably 6 aromatic ring atoms, and is preferably not a fused aromatic system such as anthracene, pyrene and the like. Other examples include aryl groups with 6 to 30 aromatic ring atoms, more preferably with 6 to 24 aromatic ring atoms. One or more hydrogen atom in these aryl substituents may be substituted and preferred substituents are for example aryl groups with 6 to 30 carbon atoms and linear, branched or cyclic alkyl groups with 1 to 20 carbon atoms. All substituents may be further substituted. It is understood that all sterically demanding and preferably also electronically inert (in other words: not active) substituents disclosed in US2017077418 (A1) may serve to sterically shield a fluorescent core (such as those described above) to afford sterically shielded fluorescent emitters suitable as small FWHM emitters SB for use according to the present invention.
Below, non-limiting examples of substituents are shown that may be used as sterically demanding (i.e., shielding) and electronically inert (i.e., not active) substituents in the context of the present invention (disclosed in US2017077418 (A1)):
It is also understood that a fluorescent core may not just bear such sterically shielding substituents, but may also be substituted by further, non-shielding substituents that may or may not be active groups in the context of the present invention (see below for a definition).
Below, examples of sterically shielded fluorescent emitters from US2017077418 (A1) are shown that may be used as small FWHM emitters SB in the context of the present invention. This does not imply that the present invention is limited to organic electroluminescent devices including the shown emitters.
From the state of the art (for example from US2017077418 (A1)), the skilled artisan also knows how to synthesize sterically shielded fluorescent molecules that may be suitable as small FWHM emitters SB in the context of the present invention.
It is understood that sterically shielding substituents (that may or may not be electronically inert as stated above) may be attached to any fluorescent molecules, for example to the aforementioned polycyclic aromatic or heteroaromatic fluorescent cores, the BODIPY-derived structures and the NRCT emitters shown herein and to emitters including a structure of Formula BNE-1. This may result in sterically shielded fluorescent emitters that may be suitable as small FWHM emitters SB according to the invention.
In one embodiment of the invention, the at least one, preferably each, small FWHM emitter SB fulfills at least one of the following requirements:
In one embodiment of the invention, the at least one, preferably each small FWHM emitter SB fulfills at least one of the following requirements
In one embodiment of the invention, each small FWHM emitter SB is a boron (B)-containing emitter, which means that at least one atom within each small FWHM emitter SB is boron (B).
In one embodiment of the invention, each small FWHM emitter SB includes a polycyclic aromatic or heteroaromatic core structure, wherein at least two aromatic rings are fused together (e.g., anthracene, pyrene or aza-derivatives thereof).
In one embodiment of the invention, the at least one, preferably each, small FWHM emitter SB fulfills at least one (or both) of the following requirements:
In one embodiment of the invention, the at least one, preferably each small FWHM emitter SB fulfills at least one (or both) of the following requirements
In one embodiment of the invention, each small FWHM emitter SB includes a pyrene core structure.
In a preferred embodiment of the invention, each small FWHM emitter SB is a boron (B)- and nitrogen (N)-containing emitter, which means that at least one atom within each small FWHM emitter SB is boron (B) and at least one atom within each small FWHM emitter SB is nitrogen (N).
The shielding parameter A of a molecule can be determined as exemplarily described in the following for (fluorescent) emitters, such as those mentioned above. It will be understood that the shielding parameter A typically refers to the unit Angstrom (Å2). This does not imply that only such compounds may be sterically shielded in the context of the present invention, nor that a shielding parameter can only be determined for such compounds.
The energy levels of the molecular orbitals may be determined via quantum chemical calculations. For this purpose, in the present case, the Turbomole software package (Turbomole GmbH), version 7.2, may be used. First, a geometry optimization of the ground state of the molecule may be performed using density functional theory (DFT), employing the def2-SV(P) basis set and the BP-86 functional. Subsequently, on the basis of the optimized geometry, a single-point energy calculation for the electronic ground state may be performed employing the B3-LYP functional. From the energy calculation, the highest occupied molecular orbital (HOMO), for example, may obtained as the highest-energy orbital occupied by two electrons, and the lowest unoccupied molecular orbital (LUMO) as the lowest-energy unoccupied orbital. The energy levels may be obtained in an analogous manner for the other molecular orbitals such as HOMO-1, HOMO-2, . . . LUMO+1, LUMO+2 etc.
The method described herein is independent of the software package used. Examples of other frequently utilized programs for this purpose may be “Gaussian09” (Gaussian Inc.) and Q-Chem 4.1 (Q-Chem, Inc.).
Charge-exchanging molecular orbitals of the (fluorescent) compound may be considered to be the HOMO and LUMO, and all molecular orbitals that may be separated in energy by 75 meV or less from the HOMO or LUMO.
For each charge-exchanging molecular orbital, a determination of which atoms may be active may be conducted. In other words, a generally different set of active atoms may be found for each molecular orbital. There follows a description of how the active atoms of the HOMO may be determined. For all other charge-exchanging molecular orbitals (e.g., HOMO-1, LUMO, LUMO+1, etc.), the active atoms may be determined analogously.
The HOMO may be calculated as described above. To determine the active atoms, the surface on which the orbital has an absolute value of 0.035 (“isosurface with cutoff 0.035”) is inspected. For this purpose, in the present case, the Jmol software (http://jmol.sourceforge.net/), version 14.6.4, is used. Atoms around which orbital lobes with values equal to or larger than the cutoff value may be localized may be considered active. Atoms around which no orbital lobes with values equal to or larger than the cutoff value may be localized may be considered inactive.
(d) Determination of the Active Atoms in the (Fluorescent) Compound
If one atom is active in at least one charge-exchanging molecular orbital, it may be considered to be active in respect of the (fluorescent) compound. Only atoms that may be inactive (non-active) in all charge-exchanging molecular orbitals may be inactive in respect of the (fluorescent) compound.
(e) Determination of the Shielding Parameter A
In a first step, the solvent accessible surface area SASA may be determined for all active atoms according to the method described in B. Lee, F. M. Richards, Journal of Molecular Biology 1971, 55(3), 379, DOI: 10.1016/0022-2836(71)90324-X. For this purpose, the van-der-Waals surface of the atoms of a molecule may be considered to be impenetrable. The SASA of the entire molecule may be then defined as the area of the surface which may be traced by the center of a hard sphere (also called probe) with radius r (the so-called probe radius) while it may be rolled over all accessible points in space at which its surface may be in direct contact with the van-der-Waals surface of the molecule. The SASA value can also be determined for a subset of the atoms of a molecule. In that case, only the surface traced by the center of the probe at points where the surface of the probe may be in contact with the van-der-Waals surface of the atoms that may be part of the subset may be considered. The Lee-Richards algorithm used to determine the SASA for the present purpose may be part of the program package Free SASA (S. Mitternacht, Free SASA: An open source C library for solvent accessible surface area calculations. F1000Res. 2016; 5:189. Published 2016 Feb. 18. doi:10.12688/f1000research.7931.1). The van-der-Waals radii rvDwof the relevant elements may be compiled in the following reference: M. Mantina, A. C. Chamberlin, R. Valero, C. J. Cramer, D. G. Truhlar, The Journal of Physical Chemistry A 2009, 113(19), 5806, DOI: 10.1021/jp8111556. The probe radius r may be set to be 4 Å (r=4 Å) for all SASA determinations for the present purpose.
In the context of the present invention, the shielding parameter A may be obtained by dividing the solvent accessible surface area of the subset of active atoms (labeled S to distinguish from the SASA of the entire molecule) by the number n of active atoms:
A=S/n
In the context of the present invention, a compound may be defined as sterically well-shielded if the shielding parameter A has a value below 2 Å2 (A<2.0 Å2).
In the context of the present invention, a compound may be defined as sterically shielded if the shielding parameter A has a value of 1.0 to 5.0 Å2 (1.0 Å2≤A≤5.0 Å2), preferably 2.0 Å2 to 5.0 Å2 (2.0 Å2≤A≤5.0 Å2).
Below, exemplary (fluorescence) emitters are shown, alongside their shielding parameters A, which were determined as stated above. It will be understood that this does not imply that the present invention is limited to organic electroluminescent devices including one of the shown emitters. The depicted emitter compounds are merely non-limiting examples that represent optional embodiments of the invention.
In one embodiment of the invention, each small FWHM emitter SB included in an organic electroluminescent device according to the invention exhibits a shielding parameter A equal to or smaller than 5.0 Å2.
In a preferred embodiment of the invention, each small FWHM emitter SB included in an organic electroluminescent device according to the invention exhibits a shielding parameter A equal to or smaller than 2.0 Å2.
The person skilled in the art understands that not only a fluorescent emitter such as a small FWHM emitter SB according to the present invention may be sterically shielded by attaching shielding substituents. It is understood that for example also a TADF material EB in the context of the present invention and also a phosphorescence material PB in the context of the present invention may be shielded.
Distance between the TADF material EB and the phosphorescence material PB.
Herein, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB is calculated as follows:
wherein ρE
In one embodiment of the invention, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB fulfills the following requirement: 0.5 nm≤d≤5.0 nm.
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B including:
E(T1H)>E(T1P) (1)
E(T1P)>E(S1S) (2), and
In one embodiment of the invention, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB fulfills the following requirement: 1.0 nm≤d≤5.0 nm.
In a preferred embodiment of the invention, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB fulfills the following requirement: 1.0 nm≤d≤4.0 nm.
In a preferred embodiment of the invention, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB fulfills the following requirement: 0.7 nm≤d≤4.0 nm.
In one embodiment of the invention, the organic electroluminescent device includes at least one light-emitting layer B which is composed of one or more sublayers, wherein within the one (sub)layer or within at least one sublayer, the average intermolecular distance d between a TADF material EB and a phosphorescence material PB fulfills the following requirement: 0.5 nm≤d≤5.0 nm.
Excited State Lifetimes
A detailed description on how the excited state lifetimes are measured is provided in a following subchapter of this text.
In one embodiment of the invention, a TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 110 μs, preferably equal to or shorter than 100 μs. In one embodiment of the invention, each TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 110 μs, preferably equal to or shorter than 100 μs.
In one embodiment of the invention, a TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 75 μs. In one embodiment of the invention, each TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 75 μs.
In one embodiment of the invention, a TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 50 μs. In one embodiment of the invention, the at least one, preferably each, TADF material EB exhibits an excited state lifetime T(EB) equal to or shorter than 50 μs.
In a preferred embodiment of the invention, a TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 10 μs. In one embodiment of the invention, the at least one, preferably each, TADF material EB exhibits an excited state lifetime T(EB) equal to or shorter than 10 μs.
In an even more preferred embodiment of the invention, a TADF material EB in the context of the present invention exhibits an excited state lifetime T(EB) equal to or shorter than 5 μs. In one embodiment of the invention, the at least one, preferably each, TADF material EB exhibits an excited state lifetime T(EB) equal to or shorter than 5 μs.
In one embodiment of the invention, a phosphorescence material PB in the context of the present invention exhibits an excited state lifetime T(PB) equal to or shorter than 50 μs. In one embodiment of the invention, the at least one, preferably each, phosphorescence material PB exhibits an excited state lifetime T(PB) equal to or shorter than 50 μs.
In a preferred embodiment of the invention, a phosphorescence material PB in the context of the present invention exhibits an excited state lifetime T(PB) equal to or shorter than 10 μs. In one embodiment of the invention, the at least one, preferably each, phosphorescence material PB exhibits an excited state lifetime T(PB) equal to or shorter than 10 μs.
In an even more preferred embodiment of the invention, a phosphorescence material PB in the context of the present invention exhibits an excited state lifetime T(PB) equal to or shorter than 5 μs. In one embodiment of the invention, the at least one, preferably each, phosphorescence material PB exhibits an excited state lifetime T(PB) equal to or shorter than 5 μs.
In one embodiment of the invention, in an organic electroluminescent device according to the invention, the addition of one or more TADF material EB into one or more sublayers of the one or more light-emitting layers B including at least one host material HB, at least one phosphorescence material PB, and at least one small FWHM emitter SB results in a decreased excited state lifetime of the organic electroluminescent device. In a preferred embodiment of the invention the aforementioned addition of a TADF material EB according to the invention decreases the excited state lifetime of the organic electroluminescent device by at least 50%.
Device Architecture
The person skilled in the art will notice that the at least one light-emitting layer B will typically be incorporated in an organic electroluminescent device of the present invention. Preferably, such an organic electroluminescent device includes at least the following layers: at least one light-emitting layer B, at least one anode layer A and at least one cathode layer C.
Preferably, at least one light-emitting layer B is located between an anode layer A and a cathode layer C. Accordingly, the general set-up is preferably A-B-C. This does of course not exclude the presence of one or more optional further layers. These can be present at each side of A, of B and/or of C.
Preferably, the anode layer A is located on the surface of a substrate. The substrate may be formed by any material or composition of materials. Most frequently, glass slides are used as substrates. Alternatively, thin metal layers (e.g., copper, gold, silver or aluminum films) or plastic films or slides may be used. This may allow a higher degree of flexibility. As at least one of both electrodes should be (essentially) transparent in order to allow light emission from the electroluminescent device (e.g., OLED). Usually, the anode layer A is mostly composed of materials allowing to obtain an (essentially) transparent film. Preferably, the anode layer A includes a large content or even consists of transparent conductive oxides (TCOs).
Such an anode layer A may exemplarily include indium tin oxide, aluminum zinc oxide, fluor tin oxide, indium zinc oxide, PbO, SnO, zirconium oxide, molybdenum oxide, vanadium oxide, wolfram oxide, graphite, doped Si, doped Ge, doped GaAs, doped polyaniline, doped polypyrrole and/or doped polythiophene and mixtures of two or more thereof.
Particularly preferably, the anode layer A (essentially) consists of indium tin oxide (ITO) (e.g., (In2O3)0.9(SnO2)0.1). The roughness of the anode layer A caused by the transparent conductive oxides (TCOs) may be compensated by using a hole injection layer (HIL). Further, the HIL may facilitate the injection of quasi charge carriers (i.e., holes) in that the transport of the quasi charge carriers from the TCO to the hole transport layer (HTL) is facilitated. The hole injection layer (HIL) may include poly-3,4-ethylenedioxy thiophene (PEDOT), polystyrene sulfonate (PSS), MoO2, V2O5, CuPC or CuI, in particular a mixture of PEDOT and PSS. The hole injection layer (HIL) may also prevent the diffusion of metals from the anode layer A into the hole transport layer (HTL). The HIL may exemplarily include PEDOT:PSS (poly-3,4-ethylenedioxy thiophene: polystyrene sulfonate), PEDOT (poly-3,4-ethylenedioxy thiophene), mMTDATA (4,4′,4″-tris[phenyl(m-tolyl)amino]triphenylamine), Spiro-TAD (2,2′,7,7′-tetrakis(n,n-diphenylamino)-9,9′-spirobifluorene), DNTPD (N1,N1′-(biphenyl-4,4′-diyl)bis(N1-phenyl-N4,N4-di-m-tolylbenzene-1,4-diamine), NPB (N,N′-bis-(1-naphthalenyl)-N,N′-bis-phenyl-(1,1′-biphenyl)-4,4′-diamine), NPNPB (N,N′-diphenyl-N,N′-di-[4-(N,N-diphenyl-amino)phenyl]benzidine), MeO-TPD (N,N,N′,N′-tetrakis(4-methoxyphenyl)-benzi-dine), HAT-CN (1,4,5,8,9,11-hexaazatriphenylen-hexacarbonitrile) and/or Spiro-NPD (N,N′-diphenyl-N,N′-bis-(1-naphthyl)-9,9′-spirobifluorene-2,7-diamine).
Adjacent to the anode layer A or hole injection layer (HIL) typically a hole transport layer (HTL) is located. Herein, any hole transport compound may be used. Exemplarily, electron-rich heteroaromatic compounds such as triarylamines and/or carbazoles may be used as hole transport compound. The HTL may decrease the energy barrier between the anode layer A and the light-emitting layer B (serving as emitting layer (EML)). The hole transport layer (HTL) may also be an electron blocking layer (EBL). Preferably, hole transport compounds bear comparably high energy levels of their triplet states T1. Exemplarily the hole transport layer (HTL) may include a star-shaped heterocycle such as tris(4-carbazol-9-ylphenyl)amine (TCTA), poly-TPD (poly(4-butylphenyl-diphenyl-amine)), [alpha]-NPD (poly(4-butylphenyl-diphenyl-amine)), TAPC (4,4′-cyclohexyliden-bis[N,N-bis(4-methylphenyl)benzenamine]), 2-TNATA (4,4′,4″-tris[2-naphthyl(phenyl)-amino]triphenylamine), Spiro-TAD, DNTPD, NPB, NPNPB, MeO-TPD, HAT-CN and/or TrisPcz (9,9′-diphenyl-6-(9-phenyl-9H-carbazol-3-yl)-9H,9′H-3,3′-bicarbazole). In addition, the HTL may include a p-doped layer, which may be composed of an inorganic or organic dopant in an organic hole-transporting matrix. Transition metal oxides such as vanadium oxide, molybdenum oxide or tungsten oxide may exemplarily be used as inorganic dopant. Tetrafluorotetracyanoquinodimethane (F4-TCNQ), copper-pentafluorobenzoate (Cu(I)pFBz) or transition metal complexes may exemplarily be used as organic dopant.
The EBL may exemplarily include mCP (1,3-bis(carbazol-9-yl)benzene), TCTA, 2-TNATA, mCBP (3,3-di(9H-carbazol-9-yl)biphenyl), 9-[3-(dibenzofuran-2-yl)phenyl]-9H-carbazole, 9-[3-(dibenzothiophen-2-yl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzofuranyl)phenyl]-9H-carbazole, 9-[3,5-bis(2-dibenzothiophenyl)phenyl]-9H-carbazole, tris-Pcz, CzSi (9-(4-tert-butylphenyl)-3,6-bis(triphenylsilyl)-9H-carbazole), and/or DCB (N,N′-dicarbazolyl-1,4-dimethylbenzene).
The composition of the at least one light-emitting layer B has been described above. Any of the one or more light-emitting layers B according to the invention preferably bears a thickness of not more than 1 mm, more preferably of not more than 0.1 mm, even more preferably of not more than 10 μm, even more preferably of not more than 1 μm, and particularly preferably of not more than 0.1 μm.
In the electron transport layer (ETL), any electron transporter may be used. Exemplarily, compounds poor of electrons such as, e.g., benzimidazoles, pyridines, triazoles, oxadiazoles (e.g., 1,3,4-oxadiazole), phosphine oxides and sulfone, may be used. Exemplarily, an electron transporter ETM may also be a star-shaped heterocycle such as 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi). The ETM may exemplarily be NBphen (2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (Aluminum-tris(8-hydroxyquinoline)), TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide), BPyTP2 (2,7-di(2,2′-bipyridin-5-yl)triphenylene), Sif87 (dibenzo[b,d]thiophen-2-yltriphenylsilane), Sif88 (dibenzo[b,d]thiophen-2-yl)diphenylsilane), BmPyPhB (1,3-bis[3,5-di(pyridin-3-yl)phenyl]benzene) and/or BTB (4,4′-bis-[2-(4,6-diphenyl-1,3,5-triazinyl)]-1,1′-biphenyl). Optionally, the electron transport layer may be doped with materials such as Liq (8-hydroxyquinolinolatolithium). Optionally, a second electron transport layer may be located between electron transport layer and the cathode layer C. The electron transport layer (ETL) may also block holes or a hole-blocking layer (HBL) is introduced.
The HBL may, for example, include HBM1:
BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=Bathocuproine), BAIq (bis(8-hydroxy-2-methylquinoline)-(4-phenylphenoxy)aluminum), NBphen (2,9-bis(naphthalen-2-yl)-4,7-diphenyl-1,10-phenanthroline), Alq3 (Aluminum-tris(8-hydroxyquinoline)), TSPO1 (diphenyl-4-triphenylsilylphenyl-phosphine oxide), T2T (2,4,6-tris(biphenyl-3-yl)-1,3,5-triazine), T3T (2,4,6-tris(triphenyl-3-yl)-1,3,5-triazine), TST (2,4,6-tris(9,9′-spirobifluorene-2-yl)-1,3,5-triazine), DTST (2,4-diphenyl-6-(3′-triphenylsilylphenyl)-1,3,5-triazine), DTDBF (2,8-bis(4,6-diphenyl-1,3,5-triazinyl)dibenzofuran) and/or TCB/TCP (1,3,5-tris(N-carbazolyl)benzene/1,3,5-tris(carbazol)-9-yl) benzene).
Adjacent to the electron transport layer (ETL), a cathode layer C may be located. Exemplarily, the cathode layer C may include or may consist of a metal (e.g., Al, Au, Ag, Pt, Cu, Zn, Ni, Fe, Pb, LiF, Ca, Ba, Mg, In, W, or Pd) or a metal alloy. For practical reasons, the cathode layer C may also consist of (essentially) intransparent (non-transparent) metals such as Mg, Ca or Al. Alternatively or additionally, the cathode layer C may also include graphite and or carbon nanotubes (CNTs). Alternatively, the cathode layer C may also consist of nanoscale silver wires.
In a preferred embodiment, the organic electroluminescent device includes at least the following layers:
In one embodiment, when the organic electroluminescent device is an OLED, it may optionally include the following layer structure:
Preferably, the order of the layers herein is A-HTL-B-ETL-C.
Furthermore, the organic electroluminescent device may optionally include one or more protective layers protecting the device from damaging exposure to harmful species in the environment including, exemplarily moisture, vapor and/or gases.
An electroluminescent device (e.g., an OLED) may further, optionally, include a protection layer between the electron transport layer (ETL) D and the cathode layer C (which may be designated as electron injection layer (EIL)). This layer may include lithium fluoride, cesium fluoride, silver, Liq (8-hydroxyquinolinolatolithium), Li2O, BaF2, MgO and/or NaF.
Unless otherwise specified, any of the layers, including any of the sublayers, of the various embodiments may be deposited by any suitable method. The layers in the context of the present invention, including at least one light-emitting layer B (which may consist of a single (sub)layer or may include more than one sublayers) and/or one or more sublayers thereof, may optionally be prepared by means of liquid processing (also designated as “film processing”, “fluid processing”, “solution processing” or “solvent processing”). This means that the components included in the respective layer are applied to the surface of a part of a device in liquid state. Preferably, the layers in the context of the present invention, including the at least one light-emitting layer B and/or one or more sublayers thereof, may be prepared by means of spin-coating. This method well-known to those skilled in the art allows obtaining thin and (essentially) homogeneous layers and/or sublayers.
Alternatively, the layers in the context of the present invention, including the at least one light-emitting layer B and/or one or more sublayers thereof, may be prepared by other methods based on liquid processing such as, e.g., casting (e.g., drop-casting) and rolling methods, and printing methods (e.g., inkjet printing, gravure printing, blade coating). This may optionally be carried out in an inert atmosphere (e.g., in a nitrogen atmosphere).
In another preferred embodiment, the layers in the context of the present invention, including the at least one light-emitting layer B and/or one or more sublayers thereof, may be prepared by any other method known in the art, including but not limited to vacuum processing methods well-known to those skilled in the art such as, e.g., thermal (co-)evaporation, organic vapor phase deposition (OVPD), and deposition by organic vapor jet printing (OVJP).
When preparing layers, optionally including one or more sublayers thereof, by means of liquid processing, the solutions including the components of the (sub)layers (i.e., with respect to the light-emitting layer B of the present invention, at least one host material HB, at least one phosphorescence material PB, at least one small FWHM emitter SB, and optionally a (i.e., at least one) TADF material EB) may further include a volatile organic solvent. Such volatile organic solvent may optionally be one selected from the group consisting of tetrahydrofuran, dioxane, chlorobenzene, diethylene glycol diethyl ether, 2-(2-ethoxyethoxy)ethanol, gamma-butyrolactone, N-methyl pyrrolidone, ethoxyethanol, xylene, toluene, anisole, phenetole, acetonitrile, tetrahydrothiophene, benzonitrile, pyridine, dihydrofuran, triarylamine, cyclohexanone, acetone, propylene carbonate, ethyl acetate, benzene and PGMEA (propylene glycol monoethyl ether acetate). Also a combination of two or more solvents may be used. After applied in liquid state, the layer may subsequently be dried and/or hardened by any means of the art, exemplarily at ambient conditions, at increased temperature (e.g., about 50° C. or about 60° C.) or at diminished pressure.
The organic electroluminescent device as a whole may also form a thin layer of a thickness of not more than 5 mm, more than 2 mm, more than 1 mm, more than 0.5 mm, more than 0.25 mm, more than 100 μm, or more than 10 μm.
An organic electroluminescent device (e.g., an OLED) may be a small-sized (e.g., having a surface not larger than 5 mm2, or even not larger than 1 mm2), medium-sized (e.g., having a surface in the range of 0.5 to 20 cm2), or a large-sized (e.g., having a surface larger than 20 cm2). An organic electroluminescent device (e.g., an OLED) according to the present invention may optionally be used for generating screens, as large-area illuminating device, as luminescent wallpaper, luminescent window frame or glass, luminescent label, luminescent poser or flexible screen or display. Next to the common uses, an organic electroluminescent device (e.g., an OLED) may exemplarily also be used as luminescent films, “smart packaging” labels, or innovative design elements. Further they are usable for cell detection and examination (e.g., as bio labelling).
As used throughout, the term “layer” in the context of the present invention preferably refers to a body that bears an extensively planar geometry. It is understood that the same is true for all “sublayers” which a layer may compose.
As used herein, the terms organic electroluminescent device and optoelectronic light-emitting device may be understood in the broadest sense as any device including one or more light-emitting layers B, each including as a whole at least one host material HB, at least one phosphorescence material PB, at least one small FWHM emitter SB, and optionally one or more TADF material EB, for all of which the above-mentioned definitions apply.
The organic electroluminescent device may be understood in the broadest sense as any device based on organic materials that is suitable for emitting light in the visible or nearest ultraviolet (UV) range, i.e., in the wavelength range from 380 to 800 nm.
Preferably, an organic electroluminescent device may be able to emit light in the visible range, i.e., from 400 to 800 nm.
Preferably, an organic electroluminescent device has a main emission peak in the visible range, i.e., from 380 to 800 nm, more preferably from 400 to 800 nm.
In one embodiment of the invention, the organic electroluminescent device emits green light from 500 to 560 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 500 to 560 nm.
In a preferred embodiment of the invention, the organic electroluminescent device emits green light from 510 to 550 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 510 to 550 nm.
In an even more preferred embodiment of the invention, the organic electroluminescent device emits green light from 515 to 540 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 515 to 540 nm.
In one embodiment of the invention, the organic electroluminescent device emits blue light from 420 to 500 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 420 to 500 nm.
In a preferred embodiment of the invention, the organic electroluminescent device emits blue light from 440 to 480 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 440 to 480 nm.
In an even more preferred embodiment of the invention, the organic electroluminescent device emits blue light from 450 to 470 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 450 to 470 nm.
In one embodiment of the invention, the organic electroluminescent device emits red or orange light from 590 to 690 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 590 to 690 nm.
In a preferred embodiment of the invention, the organic electroluminescent device emits red or orange light from 610 to 665 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 610 to 665 nm.
In an even more preferred embodiment of the invention, the organic electroluminescent device emits red light from 620 to 640 nm. In one embodiment of the invention, the organic electroluminescent device has a main emission peak in the range of from 620 to 640 nm.
In a preferred embodiment of the invention, the organic electroluminescent device is a device selected from the group consisting of an organic light-emitting diode (OLED), a light-emitting electrochemical cell (LEC), and a light-emitting transistor.
Particularly preferably, the organic electroluminescent device is an organic light-emitting diode (OLED). Optionally, the organic electroluminescent device as a whole may be intransparent (non-transparent), semi-transparent or (essentially) transparent.
As used throughout the present application, the term “cyclic group” may be understood in the broadest sense as any mono-, bi- or polycyclic moieties.
As used throughout the present application, the terms “ring” and “ring system” may be understood in the broadest sense as any mono-, bi- or polycyclic moieties.
The term “ring atom” refers to any atom which is part of the cyclic core of a ring or a ring structure, and not part of a substituent optionally attached to it.
As used throughout the present application, the term “carbocycle” may be understood in the broadest sense as any cyclic group in which the cyclic core structure includes only carbon atoms that may of course be substituted with hydrogen or any other substituents defined in the specific embodiments of the invention. It is understood that the term “carbocyclic” as adjective refers to cyclic groups in which the cyclic core structure includes only carbon atoms that may of course be substituted with hydrogen or any other substituents defined in the specific embodiments of the invention.
As used throughout the present application, the term “heterocycle” may be understood in the broadest sense as any cyclic group in which the cyclic core structure includes not just carbon atoms, but also at least one heteroatom. It is understood that the term “heterocyclic” as adjective refers to cyclic groups in which the cyclic core structure includes not just carbon atoms, but also at least one heteroatom. The heteroatoms may, unless stated otherwise in specific embodiments, at each occurrence be the same or different and be individually selected from the group consisting of N, O, S, and Se. All carbon atoms or heteroatoms included in a heterocycle in the context of the invention may of course be substituted with hydrogen or any other substituents defined in the specific embodiments of the invention.
As used throughout the present application, the term “aromatic ring system” may be understood in the broadest sense as any bi- or polycyclic aromatic moiety.
As used throughout the present application, the term “heteroaromatic ring system” may be understood in the broadest sense as any bi- or polycyclic heteroaromatic moiety.
As used throughout the present application, the term “fused” when referring to aromatic or heteroaromatic ring systems means that the aromatic or heteroaromatic rings that are “fused” share at least one bond that is part of both ring systems. For example naphthalene (or naphthyl when referred to as substituent) or benzothiophene (or benzothiophenyl when referred to as substituent) are considered fused aromatic ring systems in the context of the present invention, in which two benzene rings (for naphthalene) or a thiophene and a benzene (for benzothiophene) share one bond. It is also understood that sharing a bond in this context includes sharing the two atoms that build up the respective bond and that fused aromatic or heteroaromatic ring systems can be understood as one aromatic or heteroaromatic system. Additionally, it is understood, that more than one bond may be shared by the aromatic or heteroaromatic rings building up a fused aromatic or heteroaromatic ring system (e.g., in pyrene). Furthermore, it will be understood that aliphatic ring systems may also be fused and that this has the same meaning as for aromatic or heteroaromatic ring systems, with the exception of course, that fused aliphatic ring systems are not aromatic.
As used throughout the present application, the terms “aryl” and “aromatic” may be understood in the broadest sense as any mono-, bi- or polycyclic aromatic moieties. Accordingly, an aryl group contains 6 to 60 aromatic ring atoms, and a heteroaryl group contains 5 to 60 aromatic ring atoms, of which at least one is a heteroatom. Notwithstanding, throughout the application the number of aromatic ring atoms may be given as subscripted number in the definition of certain substituents. In particular, the heteroaromatic ring includes one to three heteroatoms. Again, the terms “heteroaryl” and “heteroaromatic” may be understood in the broadest sense as any mono-, bi- or polycyclic hetero-aromatic moieties that include at least one heteroatom. The heteroatoms may at each occurrence be the same or different and be individually selected from the group consisting of N, O, S, and Se. Accordingly, the term “arylene” refers to a divalent substituent that bears two binding sites to other molecular structures and thereby serving as a linker structure. In case, a group in the exemplary embodiments is defined differently from the definitions given here, for example, the number of aromatic ring atoms or number of heteroatoms differs from the given definition, the definition in the exemplary embodiments is to be applied. According to the invention, a condensed (annulated) aromatic or heteroaromatic polycycle is built of two or more single aromatic or heteroaromatic cycles, which formed the polycycle via a condensation reaction.
In particular, as used throughout the present application the term “aryl group” or “heteroaryl group” includes groups which can be bound via any position of the aromatic or heteroaromatic group, derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzophenanthrene, tetracene, pentacene, benzopyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene; selenophene, benzoselenophene, isobenzoselenophene, dibenzoselenophene; pyrrole, indole, isoindole, carbazole, pyridine, quinoline, isoquinoline, acridine, phenanthridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, phenothiazine, phenoxazine, pyrazole, indazole, imidazole, benzimidazole, naphthoimidazole, phenanthroimidazole, pyridoimidazole, pyrazinoimidazole, quinoxalinoimidazole, oxazole, benzoxazole, naphthooxazole, anthroxazole, phenanthroxazole, isoxazole, 1,2-thiazole, 1,3-thiazole, benzothiazole, pyridazine, benzopyridazine, pyrimidine, benzopyrimidine, 1,3,5-triazine, quinoxaline, pyrazine, phenazine, naphthyridine, carboline, benzocarboline, phenanthroline, 1,2,3-triazole, 1,2,4-triazole, benzotriazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,2,3,4-tetrazine, purine, pteridine, indolizine and benzothiadiazole or combinations of the abovementioned groups.
In certain embodiments of the invention, adjacent substituents bonded to an aromatic or heteroaromatic ring may together form an additional aliphatic or aromatic, carbocyclic or heterocyclic ring system which is fused to the aromatic or heteroaromatic ring to which the substituents are bonded. It is understood that the optionally so formed fused ring system will be larger (meaning it includes more ring atoms) than the aromatic or heteroaromatic ring to which the adjacent substituents are bonded. In these cases, the “total” amount of ring atoms included in the fused ring system is to be understood as the sum of ring atoms included in the aromatic or heteroaromatic ring to which the adjacent substituents are bonded and the ring atoms of the additional ring system formed by the adjacent substituents, wherein, however, the carbon atoms that are shared by the ring systems which are fused are counted once and not twice. For example, a benzene ring may have two adjacent substituents that form another benzene ring so that a naphthalene core is built. This naphthalene core then includes 10 ring atoms as two carbon atoms are shared by the two benzene rings and thus only counted once and not twice. The term “adjacent substituents” in this context refers to substituents attached to the same or to neighbouring ring atoms (e.g., of a ring system).
As used throughout the present application, the term “aliphatic” when referring to ring systems may be understood in the broadest sense and means that none of the rings that build up the ring system is an aromatic or heteroaromatic ring. It is understood that such an aliphatic ring system may be fused to one or more aromatic rings so that some (but not all) carbon- or heteroatoms included in the core structure of the aliphatic ring system are part of an attached aromatic ring.
As used above and herein, the term “alkyl group” may be understood in the broadest sense as any linear, branched, or cyclic alkyl substituent. In particular, the term alkyl includes the substituents methyl (Me), ethyl (Et), n-propyl (nPr), i-propyl (iPr), cyclopropyl, n-butyl (nBu), i-butyl (iBu), s-butyl (sBu), t-butyl (tBu), cyclobutyl, 2-methylbutyl, n-pentyl, s-pentyl, t-pentyl, 2-pentyl, neo-pentyl, cyclopentyl, n-hexyl, s-hexyl, t-hexyl, 2-hexyl, 3-hexyl, neo-hexyl, cyclohexyl, 1-methylcyclopentyl, 2-methylpentyl, n-heptyl, 2-heptyl, 3-heptyl, 4-heptyl, cycloheptyl, 1-methylcyclohexyl, n-octyl, 2-ethylhexyl, cyclooctyl, 1-bicyclo[2,2,2]octyl, 2-bicyclo[2,2,2]-octyl, 2-(2,6-dimethyl)octyl, 3-(3,7-dimethyl)octyl, adamantyl, 2,2,2-trifluorethyl, 1,1-dimethyl-n-hex-1-yl, 1,1-dimethyl-n-hept-1-yl, 1,1-dimethyl-n-oct-1-yl, 1,1-dimethyl-n-dec-1-yl, 1,1-dimethyl-n-dodec-1-yl, 1,1-dimethyl-n-tetradec-1-yl, 1,1-dimethyl-n-hexadec-1-yl, 1,1-dimethyl-n-octadec-1-yl, 1,1-diethyl-n-hex-1-yl, 1,1-diethyl-n-hept-1-yl, 1,1-diethyl-n-oct-1-yl, 1,1-diethyl-n-dec-1-yl, 1,1-diethyl-n-dodec-1-yl, 1,1-diethyl-n-tetradec-1-yl, 1,1-diethyl-n-hexadec-1-yl, 1,1-diethyl-n-octadec-1-yl, 1-(n-propyl)-cyclohex-1-yl, 1-(n-butyl)-cyclohex-1-yl, 1-(n-hexyl)-cyclohex-1-yl, 1-(n-octyl)-cyclohex-1-yl and 1-(n-decyl)-cyclohex-1-yl.
As used above and herein, the term “alkenyl” includes linear, branched, and cyclic alkenyl substituents. The term alkenyl group exemplarily includes the substituents ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.
As used above and herein, the term “alkynyl” includes linear, branched, and cyclic alkynyl substituents. The term alkynyl group exemplarily includes ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
As used above and herein, the term “alkoxy” includes linear, branched, and cyclic alkoxy substituents. The term alkoxy group exemplarily includes methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy and 2-methylbutoxy.
As used above and herein, the term “thioalkoxy” includes linear, branched, and cyclic thioalkoxy substituents, in which the O of the exemplarily alkoxy groups is replaced by S.
As used above and herein, the terms “halogen” and “halo” may be understood in the broadest sense as being preferably fluorine, chlorine, bromine or iodine.
All hydrogen atoms (H) included in any structure referred to herein may at each occurrence independently of each other, and without this being indicated specifically, be replaced by deuterium (D). The replacement of hydrogen by deuterium is common practice and obvious for the person skilled in the art who also knows how to achieve this synthetically.
It is understood that when a molecular fragment is described as being a substituent or otherwise attached to another moiety, its name may be written as if it were a fragment (e.g., naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g., naphthalene, dibenzofuran). As used herein, these different ways of designating a substituent or attached fragment are considered to be equivalent.
When referring to concentrations or compositions and unless stated otherwise, percentages refer to weight percentages, which has the same meaning as percent by weight or % by weight ((weight/weight), (w/w), wt. %).
Orbital and excited state energies can be determined either by means of experimental methods or by calculations employing quantum-chemical methods, in particular density functional theory calculations. Herein, the energy of the highest occupied molecular orbital EHOMO is determined by methods known to the person skilled in the art from cyclic voltammetry measurements with an accuracy of 0.1 eV.
The energy of the lowest unoccupied molecular orbital ELUMO may be determined by methods known to the person skilled in the art from cyclic voltammetry measurements with an accuracy of 0.1 eV. Alternatively, and herein preferably, ELUMO is calculated as EHOMO+Egap, wherein the energy of the first excited singlet state S1 (vide infra) is used as Egap, unless stated otherwise, for host materials HB, TADF materials EB, and small FWHM emitters SB. This is to say that for host materials HB, TADF materials EB, and small FWHM emitters SB, Egap is determined from the onset of the emission spectrum at room temperature (i.e., approx. 20° C.) (steady-state spectrum; for TADF materials EB a film of 10% by weight of EB in poly(methyl methacrylate) (PMMA) is typically used; for small FWHM emitters SB, a film of 1-5%, preferably 2% by weight of SB in PMMA is typically used; for host materials HB, a neat film of the respective host material HB is typically used). For phosphorescence materials PB, Egap is also determined from the onset of the emission spectrum at room temperature (i.e., approx. 20° C.) (steady-state spectrum, typically measured from a film of 10% by weight of PB in PMMA).
Absorption spectra are recorded at room temperature (i.e., approximately 20° C.). For TADF materials EB, absorption spectra are typically measured from a film of 10% by weight of EB in poly(methyl methacrylate) (PMMA). For small FWHM emitters SB absorption spectra are typically measured from a film of 1-5%, preferably 2% by weight of SB in PMMA. For host materials HB absorption spectra are typically measured from a neat film of the host material HB. For phosphorescence materials PB, absorption spectra are typically measured from a film of 10% by weight of PB in PMMA. Alternatively, absorption spectra may also be recorded from solutions of the respective molecules, for example in dichloromethane or toluene, wherein the concentration of the solution is typically chosen so that the maximum absorbance preferably is in a range of 0.1 to 0.5.
The onset of an absorption spectrum is determined by computing the intersection of the tangent to the absorption spectrum with the x-axis. The tangent to the absorption spectrum is set at the low-energy side of the absorption band and at the point at half maximum of the maximum intensity of the absorption spectrum.
Unless stated otherwise, the energy of the first excited triplet state T1 is determined from the onset the phosphorescence spectrum at 77K (steady-state spectrum; for TADF materials EB a film of 10% by weight of EB in PMMA is typically used; for small FWHM emitters SB a film of 1-5%, preferably 2% by weight of SB in PMMA is typically used; for host materials HB, a neat film of the respective host material HB is typically used; for phosphorescence materials PB a film of 10% by weight of PB in PMMA is typically used and the measurement is typically performed at room temperature, i.e., approximately 20° C.). As laid out for instance in EP2690681A1, it is acknowledged that for TADF materials EB with small ΔEST values, intersystem crossing and reverse intersystem crossing may both occur even at low temperatures. In consequence, the emission spectrum at 77K may include emission from both, the S1 and the T1 state. However, as also described in EP2690681A1, the contribution/value of the triplet energy is typically considered dominant.
Unless stated otherwise, the energy of the first excited singlet state S1 is determined from the onset the fluorescence spectrum at room temperature (i.e., approx. 20° C.) (steady-state spectrum; for TADF materials EB a film of 10% by weight of EB in PMMA is typically used; for small FWHM emitters SB a film of 1-5%, preferably 2% by weight of SB in PMMA is typically used; for host materials HB, a neat film of the respective host material HB is typically used; for phosphorescence materials PB a film of 10% by weight of PB in PMMA is typically used). For phosphorescence materials PB displaying efficient intersystem crossing however, room temperature emission may be (mostly) phosphorescence and not fluorescence. In this case, the onset of the emission spectrum at room temperature (i.e., approx. 20° C.) is used to determine the energy of the first excited triplet state T1 as stated above.
The onset of an emission spectrum is determined by computing the intersection of the tangent to the emission spectrum with the x-axis. The tangent to the emission spectrum is set at the high-energy side of the emission band and at the point at half maximum of the maximum intensity of the emission spectrum.
The ΔEST value, which corresponds to the energy difference between the first excited singlet state (S1) and the first excited triplet state (T1), is determined based on the first excited singlet state energy and the first excited triplet state energy, which were determined as stated above.
As known to the skilled artisan, the full width at half maximum (FWHM) of an emitter (for example a small FWHM emitter SB) is readily determined from the respective emission spectrum (fluorescence spectrum for fluorescent emitters and phosphorescence spectrum for phosphorescent emitters). For small FWHM emitters SB, the fluorescence spectrum is typically used. All reported, FWHM values typically refer to the main emission peak (i.e., the peak with the highest intensity). The means of determining the FWHM (herein preferably reported in electron volts, eV) are part of the common knowledge of those skilled in the art. Given for example that the main emission peak of an emission spectrum reaches its half maximum emission (i.e., 50% of the maximum emission intensity) at the two wavelengths A1 and A2, both obtained in nanometers (nm) from the emission spectrum, the FWHM in electron volts (eV) is commonly (and herein) determined using the following equation:
As used herein, if not defined more specifically in a particular context, the designation of the colors of emitted and/or absorbed light is as follows:
The invention is illustrated by the following examples and the claims.
Cyclic Voltammetry
Cyclic voltammograms of solutions having concentration of 10-3 mol/l of the organic molecules in dichloromethane or a suitable solvent and a suitable supporting electrolyte (e.g., 0.1 mol/l of tetrabutylammonium hexafluorophosphate) are measured. The measurements are conducted at room temperature and under nitrogen atmosphere with a three-electrode assembly (working and counter electrodes: Pt wire, reference electrode: Pt wire) and calibrated using FeCp2/FeCp2+ as internal standard. HOMO and LUMO data was corrected using ferrocene as internal standard against SCE.
Density Functional Theory Calculation
Molecular structures are optimized employing the BP86 functional and the resolution of identity approach (RI). Excitation energies are calculated using the (BP86) optimized structures employing Time-Dependent DFT (TD-DFT) methods. Orbital and excited state energies are calculated with the B3LYP functional. However, herein, orbital and excited state energies are preferably determined experimentally as stated above.
All orbital and excited state energies reported herein (see experimental results) have been determined experimentally. Def2-SVP basis sets and a m4-grid for numerical integration were used. The Turbomole program package was used for all calculations.
Photophysical Measurements
Sample Pretreatment: Vacuum-Evaporation
As stated before, photophysical measurements of individual compounds (for example organic molecules or transition metal complexes) that may be included in a light-emitting layer B of the organic electroluminescent device according to the present invention (i.e., host materials HB, TADF materials EB, phosphorescent materials PB or small FWHM emitters SB) were typically performed using either neat films (in case of host materials HB) or films of the respective material in poly(methyl methacrylate) (PMMA) (for TADF materials EB, phosphorescent materials PB, and small FWHM emitters SB). These films were spin coated films and, unless stated differently for specific measurements, the concentration of the materials in the PMMA-films was 10% by weight for TADF materials EB and for phosphorescent materials PB or 1-5%, preferably 2% by weight for small FWHM emitters SB. Alternatively (not preferred), and as stated previously, some photophysical measurements may also be performed from solutions of the respective molecules, for example in dichloromethane or toluene, wherein the concentration of the solution is typically chosen so that the maximum absorbance preferably is in a range of 0.1 to 0.5.
For the purpose of further studying compositions of certain materials as present in the EML of organic electroluminescent devices (according to the present invention or comparative), the samples for photophysical measurements were produced from the same materials used for device fabrication by vacuum deposition of 50 nm of the respective light-emitting layer B on quartz substrates. Photophysical characterization of the samples are conducted under nitrogen atmosphere.
Absorption Measurements
A Thermo Scientific Evolution 201 UV-Visible Spectrophotometer is used to determine the wavelength of the absorption maximum of the sample in the wavelength region above 270 nm. This wavelength is used as excitation wavelength for photoluminescence spectral and quantum yield measurements.
Photoluminescence Spectra
Steady-state emission spectra are recorded using a Horiba Scientific, Modell FluoroMax-4 equipped with a 150 W Xenon-Arc lamp, excitation- and emissions monochromators. The samples are placed in a cuvette and flushed with nitrogen during the measurements.
Photoluminescence Quantum Yield Measurements
For photoluminescence quantum yield (PLQY) measurements an integrating sphere, the Absolute PL Quantum Yield Measurement C9920-03G system (Hamamatsu Photonics) is used. The samples are kept under nitrogen atmosphere throughout the measurement. Quantum yields are determined using the software U6039-05 and given in %. The yield is calculated using the equation:
wherein nphoton denotes the photon count and Int. is the intensity. For quality assurance, anthracene in ethanol (known concentration) is used as reference.
TCSPC (Time-Correlated Single-Photon Counting)
Excited state population dynamics are determined employing Edinburgh Instruments FS5 Spectrofluoremeters, equipped with an emission monochromator, a temperature stabilized photomultiplier as detector unit and a pulsed LED (310 nm central wavelength, 910 μs pulse width) as excitation source. The samples are placed in a cuvette and flushed with nitrogen during the measurements.
Full Decay Dynamics
The full excited state population decay dynamics over several orders of magnitude in time and signal intensity is achieved by carrying out TCSPC measurements in 4 time windows: 200 ns, 1 μs, and 20 μs, and a longer measurement spanning>80 μs. The measured time curves are then processed in the following way:
A background correction is applied by determining the average signal level before excitation and subtracting.
The time axes are aligned by taking the initial rise of the main signal as reference.
The curves are scaled onto each other using overlapping measurement time regions.
The processed curves are merged to one curve.
Data Analysis
Data analysis was done using monoexponential and bi-exponential fitting of prompt fluorescence(PF) and delayed fluorescence(DF) decays separately. The ratio of delayed and prompt fluorescence (n-value) is calculated by the integration of respective photoluminescence decays in time.
The average excited state life time is calculated by taking the average of prompt and delayed fluorescence decay time, weighted with the respective contributions of PF and DF.
Production and Characterization of Organic Electroluminescence Devices
Via vacuum-deposition methods OLED devices including organic molecules according to the invention can be produced. If a layer contains more than one compound, the weight-percentage of one or more compounds is given in %. The total weight-percentage values amount to 100%, thus if a value is not given, the fraction of this compound equals to the difference between the given values and 100%.
The not fully optimized OLEDs are characterized using standard methods and measuring electroluminescence spectra, the external quantum efficiency (in %) in dependency on the intensity, calculated using the light detected by the photodiode, and the current. The FWHM of the devices is determined from the electroluminescence spectra as stated previously for photoluminescence spectra (fluorescence or phosphorescence). The reported FWHM refers to the main emission peak (i.e., the peak with the highest emission intensity). The OLED device lifetime is extracted from the change of the luminance during operation at constant current density. The LT50 value corresponds to the time, where the measured luminance decreased to 50% of the initial luminance, analogously LT80 corresponds to the time point, at which the measured luminance decreased to 80% of the initial luminance, LT97 to the time point, at which the measured luminance decreased to 97% of the initial luminance etc.
Accelerated lifetime measurements are performed (e.g., applying increased current densities). Exemplarily LT80 values at 500 cd/m2 are determined using the following equation:
wherein L0 denotes the initial luminance at the applied current density. The values correspond to the average of several pixels (typically two to eight).
Experimental Results
Stack Materials
TADF Materials EB
Phosphorescence Materials PB
wherein LUMOCV is the energy of the lowest unoccupied molecular orbital, which is determined by Cyclic voltammetry. aThe emission spectrum was recorded from a solution of Ir(ppy)3 in chloroform. bThe emission spectrum was recorded from a 0.001 mg/mL solution of PB-2 in dichloromethane. cThe emission spectrum was recorded from a 0.001 mg/mL solution of PB-3 in toluene.
Small FWHM Emitters SB
In order to evaluate the results of the invention, comparison experiments were performed, wherein solely the composition of the emission layer (6) was varied. Additionally, the ratio of EB and SB was kept constant in the comparison experiments.
Results I: Variation of the Content of the Phosphorescence Material PB in the light-emitting layer (emission layer, 6)
Composition of the light-emitting layer B of devices D1 to D4 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), EB-10 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as the small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
Device Results I
Comparing the device results, D1 and D2, similar optical properties (FWHM, λmax, CIEx and CIEy) and efficiency (FOE) can be observed, while for D2 an extension of the relative lifetime of 147% compared to D1 (from 1.00 to 2.47) can be observed. For D3 extension of the relative lifetime of 21% compared to D1 (from 1.00 to 1.21), while the relative lifetime of D4 decreased by 1% compared to D1 (from 1.00 to 0.99).
Results II: Variation of Composition of Components
Composition of the light-emitting layer B of devices D5 to D13 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-11 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB and SB-1 was used as the small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
Devices D5 and D6 are typical phosphorescence devices, which include a mixed-host system, i.e., HB and HN, and a phosphorescence emitter.
Device D7 and D8 are devices, which include a mixed-host system, i.e., HB and HN, a phosphorescence material and a small FWHM emitter SB
Device D9 is a device, which includes a Host HB, a TADF material EB and a small FWHM emitter SB
Devices D10 is a devices, which includes a Host HB, a TADF material EB a phosphorescence material PB and a small FWHM emitter SB
Comparing the composition of the emission layer of devices D5 and D6 to D7 and D8, D7 and D8 contain additionally a small FWHM emitter SB, which is not present in D5 and D6. A longer lifetime, similar efficiency and smaller FWHM of the emission can be observed for D7 and D8.
Device D10 according to the present invention shows a superior overall performance over D9 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3).
Composition of the light-emitting layer B of devices D14 to D21 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-10 was used as TADF material EB, PB-2 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results III, the absence of the small FWHM emitter SB (here exemplarily SB-1) results in an undesirably broad emission reflected by the FWHM values being significantly larger than 0.25 eV in all cases (see devices D14, D15, and D18). For D15, the very high EQE of 22.7% comes along with a significantly reduced lifetime. When using a small FWHM emitter SB (here exemplarily SB-1) alongside either a TADF material EB (here exemplarily EB-10) or a phosphorescence material PB (here exemplarily PB-2), a narrow emission can be achieved, which is then reflected by the FWHM values being significantly smaller than 0.25 eV (see devices D16 and D17). At the same time, these devices exhibit high EQE-values of 20.4% and 22.4%, respectively. However, in terms of lifetime, all of these devices are clearly outcompeted by device D19, which was prepared according to the present invention. D19 also exhibits a very good efficiency (EQE of 20.4%) and a narrow emission (FWHM of 0.17 eV). In summary, the skilled artisan will acknowledge that D19 (according to the present invention) clearly shows the best overall device performance. The EML of D19 includes 1% of the phosphorescence material PB. Increasing this value to 4% (in D20) or even to 7% (in D21) results in a somewhat poorer device performance reflected by a slight increase of the FWHM to 0.20 eV, a reduction of the EQE to 16.3% or 13.6%, respectively, and a reduction of the device lifetime. Nevertheless, D20 and D21 still display a good overall performance, in particular with regard to the device lifetime.
In the absence of the TADF material EB-10, an n-host (here exemplarily HB-5) was generally used to increase the electron mobility within the EML.
Composition of the light-emitting layer B of devices D22 to D29 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-11 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results IV, using the TADF material EB(here exemplarily EB-11) or the phosphorescence material PB (here exemplarily Ir(ppy)3) as the main emitter in the absence of a small FWHM emitter SB results in a relatively broad emission of the organic electroluminescent device, which is reflected by FWHM values of the main emission peak of clearly more than 0.25 eV (here 0.41 and 0.31 eV, respectively, see D22 and D23). Both, D22 and D23, exhibit high efficiencies (EQE of 22.5% and 19.5%, respectively). The addition of a small FWHM emitter SB (here exemplarily SB-1) to for example the phosphorescent OLED D23 results in a significantly reduced FWHM of the main emission peak (then 0.17 eV) while slightly improving the EQE and the lifetime (see D24). However, device D24 as well as the OLEDs D22 and D23 are strongly outperformed by device D25, which was prepared according to the present invention. As compared to D22, D23, and D24, device D25 exhibits a dramatically prolonged lifetime, while still displaying an equally high efficiency and a narrow FWHM. The skilled artisan will acknowledge that the overall performance of device D25 according to the present invention is clearly superior to the performance of D22, D23, and D24. The overall device performance could be improved even further by reducing the content of the small FWHM emitter SB (here exemplarily SB-1) from 1% (in the EML of D25) to 0.5% (in the EML of D26). Again, a comparative example D27, not fulfilling the conditions of the present invention (exemplarily lacking the phosphorescence material PB) showed a drastically reduced lifetime and a somewhat reduced efficiency (EQE). Increasing the content of the phosphorescence material PB (here exemplarily Ir(ppy)3) from 1% in the devices D25 and D26 according to the present invention to 4% (in devices D28 and D29 according to the present invention) led to a reduction of the device lifetime and the efficiency. However, these devices (D28 and D29) still clearly outperform the aforementioned comparative devices which were manufactured according to the state of the art and not according to the present invention. In the absence of the TADF material EB-11, an n-host (here exemplarily HB-5) was generally used to increase the electron mobility within the EML.
Composition of the light-emitting layer B of devices D30 to D32 (the percentages refer to weight percent)
Setup 2 from Table 3 was used, wherein HB-1 (mCBP) was used as host material HB (p-host HP; also used as material for the electron blocking layer 5), EB-14 was used as TADF material EB, PB-3 was used as phosphorescence material PB, and SB-14 was used as small FWHM emitter SB.
Among the organic electroluminescent devices D30-D32, D32 according to the present invention shows the best overall performance when taking the narrow emission (small FWHM), the high EQE, and the relative lifetime into account.
Composition of the light-emitting layer B of devices D33 to D35 (the percentages refer to weight percent):
Setup 2 from Table 3 was used, wherein HB-14 was used as host material HB (p-host HP; also used as material for the electron blocking layer 5), EB-14 was used as TADF material EB, PB-3 was used as phosphorescence material PB, and SB-14 was used as small FWHM emitter SB.
Among the organic electroluminescent devices D33-D35, D35 according to the present invention clearly shows the best overall performance when taking the narrow emission (small FWHM), the high EQE, and the relative lifetime into account.
As stated before, each light-emitting layer B according to the present invention may be a single layer or may be composed of two or more sublayers. Exemplary organic electroluminescent devices with a light-emitting layer B including two or more sublayers are shown below (see device results VII and VIII).
Composition of the light-emitting layer B of devices D36 to D38 (the percentages refer to weight percent):
Setup 3 from Table 4 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-10 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB.
As can be concluded from device results VII, D38 according to the present invention shows a significantly prolonged lifetime as compared to D36 and D37. This comes along with a somewhat reduced, but still high efficiency (EQE). All three devices display a narrow emission which is expressed by FWHM values below 0.25 eV in all cases. D38 displays the best overall device performance, when taking the narrow emission, the still high EQE and the very long lifetime into account.
Composition of the light-emitting layer B of device D39 (the percentages refer to weight percent):
Setup 4 from Table 5 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-10 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB and SB-1 was used as small FWHM emitter SB.
As can be concluded from device results VIII, reducing the thickness of the HB:EB:PB-sublayers from 8 nm (D38) to 5 nm (D39) while using a largely analogue stack architecture, did not result in an improved device performance. Nevertheless, D39 still displays a narrow emission, high EQE and good lifetime.
Composition of the light-emitting layer B of devices D40 and D41 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-15 was used as host material HB (p-host HP; also used as material for the electron blocking layer 5), EB-10 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results IX, device D41 according to the present invention shows a superior overall performance as compared to device D40 which lacks the TADF material EB (here exemplarily EB-10) when taking the narrow emission (FWHM), the efficiency (EQE), and most the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D42 to D44 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), HB-5 was used as host material HN, EB-10 was used as TADF material EB, PB-2 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results X, device D44 according to the present invention shows a superior overall performance as compared to device D43 which lacks the TADF material EB (here exemplarily EB-10) and device D42 which lacks the phosphorescence material PB (here exemplarily PB-2) when taking the narrow emission (FWHM), the efficiency (FOE), and the device lifetime (LT95) into account. In the absence of the TADF material EB-10, an n-host (here exemplarily HB-5) was used to increase the electron mobility within the EML.
Composition of the light-emitting layer B of devices D45 to D49 (the percentages refer to weight percent):
Setup 1 from Table 2 was used, wherein HB-4 was used as host material HB(p-host HP; also used as material for the electron blocking layer 5), HB-5 was used as host material HN, EB-10 was used as TADF material EB, PB-4 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XI, device D49 according to the present invention shows a superior overall performance as compared to device D48 which lacks the TADF material EB (here exemplarily EB-10) and device D47 which lacks the phosphorescence material PB (here exemplarily PB-4) and device D46 which employs PB-4 as the emitter material in spite of SB-1 and device D45 which employs EB-10 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account. In the absence of the TADF material EB-10, an n-host (here exemplarily HB-5) was used to increase the electron mobility within the EML.
Composition of the light-emitting layer B of devices D50 to D64 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), HB-5 was used as host material HN, EB-11 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XII, device D54 according to the present invention shows a superior overall performance as compared to device D53 which lacks the TADF material EB (here exemplarily EB-11) and device D52 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3) and device D51 which employs Ir(ppy)3 as the emitter material in spite of SB-1 and device D50 which employs EB-11 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account. When comparing the performance of devices D55 to D58, it can be concluded that the reduction of the concentration of the small FWHM emitter (here exemplarily SB-1) in the EML from 1% to 0.5% may result in a prolonged device lifetime. Devices D59 to D61 were also prepared according to the present invention and, especially in comparison with D55 according to the present invention, indicate that increasing the concentration of the TADF material EB (here exemplarily EB-11) from 20% to 30% or even to 40% may result in an improved overall device performance. The comparison between the devices D55 to D58 and between D60 and D61 indicates that in contrast, a low concentration of the phosphorescence material PB (here exemplarily Ir(ppy)3) is beneficial for the device performance. In the absence of the TADF material EB-11, an n-host (here exemplarily HB-5) was used to increase the electron mobility within the EML.
Composition of the light-emitting layer B of devices D62 to D71 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), HB-5 was used as host material HN, EB-11 was used as TADF material EB, PB-2 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XIII, device D67 according to the present invention shows a superior overall performance as compared to device D66 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D65 which lacks the TADF material EB (here exemplarily EB 21) and device D64 which lacks the phosphorescence material PB (here exemplarily PB-2) and device D63 which employs PB-2 as the emitter material in spite of SB-1 and device D62 which employs EB-11 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (FOE), and the device lifetime (LT95) into account. When comparing the performance of devices D67 to D71, it can be concluded that for the given set of materials, a concentration of 30% of EB-11 and 2.5% of PB-2 and of 0.5% of SB-1 afforded the best performing device (D69).
Composition of the light-emitting layer B of devices D72 to D79 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), HB-5 was used as host material HN, EB-11 was used as TADF material EB, PB-4 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XIV, device D76 according to the present invention shows a superior overall performance as compared to device D75 which lacks the TADF material EB (here exemplarily EB-11) and device D74 which lacks the phosphorescence material PB (here exemplarily PB-4) and device D73 which employs PB_4 as the emitter material in spite of SB-1 and device D72 which employs EB-11 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account. When comparing the performance of devices D76 to D79, it can be concluded that the reduction of the concentration of the small FWHM emitter SB (here exemplarily SB-1 from 1% to 0.5% may improve the overall device performance.
Composition of the light-emitting layer B of devices D80 to D85 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-15 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XV, device D84 according to the present invention shows a superior overall performance as compared to device D81 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3). Furthermore, D85 according to the present invention shows a superior overall performance as compared to device D83 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D81 which lacks the phosphorescence material PB (here exemplarily PB-4) and device D80 which employs EB-15 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D86 to D90 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-15 was used as TADF material EB, PB-2 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XVI, devices D89 and D90 according to the present invention show a superior overall performance as compared to device D87 and D88 which lack the phosphorescence material PB (here exemplarily PB-2) and device D86 which employs EB-15 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D91 to D94 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-16 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XVII, device D94 according to the present invention shows a superior overall performance as compared to device D93 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D92 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3) and device D91 which employs EB-16 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D91 to D94 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-17 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XVIII, device D97 according to the present invention shows a superior overall performance as compared to device D96 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D95 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3), when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D98 to D101 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-18 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB, and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XIX, device D101 according to the present invention shows a superior overall performance as compared to device D100 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D99 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3) and device D98 which employs EB-18 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D102 to D105 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-19 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XX, device D105 according to the present invention shows a superior overall performance as compared to device D104 which lacks the small FWHM emitter SB (here exemplarily SB-1) and device D103 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3) and device D102 which employs EB-19 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
Composition of the light-emitting layer B of devices D106 to D108 (the percentages refer to weight percent):
Setup 5 from Table 6 was used, wherein HB-15 was used as host material HB (p-host HP), EB-21 was used as TADF material EB, Ir(ppy)3 was used as phosphorescence material PB and SB-1 was used as small FWHM emitter SB. A weight percentage of 0% means the absence of the material in the light-emitting layer B.
As can be concluded from device results XXI, device D108 according to the present invention shows a superior overall performance as compared to device D107 which lacks the phosphorescence material PB (here exemplarily Ir(ppy)3) and device D106 which employs EB-21 as the emitter material in spite of SB-1, when taking the narrow emission (FWHM), the efficiency (EQE), and the device lifetime (LT95) into account.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20197071.2 | Sep 2020 | EP | regional |
| 20197072.0 | Sep 2020 | EP | regional |
| 20197073.8 | Sep 2020 | EP | regional |
| 20197074.6 | Sep 2020 | EP | regional |
| 20197075.3 | Sep 2020 | EP | regional |
| 20197076.1 | Sep 2020 | EP | regional |
| 20197588.5 | Sep 2020 | EP | regional |
| 20197589.3 | Sep 2020 | EP | regional |
| 20217041.1 | Dec 2020 | EP | regional |
| 21170775.7 | Apr 2021 | EP | regional |
| 21170776.5 | Apr 2021 | EP | regional |
| 21170779.9 | Apr 2021 | EP | regional |
| 21170783.1 | Apr 2021 | EP | regional |
| 21184616.7 | Jul 2021 | EP | regional |
| 21184619.1 | Jul 2021 | EP | regional |
| 21185402.1 | Jul 2021 | EP | regional |
| 21186615.7 | Jul 2021 | EP | regional |
This application is a U.S. National Phase Patent Application of International Patent Application Number PCT/EP2021/075628, filed on Sep. 17, 2021, which claims priority to European Patent Application Number 20197076.1, filed on Sep. 18, 2020, European Patent Application Number 20197075.3, filed on Sep. 18, 2020, European Patent Application Number 20197074.6, filed on Sep. 18, 2020, European Patent Application Number 20197073.8, filed on Sep. 18, 2020, European Patent Application Number 20197072.0, filed on Sep. 18, 2020, European Patent Application Number 20197071.2, filed on Sep. 18, 2020, European Patent Application Number 20197589.3, filed on Sep. 22, 2020, European Patent Application Number 20197588.5, filed on Sep. 22, 2020, European Patent Application Number 20217041.1, filed on Dec. 23, 2020, European Patent Application Number 21170783.1, filed on Apr. 27, 2021, European Patent Application Number 21170775.7, filed on Apr. 27, 2021, European Patent Application Number 21170776.5, filed on Apr. 27, 2021, European Patent Application Number 21170779.9, filed on Apr. 27, 2021, European Patent Application Number 21184616.7, filed on Jul. 8, 2021, European Patent Application Number 21184619.1, filed on Jul. 8, 2021, European Patent Application Number 21185402.1, filed on Jul. 13, 2021, and European Patent Application Number 21186615.7, filed on Jul. 20, 2021, the entire content of each of which is incorporated herein by reference. The present invention relates to organic electroluminescent devices including one or more light-emitting layers B, each of which is composed of one or more sublayers, wherein the one or more sublayers of each light-emitting layer B as a whole include at least one host material HB, at least one phosphorescence material PB, at least one small FWHM emitter SB, and optionally at least one TADF material EB, wherein the at least one, preferably each, SB emits light with a full width at half maximum (FWHM) of less than or equal to 0.25 eV. Furthermore, the present invention relates to a method for generating light by means of an organic electroluminescent device according to the present invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/075628 | 9/17/2021 | WO |
