Patent Application
20230034026
The present invention relates to organic electroluminescent devices comprising at least one light-emitting layer B comprising at least one host material HB, at least one thermally activated delayed fluorescence (TADF) material EB, and at least one small full width at half maximum (FWHM) emitter SB, wherein EB transfers energy to SB, and SB emits light. SB exhibits a narrow—expressed by a small full width at half maximum (FWHM)—green emission with an emission maximum of 500 nm to 560 nm. Furthermore, the present invention relates to a method for generating green light by means of an organic electroluminescent device according to the present invention.
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 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.
Thus, there is still an unmet technical need for organic electroluminescent devices which have a high quantum yield, a 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 coordinates 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 typically desired.
Recently, some fluorescent near-range-charge-transfer (NRCT) emitters have been developed that display a rather narrow emission spectrum with a FWHM that is smaller than or equal to 0.25 eV, and therefore more suitable to achieve the BT-2020 and DCPI3 color gamut.
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 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 the light-emitting layer and the anode, and an electron transport layer is typically located between the light-emitting layer and the cathode. The different layers are sequentially disposed. Excitons of high energy are then generated by recombination of the holes and the electrons in the 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 comprising at least one TADF material, at least one small full width at half maximum (FWHM) emitter, and at least one host 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, at least one TADF material transfers energy to at least one small full width at half maximum (FWHM) emitter displaying green emission with an emission maximum of 500 nm to 560 nm.
Accordingly, one aspect of the present invention relates to an organic electroluminescent device which comprises one or more light-emitting layers B, each independently of each other comprising:
wherein (each) EB transfers energy to (at least one) SB and (each) SB emits green light with an emission maximum (in the wavelength range) between 500 nm and 560 nm; and wherein the relations expressed by the following formulas (1) to (5) apply:
E(S1H)>E(S1E) (1)
E(S1H)>E(S1S) (2)
E(S1E)>E(S1S) (3)
E(T1H)>E(T1S) (4)
E(T1H)>E(T1E) (5).
In a preferred embodiment, at least one small full width at half maximum (FWHM) emitter SB is a boron containing emitter. In a preferred embodiment, each small full width at half maximum (FWHM) emitter SB is a boron containing emitter.
Accordingly, the lowermost excited singlet state S1H of a host material HB is higher in energy than the lowermost excited singlet state S1E of a TADF material EB. The lowermost excited singlet state S1H of a host material HB is higher in energy than the lowermost excited singlet state S1S of any small FWHM emitter SB. The lowermost excited singlet state S1E of a TADF material EB is higher in energy than the lowermost excited singlet state S1S of any small FWHM emitter SB. The lowermost excited triplet state T1H of a host material HB is higher in energy than the lowermost excited triplet state T1S of any small FWHM emitter SB. The lowermost excited triplet state T1H of a host material HB is higher in energy than the lowermost excited triplet state T1E of a TADF material EB.
In a preferred embodiment of the invention, the lowermost excited triplet state T1E of a TADF material EB is higher in energy than the lowermost excited triplet state T1S of any small FWHM emitter SB: E(T1E)>E(T1S).
In a preferred embodiment of the invention, an electroluminescent device according to the invention comprises exactly one light-emitting layer B.
In another embodiment of the invention, an electroluminescent device according to the invention comprises exactly two light-emitting layers B.
In another embodiment of the invention, an electroluminescent device according to the invention comprises more than two light-emitting layers B.
It is understood that different light-emitting layers B optionally comprised in the same organic electroluminescent device according to the invention do not necessarily all comprise the same materials or even the same materials in the same ratios.
In one embodiment of the invention, at least one light-emitting layer B comprises at least one host material HB, exactly one TADF material EB, and exactly one small FWHM emitter SB.
In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one host material HB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one TADF material EB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one small FWHM emitter SB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one host material HB and exactly one TADF material EB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one host material HB and exactly one FWHM emitter SB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one TADF material EB and exactly one FWHM emitter SB. In a preferred embodiment of the invention, at least one light-emitting layer B comprises exactly one host material HB, exactly one TADF material EB, and exactly one small FWHM emitter SB.
In one embodiment, a small FWHM emitter SB displays thermally activated delayed fluorescence (TADF). In one embodiment, a TADF material EB displays a small FWHM. A TADF material EB may optionally emit light in the visible wavelength range, for example with an emission maximum within the wavelength range of 500 nm to 560 nm. In one embodiment, a TADF material EB displays a small FWHM (e.g., less than or equal to 0.30 eV, less than or equal to 0.25 eV, less than or equal to 0.20 eV, less than or equal to 0.15 eV, or less than or equal to 0.13 eV).
Surprisingly, it was found that the main contribution to the emission band of the optoelectronic device according to the invention can typically be attributed to the emission of SB indicating a sufficient transfer of energy from EB to SB as well as preferably from the at least one host material HB to EB and/or SB. This indicates that at least one TADF material EB may act as energy pump for the at least one small FWHM emitter SB, whose main function may be the emission of green light.
The emission of devices according to the invention shows longer lifetimes and/or higher efficiencies compared to that of devices with similar device architecture, wherein all of the at least one light-emitting layers comprise at least one host material HB in combination with either at least one TADF material EB or at least one small FWHM emitter SB (but not both).
Particularly interesting is that, depending on the combinations of EB and SB of the present invention, energy from lower energy states can also be transferred to higher energy states of the other compound. Also taking the reverse intersystem crossing (RISC) occurring in TADF materials into account, the combinations of EB and SB of the present invention may lead to particularly efficient emission of the small FWHM emitter SB.
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 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 520 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.
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, comprising 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, comprising 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.
The examples and claims further illustrate the invention.
Host Material(s) HB
According to the invention, any of the one or more host materials HB comprised in any of the at least one light-emitting layers 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.
In one embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises one or more p-hosts HP. In one embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises only one p-host HP.
In one embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises one or more n-hosts HN. In another embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises only one n-host HN.
In one embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises one or more bipolar hosts HBP. In one embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises only one bipolar host HBP.
In another embodiment of the invention, the at least one light-emitting layer B of an organic electroluminescent device according to the invention comprises at least two different host materials. In this case, the more than one host materials present in the at least one light-emitting layer B may either all be p-hosts or all be n-hosts, or all be bipolar hosts, but may also be a combination thereof.
It is understood that, if an organic electroluminescent device according to the invention comprises more than one light-emitting layer B, any of them may independently of the other light-emitting layers comprise 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 comprised in an organic electroluminescent device according to the invention do not necessarily all comprise the same materials or even the same materials in the same concentrations.
If comprised 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 bipolar host 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 bipolar host 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, preferably all host materials HB (HP, HN and/or bipolar host HBP) predominantly consist of the elements hydrogen (H), carbon (C), and nitrogen (N), but may for example also comprise oxygen (O), boron (B), silicon (Si), fluorine (F), and bromine (Br).
According to the invention, a p-host HP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HP) having an energy EHOMO(HP), wherein preferably: −6.1 eV≤EHOMO(HP))≤−5.6 eV.
According to the invention, a p-host HP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP), wherein preferably: −2.6 eV≤ELUMO(HP).
According to the invention, a p-host HP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited singlet state energy level E(S1p-H), wherein preferably: E(S1p-H)≥3.0 eV.
According to the invention, a p-host HP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited triplet state energy level E(T1p-H), wherein preferably: E(T1p-H)≥2.7 eV.
It is understood that any requirements or preferred features previously defined for a host material HB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention are preferably also valid for a p-host HP according to the invention. Thus, in a preferred embodiment, the relations expressed by the following formulas (6) to (9) apply:
E(S1p-H)>E(S1E) (6)
E(S1p-H)>E(S1S) (7)
E(T1p-H)>E(T1S) (8)
E(T1p-H)>E(T1E) (9).
Accordingly, the lowermost excited singlet state S1p-H of a p-host HP is preferably higher in energy than the lowermost excited singlet state S1E of a TADF material EB. The lowermost excited singlet state S1p-H of a p-host HP is preferably higher in energy than the lowermost excited singlet state S1S of any small FWHM emitter SB. The lowermost excited triplet state T1p-H of a p-host HP is preferably higher in energy than the lowermost excited triplet state T1S of any small FWHM emitter SB. The lowermost excited triplet state T1p-H of a p-host HP is preferably higher in energy than the lowermost excited triplet state T1E of a TADF material EB.
In a preferred embodiment of the invention, a p-host HP, optionally comprised in any of the at least one light-emitting layers B, optionally comprises or consists of:
and
wherein each of the at least one second chemical moieties which is present in the p-host material HP is linked to the first chemical moiety via a single bond which is represented in the formulas above by a dashed line;
wherein
Z1 is at each occurrence independently of each other selected from the group consisting of a direct bond, C(RII)2, C═C(RII)2, C═O, C═NRII, NRII, O, Si(RII)2, S, S(O) and S(O)2;
RI is at each occurrence independently of each other a binding site of a single bond linking the first chemical moiety to a second chemical moiety or is selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, wherein at least one RI is a binding site of a single bond linking the first chemical moiety to a second chemical moiety, and
wherein two or more adjacent substituents RH may optionally form an aromatic or heteroaromatic ring system with 3-18 carbon atoms.
In an even more preferred embodiment of the invention, Z1 is at each occurrence a direct bond and adjacent substituents RH do not combine to form an additional ring system.
In a still even more preferred embodiment of the invention, the one or more p-host HP optionally comprised in an organic electroluminescent device according to the invention is selected from the group consisting of the following structures:
According to the invention, an n-host HN optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN), wherein preferably: EHOMO(HN)≥−5.9 eV.
According to the invention, an n-host HN optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN), wherein preferably: −3.5 eV≤ELUMO(H)≤−2.9 eV.
According to the invention, an n-host HN optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited singlet state energy level E(S1n-H), wherein preferably: E(S1n-H)≤3.0 eV.
According to the invention, an n-host HN optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited triplet state energy level E(T1n-H), wherein preferably: E(T1n-H)≥2.7 eV.
It is understood that any requirements or preferred properties previously defined for a host material HB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention are preferably also valid for an n-host HN according to the invention. Thus, in a preferred embodiment, the relations expressed by the following formulas (10) to (13) apply:
E(S1n-H)>E(S1E) (10)
E(S1n-H)>E(S1S) (11)
E(T1n-H)>E(T1S) (12)
E(T1n-H)>E(T1E) (13).
Accordingly, the lowermost excited singlet state S1n-H of an n-host HN is preferably higher in energy than the lowermost excited singlet state S1E of a TADF material EB. The lowermost excited singlet state S1n-H of an n-host HN is preferably higher in energy than the lowermost excited singlet state S1S of any small FWHM emitter SB. The lowermost excited triplet state T1n-H of an n-host HN is preferably higher in energy than the lowermost excited triplet state T1S of any small FWHM emitter SB. Preferably, the lowermost excited triplet state T1n-H of any n-host HN is higher in energy than the lowermost excited triplet state T1E of any TADF material EB.
In a preferred embodiment of the invention, an n-host HN optionally comprised in any of the at least one light-emitting layers B comprises or consists of a structure according to any of the formulas HN-I, HN-II, and HN-III:
wherein RIII and RIV are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3,
a structure represented by any of the formulas HN-IV, HN-V, HN-VI, HN-VII, HN-VIII, HN-IX, HN-X, HN-XI, HN-XII, HN-XIII, and HN-XIV:
wherein X1 is oxygen (O), sulfur (S) or C(Rv)2;
Rv is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, and
Ph, which is optionally substituted with one or more substituents independently of
wherein two or more adjacent substituents Rv may optionally form an aromatic or heteroaromatic ring system with 3-18 carbon atoms; and
wherein in formulas HN-I and HN-II, at least one substituent RIII is CN; and the dashed line indicates the binding site to any of Formulas HN-I, HN-II, HN-III.
In an even more preferred embodiment of the invention, the one or more n-host HN optionally comprised 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 comprised in at least one 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 bipolar host HBP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HBP) having an energy EHOMO(HBP), wherein preferably: −6.1 eV≤EHOMO(HBP)≤−5.6 eV.
According to the invention, a bipolar host HBP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP), wherein preferably: −3.5 eV≤ELUMO(HBP)≤−2.9 eV.
According to the invention, a bipolar host HBP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited singlet state energy level E(S1bp-H), wherein preferably: E(S1bp-H)≥3.0 eV.
According to the invention, abipolar host HBP optionally comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited triplet state energy level E(T1bp-H), wherein preferably: E(T1bp-H)≥2.7 eV.
It is understood that any requirements or preferred properties previously defined for a host material HB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention are preferably also valid for a bipolar host HBP according to the invention. Thus, in a preferred embodiment, the relations expressed by the following formulas (14) to (17) apply:
E(S1bp-H)>E(S1E) (14)
E(S1bp-H)>E(S1S) (15)
E(T1bp-H)>E(T1S) (16)
E(T1bp-H)>E(T1E) (17).
Accordingly, the lowermost excited singlet state S1bp-H of a bipolar host HBP is preferably higher in energy than the lowermost excited singlet state S1E of a TADF material EB. The lowermost excited singlet state S1bp-H of a bipolar host HBP is preferably higher in energy than the lowermost excited singlet state S1S of any small FWHM emitter SB. The lowermost excited triplet state T1bp-H of a bipolar host HBP is preferably higher in energy than the lowermost excited triplet state T1S of any small FWHM emitter SB. Preferably, the lowermost excited triplet state T1bb-H of any bipolar host HBP is higher in energy than the lowermost excited triplet state T1E of any TADF material EB.
TADF Material(s) EB
According to the invention, any of the one or more thermally activated delayed fluorescence (TADF) materials EB is preferably characterized by exhibiting a ΔEST value, which corresponds to the energy difference between the lowermost excited singlet state S1E and the lowermost excited triplet state 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 preferably sufficiently small to allow for thermal repopulation of the lowermost excited singlet state S1E to the lowermost excited triplet state T1E (also referred to as up-intersystem crossing or reverse intersystem crossing) at room temperature (RT).
It is understood that a small FWHM emitter SB comprised in the at least one 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. Additionally, a TADF material EB in the context of the invention preferably differs from a small FWHM emitter SB in the context of the invention in that a TADF material EB mainly functions as energy pump transferring energy to at least one small FWHM emitter SB while the main contribution to the emission band of the optoelectronic device according to the invention can preferably be attributed to the emission of at least one small FWHM emitter SB.
According to the invention, a TADF material EB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(EB) having an energy EHOMO(EB) wherein preferably: −6.0 eV≤EHOMO(EB))≤−5.8 eV.
According to the invention, a TADF material EB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB), wherein preferably: −3.4 eV≤ELUMO(EB)≤−3.0 eV.
According to the invention, a TADF material EB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited singlet state energy level E(S1E), wherein preferably: 2.5 eV≤E(S1E)≤2.8 eV.
According to the invention, a TADF material EB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited triplet state energy level E(T1E), whose preferred range may be defined by the above-mentioned preferred range for the singlet state energy level E(S1E) in combination with the above-mentioned preferred range for ΔEST.
In a preferred embodiment of the invention, a TADF material EB has an emission maximum in the wavelength range of 480 nm to 560 nm, preferably of 500 nm to 540 nm.
In a preferred embodiment of the invention, a 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, a TADF material EB according to the invention predominantly consists of the elements hydrogen (H), carbon (C), and nitrogen (N), but may for example also comprise oxygen (O), boron (B), silicon (Si), fluorine (F), and bromine (Br).
In one embodiment of the invention, each of the at least one TADF materials EB comprises at least one electron-donating moiety D (i.e., donor) and at least one electron-withdrawing moiety A (i.e., acceptor), wherein the at least one donor D and the at least one acceptor A are covalently attached to the same linker; wherein this linker is an aromatic or heteroaromatic group with 3 to 30 carbon atoms, most preferably benzene or biphenyl.
In a preferred embodiment of the invention, each moiety D each comprises or consist of a structure represented by any of the formulas shown below:
wherein
Z2 is at each occurrence independently of each other selected from the group consisting of a direct bond, CR1R2, C═CR1R2, C═O, C═NR1, NR1, O, SiR1R2, S, S(O) and S(O)2;
# represents the binding site of a donor moiety D to the aforementioned linker;
Ra, R1, and R2 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(R3)2, OR3, Si(R3)3, B(OR3)2, OSO2R3, CF3, CN, F, Cl, Br, I,
C1-C40-alkyl,
C1-C40-alkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3—O57-heteroaryl,
R3 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, OPh, CF3, CN, F,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2;
N(C3-C17-heteroaryl)2, and
N(C3-C17-heteroaryl)(C6-C18-aryl);
wherein, optionally, any of the substituents Ra, R1, and R2 may independently of each other form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system with one or more adjacent substituents Ra, R1, and R2, wherein one or more hydrogen atoms of the optionally so formed ring system may be substituted by R3.
In a preferred embodiment of the invention, the donor moiety D is not an unsubstituted carbazole.
In a preferred embodiment of the invention, each acceptor moiety A each comprises or consists of a structure represented by any of the formulas shown below:
wherein
the dashed line represents a single bond linking the acceptor moiety A to the aforementioned linker;
R4 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(R5)2, OR5, Si(R5)3, B(OR5)2, OSO2R5, CF3, CN, F, Cl, Br, I,
C1-C40-alkyl,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C3-C57-heteroaryl, which is optionally substituted with one or more substituents R5;
R5 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, OPh, CF3, CN, F,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2;
N(C3-C17-heteroaryl)2, and
N(C3-C17-heteroaryl)(C6-C18-aryl);
wherein, optionally, two or more adjacent substituents R4 may independently of each other form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system, wherein one or more hydrogen atoms of the optionally so formed ring system may be substituted by R5.
In an even more preferred embodiment of the invention, each of the at least one TADF materials EB comprises at least one electron-donating moiety D (i.e., donor) and at least one electron-withdrawing moiety A (i.e., acceptor), wherein all donors D and all acceptors A are covalently attached to the same linker;
wherein this linker is an aromatic or heteroaromatic group with 3 to 30 carbon atoms, most preferably benzene or biphenyl;
wherein, the above-mentioned donor moieties D each comprise or consist of a structure represented by any of the formulas shown above; and
wherein, the above-mentioned acceptor moieties A each comprise or consist of a structure represented by any of the formulas shown above; and
wherein R1 and R2 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
R4 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
R3 and R5 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
Ra is at each occurrence independently of each other selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3,
In a still even more preferred embodiment of the invention, each of the at least one TADF materials EB comprises at least one electron-donating moiety D (i.e., donor) and at least one electron-withdrawing moiety A (i.e., acceptor), wherein all donors D and all acceptors A are covalently attached to the same linker;
wherein this linker is an aromatic or heteroaromatic group with 3 to 30 carbon atoms, most preferably benzene or biphenyl;
wherein, the above-mentioned donor moieties D each comprise or consist of a structure represented by any of the formulas shown above; and
wherein, the above-mentioned acceptor moieties A each comprise or consist of a structure represented by any of the formulas shown above; and
wherein R1, R2, R3, and R4 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
Ra is at each occurrence independently of each other selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3,
In one embodiment of the invention, each of the at least one TADF materials EB is an organic TADF material comprising:
and
wherein each second chemical moiety (if present) is linked to a first chemical moiety R6 via a single bond;
wherein
# represents the binding site of a first chemical moiety R6 to a second chemical moiety or is hydrogen;
k is at each occurrence independently of each other 0, 1, 2, 3, or 4;
m is at each occurrence independently of each other 0, 1 or 2;
n is at each occurrence independently of each other 0, 1 or 2;
o is at each occurrence independently of each other 0 or 1;
p is at each occurrence independently of each other 0, 1 or 2;
q is at each occurrence independently of each other 0, 1 or 2;
r is at each occurrence independently of each other 0, 1, 2, 3, 4 or 5;
which are bonded to the core structure (here preferably formula EB-I) via the position marked by the dashed line;
RZ1 is at each occurrence independently of each other selected from the group consisting of CN and CF3;
Z3 is at each occurrence independently of each other selected from the group consisting of a direct bond, CR9R10, C═CR9R10, C═O, C═NR9, NR9, O, SiR9R10, S, S(O) and S(O)2;
Re is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, F, Cl, Br, and I,
C1-C5-alkyl,
C6-C18-aryl,
R7 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
R8 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
RQ2 is at is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, Ph, and
Rb, Rc, Rd, R9, and R10 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(R12)2, OR12, Si(R12)3, B(OR12)2, OSO2R12, CF3, CN, F, Br, I,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3-C57-heteroaryl,
R11 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
R12 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, OPh, CF3, CN, F,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2;
N(C3-C17-heteroaryl)2,
N(C3-C17-heteroaryl)(C6-C18-aryl), and
an aliphatic cyclic amino group comprising 5 to 8 carbon atoms (preferably pyrrolidinyl and piperidinyl);
wherein, optionally, any adjacent substituents Rb, Rc, Rd, R9, and R10 independently of each other form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system; wherein one or more hydrogen atoms of the optionally so formed ring system may be substituted by R12; and
wherein at least one, but not more than three groups Q1 are nitrogen (N), with the restriction that in formula EB-II two adjacent groups Q1 are not both N; and
at least one, but not more than three groups Q1 are CR6, with the restriction that in formula EB-II, two adjacent groups Q1 are not both CR6; and
wherein in formula EB-III, at least one group Q3 is nitrogen (N); and
wherein preferably: 1≤(m+p)≤4; and
In a preferred embodiment of the invention, at least one substituent of the group consisting of Rb, Rc, and Rd is not hydrogen, whenever Z3 is a direct bond, so that preferably no donor moiety within a TADF material EB is an unsubstituted carbazolyl group.
In a preferred embodiment of the invention,
R7 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
R8 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
RQ2 is at is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Ph,
Rb, Rc, and Rd are at each occurrence independently from another selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3,
Re is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium,
C1-C5-alkyl,
C1-C5-alkyl,
wherein, optionally, any adjacent substituents Rb, Rc, Rd, R9, and R10 independently of each other form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system comprising 3 to 30 carbon atoms; and wherein apart from that the above-mentioned definitions apply.
In an even more preferred embodiment of the invention, Z3 is at each occurrence a direct bond; and
R7 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
R8 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C17-heteroaryl,
RQ2 is at is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Ph, and
Rb, Rc, and Rd are at each occurrence independently from another selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3, and
C1-C5-alkyl,
wherein, optionally, any adjacent substituents Rb, Rc, Rd, R9, and R10 independently of each other form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system comprising 3 to 18 carbon atoms; and wherein apart from that the above-mentioned definitions apply.
In a still even more preferred embodiment of the invention, Z3 is at each occurrence a direct bond; and
R7 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
R8 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
RQ2 is at is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, and
Rb is at each occurrence hydrogen;
Rc and Rd are at each occurrence independently of each other selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3,
Re is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, and
wherein apart from that the above-mentioned definitions apply.
In a particularly preferred embodiment of the invention, Z3 is at each occurrence a direct bond; and
ArEWG is at each occurrence independently of each other represented by a structure according to any of formulas, ArEWG-I, ArEWG-VII, ArEWG-VIII, ArEWG-IX, ArEWG-X, ArEWG-XI ArEWG-XII, and ArEWG-XIII;
R7 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
R8 is at each occurrence independently of each other selected from the group consisting of hydrogen, deuterium, Me, iPr, tBu, CN, CF3, and
RQ2 is at is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, and
Rb is at each occurrence hydrogen;
Rc and Rd are at each occurrence independently from another selected from the group consisting of: hydrogen, Me, iPr, tBu, CN, CF3, and
wherein apart from that the above-mentioned definitions apply.
In one embodiment of the invention, each of the one or more TADF materials EB has a structure represented by any of the formulas EB-I-1, EB-I-2, EB-I-3, EB-I-4, EB-I-5, EB-I-6, EB-I-7, and EB-I-8:
wherein
Y1 is at each occurrence nitrogen (N) or CH, and at least one Y1 is N;
R13 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3, ArEWG,
C1-C5-alkyl,
C6-C18-alkyl,
R14 and R15 are at each occurrence independently of each other selected from the group consisting of C—ArEWG and CRQ2;
R16 is at each occurrence independently of each other selected from the group consisting of CR6, C—ArEWG and CRQ2;
wherein not more than two groups R13 are CN, CF3 or ArEWG; and
wherein apart from that the above-mentioned definitions apply.
In a preferred embodiment of the invention, each of the one or more TADF materials EB has a structure represented by any of the formulas EB-I-1a, EB-I-2a, EB-I-3a, EB-I-4a, EB-I-5a, EB-I-6a, EB-I-7 (see above), and EB-I-8 (see above),
wherein R13 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, ArEWG, and
wherein not more than two groups R13 are CN, CF3 or ArEWG; and
wherein apart from that the above-mentioned definitions apply.
Optionally, any adjacent substituents Rb, Rc, Rd, R9, and R10 independently of each other may form a mono- or polycyclic, aliphatic, aromatic and/or benzo-fused ring system; wherein one or more hydrogen atoms of the optionally so formed ring system may be substituted by R12.
In a preferred embodiment, not more than two groups R13 are CN, CF3 or ArEWG.
In a preferred embodiment: 1≤(m+p) and/or 1≤(n+q).
In an even more preferred embodiment of the invention, each of the one or more TADF materials EB has a structure represented by any of the formulas EB-I-1a-1, EB-I-2a-1, EB-I-3a-1, EB-I-4a-1, EB-I-5a-1, EB-I-6a-1, EB-I-7 (see above), and EB-I-8 (see above),
wherein R13 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, ArEWG, and
wherein not more than two groups R13 attached to the same benzene ring are CN, CF3 or ArEWG; and
wherein apart from that the above-mentioned definitions apply.
In a still even more preferred embodiment of the invention, each of the one or more TADF materials EB has a structure represented by any of the formulas EB-I-1a-1, EB-I-2a-1, EB-I-3a-1, EB-I-4a-1, EB-I-5a-1, EB-I-6a-1, EB-I-7 (see above), and EB-I-8,
wherein Z3 is at each occurrence a direct bond; and
wherein apart from that the above-mentioned definitions apply.
In a preferred embodiment of the invention, X2 is at each occurrence independently of each other selected from the group consisting of CN,
which are bonded via the position marked by the dashed line;
In a preferred embodiment of the invention, Y1 is at each occurrence nitrogen (N).
In a particularly preferred embodiment of the invention, each of the one or more TADF materials EB has a structure represented by any of the formulas EB-I-3a-1a, EB-I-3a-1b, EB-I-4a-1a, and EB-I-4a-1b:
wherein preferably REWG is at each occurrence independently of each other selected from the group consisting of: hydrogen, CN, and
wherein, in formulas EB-I-3a-1a and EB-I-4a-1a preferably exactly one of the two REWG attached to the same benzene ring is hydrogen.
Examples of TADF materials EB for use in organic electroluminescent devices according to the invention are listed below, whereat the invention is of course not limited to devices comprising one of these molecules.
Particularly preferred examples of TADF materials EB according to formula EB-I-3a-1a are listed below:
Particularly preferred examples of TADF materials EB according to formula EB-I-3a-1 b are listed below:
Particularly preferred examples of TADF materials EB according to formula EB-I-4a-1a are listed below:
Particularly preferred examples of TADF materials EB according to formula EB-I-4a-1b are listed below:
Additional examples of TADF materials EB for use according to the present invention are listed 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 a TADF material EB according to formula EB-I-3a-1:
E1 can be any boronic acid (RB═H) or an equivalent boronic acid ester (RB=alkyl or aryl), in particular two RB form a ring to give e.g. boronic acid pinacol esters, of fluoro-(trifluoromethyl)phenyl, difluoro-(trifluoromethyl)phenyl, fluoro-(cyano)phenyl or difluoro-(cyano)phenyl. As second reactant E2 is used, wherein Hal refers to halogen and may be I, Br or CI, 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 molecules according to formula EB-I-3a-1 are obtained via the reaction of a nitrogen heterocycle in a nucleophilic aromatic substitution with the aryl halide, preferably aryl fluoride, or aryl dihalide, preferably aryl difluoride, 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-ylboronic acid ester or carbazol-3-ylboronic acid, e.g., via the reaction with bis(pinacolato)diboron (CAS No. 73183-34-3). Subsequently, one or more substituents Rb, Rc 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. Fe-Hal, preferably Rc—CI and Rc—Br.
Alternatively, one or more substituents Rb, Rc 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 Rb [Rb—B(OH)2], Rc [Rc-B(OH)2] or Rd [Rd—B(OH)2] or a corresponding boronic acid ester.
Further TADF emitter materials EB may be obtained analogously. A TADF emitter material EB may also be obtained by any alternative synthesis route suitable for this purpose.
An alternative synthesis route may comprise 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.
Small FWHM Emitter(s) SB
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), measured with 1 to 5% by weight, in particular with 1% by weight of emitter in poly(methyl methacrylate) PMMA at room temperature (i.e., (approximately) 20° C.).
In a preferred embodiment of the present invention, a small FWHM emitter SB in the context of the present invention 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 (with 1 to 5% by weight, in particular with 1% by weight of emitter SB) in PMMA at room temperature. In other embodiments of the present invention, any of the at least one small FWHM emitters 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.
Additionally, a small FWHM emitter SB in the context of the present invention exhibits an emission maximum within the wavelength range of 500 nm to 560 nm, measured (with 1 to 5% by weight, in particular with 1% by weight of the emitter SB) in PMMA at room temperature.
In a preferred embodiment of the invention, one or more of the at least one small FWHM emitters SB exhibit an emission maximum within the wavelength range of 520 nm to 540 nm, measured (with 1 to 5% by weight, in particular with 1% by weight) of the emitter SB in PMMA at room temperature.
It is understood that a TADF material EB comprised in the at least one 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 comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention may also exhibit an emission maximum within the wavelength range of 500 nm to 560 nm. A TADF material EB in the context of the present invention differs from any small FWHM emitter SB in the context of the present invention in that EB typically mainly functions as energy pump transferring energy to at least one small FWHM emitter SB while the main contribution to the emission band of the optoelectronic device according to the invention can preferably be attributed to the emission of at least one small FWHM emitter SB.
In a preferred embodiment of the invention, any 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, any 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 comprise oxygen (O), silicon (Si), fluorine (F), and bromine (Br).
In a preferred embodiment of the invention, a small FWHM emitter SB in the context of the invention is a near-range-charge-transfer (NRCT) emitter.
Typical NRCT emitters are described in literature by Hatakeyama et al. (Advanced Materials, 2016, 28(14):2777-2781, DOI: 10.1002/adma.201505491) to show a delayed component in the time-resolved photoluminescence spectrum and exhibit a near-range HOMO-LUMO separation.
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.
According to the invention, any small FWHM emitter SB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(SB) having an energy EHOMO(SB) wherein preferably: −5.6 eV≤EHOMO(SB)≤−5.4 eV.
According to the invention, any small FWHM emitter SB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(SB) having an energy ELUMO(SB), wherein preferably: −3.1 eV≤ELUMO(SB)≤−2.9 eV.
According to the invention, any small FWHM emitter SB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited singlet state energy level E(S1S), wherein preferably: 2.4 eV≤E(S1S)≤2.6 eV.
According to the invention, any small FWHM emitter SB comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention has a lowermost excited triplet state energy level E(T1S), whose preferred range may be defined by the above-mentioned preferred range for the singlet state energy level E(S1S) and the preferred feature that ΔEST of the small FWHM emitter SB is smaller than or equal to 0.5 eV.
In a preferred embodiment of the invention, each of the at least one small FWHM emitter SB is a boron (B)-containing emitter.
Known examples of boron (B)-containing small FWHM emitters comprise structures with a boron-dipyrromethene core, wherein typically, the boron atom is additionally substituted with either two fluorine substituents or two alkoxy substituents, wherein one or more hydrogen atoms may be substituted by fluorine (F), or two aryloxy substituents. Specific examples of such emitters are shown in the following:
In one embodiment, each of the at least one small FWHM emitters SB comprises or consists of a polycyclic aromatic compound.
In one embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to formula B-I:
wherein B is boron,
Ar1, Ar2, and Ar3 are at each occurrence independently of each other selected from the group consisting of an aromatic ring and a heteroaromatic ring, and Ar1, Ar2, Ar3 may optionally be linked to each other to form one or more additional rings.
The aromatic ring as Ar1, Ar2, Ar3 of the general formula B-I is, for example, an aryl ring having 6 to 30 carbon atoms, and the aryl ring is preferably an aryl ring having 6 to 16 carbon atoms, more preferably an aryl ring having 6 to 12 carbon atoms, and particularly preferably an aryl ring having 6 to 10 carbon atoms.
Specific examples of the aromatic ring as Ar1, Ar2, Ar3 of the general formula B-I include a benzene ring which is a monocyclic system; a biphenyl ring which is a bicyclic system; a naphthalene ring which is a fused bicyclic system; a terphenyl ring (m-terphenyl, o-terphenyl, or p-terphenyl) which is a tricyclic system; an acenaphthylene ring, a fluorene ring, a phenalene ring and a phenanthrene ring, which are fused tricyclic systems; a triphenylene ring, a pyrene ring and a naphthacene ring, which are fused tetracyclic systems; and a perylene ring and a pentacene ring, which are fused pentacyclic systems.
The heteroaromatic ring as Ar1, Ar2, Ar3 of the general formula B-I is, for example, a heteroaryl ring having 2 to 30 carbon atoms, and the heteroaryl ring is preferably a heteroaryl ring having 2 to 25 carbon atoms, more preferably a heteroaryl ring having 2 to 20 carbon atoms, even more preferably a heteroaryl ring having 2 to 15 carbon atoms, and particularly preferably a heteroaryl ring having 2 to 10 carbon atoms. Furthermore, the heteroaromatic ring as Ar1, Ar2, Ar3 of the general formula B-I may be, for example, a heterocyclic ring containing 1 to 5 heteroatoms selected from oxygen, sulfur, and nitrogen in addition to carbon as the ring-constituting atoms.
Specific examples of the heteroaromatic ring as Ar1, Ar2, Ar3 of the general formula B-I include a pyrrole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, an imidazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, a tetrazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an isoindole ring, a 1H-indazole ring, a benzimidazole ring, a benzoxazole ring, a benzothiazole ring, a 1H-benzotriazole ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinazoline ring, a quinoxaline ring, a phthalazine ring, a naphthyridine ring, a purine ring, a pteridine ring, a carbazole ring, an acridine ring, a phenoxathiin ring, a phenoxazine ring, a phenothiazine ring, a phenazine ring, an indolizine ring, a furan ring, a benzofuran ring, an isobenzofuran ring, a dibenzofuran ring, a thiophene ring, a benzothiophene ring, a dibenzothiophene ring, a furazane ring, an oxadiazole ring, and a thianthrene ring.
One or more hydrogen atoms in the aforementioned aromatic or heteroaromatic ring as Ar1, Ar2, Ar3 of the general formula B-I may be substituted by a substituent Rf,
wherein Rf is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, N(R17)2, OR17, SR17, Si(R17)3, B(OR17)2, OSO2R17, CF3, CN, halogen,
C1-C40-alkyl,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3—O57-heteroaryl,
R17 is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, OPh, SPh, CF3, CN, F, Si(C1-C5-alkyl)3, Si(Ph)3,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2,
N(C3-C17-heteroaryl)2; and
N(C3-C17-heteroaryl)(C6-C18-aryl); wherein
any of the substituents Rf and R17 independently of each other may optionally form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents Rf, R17 and/or the aromatic or heteroaromatic rings Ar1, Ar2, and Ar3, whereat the so formed rings may optionally be substituted with one or more substituents Rf.
In one embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of formulas SB-II, SB-III, and SB-IV:
wherein
for Ar1, Ar2, Ar3, Rf, and R17 the aforementioned definitions apply;
Y2, Y3, and Y4 are at each occurrence independently of each other selected from the group consisting of:
NR18, O, C(R18)2, S or Si(R18)2; wherein
R18 is at each occurrence independently of each other selected from the group consisting of:
R19 is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, N(R20)2, OR20, SR20, Si(R20)3, B(OR20)2, OSO2R20, CF3, CN, halogen,
C1-C40-alkyl,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3-C57-heteroaryl,
R20 is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, OPh, SPh, CF3, CN, F, Si(C1-C5-alkyl)3, Si(Ph)3,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2,
N(C3-C17-heteroaryl)2; and
N(C3-C17-heteroaryl)(C6-C18-aryl); wherein
any of the substituents Rf, R17, R18, and R19 independently of each other may optionally form a mono- or polycyclic, aliphatic, aromatic, heteroaromatic and/or benzo-fused ring system with one or more substituents Rf, R17, R18, R19 and/or the aromatic or heteroaromatic rings Ar1, Ar2, and Ar3, whereat the so formed rings may optionally be substituted with one or more substituents Rf.
In one embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure of formula SB-III-3a:
wherein RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RXVII, RXVIII, RXIX, RXX, RXXI, RXXII and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, N(R21)2, OR21, SR21, Si(R21)3, B(OR21)2, OSO2R21, CF3, CN, halogen,
C1-C40-alkyl,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3-C57-heteroaryl,
wherein optionally one or more pair of adjacent groups RVI and RVII, RVII and RVIII, RVIII and RIX, RX and RXI, RXI and RXII, RXII and RXIII, RXIV and RXV, RXV and RXVI, RXVI and RXVII, RXVII and RXVIII, RXIX and RXX, RXX and RXXI, RXXI and RXXII, RXXII and RXXIII forms an aromatic ring system which is fused to the adjacent benzene ring a, c or d of general formula SB-III-3a and which is optionally substituted with one or more substituents R21;
wherein optionally one or both pairs RVI and RXXIII, RXIII and KXIV are joint to form a group Z4 which is at each occurrence independently of each other selected from the group consisting of: a direct bond, CR22R23, C═CR22R23, C═O, C═NR22, NR22, O, SiR22R23, S, S(O), and S(O)2;
R21 is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, OPh, SPh, CF3, CN, F, Si(C1-C5-alkyl)3, Si(Ph)3,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2,
N(C3-C17-heteroaryl)2; and
N(C3-C17-heteroaryl)(C6-C18-aryl);
R22 and R23 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, N(R24)2, OR24, Si(R24)3, B(OR24)2, OSO2R24, CF3, CN, F, Br, I,
C1-C40-alkyl,
C1-C40-alkoxy,
C1-C40-thioalkoxy,
C2-C40-alkenyl,
C2-C40-alkynyl,
C6-C60-aryl,
C3-C57-heteroaryl,
R24 is at each occurrence independently from another selected from the group consisting of: hydrogen, deuterium, OPh, SPh, CF3, CN, F, Si(C1-C5-alkyl)3, Si(Ph)3,
C1-C5-alkyl,
C1-C5-alkoxy,
C1-C5-thioalkoxy,
C2-C5-alkenyl,
C2-C5-alkynyl,
C6-C18-aryl,
C3-C17-heteroaryl,
N(C6-C18-aryl)2,
N(C3-C17-heteroaryl)2; and
N(C3-C17-heteroaryl)(C6-C18-aryl);
RA is selected from the group consisting of: hydrogen,
In a highly preferred embodiment of the invention, RA is selected from the group consisting of:
C3-C15-heteroaryl, wherein optionally one or more hydrogen atoms are independently of each other substituted by deuterium, halogen, C1-C5-alkyl, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), C3-C15-heteroaryl, and
C6-C18-aryl, in which optionally one or more hydrogen atoms are independently from each other substituted by C1-C5-alkyl, CN, CF3 and Ph;
In a particularly preferred embodiment of the invention, RA is selected from the group consisting of:
C3-C15-heteroaryl, wherein optionally one or more hydrogen atoms are independently of each other substituted by deuterium, halogen, C1-C5-alkyl, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), C3-C15-heteroaryl, and
C6-C18-aryl, in which optionally one or more hydrogen atoms are independently from each other substituted by C1-C5-alkyl, CN, CF3 and Ph, wherein the binding site of RA according to formula SB-III-3a is one of the C3-C15-carbon atoms of the C3-C15-heteroaryl.
In one embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of formulas SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, SB-III-3a-6, SB-III-3a-7, SB-III-3a-8, SB-III-3a-9, SB-III-3a-10, SB-III-3a-11, SB-III-3a-12, SB-III-3a-13, SB-III-3a-14, SB-III-3a-15, SB-III-3a-16, SB-III-3a-17, SB-III-3a-18, SB-III-3a-19, SB-III-3a-20, SB-III-3a-21, SB-III-3a-22, SB-III-3a-23, SB-III-3a-24, SB-III-3a-25, SB-III-3a-26, SB-III-3a-27, SB-III-3a-28, SB-III-3a-29, SB-III-3a-30:
In a preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of formulas SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, SB-III-3a-6, SB-III-3a-9, and SB-III-3a-10:
In a preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, SB-III-3a-6, SB-III-3a-7, SB-III-3a-8, SB-III-3a-9, SB-III-3a-10, SB-III-3a-11, SB-III-3a-12, SB-III-3a-13, SB-III-3a-14, SB-III-3a-15, SB-III-3a-16, SB-III-3a-17, SB-III-3a-18, SB-III-3a-19, SB-III-3a-20, SB-III-3a-21, SB-III-3a-22, SB-III-3a-23, SB-III-3a-24, SB-III-3a-25, SB-III-3a-26, SB-III-3a-27, SB-III-3a-28, SB-III-3a-29, SB-III-3a-30, wherein RA is hydrogen or has a structure represented by any of the formulas RA-I, RA-II, RA-III, RA-IV, RA-V, RA-VI, RA-VII, RA-VIII, RA-IX, RA-X, RA-XI, RA-XII, and RA-XIII,
wherein
the dashed line indicates the binding site to the core structure;
Q5 is at each occurrence independently of each other selected from the group consisting of nitrogen (N) and R25;
X3 is at each occurrence independently of each other selected from the group consisting of oxygen (O), sulfur (S), C(R25)2, and NR25;
R25 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, C1-C5-alkyl, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), and
R26 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, C1-C5-alkyl, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), and
wherein two or more adjacent substituents R25 and/or R26 may optionally form an C3-C30-aromatic or a C3-C15-heteroaromatic ring system; and
wherein in formulas RA-III, RA-IV, RA-V, and RA-VI, at least one Q5 is N; and
wherein in formulas RA-III, RA-IV, RA-V, and RA-VI, two adjacent groups Q5 are not both N.
In an even more preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, 5B-III-3a-5, SB-III-3a-6, SB-III-3a-7, SB-III-3a-8, SB-III-3a-9, SB-III-3a-10, SB-III-3a-11, SB-III-3a-12, SB-III-3a-13, SB-III-3a-14, SB-III-3a-15, SB-III-3a-16, SB-III-3a-17, SB-III-3a-18, SB-III-3a-19, SB-III-3a-20, SB-III-3a-21, SB-III-3a-22, SB-III-3a-23, SB-III-3a-24, SB-III-3a-25, SB-III-3a-26, SB-III-3a-27, SB-III-3a-28, SB-III-3a-29, SB-III-3a-30,
wherein RA is hydrogen or has a structure represented by any of the formulas RA-I, RA-II, RA-III, RA-IV, RA-V, RA-VI, RA-VII, RA-VIII, RA-IX, RA-X, RA-XI, RA-XII, and RA-XIII; and
wherein R26 is at each occurrence hydrogen.
In a still even more preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, 5B-III-3a-5, SB-III-3a-6, SB-III-3a-7, SB-III-3a-8, SB-III-3a-9, SB-III-3a-10, SB-III-3a-11, SB-III-3a-12, SB-III-3a-13, SB-III-3a-14, SB-III-3a-15, SB-III-3a-16, SB-III-3a-17, SB-III-3a-18, SB-III-3a-19, SB-III-3a-20, SB-III-3a-21, SB-III-3a-22, SB-III-3a-23, SB-III-3a-24, SB-III-3a-25, SB-III-3a-26, SB-III-3a-27, SB-III-3a-28, SB-III-3a-29, SB-III-3a-30,
wherein RA is hydrogen or has a structure represented by any of the formulas RA-Ia, RA-Ib, RA-Ic, RA-Id, RA-Ie, RA-If, RA-Ig, RA-IIIa, RA-IIIb, RA-IVa, RA-IVb, RA-Va, RA-Vb, RA-Vc, RA-Vd, RA-Ve, RA-Vf, RA-VIa, RA-VIb, RA-VIc, RA-VId, RA-VIe, RA-VIf, RA-VII, RA-VIIIa, RA-VIIIb, RA-VIIIc, RA-IXa, RA-IXb, and RA-IXc:
wherein
the dashed line indicates the binding site to the core structure;
R25 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, C1-C5-alkyl, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), and
In a still even more preferred embodiment of the invention, R25 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), and
adjacent groups R25 do not combine to form any kind of additional ring system.
In a still even more preferred embodiment of the invention, R25 is at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, SiMe3, SiPh3 (Ph=phenyl), and
adjacent groups R25 do not combine to form any kind of additional ring system.
In one embodiment RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RVXII, RVXIII RXIX, RXX, RXXI, RXXII and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, CN, CF3, SiMe3, SiPh3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
N(Ph)2;
wherein, optionally, at least one pair of adjacent groups RVI and RVII, RVII and RVIII, RVIII and RIX forms an aromatic ring system which is fused to the adjacent benzene ring a of formula SB-III-3a and/or, optionally, at least one pair of adjacent groups RX and RXI, RXI and RXII, RXII and RXIII forms an aromatic ring system which is fused to the adjacent benzene ring b of general formula SB-III-3a;
wherein each of the optionally so formed aromatic ring systems comprises 3 to 30 carbon atoms and is optionally substituted with one or more substituents R21; and wherein it is particularly preferred that the optionally so formed two aromatic ring systems are identical; and
wherein optionally one or both pairs RVI and RXXIII, RXIII and RXIV are joint to form a group Z4 which is at each occurrence independently of each other selected from the group consisting of: a direct bond, CR22R23, C═CR22R23, C═O, C═NR22, NR22, O, SiR22R23, S, S(O), and S(O)2;
wherein R21, R22, and R23 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, CN, CF3, SiMe3, SiPh3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
N(Ph)2.
In a still even more preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, 5B-III-3a-5, SB-III-3a-6, SB-III-3a-9, SB-III-3a-10;
wherein RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RXVII, RXVIII, RXIX, RXX, RXXI, RXXII and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, CN, CF3, SiMe3, SiPh3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
N(Ph)2;
wherein, optionally, at least one pair of adjacent groups RVI and RVII, RVII and RVIII, RVIII and RIX forms an aromatic ring system which is fused to the adjacent benzene ring a of formula SB-III-3a and/or, optionally, at least one pair of adjacent groups RX and RXI, RXI and RXII, RXII and RXIII forms an aromatic ring system which is fused to the adjacent benzene ring b of general formula SB-III-3a;
wherein each of the optionally so formed aromatic ring systems comprises 3 to 30 carbon atoms and is optionally substituted with one or more substituents R21; and wherein it is particularly preferred that the optionally so formed two aromatic ring systems are identical; and
wherein optionally one or both pairs RVI and RXXIII, RXIII and RXIV are joint to form a group Z4 which is at each occurrence independently of each other selected from the group consisting of: a direct bond, CR22R23, C═CR22R23, C═O, C═NR22, NR22, O, SiR22R23, S, S(O), and S(O)2;
wherein R21, R22, and R23 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, halogen, CN, CF3, SiMe3, SiPh3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
N(Ph)2.
In an even more preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, 5B-III-3a-5, SB-III-3a-6, SB-III-3a-9, SB-III-3a-10;
wherein RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RXVII, RXVIII, RXIX, RXX, RXXI, RXXII, and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3, SiMe3, SiPh3, N(Ph)2,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
wherein, optionally, at least one pair of adjacent groups RVI and RVII, RVII and RVIII, RVIII and RIX forms an aromatic ring system which is fused to the adjacent benzene ring a of formula SB-III-3a and/or, optionally, at least one pair of adjacent groups RX and RXI, RXI and RXII, RXII and RXIII forms an aromatic ring system which is fused to the adjacent benzene ring b of general formula SB-III-3a;
wherein each of the optionally so formed aromatic ring systems comprises 3 to 30 carbon atoms; and
wherein it is particularly preferred that the optionally so formed two aromatic ring systems are identical; and
wherein optionally one or both pairs RVI and RXXIII, RXIII and RXIV are joint to form a group Z4 which is at each occurrence independently of each other selected from the group consisting of: a direct bond, CR22R23, C═CR22R23C═O, C═NR22, NR22, O, SiR22R23, S, S(O), and S(O)2;
wherein R22, and R23 are at each occurrence independently of each other selected from the group consisting of: hydrogen, deuterium, CN, CF3, SiMe3, SiPh3,
C1-C5-alkyl,
C6-C18-aryl,
C3-C15-heteroaryl,
In a preferred embodiment of the invention, RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RXVII, RXVIII, RXIX, RXX, RXXI, RXXII, and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, N(Ph)2, and
wherein optionally one or both pairs RVI and RXXIII, RXIII and RXIV are joint to form a group Z4 which is at each occurrence a direct bond.
In a particularly preferred embodiment of the invention, each of the at least one small FWHM emitters SB comprises or consists of a structure according to any of the formulas SB-III-3a, SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, SB-III-3a-6, SB-III-3a-9, SB-III-3a-10; wherein RVI, RVII, RVIII, RIX, RX, RXI, RXII, RXIII, RXIV, RXV, RXVI, RXVII, RXVIII, RXIX, RXX, RXXI, RXXII, and RXXIII are independently of each other selected from the group consisting of: hydrogen, deuterium, Me, iPr, tBu, CN, CF3, N(Ph)2, and
wherein optionally one or both pairs RVI and RXXIII, RXIII and RXIV are joint to form a group Z4 which is at each occurrence a direct bond.
Examples of small FWHM emitters SB for use in organic electroluminescent devices according to the invention are listed below, whereat the invention is of course not limited to devices comprising one of these molecules.
Examples of small FWHM emitters SB according to formula SB-III-3a-1 are listed below:
Examples of small FWHM emitters SB according to formula SB-III-3a-2 are listed below:
Examples of small FWHM emitters SB according to formulas SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, and SB-III-3a-6 are listed below:
Examples of small FWHM emitters SB according to formulas SB-III-3a-9, are listed below:
The synthesis of small FWHM emitters SB may be accomplished via standard reactions and reaction conditions known to the skilled artisan. An example of a typical reaction scheme for small FWHM emitters SB comprising or consisting of a structure of formula SB-III-3a is described in the following, wherein RXVIII═RXIX, RXVII═RXX, RXVI═RXXI, RXV═RXXII, RXIV═RXXIII, RXIII═RVI, RXII═RVII, RXI═RVIII and RX═RIX:
1,3-Dibromo-2,5-dichlorbenzene (CAS: 81067-41-6, 1.00 equivalents), E1 (2.20 equivalents), tris(dibenzylideneacetone)dipalladium Pd2(dba)3 (0.02 equivalents; CAS: 51364-51-3), tri-tert-butyl-phosphine (P(tBu)3, CAS: 13716-12-6, 0.08 equivalents) and sodium tert-butoxide (NaOtBu; 6.00 equivalents) are stirred under nitrogen atmosphere in toluene at 80° C. for 2 h. After cooling down to room temperature (rt) the reaction mixture is extracted with toluene and brine and the phases are separated. The combined organic layers are dried over MgSO4 and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and I1 is obtained as solid.
I1 (1.00 equivalents), E2 (2.20 equivalents, tris(dibenzylideneacetone)dipalladium Pd2(dba)3 (0.02 equivalents; CAS: 51364-51-3), tri-tert-butyl-phosphine (0.08 equivalents, P(tBu)3, CAS: 13716-12-6) and sodium tert-butoxide (NaOtBu; 5.00 equivalents) are stirred under nitrogen atmosphere in toluene at 100° C. for 5 h. After cooling down to room temperature (rt) the reaction mixture is extracted with toluene and brine and the phases are separated. The combined organic layers are dried over MgSO4 and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and 12 is obtained as solid.
After dissolving I2 (1 equivalent) under nitrogen atmosphere in THF and cooling to −20° C. or in tert-butylbenzene and cooling to −10° C., tBuLi (2 equivalents, CAS: 594-19-4) is added and the reaction mixture is stirred at 0° C. After complete lithiation, the reaction is quenched and 1,3,2-dioxaborolane (2 equivalents, CAS: 61676-62-8) is added and the reaction mixture is stirred under reflux at 70° C. for 2 h. After cooling down to room temperature (rt), the reaction mixture is extracted between toluene and brine and the phases are separated. The combined organic layers are dried over MgSO4 and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and I3 is obtained as solid.
I3 (1 equivalent), N,N-diisopropylethylamine (10 equivalents, CAS: 7087-68-5) and AlCl3 (10 equivalents, CAS: 7446-70-0) are stirred under nitrogen atmosphere in chlorobenzene at 120° C. for 16 h. After cooling down to room temperature (rt) the reaction mixture is extracted between toluene and brine and the phases are separated. The combined organic layers are dried over MgSO4 and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and 14 is obtained as solid.
I4 (1 equivalent), E3 (1.1 equivalents), palladium(II) acetate (CAS: 3375-31-3, 0.1 equivalents), S-Phos (CAS: 657408-07-6, 0.24 equivalents) and potassium phosphate tribasic (5 equivalents) are stirred under nitrogen atmosphere in dioxane/water 5:1 at 100° C. for 16 h. After cooling down to room temperature (rt) the reaction mixture is extracted between toluene and brine and the phases are separated. The combined organic layers are dried over MgSO4 and then the solvent is removed under reduced pressure. The crude product obtained is purified by recrystallization or column chromatography and P1 is obtained as solid.
Further FWHM emitters SB may be obtained analogously. An FWHM emitter SB may also be obtained by any alternative synthesis route suitable for this purpose.
In a preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to formula EB-I and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to formula SB-I.
In an even more preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the formulas EB-I-1, EB-I-2, EB-I-3, EB-I-4, EB-I-5, EB-I-6, EB-I-7, and EB-I-8 and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of formulas SB-II, SB-III, and SB-IV.
In a still even more preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the formulas EB-I-1a, EB-I-2a, EB-I-3a, EB-I-4a, EB-I-5a, EB-I-6a, EB-I-7, and EB-I-8, and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of formula SB-III-3a.
In a still even more preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the formulas EB-I-1a-1, EB-I-2a-1, EB-I-3a-1, EB-I-4a-1, EB-I-5a-1, EB-I-6a-1, EB-I-7, and EB-I-8, and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of formula SB-III-3a.
In a still even more preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the formulas EB-I-3a-1a, EB-I-3a-1 b, EB-I-5a-1a, and EB-I-6a-1a, and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of formulas SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, 5B-III-3a-5, SB-III-3a-6, SB-III-3a-9, and SB-III-3a-1 0.
In a particularly preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the formulas EB-I-3a-1a, EB-I-3a-1 b, EB-I-5a-1a, and EB-I-6a-1a, and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of formulas SB-III-3a-1, SB-III-3a-2, SB-III-3a-3, SB-III-3a-4, SB-III-3a-5, SB-III-3a-6, SB-III-3a-9, and SB-III-3a-10.
In a particularly preferred embodiment of the invention, each TADF material EB comprised in the at least one light-emitting layer B has a structure according to any of the particularly preferred examples shown herein and each FWHM emitter SB comprised in the at least one light-emitting layer B has a structure according to any of the particularly preferred examples shown herein.
Relations of HOMO- and LUMO-energy levels of components within the light-emitting layer(s) B
In a preferred embodiment of the invention, as far as at least one p-host HP is present in a light-emitting layer B, one or more or all of the relations expressed by the following formulas (20) to (22) preferably apply:
E
LUMO(HP)>ELUMO(EB) (20)
E
HOMO(HP)≤EHOMO(SB) (21)
E
LUMO(HP)>ELUMO(SB) (22).
In a preferred embodiment of the invention, as far as at least one p-host HP and at least one n-host HN are present in a light-emitting layer B, one or more or all of the relations expressed by the following formulas (18) to (22) preferably apply:
E
HOMO(HP)>EHOMO(HN) (18)
E
LUMO(HP)>ELUMO(HN) (19)
E
LUMO(HP)>ELUMO(EB) (20)
E
HOMO(HP)≤EHOMO(SB) (21)
E
LUMO(HP)>ELUMO(SB) (22).
In a preferred embodiment of the invention, as far as at least one p-host HP and at least one n-host HN and at least one bipolar host HBP are present in a light-emitting layer B, one or more or all of the relations expressed by the following formulas (18) to (23) preferably apply:
E
HOMO(HP)>EHOMO(HN) (18)
E
LUMO(HP)>ELUMO(HN) (19)
E
LUMO(HP)>ELUMO(EB) (20)
E
HOMO(HP)≤EHOMO(SB) (21)
E
LUMO(HP)>ELUMO(SB) (22)
E
LUMO(HP)>ELUMO(HBP) (23).
Accordingly, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HP) having an energy EHOMO(HP) which preferably is higher than the energy EHOMO(HN) of the highest occupied molecular orbital HOMO(HN) of an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Furthermore, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) which preferably is higher than the energy ELUMO(HN) of the lowest unoccupied molecular orbital LUMO(HN) of an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Additionally, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) which preferably is higher than the energy ELUMO(EB) of the lowest unoccupied molecular orbital LUMO(EB) of a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
A p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HP) having an energy EHOMO(HP) which preferably is lower than or equal to the energy EHOMO(SB) of the highest occupied molecular orbital HOMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Furthermore, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) which preferably is higher than the energy ELUMO(SB) of the lowest unoccupied molecular orbital LUMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Additionally, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) which preferably is higher than the energy ELUMO(HBP) of the lowest unoccupied molecular orbital LUMO(HBP) of a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, as far as a p-host HP is present in a light-emitting layer EB, one or both of the relations selected from the group consisting of those expressed by the following formulas (26) and/or (27) preferably apply:
−0.3 eV≤EHOMO(HP)−EHOMO(EB)≤0.3 eV (26)
E
LUMO(HP)−ELUMO−(EB)≥0.3 eV (27).
In a preferred embodiment of the invention, as far as a p-host HP and n-host HN are present in a light-emitting layer EB, one or more or all of the relations selected from the group consisting of those expressed by the following formulas (24) to (27) preferably apply:
E
HOMO(HP)−EHOMO(HN)≥0.3 eV (24)
E
LUMO(HP)−ELUMO(HN)≥0.3 eV (25)
−0.3 eV≤EHOMO(HP)−EHOMO(EB)≤0.3 eV (26)
E
LUMO(HP)−ELUMO(EB)≥0.3 eV (27).
In a preferred embodiment of the invention, as far as a p-host HP and n-host HN and a bipolar host HBP are present in a light-emitting layer EB, one or more or all of the relations selected from the group consisting of those expressed by the following formulas (24) to (28) preferably apply:
E
HOMO(HP)−EHOMO(HN)≥0.3 eV (24)
E
LUMO(HP)−ELUMO(HN)≥0.3 eV (25)
−0.3 eV≤EHOMO(HP)−EHOMO(EB)≤0.3 eV (26)
E
LUMO(HP)−ELUMO(EB)≥0.3 eV (27)
E
LUMO(HP)−ELUMO(HBP)≥0.3 eV (28),
Accordingly, in a preferred embodiment of the invention, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HP) having an energy EHOMO(HP) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN), wherein preferably: EHOMO(HP)−EHOMO(HN) 0.3 eV. In other words, the energy difference between EHOMO(HP) and EHOMO(HN) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN) wherein preferably: ELUMO(HP)−ELUMO(HN)≥0.3 eV. In other words, the energy difference between ELUMO(HP) and ELUMO(HN) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HP) having an energy EHOMO(HP) and a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(EB) having an energy EHOMO(EB), wherein preferably: −0.3 eV≤EHOMO(HP)−EHOMO(EB)≤0.3 eV. In other words, the HOMO(HP) of a p-host HP comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention may be higher or lower in energy than the HOMO(EB) of a TADF emitter EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention, but the energy difference does preferably not exceed 0.3 eV.
In a preferred embodiment of the invention, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) and a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB) wherein preferably: ELUMO(HP)−ELUMO(EB)≥0.3 eV. In other words, the energy difference between ELUMO(HP) and ELUMO(EB) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, a p-host HP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HP) having an energy ELUMO(HP) and a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP), wherein preferably: ELUMO(HP)−ELUMO(HBP)≥0.3 eV. In other words, the energy difference between ELUMO(HP) and ELUMO(HBP) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, as far as an n-host HN is present in a light-emitting layer EB, one or more or all of the relations expressed by the following formulas (29) to (32) preferably apply:
E
HOMO(HN)≤EHOMO(EB) (29)
E
LUMO(HN)≤ELUMO(EB) (30)
E
HOMO(HN)<EHOMO(SB) (31)
E
LUMO(HN)<ELUMO(SB) (32).
In a preferred embodiment of the invention, as far as an n-host HN and a bipolar host HBP are present in a light-emitting layer EB, one or more or all of the relations expressed by the following formulas (29) to (33) preferably apply:
E
HOMO(HN)≤EHOMO(EB) (29)
E
LUMO(HN)≤ELUMO(EB) (30)
E
HOMO(HN)<EHOMO(SB) (31)
E
LUMO(HN)<ELUMO(SB) (32)
E
HOMO(HN)<EHOMO(HBP) (33).
Accordingly, an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN) which preferably is lower than or equal to the energy EHOMO(EB) of the highest occupied molecular orbital HOMO(EB) of a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Furthermore, an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN) which preferably is equal to or lower than the energy ELUMO(EB) of the lowest unoccupied molecular orbital LUMO(EB) of a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Additionally, an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN) which preferably is lower than the energy EHOMO(SB) of the highest occupied molecular orbital HOMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
An n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN) which preferably is lower than the energy ELUMO(SB) of the lowest unoccupied molecular orbital LUMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Furthermore, an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN) which preferably is lower than the energy EHOMO(HBP) of the highest occupied molecular orbital HOMO(HBP) of a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, as far as an n-host HN is present in a light-emitting layer EB, one or more or all of the relations expressed by the following formulas (34) to (36) preferably apply:
E
HOMO(EB)−EHOMO(HN)≥0.3 eV (34)
E
LUMO(EB)−ELUMO(HN)≥0.2 eV (35)
E
LUMO(SB)−ELUMO(HN)≥0.2 eV (36)
In a preferred embodiment of the invention, as far as an n-host HN and a bipolar host HBP are present in a light-emitting layer EB, one or more or all of the relations expressed by the following formulas (34) to (37) apply:
E
HOMO(EB)−EHOMO(HN)≥0.3 eV (34)
E
LUMO(EB)−ELUMO(HN)≥0.2 eV (35)
E
LUMO(SB)−ELUMO(HN)≥0.2 eV (36)
E
HOMO(HBP)−EHOMO(HN)≥0.3 eV (37).
Accordingly, in a preferred embodiment of the invention, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(EB) having an energy EHOMO(EB) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN), wherein preferably: EHOMO(EB)−EHOMO(HN)≥0.3 eV. In other words, the energy difference between EHOMO(EB) and EHOMO(HN) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN) wherein preferably: ELUMO(EB)−ELUMOHN)≥0.2 eV. In other words, the energy difference between ELUMO(EB) and ELUMO(HN) preferably is equal to or larger than 0.2 eV.
In a preferred embodiment of the invention, a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(SB) having an energy ELUMO(SB) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HN) having an energy ELUMO(HN), wherein preferably: ELUMO(SB)−ELUMO(HN)≥0.2 eV. In other words, the energy difference between ELUMO(SB) and ELUMO(HN) preferably is equal to or larger than 0.2 eV.
In a preferred embodiment of the invention, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HBP) having an energy EHOMO(HBP) and an n-host HN optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HN) having an energy EHOMO(HN), wherein preferably: EHOMO(HBP)−EHOMO(HN) 0.3 eV. In other words, the energy difference between EHOMO(HBP) and EHOMO(HN) preferably is equal to or larger than 0.3 eV.
In a preferred embodiment of the invention, as far as a bipolar host HBP is present in a light-emitting layer B, one, two or all of the relations expressed by the following formulas (38) to (40) preferably apply:
E
HOMO(HBP)≤EHOMO(SB) (38)
E
LUMO(HBP)≤ELUMO(EB) (39)
E
LUMO(HBP)<ELUMO(SB) (40).
Accordingly, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HBP) having an energy EHOMO(HBP) which preferably is lower than or equal to the energy EHOMO(SB) of the highest occupied molecular orbital HOMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Furthermore, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP) which preferably is lower than or equal to the energy ELUMO(EB) of the lowest unoccupied molecular orbital LUMO(EB) of a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
Additionally, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP) which preferably is lower than the energy ELUMO(SB) of the lowest unoccupied molecular orbital LUMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, as far as a bipolar host HBP is present in a light-emitting layer B, one, two or all of the relations expressed by the following formulas (41) to (43) preferably apply:
−0.3 eV≤EHOMO(HBP)−EHOMO(EB)≤0.3 eV (41)
E
LUMO(EB)−ELUMO(HBP)≥0.2 eV (42)
E
LUMO(HBP)−ELUMO(SB))≥0.2 eV (43).
Accordingly, in a preferred embodiment of the invention, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(HBP) having an energy EHOMO(HBP) and a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(EB) having an energy EHOMO(EB), wherein preferably: −0.3 eV≤EHOMO(HBP)−EHOMO(EB)≤0.3 eV. In other words, the HOMO(HBP) of a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention may be higher or lower in energy than the HOMO(EB) of a TADF emitter EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention, but the energy difference does preferably not exceed 0.3 eV.
Furthermore, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB) and a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP), wherein preferably: ELUMO(EB)−ELUMO(HBP)≥0.2 eV. In other words, the energy difference between ELUMO(EB) and ELUMO(HBP) preferably is equal to or larger than 0.2 eV.
Additionally, a bipolar host HBP optionally comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(HBP) having an energy ELUMO(HBP) and a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB), wherein preferably: ELUMO(HBP)−ELUMO(SB)≥0.2 eV. In other words, the energy difference between ELUMO(HBP) and ELUMO(EB) preferably is equal to or larger than 0.2 eV.
In a preferred embodiment of the invention, the relations expressed by the following formulas (44) and (45) apply:
E
HOMO(EB)≤EHOMO(SB) (44)
E
LUMO(EB)<ELUMO(SB) (45).
Accordingly, in a preferred embodiment of the invention, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a highest occupied molecular orbital HOMO(EB) having an energy EHOMO(EB) which preferably is equal to or lower than the energy EHOMO(SB) of the highest occupied molecular orbital HOMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB) which is lower than the energy ELUMO(SB) of the lowest unoccupied molecular orbital LUMO(SB) of a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention.
In a preferred embodiment of the invention, the relation expressed by the following formula (46) applies:
E
LUMO(EB)−ELUMO(SB)≥0.2 eV (46).
Accordingly, in a preferred embodiment of the invention, a TADF material EB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(EB) having an energy ELUMO(EB) and a small FWHM emitter SB comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention has a lowest unoccupied molecular orbital LUMO(SB) having an energy ELUMO(SB), wherein preferably: ELUMO(EB)−ELUMO(SB)≥0.2 eV. In other words, the energy difference between ELUMO(EB) and ELUMO(SB) preferably is equal to or larger than 0.2 eV.
In an even more preferred embodiment of the invention, two, three, more than three or all relations expressed by the above-mentioned formulas (1) to (23), (29) to (33), (38) to (40), (44), and (45) apply, wherein this does not imply that all species referred to in these relations are preferably comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention, but instead that it is particularly preferred that all relations selected from the group of the listed relations which refer to any comprised species apply. For example, if no n-host HN is comprised in any of the at least one light-emitting layers B of an organic electroluminescent device according to the invention, it is understood, that the relations referring to an n-host HN do not apply in this particular case while they preferably apply whenever an n-host HN is comprised.
In a particularly preferred embodiment of the invention, two, three, more than three or all relations expressed by the above-mentioned formulas (1) to (46) apply, wherein this does not imply that all species referred to in these relations are preferably comprised in the at least one light-emitting layer B of an organic electroluminescent device according to the invention, but instead that it is particularly preferred that all relations selected from the group of relations which refer to any comprised species apply.
Composition of the at Least One Light-Emitting Layer B
The one or more hosts HB (e.g., one or more p-host HP and/or one or more n-hosts HN and/or one or more bipolar host(s) HBP), one or more TADF emitters EB, and one or more FWHM emitters SB may be comprised in the organic electroluminescent device in any amount and any ratio.
In a preferred embodiment of the invention, each of the at least one light-emitting layers B in an organic electroluminescent device according to the present invention comprises 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 layers B in an organic electroluminescent device according to the present invention comprises 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 an organic electroluminescent device according to the present invention, any of the at least one light-emitting layers B comprises (or consists of):
(i) 30-89.9% by weight of one or more host compound HB;
(ii) 10-60% by weight of one or more TADF material EB; and
(iii) 0.1-10% by weight of one or more small FWHM emitter SB; and optionally
(iv) 0-72% by weight of one or more solvents.
In a preferred embodiment, wherein HN is optional, in an organic electroluminescent device according to the present invention, any of the at least one light-emitting layers B comprises (or consists of):
(i) 10-89.9% by weight of one or more p-host compound HP; optionally
(ii) 0-79.9% by weight of one or more n-host compound HN;
(iii) 10-50% by weight of one or more TADF material EB; and
(iv) 0.1-10% by weight of one or more small FWHM emitter SB; and optionally
(v) 0-72% by weight of one or more solvents.
In an even more preferred embodiment, wherein HN is optional, in an organic electroluminescent device according to the present invention, any of the at least one light-emitting layer B comprises (or consists of):
(i) 22-87.5% by weight of one or more p-host compound HP; optionally
(ii) 0-65.5% by weight of one or more n-host compound HN;
(iii) 12-40% by weight of one or more TADF material EB; and
(iv) 0.5-5% by weight of one or more small FWHM emitter SB; and optionally
(v) 0-65.5% by weight of one or more solvents.
In another preferred embodiment, wherein HN is necessary, in an organic electroluminescent device according to the present invention, the light-emitting layer B comprises (or consists of):
(i) 10-30% by weight of one or more p-host compound HP;
(ii) 40-79.9% by weight of one or more n-host compound HN;
(iii) 10-49% by weight of one or more TADF material EB; and
(iv) 0.1-10% by weight of one or more small FWHM emitter SB; and optionally
(v) 0-34% by weight of one or more solvents.
In another preferred embodiment, wherein HN is necessary, in an organic electroluminescent device according to the present invention, the light-emitting layer B comprises (or consists of):
(i) 40-74% by weight of one or more p-host compound HP;
(ii) 10-30% by weight of one or more n-host compound HN;
(iii) 10-49% by weight of one or more TADF material EB; and
(iv) 0.1-10% by weight of one or more small FWHM emitter SB; and optionally
(v) 0-34% by weight of one or more solvents.
As stated previously, it is understood that different light-emitting layers B optionally comprised in the same organic electroluminescent device according to the invention do not necessarily all comprise the same materials or even the same materials in the same ratios.
In one embodiment, the light-emitting layer comprises not only the organic molecules according to the invention, but also a host material whose triplet (T1) and singlet (S1) energy levels are energetically higher than the triplet (T1) and singlet (S1) energy levels of one or more other organic molecules, in particular the at least one TADF material EB and/or the at least one FWHM emitter SB.
A further aspect of the invention relates to a composition comprising or consisting of:
In one embodiment, the light-emitting layer comprises (or essentially consists of) a composition comprising or consisting of:
In an embodiment, the light-emitting layer EML comprises (or essentially consists of) a composition comprising or consisting of:
Preferably, energy can be transferred from the host compound HB to the one or more FWHM emitters SB according to the invention, in particular transferred from the first excited triplet state T1(HB) of the host compound HB to the first excited triplet state T1(SB) of the one or more organic molecules according to the invention SB and/or from the first excited singlet state S1(HB) of the host compound HB to the first excited singlet state S1(SB) of the one or more organic molecules according to the invention SB.
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 comprises 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 comprises a large content or even consists of transparent conductive oxides (TCOs).
Such an anode layer A may exemplarily comprise 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 polypyrrol 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., (InO3)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 comprise poly-3,4-ethylendioxy 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 comprise PEDOT:PSS (poly-3,4-ethylendioxy thiophene: polystyrene sulfonate), PEDOT (poly-3,4-ethylendioxy 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′-nis-(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)-benzidine), 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 comprise a star-shaped heterocycle such as tris(4-carbazoyl-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 comprise 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 comprise 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-(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), phosphinoxides 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-phosphinoxide), BPyTP2 (2,7-di(2,2′-bipyridin-5-yl)triphenyle), 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, comprise HBM1:
BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline=Bathocuproine), BAlq (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-phosphinoxide), 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)dibenzofurane) and/or TCB/TCP (1,3,5-tris(N-carbazolyl)benzol/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 comprise 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 metals such as Mg, Ca or Al. Alternatively or additionally, the cathode layer C may also comprise 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 comprises at least the following layers:
wherein the light-emitting layer B is located between the anode layer A and the a cathode layer C.
In one embodiment, when the organic electroluminescent device is an OLED, it may optionally comprise the following layer structure:
A) an anode layer A, exemplarily comprising indium tin oxide (ITO);
HTL) a hole transport layer HTL;
B) a light-emitting layer B according to present invention as described herein;
ETL) an electron transport layer ETL; and
C) a cathode layer, exemplarily comprising Al, Ca and/or Mg.
Preferably, the order of the layers herein is A-HTL-B-ETL-C.
Furthermore, the organic electroluminescent device may optionally comprise 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, comprise 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 comprise lithium fluoride, caesium fluoride, silver, Liq (8-hydroxyquinolinolatolithium), Li2O, BaF2, MgO and/or NaF.
Unless otherwise specified, any of the layers of the various embodiments may be deposited by any suitable method. The layers in the context of the present invention, including the light-emitting layer B, 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 comprised 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 light-emitting layer B, 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.
Alternatively, the layers in the context of the present invention, including the at least one light-emitting layer B, 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, 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 by means of liquid processing, the solutions including the components of the layers (i.e., with respect to the light-emitting layer B of the present invention, at least one host compound HB, at least one TADF material EB, and at least one small FWHM emitter SB) may further comprise 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, gam ma-butyrolactone, N-methyl pyrrolidinon, ethoxyethanol, xylene, toluene, anisole, phenetol, acetonitrile, tetrahydrothiophene, benzonitrile, pyridine, trihydrofuran, triarylamine, cyclohexanone, acetone, propylene carbonate, ethyl acetate, benzene and PGMEA (propylen 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).
Further Definitions and Information
As used throughout, the term “layer” in the context of the present invention preferably refers to a body that bears an extensively planar geometry.
As used herein, the terms organic electroluminescent device and optoelectronic light-emitting device may be understood in the broadest sense as any device comprising one or more light-emitting layers B, each comprising at least one host material HB, at least one TADF material EB, and at least one small FWHM emitter SB, 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. More preferably, an organic electroluminescent device may be able to emit light in the visible range, i.e., from 400 to 800 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, semi-transparent or (essentially) transparent.
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, for which the following definitions apply.
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 and S. 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” comprises groups which can be bound via any position of the aromatic or heteroaromatic group, derived from benzene, naphthaline, anthracene, phenanthrene, pyrene, dihydropyrene, chrysene, perylene, fluoranthene, benzanthracene, benzphenanthrene, tetracene, pentacene, benzpyrene, furan, benzofuran, isobenzofuran, dibenzofuran, thiophene, benzothiophene, isobenzothiophene, dibenzothiophene; 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, napthooxazole, anthroxazol, phenanthroxazol, 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.
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 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 comprises 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-diethyln-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” comprises linear, branched, and cyclic alkenyl substituents. The term alkenyl group exemplarily comprises the substituents ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl or cyclooctadienyl.
As used above and herein, the term “alkynyl” comprises linear, branched, and cyclic alkynyl substituents. The term alkynyl group exemplarily comprises ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl or octynyl.
As used above and herein, the term “alkoxy” comprises linear, branched, and cyclic alkoxy substituents. The term alkoxy group exemplarily comprises methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy and 2-m ethylbutoxy.
As used above and herein, the term “thioalkoxy” comprises linear, branched, and cyclic thioalkoxy substituents, in which the 0 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.
Whenever hydrogen (H) is mentioned herein, it could also be replaced by deuterium at each occurrence.
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.
If not stated otherwise, percentages refer to weight percentages ((weight/weight), (w/w), wt. %).
For host compounds HB (more specific: HP and HN), the energy of the first excited triplet state T1 is determined from the onset of the time-gated emission spectrum at 77 K, typically with a delay time of 1 ms and an integration time of 1 ms, if not otherwise stated measured in a neat film of the host material HB.
For TADF materials EB, the energy of the first excited triplet state T1 is determined from the onset of the time-gated emission spectrum at 77 K, typically with a delay time of 1 ms and an integration time of 1 ms, if not otherwise stated measured in a film of poly(methyl methacrylate) (PMMA) with 10% by weight of emitter.
For small full width at half maximum (FWHM) emitters SB, the energy of the first excited triplet state T1 is determined from the onset of the time-gated emission spectrum at 77 K, typically with a delay time of 1 ms and an integration time of 1 ms, if not otherwise stated measured in a film of poly(methyl methacrylate) (PMMA) with 1 to 5% by weight, in particular 1% by weight of emitter.
Orbital and excited state energies can be determined by means of experimental methods known to the person skilled in the art. Experimentally, 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 is calculated as EHOMO+Egap, where Egap is determined as follows:
For host compounds HB (more specific: HP and HN), the onset of emission of a neat film of the host material, which corresponds to the energy of the first excited singlet state S1, is used as Egap, unless stated otherwise.
For TADF materials EB, the onset of emission of a film with 10% by weight of TADF material in poly(methyl methacrylate) (PMMA), which corresponds to the energy of the first excited singlet state S1, is used as Egap, unless stated otherwise.
For small full width at half maximum (FWHM) emitters SB, the onset of emission of a film with 1 to 5% by weight, in particular 1% by weight of small full width at half maximum (FWHM) emitter SB in poly(methyl methacrylate) (PMMA), which corresponds to the energy of the first excited singlet state S1, is used as Egap, unless stated otherwise.
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:
violet: wavelength range of >380-420 nm;
deep blue: wavelength range of >420-475 nm;
sky blue: wavelength range of >475-500 nm;
green: wavelength range of >500-560 nm;
yellow: wavelength range of >560-580 nm;
orange: wavelength range of >580-620 nm;
red: wavelength range of >620-800 nm.
If not stated otherwise, with respect to small FWHM emitters SB, such colors refer to the emission maximum λmaxPMMA of a poly(methyl methacrylate) (PMMA) film with 2% by weight of the emitter SB. For TADF materials EB, such colors refer to the emission maximum λmaxPMMA of a poly(methyl methacrylate) (PMMA) film with 10%, unless stated otherwise.
Cyclic Voltammetry
Cyclic voltammograms of solutions having concentration of 10−3 mol/1 of the organic molecules in dichloromethane or a suitable solvent and a suitable supporting electrolyte (e.g. 0.1 mol/1 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 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. 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: Spin-coating
Apparatus: Spin150, SPS euro.
The sample concentration is 10 mg/ml, dissolved in a suitable solvent.
Program: 1) 3 s at 400 U/min; 20 s at 1000 U/min at 1000 Upm/s. 3) 10 s at 4000 U/m in at 1000 Upm/s. After coating, the films are tried at 70° C. for 1 min.
Photoluminescence spectroscopy and TCSPC (Time-correlated single-photon counting)
Steady-state emission spectroscopy is recorded using a Horiba Scientific, Modell FluoroMax-4 equipped with a 150 W Xenon-Arc lamp, excitation- and emissions monochromators and a Hamamatsu R928 photomultiplier and a time-correlated single-photon counting option. Emissions and excitation spectra are corrected using standard correction fits.
Excited state lifetimes are determined employing the same system using the TCSPC method with FM-2013 equipment and a Horiba Yvon TCSPC hub.
Excitation sources:
NanoLED 370 (wavelength: 371 nm, puls duration: 1.1 ns)
NanoLED 290 (wavelength: 294 nm, puls duration: <1 ns)
SpectraLED 310 (wavelength: 314 nm)
SpectraLED 355 (wavelength: 355 nm).
Data analysis (exponential fit) was done using the software suite DataStation and DAS6 analysis software. The fit is specified using the chi-squared-test.
Photoluminescence Quantum Yield Measurements
For photoluminescence quantum yield (PLQY) measurements an Absolute PL Quantum Yield Measurement C9920-03G system (Hamamatsu Photonics) is used. Quantum yields and CIE coordinates were determined using the software U6039-05 version 3.6.0.
Emission maxima are given in nm, quantum yields ϕ in % and CIE coordinates as x,y values.
PLQY was determined using the following protocol:
Production and Characterization of Organic Electroluminescence Devices
Via vacuum-deposition methods OLED devices comprising 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 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), the standard deviation between these pixels is given. Figures show the data series for one OLED pixel.
Experimental Results
Stack Materials
Host Materials HB (Here for Example p-Hosts HP)
TADF Materials EB
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.
Results I: Variation of Host HB (Exemplified as p-Host HP) and Emitter SB
Composition of the light-emitting layer B (the percentages refer to weight percent):
Device results for EB=EB-10 and HP=mCBP:
Device results for EB=EB-10 and HP=PYD2:
Results II: Variation of Host HB and TADF EB
Setup of the light-emitting layer B (the percentages refer to weight percent):
Device results for SB=SB-1 and HP=mCBP:
Device results for SB=SB-1 and HP=PYD2:
For all electroluminescent devices using a combination of a host, a TADF emitter and an FWHM emitter (H-type device), comprising mCBP as HP and EB-10 as EB, an extension of the relative lifetime of 374% (from 1.00 to 4.74) could be observed for emitter SB-1, and an extension of the relative lifetime of 188% (from 1.00 to 2.88) could be observed for Emitter SB-2, and an extension of the relative lifetime of 193% (from 1.00 to 2.93) could be observed for Emitter SB-3 as compared to the comparative T-type device, whereas the efficiencies (EQE) stayed almost constant.
Furthermore, for all H-type devices using mCBP as HP and EB-10 as EB, a decrease of the full width at half maximum (FWHM) of 47% (from 76 nm to 36 nm) could be observed for emitter SB-1, and a decrease of the FWHM of 47% (from 76 nm to 36 nm) could be observed for Emitter SB-2, and a decrease of the FWHM of 47% (from 76 nm to 40 nm) could be observed for Emitter SB-3 as compared to the comparative T-type device. All H-type and T-type devices using mCBP as HP, EB-10 as EB, and SB-1, SB-2 or SB-3 as SB exhibit emission maxima in the desired green wavelength range of 500 nm to 560 nm, even in the more preferred range of 510 nm to 550 nm.
For all H-type devices using PYD2 as HP and EB-10 as EB, an extension of the relative lifetime of 603% (from 1.00 to 7.03) could be observed for emitter SB-1, and an extension of the relative lifetime of 303% (from 1.00 to 4.03) could be observed for Emitter SB-2, and an extension of the relative lifetime of 58% (from 1.00 to 1.58) could be observed for Emitter SB-3 as compared to the comparative T-type device, whereas the efficiencies (EQE) stayed almost constant. Furthermore, for all H-type devices using PYD2 as HP and EB-10 as EB, a decrease of the full width at half maximum (FWHM) of 46% (from 78 nm to 42 nm) could be observed for emitter SB-1, and a decrease of the FWHM of 46% (from 78 nm to 42 nm) could be observed for Emitter SB-2, and a decrease of the FWHM of 46% (from 78 nm to 42 nm) could be observed for Emitter SB-3 as compared to the comparative T-type device. All H-type and T-type devices using PYD2 as HP, EB-10 as EB, and SB-1, SB-2 or SB-3 as SB exhibit emission maxima in the desired green wavelength range of 500 nm to 560 nm, even in the more preferred range of 510 nm to 550 nm.
For all H-type devices using mCBP as HP and SB-1 as SB, an extension of the relative lifetime of 89% (from 1.00 to 1.89) could be observed for using EB-1, and an extension of the relative lifetime of 120% (from 0.59 to 1.79) could be observed for EB-3, and an extension of the relative lifetime of 120% (from 1.09 to 2.29) could be observed for EB-4, and an extension of the relative lifetime of 700% (from 2.20 to 9.20) could be observed for EB-8, and an extension of the relative lifetime of 859% (from 2.29 to 10.88) could be observed for EB-8, as compared to the respective comparative T-type device, whereas the efficiency (EQE) stayed almost constant. Furthermore, for all H-type devices using mCBP as HP and SB-1 as SB, a decrease of the full width at half maximum (FWHM) of 23% (from 86 nm to 68 nm) could be observed for EB-1, and a decrease of the FWHM of 53% (from 76 nm to 36 nm) could be observed for EB-3, and a decrease of the FWHM of 50% (from 80 nm to 40 nm) could be observed for EB-4, and a decrease of the FWHM of 46% (from 78 nm to 42 nm) could be observed for EB-8, and a decrease of the FWHM of 53% (from 76 nm to 36 nm) could be observed for EB-10, as compared to the respective comparative T-type device. All H-type and T-type devices using mCBP as HP, SB-1 as SB, and EB-1, EB-3, EB-4, EB-8 or EB-10 as EB exhibit emission maxima in the desired green wavelength range of 500 nm to 560 nm, even in the more preferred range of 510 nm to 550 nm.
For all H-type devices using PYD2 as HP and SB-1 as SB, an extension of the relative lifetime of 399% (from 1.00 to 4.99) could be observed for using EB-3, and an extension of the relative lifetime of 590% (from 1.86 to 7.76) could be observed for EB-4, and an extension of the relative lifetime of 120% (from 0.44 to 2.37) could be observed for EB-5, and an extension of the relative lifetime of 136% (from 1.08 to 2.44) could be observed for EB-6, and an extension of the relative lifetime of 781% (from 2.56 to 10.37) could be observed for EB-8, and an extension of the relative lifetime of 981% (from 1.63 to 11.44) could be observed for EB-10, as compared to the respective comparative T-type device, whereas no significant changes in the efficiency (EQE) were observed. Furthermore, for all H-type devices using PYD2 as HP and SB-1 as SB, a decrease of the full width at half maximum (FWHM) of 47% (from 76 nm to 40 nm) could be observed for EB-3, and a decrease of the FWHM of 48% (from 80 nm to 42 nm) could be observed for EB-4, and a decrease of the FWHM of 46% (from 78 nm to 42 nm) could be observed for EB-5, and a decrease of the FWHM of 47% (from 75 nm to 40 nm) could be observed for EB-6, and a decrease of the FWHM of 45% (from 76 nm to 42 nm) could be observed for EB-8, and a decrease of the FWHM of 47% (from 78 nm to 42 nm) could be observed for EB-10, as compared to the respective comparative T-type device. All H-type and T-type devices using PYD2 as HP, SB-1 as SB, and EB-3, EB-4, EB-5, EB-5, EB-8 or EB-10 as EB exhibit emission maxima in the desired green wavelength range of 500 nm to 560 nm, even in the more preferred range of 510 nm to 550 nm.
Additional examples of organic electroluminescent devices according to the invention:
The small FWHM emitter SB-1 was also tested in the OLED D1, which was fabricated with the following layer structure:
EB-11
OLED D1 yielded an external quantum efficiency (EQE) at 1000 cd/m2 of 16.1%. The emission maximum is at 532 nm with a FWHM of 38 nm at 7.6 V. The corresponding CIEx value is 0.32 and the CIEy value is 0.65. A LT95-value at 1200 cd/m2 of 1522 h was determined.
The small FWHM emitter SB-1 was also tested in the OLED D2, which was fabricated with the following layer structure:
OLED D2 yielded an external quantum efficiency (EQE) at 1000 cd/m2 of 17.7%. The emission maximum is at 532 nm with a FWHM of 36 nm at 7.6 V. The corresponding CIEx value is 0.31 and the CIEy value is 0.65. A LT95-value at 1200 cd/m2 of 2006 h was determined.
The small FWHM emitter SB-1 was also tested in the OLED D3, which was fabricated with the following layer structure:
OLED D3 yielded an external quantum efficiency (EQE) at 1000 cd/m2 of 20.2%. The emission maximum is at 532 nm with a FWHM of 38 nm at 7.6 V. The corresponding CIEx value is 0.32 and the CIEy value is 0.65. A LT95-value at 1200 cd/m2 of 1866 h was determined.
The small FWHM emitter SB-3 was also tested in the OLED D4, which was fabricated with the following layer structure:
OLED D4 yielded an external quantum efficiency (EQE) at 1000 cd/m2 of 16.3%. The emission maximum is at 516 nm with a FWHM of 40 nm at 7.0 V. The corresponding CIEx value is 0.27 and the CIEy value is 0.65. A LT95-value at 1200 cd/m2 of 1162 h was determined.
| Number | Date | Country | Kind |
|---|---|---|---|
| 19188361.0 | Jul 2019 | EP | regional |
| 19202645.8 | Oct 2019 | EP | regional |
| 19218997.5 | Dec 2019 | EP | regional |
| 19219378.7 | Dec 2019 | EP | regional |
| 20162459.0 | Mar 2020 | EP | regional |
| 20163321.1 | Mar 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/071054 | 7/24/2020 | WO |
