Patent Application
20230200102
This application is based on and claims priority to Korean Patent Application No. 10-2021-0181735, filed on Dec. 17, 2021, in the Korean Intellectual Property Office, and all the benefits accruing therefrom under 35 U.S.C. § 119, the content of which is incorporated by reference herein in its entirety.
The present disclosure relates to a mixed layer, a method of preparing the mixed layer, a light-emitting device including the mixed layer, and an electronic apparatus including the light-emitting device.
From among light-emitting devices, organic light-emitting devices (OLEDs) are self-emissive devices, which have improved characteristics in terms of viewing angles, response time, luminance, driving voltage, and response speed. In addition, OLEDs may produce full-color images.
In an example, an organic light-emitting device includes an anode, a cathode, and an organic layer arranged between the anode and the cathode, wherein the organic layer includes an emission layer. A hole transport region may be located between the anode and the emission layer, and an electron transport region may be located between the emission layer and the cathode. Holes provided from the anode move toward the emission layer through the hole transport region, and electrons provided from the cathode move toward the emission layer through the electron transport region. The holes and the electrons recombine in the emission layer to produce excitons. These excitons transition from an excited state to a ground state, thereby generating light.
Provided are a mixed layer in which a first dopant and a second dopant are effectively doped at substantially the same time (e.g., at the same time) without thermal denaturation, a light-emitting device having excellent luminescence efficiency and/or a long lifespan by including the mixed layer, and an electronic apparatus including the light-emitting device. In addition, provided is a method of preparing a mixed layer, the method being capable of providing excellent process stability and reduction in manufacturing costs.
Additional aspects will be set forth in part in the detailed description which follows and, in part, will be apparent from the detailed description, or may be learned by practice of the exemplary embodiments of the detailed description.
According to an aspect, provided is a mixed layer including:
The mixed layer may be a layer formed by deposition of a vapor-state matrix material and a vapor-state dopant composition, and the vapor-state dopant composition may be a mixture of a vapor-state first dopant and a vapor-state second dopant.
The second dopant may or may not include a transition metal.
The mixed layer may be an emission layer, and
The mixed layer may be an emission layer, and
According to another aspect, provided is a method of preparing the mixed layer as described above, the method including:
The vapor-state dopant composition provision unit may include:
A deposition temperature of the depositing may be lower than a melting point of the first dopant, and
According to still another aspect, provided is a light-emitting device including:
The mixed layer included in the light-emitting device may be an emission layer.
The interlayer may include:
The mixed layer included in the light-emitting unit may be an emission layer.
At least one light-emitting unit of the m light-emitting units may emit green light, and at least one light-emitting unit of the remaining light-emitting units may emit blue light.
According to still another aspect, provided is an electronic apparatus including the light-emitting device.
The above and other aspects, features, and advantages of certain exemplary embodiments of the disclosure will be more apparent from the following detailed description and when taken in conjunction with the accompanying drawings, in which:
Reference will now be made in further detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout. In this regard, the present exemplary embodiments may have different forms and should not be construed as being limited to the detailed descriptions set forth herein. Accordingly, the exemplary embodiments are described in further detail below, and by referring to the figures, to explain certain aspects. As used herein, the term “and/or” includes any and all combinations of one or more of the associated listed items. Expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.
The terminology used herein is for the purpose of describing one or more exemplary embodiments only and is not intended to be limiting. As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. The term “or” means “and/or.” It will be further understood that the terms “comprises” and/or “comprising,” or “includes” and/or “including” when used in this specification, specify the presence of stated features, regions, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, regions, integers, steps, operations, elements, components, and/or groups thereof.
It will be understood that, although the terms first, second, third etc. may be used herein to describe various elements, components, regions, layers, and/or sections, these elements, components, regions, layers, and/or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of the present embodiments.
Exemplary embodiments are described herein with reference to cross section illustrations that are schematic illustrations of idealized embodiments. As such, variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, embodiments described herein should not be construed as limited to the particular shapes of regions as illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, a region illustrated or described as flat may, typically, have rough and/or nonlinear features. Moreover, sharp angles that are illustrated may be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
It will be understood that when an element is referred to as being “on” another element, it can be directly in contact with the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this general inventive concept belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
“About” or “approximately” as used herein is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” can mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Hereinafter, a work function or a highest occupied molecular orbital (HOMO) energy level is expressed as an absolute value from a vacuum level. In addition, when the work function or the HOMO energy level is referred to be “deep,” “high” or “large,” the work function or the HOMO energy level has a large absolute value based on “0 electron Volts (eV)” of the vacuum level, while when the work function or the HOMO energy level is referred to be “shallow,” “low,” or “small,” the work function or HOMO energy level has a small absolute value based on “0 eV” of the vacuum level.
A mixed layer 15 in
The dopant composition is doped in the matrix material.
The dopant composition includes (e.g., may be a mixture of) a first dopant and a second dopant. The dopant composition may further include materials other than the first dopant and the second dopant.
An amount by weight of the matrix material in the mixed layer may be greater than an amount by weight of the dopant composition in the mixed layer.
For example, a weight ratio of the matrix material to the dopant composition may be in a range of about 60:40 to about 99:1, about 70:30 to about 99:1, about 80:20 to about 99:1, about 60:40 to about 95:5, about 70:30 to about 95:5, or about 80:20 to about 95:5.
The matrix material, the first dopant, and the second dopant are different from each other.
The matrix material does not include a transition metal.
For example, the matrix material may include a hole-transporting compound, an electron-transporting compound, a bipolar compound, or a combination thereof.
In one or more embodiments, the matrix material may not be an organometallic compound including a transition metal and at least one ligand bonded to the transition metal.
In one or more embodiments, the matrix material may be a mixture of a hole-transporting compound and an electron-transporting compound.
The first dopant includes a transition metal (for example, one transition metal).
For example, the first dopant may be an organometallic compound including a transition metal and at least one ligand bonded to the transition metal.
The first dopant may be electrically neutral, or have a net zero charge.
In one or more embodiments, the first dopant may include iridium or platinum.
The second dopant may or may not include a transition metal.
Each of the matrix material, the first dopant, and the second dopant will be described in further detail herein.
The mixed layer 15 may be a layer formed by deposition of the matrix material, the first dopant, and the second dopant. The deposition may be co-deposition in which the matrix material, the first dopant, and the second dopant are vaporized at substantially the same time (e.g., at the same time) and deposited on a surface of a substrate including a region in which the mixed layer 15 is to be formed. The deposition may be vacuum deposition performed under a substantially vacuum atmosphere.
x in Dcon(x) in
The unit of x may be any arbitrary unit. For example, the unit of x may be nanometers (nm).
Dcon(x) may be evaluated through material analysis for each thickness of the mixed layer 15. For example, Dcon(x) may be evaluated using Orbitrap mass spectrometry and/or secondary ion mass spectrometry (SIMS). Dcon(x) may be expressed as a function of the thickness of the mixed layer 15 (the variable represented by x). Accordingly, the mixed layer 15 may have a concentration profile of the dopant composition with respect to the thickness of the mixed layer 15. The concentration profile of the dopant composition in the mixed layer 15 may be discontinuous or continuous.
First, a) the substrate 12 on which the mixed layer 15 is to be formed, b) the first deposition source 300 includes (e.g., is loaded with) the first dopant and the second dopant, c) a second deposition source 400 includes (e.g., is loaded with) the matrix material, and d) the vapor-state dopant composition provision unit 320 (not shown in
The substrate 12 may vary according to the use of the mixed layer 15. For example, when the mixed layer 15 is an emission layer of a light-emitting device, the substrate 12 may be a hole transport region formed on a first electrode.
The first deposition source 300 includes a first region and a second region, the first region includes the first dopant and does not include the second dopant, and the second region includes the second dopant and does not include the first dopant, so that the first dopant and the second dopant loaded in the first deposition source 300 are not mixed with each other. For example, the first dopant and the second dopant loaded in the first deposition source 300 are not in contact with each other. In one or more embodiments, the first dopant and the second dopant are loaded in the first deposition source 300 and do not form a pre-mixed composition (e.g., mixture) of the first dopant and the second dopant. The first deposition source 300 may further include materials other than the first dopant and the second dopant.
For example, a solid-state block-type first dopant and a solid-state block-type second dopant obtained by pressing the first dopant and the second dopant, respectively and separately, and may be spaced apart from each other and loaded into the first deposition source 300.
In one or more embodiments, the first deposition source 300 may further include a separation unit for separating the first region and the second region. For example, the separation unit may include a blocking plate for separating the first region and the second region, individual pockets for accommodating the first dopant and the second dopant, respectively, and the like.
The second deposition source 400 is loaded with the matrix material as described herein. When the matrix material includes two or more different materials, a pre-mixed composition of the different materials may be loaded in the second deposition source 400.
The vapor-state dopant composition provision unit 320 may be installed in combination with the first deposition source 300.
The first deposition source 300 in
The vapor-state dopant composition provision unit 320 includes a first unit 321 for forming a vapor-state dopant composition 319 and a second unit 322 for discharging the vapor-state dopant composition 319 from the first unit 321.
When the first deposition source 300 is turned on, a vapor-state first dopant 311V and a vapor-state second dopant 312V may be released from the first deposition source 300 to be accommodated and mixed in a space formed by the first unit 321, thereby forming the vapor-state dopant composition 319 which is a composition comprising the vapor-state first dopant 311V and the vapor-state second dopant 312V. The first unit 321 may be, for example, an inner plate as shown in
The term “pre-mixed composition of a material A and a material B” as used herein refers to a composition or mixture formed by pre-mixing the material A and the material B before forming a layer including the material A and the material B, and each of the material A and the material B may be in a solid state or a liquid state. For example, the pre-mixed composition may be prepared by a physical mixing method in which the material A and the material B are physically mixed, a sublimation mixing method in which the material A and the material B are sublimated in a sublimation purifier and then solidified, or the like.
Accordingly, the “pre-mixed composition of the first dopant and the second dopant” refers to a composition that is formed by pre-mixing the first dopant and the second dopant before forming the mixed layer 15, and thus is clearly distinguished from the “composition comprising the first dopant and the second dopant” in the mixed layer, which is a dopant composition doped in the mixed layer 15 through a deposition process. In other words, the pre-mixed composition includes the first dopant and the second dopant, and is not doped in the matrix material.
Next, a deposition source moving unit 350 on which the first deposition source 300 and the second deposition source 400 are arranged with a distance therebetween such that a deposition region C1 in which the vapor-state dopant composition 319 is present overlaps a deposition region C2 in which a vapor-state matrix material is present, the vapor-state matrix material being released from the second deposition source 400, is prepared. Here, an angle limiting plate 300A capable of defining each of the deposition region C1 in which the vapor-state dopant composition 319 is present and the deposition region C2 in which the vapor-state matrix material is present may be arranged at both sides of each of the first deposition source 300 and the second deposition source 400 (for convenience, illustration of the angle limiting plate 300A is omitted in
Next, as shown in
The first deposition source 300 and the second deposition source 400 may be arranged on the deposition source moving unit 350, and the deposition source moving unit 350 may be installed to reciprocate along a guide rail 340 arranged in a chamber. To this end, the deposition source moving unit 350 may be connected to a separate driving unit (not shown) to be driven.
As shown in
Then, as shown in
Next, as shown in
Then, when the deposition source moving unit 350 on which the first deposition source 300 and the second deposition source 400 are arranged is moved in the direction B away from the first end A and toward the second end E, and arrives at the second end E below the substrate 12, as shown in
Immediately afterwards, as shown in
Next, when the deposition source moving unit 350 is moved in the direction F away from the second end E and toward the first end A, as shown in
Then, as the deposition source moving unit 350 including the first deposition source 300 and the second deposition source 400 arrives at the first end A below the surface of the substrate 12, as shown in
As described with reference to
The mixed layer 15 may be formed, for example, by a deposition process in which the reciprocating process of the deposition source moving unit 350 described with reference to
For example,
As described above, the mixed layer 15 is a layer formed by deposition of the vapor-state matrix material and the vapor-state dopant composition 319. The vapor-state dopant composition 319 is a mixture of a vapor-state first dopant and a vapor-state second dopant. Thus, for example, as shown in
Meanwhile, the mixed layer 15 may be formed by one-way movement of the deposition source moving unit 350 as shown in
The wording “concentration profile of the dopant composition” as used herein is a wording used for representing that a concentration profile of the first dopant with respect to the thickness of the mixed layer 15 and a concentration profile of the second dopant with respect to the thickness of the mixed layer 15 are substantially the same (e.g., are the same) at each thickness, and thus are not distinguished from each other based on the thickness of the mixed layer.
For comparison,
In
However, in the mixed layer 15, the concentrations of the first dopant and the second dopant may be substantially the same (e.g., the same) in all thickness x (nm) ranges satisfying 0≤x≤L, and thus, the effects that may be obtained by doping the first dopant and the second dopant in the matrix material at substantially the same time (e.g. at the same time) may be fully realized.
Meanwhile, the mixed layer 15 satisfies the relationship where Tm1>Tp>Tm1+2.
Here, Tm1 is a melting point of the first dopant,
In the present specification, a melting point and a fusion temperature may be evaluated according to a known method. For example, the melting point and the fusion temperature may be evaluated by performing differential scanning calorimeter (DSC) analysis on the pre-mixed composition, or using a melting point apparatus.
In addition, a deposition temperature of the depositing process in the formation of the mixed layer 15 illustrated in
When the first dopant including the transition metal is sublimed after melting, thermal denaturation such as separation of the transition metal and the ligand included in the first dopant may occur. However, since the mixed layer 15 satisfies Tm1>Tp, the first dopant including the transition metal is sublimated before melting and used for deposition, and thus, the first dopant may be doped in the mixed layer 15 without thermal denaturation.
In addition, as illustrated in
In the case where, to solve the issue that the concentration profile of the first dopant and the concentration profile of the second dopant separately exist (see
To summarize the above,
In one or more embodiments, the second dopant in the mixed layer 15 may include a transition metal (for example, one transition metal).
For example, the second dopant may be an organometallic compound including a transition metal and at least one ligand bonded to the transition metal.
The second dopant may be neutral or have net neutral charge.
In one or more embodiments, the second dopant may include iridium or platinum.
In one or more embodiments, the second dopant may include a transition metal, and the mixed layer may satisfy Tm2>Tp. Here, Tp is the same as described in the present specification, and Tm2 indicates the melting point of the second dopant. Accordingly, since the second dopant including the transition metal is sublimated before melting and used for deposition, the second dopant may be doped in the mixed layer 15 without thermal denaturation.
In one or more embodiments, the second dopant may not include a transition metal. For example, the second dopant may be a fluorescent material. In one or more embodiments, the second dopant may be a compound including a cyclic group including a boron atom and a nitrogen atom as ring forming atoms.
In one or more embodiments, the mixed layer 15 may be an emission layer, and depending on the highest occupied molecular orbital (HOMO) energy level, the lowest unoccupied molecular orbital (LUMO) energy level, the triplet (T1) energy level, the singlet (S1) energy level, and the like between the matrix material, the first dopant, and the second dopant included in the mixed layer 15,
In one or more embodiments, the mixed layer 15 may be an emission layer, and
The mixed layer 15 may be used in various electronic devices, for example, light-emitting devices (for example, organic light-emitting devices). Thus, according to another aspect, provided is a light-emitting device including a first electrode, a second electrode facing the first electrode, and an interlayer arranged between the first electrode and the second electrode, wherein the interlayer includes the mixed layer 15.
In one or more embodiments, the interlayer may include an emission layer, and the emission layer may be the mixed layer 15.
In one or more embodiments, the interlayer may include a hole transport region arranged between the first electrode and the emission layer and an electron transport region arranged between the emission layer and the second electrode.
Meanwhile, the interlayer may include:
That is, the light-emitting device may be a tandem light-emitting device.
In one or more embodiments, at least one light-emitting unit of the light-emitting units in the number of m may include the mixed layer 15 as described herein. For example, the mixed layer 15 included in the light-emitting unit may be an emission layer.
In one or more embodiments, at least one light-emitting unit of the light-emitting units in the number of m may emit green light.
In one or more embodiments, at least one light-emitting unit of the light-emitting units in the number of m may include the mixed layer 15 as described herein, the mixed layer 15 may be an emission layer, and the emission layer may emit green light.
In one or more embodiments, at least one light-emitting unit of the light-emitting units in the number of m may include the mixed layer 15 as described herein, and the light-emitting unit including the mixed layer 15 may emit green light.
In one or more embodiments, at least one light-emitting unit of the light-emitting units in the number of m may emit green light, and at least one light-emitting unit of the remaining light-emitting units may emit blue light.
According to another aspect, the light-emitting device may be included in an electronic apparatus. Thus, an electronic apparatus including the light-emitting device is provided. The electronic apparatus may include, for example, a display, an illumination, a sensor, and the like.
Hereinafter, a first dopant and a second dopant will be described in detail.
The first dopant may be a first compound, and the second dopant may be a second compound. Accordingly, the term “composition of the first compound and the second compound” as used herein refers to a “composition of the first dopant and the second dopant”.
The first compound may emit first light having a first spectrum and λP(1) is the emission peak wavelength (nm) in the first spectrum, and the second compound may emit second light having a second spectrum and λP(2) is the emission peak wavelength (nm) in the second spectrum, wherein the absolute value of the difference between λP(1) and λP(2) may be in a range of about 0 nm to about 30 nm, about 0 nm to about 25 nm, about 0 nm to about 20 nm, about 0 nm to about 15 nm, or about 0 nm to about 10 nm, and λP(1) and λP(2) may each be in a range of about 500 nm to about 570 nm or about 500 nm to about 550 nm. In one or more embodiments, λP(1) and λP(2) may each be in a range of about 500 nm to about 540 nm or about 510 nm to about 540 nm.
λP(1) and λP(2) may be evaluated from the photoluminescence (PL) spectra measured with respect to a first film and a second film, respectively.
The term “first film” as used herein refers to a film including the first compound, and the term “second film” as used herein refers to a film including the second compound. The first film and the second film may be manufactured using various methods, such as a vacuum deposition method, a coating method, and a heating method. The first film and the second film may further include a compound, for example, a host described herein, other than the first compound and the second compound.
In one or more embodiments, the first compound and the second compound may each independently be an emitter.
In one or more embodiments, the first compound and the second compound may each be an emitter, and λP(1) and λP(2) may each be in a range of about 510 nm to about 540 nm.
In one or more embodiments, the first compound may be an emitter, and the second compound may be a sensitizer.
In one or more embodiments, the first compound may be a sensitizer, and the second compound may be an emitter.
In one or more embodiments, the first compound may be a sensitizer, the second compound may be an emitter, λP(1) may be in a range of about 500 nm to about 520 nm, and λP(2) may be in a range of about 510 nm to about 540 nm.
In one or more embodiments, the first compound and the second compound may each independently be a phosphorescent compound.
The phosphorescent compound may be an organometallic compound including a transition metal (for example, iridium, platinum, osmium, or the like), and may be electrically neutral.
For example, the phosphorescent compound may be a platinum-containing organometallic compound or an iridium-containing organometallic compound. In one or more embodiments, the platinum-containing organometallic compound may be a platinum-containing organometallic compound including platinum and a tetradentate ligand bonded to the platinum. For example, the tetradentate ligand may include carbon and oxygen (or, sulfur), and the platinum-containing organometallic compound may include a) a chemical bond between the carbon of the tetradentate ligand and the platinum and b) a chemical bond between the oxygen (or, sulfur) of the tetradentate ligand and the platinum.
In one or more embodiments, the first compound may be a phosphorescent compound, and the second compound may be a fluorescent compound.
The fluorescent compound may be a thermally activated delayed fluorescence compound or a prompt fluorescent compound.
The first compound and the second compound may each independently satisfy Condition 1 or Condition 2:
In one or more embodiments, the first compound and the second compound may satisfy Condition 1,
In the case of a composition of the first compound and the second compound that satisfy Condition 1, aggregation among molecules of the first compound in the composition, aggregation among molecules of the second compound in the composition, and/or aggregation among molecules of the first compound and molecules of the second compound in the composition may be substantially minimized. Accordingly, without any consideration about intermolecular aggregation, the amounts (for example, weight) of the first compound and the second compound in the composition may be relatively increased. Accordingly, the mixed layer 15 including the composition and a light-emitting device including the composition may have excellent luminescence efficiency and lifespan characteristics. In addition, when an light-emitting unit of a light-emitting device includes the composition of the first compound and the second compound that satisfy Condition 1, the hole flux in the light-emitting unit may be increased due to the composition, so that an exciton recombination zone in the light-emitting unit may be spaced apart from each of the interface between an emission layer and a hole transport region and the interface between an emission layer and an electron transport region, resulting in improved lifespan characteristics of the light-emitting device.
The platinum-containing organometallic compound may include one platinum atom and may not include metals other than platinum.
The platinum-containing organometallic compound may not include ligands other than the tetradentate ligand bonded to the platinum.
The tetradentate ligand bonded to the platinum in the platinum-containing organometallic compound may have excellent electrical characteristics and structural rigidity. In addition, the platinum-containing organometallic compound having the tetradentate ligand bonded to the platinum has a planar structure, and thus may have a relatively small dipole moment.
The iridium-containing organometallic compound may include one iridium atom, may not include metals other than iridium.
The terms “dipole moment of the first compound” and “dipole moment of the second compound” as used herein may refer to “total permanent dipole moment in the molecule of the first compound” and “total permanent dipole moment in the molecule of the second compound”, respectively.
In one or more embodiments, μ(Pt) may be in a range of about 1.5 debye to about 5.0 debye.
In one or more embodiments, μ(Pt) may be in a range of about 0.5 debye to about 3.0 debye, about 1.0 debye to about 3.0 debye, about 1.5 debye to about 3.0 debye, about 1.7 debye to about 3.0 debye, or about 1.7 debye to about 2.7 debye.
In one or more embodiments, μ(Pt) may be in a range of about 2.0 debye to about 5.0 debye, about 3.0 debye to about 5.0 debye, or about 4.0 debye to about 5.0 debye.
In one or more embodiments, μ(Ir) may be in a range of about 4.0 debye to about 9.0 debye, about 4.5 debye to about 7.5 debye, or about 5.0 debye to about 7.0 debye.
In one or more embodiments, μ(Ir)−μ(Pt) may be in a range of about 0.3 debye to about 4.0 debye.
In one or more embodiments, μ(Ir)−μ(Pt) may be in a range of about 2.0 debye to about 4.0 debye or about 2.0 debye to about 3.0 debye.
In one or more embodiments, μ(Ir)−μ(Pt) may be in a range of about 0.3 debye to about 1.0 debye.
In one or more embodiments, in Condition 1,
In one or more embodiments, the composition of the first compound and the second compound may satisfy Condition 2, and at least one of Equation 1 to Equation 4. Accordingly, a light-emitting device including the mixed layer 15 including the composition of the first compound and the second compound that satisfies Condition 2 may have better luminescence efficiency and long lifespan:
λP(Ir1)>λP(Ir2) Equation 1
PLQY(Ir1)>PLYQ(Ir2) Equation 2
k
r(Ir1)>kr(Ir2) Equation 3
HOR(Ir1)>HOR(Ir2) Equation 4
wherein, in Equations 1 to 4,
In relation to Equation 2, PLQY(Ir1) is the PL quantum yield of the first compound, and PLQY(Ir2) is the PL quantum yield of the second compound.
PLQY(Ir1) and PLYQ(Ir2) may be measured with respect to the first film and the second film, respectively.
In relation to Equation 3, kr(Ir1) is the radiative decay rate of the first compound, and kr(Ir2) is the radiative decay rate of the second compound.
kr(Ir1) and kr(Ir2) may be evaluated from PL spectra and time-resolved PL spectra measured with respect to the first film and the second film, respectively.
In relation to Equation 4, HOR(Ir1) is the horizontal orientation ratio of the first compound, and HOR(Ir2) is the horizontal orientation ratio of the second compound.
HOR(Ir1) and HOR(Ir2) may be respectively evaluated from the emission intensity of the first film and the second film with respect to angle.
The first film and the second film are respectively the same as those described in the present specification.
In one or more embodiments, the composition of the first compound and the second compound that satisfies Condition 2 may satisfy
In one or more embodiments, the composition of the first compound and the second compound that satisfies Condition 2 may further satisfy Equation 5:
HOMO(Ir1)<HOMO(Ir2) Equation 5
Each of HOMO(Ir1) and HOMO(Ir2) may be a negative value measured using an atmospheric photoelectron spectrometer, for example, AC3 manufactured by RIKEN KEIKI Co., Ltd.
Since the composition of the first compound and the second compound satisfying Condition 2 satisfies Equation 5, the second compound in the composition has a shallower HOMO energy level than the first compound, and a relatively greater amount of holes may be trapped in the second compound. As a result, in a light-emitting device including the mixed layer 15 including the composition of the first compound and the second compound, without the phenomenon in which the first compound and the second compound are changed into an anionic state due to electrons injected into the composition and the increase in the driving voltage, holes and electrons may effectively recombine in the first compound and/or the second compound. Accordingly, the light-emitting device may have excellent luminescence efficiency characteristics and excellent lifespan characteristics.
In one or more embodiments, regarding the composition of the first compound and the second compound satisfying Condition 2,
In one or more embodiments, the platinum-containing organometallic compound in Condition 1 may be an organometallic compound comprising a) a chemical bond between the carbon of the tetradentate ligand and the platinum and b) a chemical bond between the oxygen of the tetradentate ligand and the platinum.
In one or more embodiments, each of the iridium-containing organometallic compounds in Condition 1 and Condition 2 may include a first ligand, a second ligand, and a third ligand,
In one or more embodiments, the platinum-containing organometallic compound may be an organometallic compound represented by Formula 1, and the iridium-containing organometallic compound may be an organometallic compound represented by Formula 2:
wherein,
In Formula 2, n11 to n13 indicate the number of L11(s) to the number of L13(s), respectively, and may each independently be 0, 1, 2, or 3, wherein a sum of n11, n12, and n13 may be 3.
For example, in Formula 2, n11 may be 1, 2, or 3, and n12 and n13 may each independently be 0, 1, or 2.
In one or more embodiments, in Formula 2, n12 may be 1, 2, or 3, and n11 and n13 may each independently be 0, 1, or 2.
In one or more embodiments, n11 may be 1, n12 may be 2, and n13 may be 0.
In one or more embodiments, n11 may be 2, n12 may be 1, and n13 may be 0.
In one or more embodiments, n11 may be 3, and n12 and n13 may each be 0.
In one or more embodiments, n12 may be 3, and n11 and n13 may each be 0.
The iridium-containing organometallic compound represented by Formula 2 may be a heteroleptic complex or a homoleptic complex.
For example, the iridium-containing organometallic compound may be a heteroleptic complex.
X1 to X4 and Y1 to Y4 in Formulae 1, 2-1, and 2-2 may each independently be C or N.
For example, at least one of X1 to X4 in Formula 1 may be C.
In one or more embodiments, X1 in Formula 1 may be C.
In one or more embodiments, in Formula 1, i) X1 and X3 may each be C, and X2 and X4 may each be N, or ii) X1 and X4 may each be C, and X2 and X3 may each be N.
In one or more embodiments, in Formulae 2-1 and 2-2, Y1 and Y3 may each be N, and Y2 and Y4 may each be C.
In Formula 1, X5 to X8 may each independently be a chemical bond, O, S, N(R′), C(R′)(R″), or C(═O), and at least one of X5 to X8 may not be a chemical bond. R′ and R″ are respectively the same as those described in the present specification.
In one or more embodiments, X5 in Formula 1 may not be a chemical bond.
In one or more embodiments, X5 in Formula 1 may be O or S.
In one or more embodiments, in Formula 1, X5 may be O or S, and X6 to X8 may each be a chemical bond.
In Formula 1, two of a bond between X5 or X1 and M1, a bond between X6 or X2 and M1, a bond between X7 or X3 and M1, and a bond between X8 or X4 and M1 may each be a coordinate bond, and the other two may each be a covalent bond.
For example, a bond between X2 and M in Formula 1 may be a coordinate bond.
In one or more embodiments, in Formula 1, a bond between X5 or X1 and M and a bond between X3 and M may each be a covalent bond, and a bond between X2 and M and a bond between X4 and M may each be a coordinate bond.
In one or more embodiments, the platinum-containing organometallic compound and the iridium-containing organometallic compound may each be electrically neutral.
Ring CY1 to ring CY4 and ring A1 to ring A4 in Formulae 1, 2-1, and 2-2 may each independently be a C5-C30 carbocyclic group or a C1-C30 heterocyclic group.
For example, each of ring CY1, ring CY3, and ring CY4 may not be a benzimidazole group.
For example, ring CY1 to ring CY4 and ring A1 to ring A4 in Formulae 1, 2-1, and 2-2 may each independently be i) a first ring, ii) a second ring, iii) a condensed ring in which two or more first rings are condensed with each other, iv) a condensed ring in which two or more second rings are condensed with each other, or v) a condensed ring in which at least one first ring and at least one second ring are condensed with each other,
In one or more embodiments, ring CY1 to ring CY4 and ring A1 to ring A4 in Formulae 1, 2-1, and 2-2 may each independently be a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, a pyrrole group, a furan group, a thiophene group, a silole group, a borole group, a phosphole group, a germole group, a selenophene group, an indene group, an indole group, a benzofuran group, a benzothiophene group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzogermole group, a benzoselenophene group, a fluorene group, a carbazole group, a dibenzofuran group, a dibenzothiophene group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzogermole group, a dibenzoselenophene group, a benzofluorene group, a benzocarbazole group, a naphthobenzofuran group, a naphthobenzothiophene group, a naphthobenzosilole group, a naphthobenzoborole group, a naphthobenzophosphole group, a naphthobenzogermole group, a naphthobenzoselenophene group, a dibenzofluorene group, a dibenzocarbazole group, a dinaphthofuran group, a dinaphthothiophene group, a dinaphthosilole group, a dinaphthoborole group, a dinaphthophosphole group, a dinaphthogermole group, a dinaphthoselenophene group, an indenophenanthrene group, an indolophenanthrene group, a phenanthrobenzofuran group, a phenanthrobenzothiophene group, a phenanthrobenzosilole group, a phenanthrobenzoborole group, a phenanthrobenzophosphole group, a phenanthrobenzogermole group, a phenanthrobenzoselenophene group, a dibenzothiophene 5-oxide group, a 9H-fluorene-9-one group, a dibenzothiophene 5,5-dioxide group, an azaindene group, an azaindole group, an azabenzofuran group, an azabenzothiophene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzogermole group, an azabenzoselenophene group, an azafluorene group, an azacarbazole group, an azadibenzofuran group, an azadibenzothiophene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzogermole group, an azadibenzoselenophene group, an azabenzofluorene group, an azabenzocarbazole group, an azanaphthobenzofuran group, an azanaphthobenzothiophene group, an azanaphthobenzosilole group, an azanaphthobenzoborole group, an azanaphthobenzophosphole group, an azanaphthobenzogermole group, an azanaphthobenzoselenophene group, an azadibenzofluorene group, an azadibenzocarbazole group, an azadinaphthofuran group, an azadinaphthothiophene group, an azadinaphthosilole group, an azadinaphthoborole group, an azadinaphthophosphole group, an azadinaphthogermole group, an azadinaphthoselenophene group, an azaindenophenanthrene group, an azaindolophenanthrene group, an azaphenanthrobenzofuran group, an azaphenanthrobenzothiophene group, an azaphenanthrobenzosilole group, an azaphenanthrobenzoborole group, an azaphenanthrobenzophosphole group, an azaphenanthrobenzogermole group, an azaphenanthrobenzoselenophene group, an azadibenzothiophene 5-oxide group, an aza9H-fluorene-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a benzoquinoline group, a benzoisoquinoline group, a benzoquinoxaline group, a benzoquinazoline group, a phenanthroline group, a phenanthridine group, a pyrrole group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isoxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, an azasilole group, an azaborole group, an azaphosphole group, an azagermole group, an azaselenophene group, a benzopyrrole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzisoxazole group, a benzothiazole group, a benzisothiazole group, a benzoxadiazole group, a benzothiadiazole group, a pyridinopyrrole group, a pyridinopyrazole group, a pyridinoimidazole group, a pyridinooxazole group, a pyridinoisoxazole group, a pyridinothiazole group, a pyridinoisothiazole group, a pyridinooxadiazole group, a pyridinothiadiazole group, a pyrimidinopyrrole group, a pyrimidinopyrazole group, a pyrimidinoimidazole group, a pyrimidinooxazole group, a pyrimidinoisoxazole group, a pyrimidinothiazole group, a pyrimidinoisothiazole group, a pyrimidinooxadiazole group, a pyrimidinothiadiazole group, a naphthopyrrole group, a naphthopyrazole group, a naphthoimidazole group, a naphthooxazole group, a naphthoisoxazole group, a naphthothiazole group, a naphthoisothiazole group, a naphthooxadiazole group, a naphthothiadiazole group, a phenanthrenopyrrole group, a phenanthrenopyrazole group, a phenanthrenoimidazole group, a phenanthrenooxazole group, a phenanthrenoisoxazole group, a phenanthrenothiazole group, a phenanthrenoisothiazole group, a phenanthrenooxadiazole group, a phenanthrenothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, a 5,6,7,8-tetrahydroquinoline group, an adamantane group, a norbornane group, a norbornene group, a benzene group condensed with a cyclohexane group, a benzene group condensed with a norbornane group, a pyridine group condensed with a cyclohexane group, or a pyridine group condensed with a norbornane group.
In one or more embodiments, ring CY1 and ring CY3 in Formula 1 may each independently be:
In one or more embodiments, ring CY2 in Formula 1 may be:
In one or more embodiments, ring CY4 in Formula 1 may be:
Ring A1 and ring A3 in Formulae 2-1 and 2-2 may be different from each other.
In one or more embodiments, a Y1-containing monocyclic group in ring A1, a Y2-containing monocyclic group in ring A2, and Y4-containing monocyclic group in ring A4 may each be a 6-membered ring.
In one or more embodiments, a Y3-containing monocyclic group in ring A3 may be a 6-membered ring.
In one or more embodiments, a Y3-containing monocyclic group in ring A3 may be a 5-membered ring.
In one or more embodiments, a Y1-containing monocyclic group in ring A1 may be a 6-membered ring, and a Y3-containing monocyclic group in ring A3 may be a 5-membered ring.
In one or more embodiments, ring A1 and ring A3 in Formulae 2-1 and 2-2 may each independently be i) an A group, ii) a polycyclic group in which two or more A groups are condensed with each other, or iii) a polycyclic group in which at least one A group and at least one B group are condensed with each other,
In one or more embodiments, in Formula 2-2, ring A3 may be i) a C group, ii) a polycyclic group in which two or more C groups are condensed with each other, or iii) a polycyclic group in which at least one C group and at least one D group are condensed with each other,
In one or more embodiments, ring A1 in Formula 2-1 may be:
In one or more embodiments, ring A3 in Formula 2-2 may be:
In one or more embodiments, ring A2 and ring A4 in Formulae 2-1 and 2-2 may be different from each other.
In one or more embodiments, ring A2 and ring A4 in Formulae 2-1 and 2-2 may each independently be i) an E group, ii) a polycyclic group in which two or more E groups are condensed with each other, or iii) a polycyclic group in which at least one E group and at least one F group are condensed with each other,
In one or more embodiments, ring A2 in Formula 2-1 may be a polycyclic group in which two or more E groups and at least one F group are condensed with each other.
In one or more embodiments, ring A4 in Formula 2-2 may be a polycyclic group in which two or more E groups and at least one F group are condensed with each other.
In one or more embodiments, ring A2 in Formula 2-1 may be:
In one or more embodiments, ring A4 in Formula 2-2 may be:
T11 to T14 in Formula 1 may each independently be a single bond, a double bond, *—N(R5a)—*′, *—B(R5a)—*′, *—P(R5a)—*′, *—C(R5a)(R5b)—*′, *—Si(R5a)(R5b)—*′, *—Ge(R5a)(R5b)—*′, *—S—*′, *—Se—*′, *—O—*′, *—C(═O)—*′, *—S(═O)—*′, *—S(═O)2—*, *—C(R5a)═*′, *═C(R5a)—*′, *—C(R5a)═C(R5b)—*, *—C(═S)—*′, *—C≡C—*′, a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a.
For example, T11 and T12 in Formula 1 may each be a single bond, and T13 may be a single bond, *—N(R5a)—*′, *—B(R5a)—*′, *—P(R5a)—*′, *—C(R5a)(R5b)—*′, *—Si(R5a)(R5b)—*′, *—Ge(R5a)(R5b)—*′, *—S—*′, or *—O—*′.
n1 to n4 in Formula 1 indicate the numbers of T11 to T14, respectively, and may each independently be 0 or 1, wherein three or more of n1 to n4 may each be 1. That is, the organometallic compound represented by Formula 1 may have a tetradentate ligand.
In Formula 1, when n1 is 0, T11 may not exist (that is, ring CY1 and ring CY2 are not connected to each other), when n2 is 0, T12 may not exist (that is, ring CY2 and ring CY3 are not connected to each other), when n3 is 0, T13 may not exist (that is, ring CY3 and ring CY4 are not connected to each other), and when n4 is 0, T14 may not exist (that is, ring CY4 and ring CY1 are not connected to each other).
In one or more embodiments, in Formula 1, n1 to n3 may each be 1, and n4 may be 0.
L1 to L4 and W1 to W4 in Formulae 1, 2-1, and 2-2 may each independently be a single bond, a C1-C20 alkylene group unsubstituted or substituted with at least one R10a, a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a, or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a.
For example, L1 to L4 and W1 to W4 in Formulae 1, 2-1, and 2-2 may each independently be:
In one or more embodiments, L1 to L4 and W1 to W4 in Formulae 1, 2-1, and 2-2 may each independently be:
In one or more embodiments, L1 to L4 and W1 to W4 in Formulae 1, 2-1, and 2-2 may each independently be:
b1 to b4 in Formula 1 indicate the number of L1(s) to the number of L4(s), respectively, and may each independently be an integer from 1 to 10. When b1 is 2 or more, two or more of L1(s) may be identical to or different from each other, when b2 is 2 or more, two or more of L2(s) may be identical to or different from each other, when b3 is 2 or more, two or more of L3(s) may be identical to or different from each other, and when b4 is 2 or more, two or more of L4(s) may be identical to or different from each other. For example, b1 to b4 may each independently be 1, 2, or 3.
R1 to R4, R5a, R5b, R′, R″, and Z1 to Z4 in Formulae 1, 2-1, and 2-2 may each independently be hydrogen, deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a substituted or unsubstituted C1-C60 alkyl group, a substituted or unsubstituted C2-C60 alkenyl group, a substituted or unsubstituted C2-C60 alkynyl group, a substituted or unsubstituted C1-C60 alkoxy group, a substituted or unsubstituted C1-C60 alkylthio group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 heterocycloalkyl group, a substituted or unsubstituted C3-C10 cycloalkenyl group, a substituted or unsubstituted C1-C10 heterocycloalkenyl group, a substituted or unsubstituted C6-C60 aryl group, a substituted or unsubstituted C7-C60 alkyl aryl group, a substituted or unsubstituted C7-C60 aryl alkyl group, a substituted or unsubstituted C6-C60 aryloxy group, a substituted or unsubstituted C6-C60 arylthio group, a substituted or unsubstituted C1-C60 heteroaryl group, a substituted or unsubstituted C2-C60 heteroarylalkyl group, a substituted or unsubstituted C2-C60 heteroaryl alkyl group, a substituted or unsubstituted C1-C60 heteroaryloxy group, a substituted or unsubstituted C1-C60 heteroarylthio group, a substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, a substituted or unsubstituted monovalent non-aromatic condensed heteropolycyclic group, —N(Q1)(Q2), —Si(Q3)(Q4)(Q5), —Ge(Q3)(Q4)(Q5), —B(Q6)(Q7), —P(═O)(Q8)(Q9), or —P(Q8)(Q9). Q1 to Q9 are respectively the same as those described in the present specification.
In one or more embodiments, R1 to R4, R5a, R5b, R, R″, and Z1 to Z4 in Formulae 1, 2-1, and 2-2 may each independently be:
In one or more embodiments, R1 to R4, R5a, R5b, R′, R″, and Z1 to Z4 in Formulae 1, 2-1, and 2-2 may each independently be:
In one or more embodiments, e1 and d1 in Formula 2-1 may each not be 0, and at least one of Z1(s) may be a deuterated C1-C20 alkyl group, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5). Q3 to 05 are respectively the same as those described in the present specification.
For example, Q3 to Q5 may each independently be:
In one or more embodiments, Q3 to Q5 may each independently be:
an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, a phenyl group, a biphenyl group, or a naphthyl group, each unsubstituted or substituted with at least one of deuterium, a C1-C10 alkyl group, a phenyl group, or a combination thereof.
In one or more embodiments, Q3 to Q5 may be identical to each other.
In one or more embodiments, two or more of Q3 to Q5 may be different from each other.
In one or more embodiments, the iridium-containing organometallic compound may satisfy at least one of Condition 10-1 to Condition 10-8:
In one or more embodiments, R1 to R4, R5a, R5b, R′, R″, and Z1 to Z4 in Formulae 1, 2-1, and 2-2 may each independently be hydrogen, deuterium, —F, —CH3, —CD3, —CD2H, —CDH2, —CF3, —CF2H, —CFH2, a C2-C10 alkenyl group, a C1-C10 alkoxy group, a C1-C10 alkylthio group, a group represented by one of Formulae 9-1 to 9-39, a group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 9-201 to 9-227, a group represented by one of Formulae 9-201 to 9-227 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 9-201 to 9-227 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-1 to 10-129, a group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with —F, a group represented by one of Formulae 10-201 to 10-350, a group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with deuterium, a group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with —F, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5) (wherein Q3 to Q5 are respectively the same as those described in the present specification):
wherein, in Formulae 9-1 to 9-39, 9-201 to 9-227, 10-1 to 10-129, and 10-201 to 10-350, * indicates a binding site to an adjacent atom, “Ph” is a phenyl group, “TMS” is a trimethylsilyl group, and “TMG” is a trimethylgermyl group.
The “group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with deuterium” and the “group represented by one of Formulae 9-201 to 9-227 in which at least one hydrogen is substituted with deuterium” may each be, for example, a group represented by one of Formulae 9-501 to 9-514 and 9-601 to 9-636:
The “group represented by one of Formulae 9-1 to 9-39 in which at least one hydrogen is substituted with —F” and the “group represented by one of Formulae 9-201 to 9-227 in which at least one hydrogen is substituted with —F” may each be, for example, a group represented by one of Formulae 9-701 to 9-710:
The “group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with deuterium” and “the group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with deuterium” may each be, for example, a group represented by one of Formulae 10-501 to 10-553:
The “group represented by one of Formulae 10-1 to 10-129 in which at least one hydrogen is substituted with —F” and the “group represented by one of Formulae 10-201 to 10-350 in which at least one hydrogen is substituted with —F” may each be, for example, a group represented by one of Formulae 10-601 to 10-617:
In Formulae 1, 2-1, and 2-2, c1 to c4 indicate the number of R1(s) to the number of R4(s), respectively; a1 to a4 indicate the number of groups represented by *-[(L1)b1-(R1)c1], the number of groups represented by *-[(L2)b2-(R2)c2], the number of groups represented by *-[(L3)b3-(R3)c3], and the number of groups represented by *-[(L4)b4-(R4)c4], respectively; e1 to e4 indicate the number of Z1(s) to the number of Z4(s), respectively; and d1 to d4 indicate the number of groups represented by *—[W1—(Z1)e1], the number of groups represented by *—[W2—(Z2)e2], the number of groups represented by *—[W3—(Z3)e3], and the number of groups represented by *—[W4—(Z4)e4], respectively, and c1 to c4, a1 to a4, e1 to e4, and d1 to d4 may each independently be an integer from 0 to 20. When c1 is 2 or more, two or more of R1(s) may be identical to or different from each other, when c2 is 2 or more, two or more of R2(s) may be identical to or different from each other, when c3 is 2 or more, two or more of R3(s) may be identical to or different from each other, when c4 is 2 or more, two or more of R4(s) may be identical to or different from each other, when a1 is 2 or more, two or more of groups represented by *-[(L1)b1-(R1)c1] may be identical to or different from each other, when a2 is 2 or more, two or more of groups represented by *-[(L2)b2-(R2)c2] may be identical to or different from each other, when a3 is 2 or more, two or more of groups represented by *-[(L3)b3-(R3)c3] may be identical to or different from each other, when a4 is 2 or more, two or more of groups represented by *-[(L4)b4-(R1)c4] may be identical to or different from each other, when e1 is 2 or more, two or more of Z1(s) may be identical to or different from each other, when e2 is 2 or more, two or more of Z2(s) may be identical to or different from each other, when e3 is 2 or more, two or more of Z3(s) may be identical to or different from each other, when e4 is 2 or more, two or more of Z4(s) may be identical to or different from each other, when d1 is 2 or more, two or more of groups represented by *—[W1—(Z1)e1] may be identical to or different from each other, when d2 is 2 or more, two or more of groups represented by *—[W2—(Z2)e2] may be identical to or different from each other, when d3 is 2 or more, two or more of groups represented by *—[W3—(Z3)e3] may be identical to or different from each other, and when d4 is 2 or more, two or more of groups represented by *—[W4—(Z4)e1] may be identical to or different from each other. For example, in Formulae 1, 2-1, and 2-2, c1 to c4, a1 to a4, e1 to e4, and d1 to d4 may each independently be 0, 1, 2, or 3.
In one or more embodiments, in Formula 2-1, a case where Y1 is N, ring A1 is a pyridine group, Y2 is C, ring A2 is a benzene group, and d1 and d2 are each 0 may be excluded.
In Formulae 1, 2-1, and 2-2, at least one of i) two or more of a plurality of R1(s), ii) two or more of a plurality of R2(s), iii) two or more of a plurality of R3(s), iv) two or more of a plurality of R4(s), v) R5a and R5b, vi) two or more of a plurality of Z1(s), vii) two or more of a plurality of Z2(s), viii) two or more of a plurality of Z3(s), ix) two or more of a plurality of Z4(s), x) two or more of R1 to R4, R5a, and R5b, and xi) two or more of Z1 to Z4 may optionally be bonded to each other to form a C5-C30 carbocyclic group unsubstituted or substituted with at least one R10a or a C1-C30 heterocyclic group unsubstituted or substituted with at least one R10a.
R10a is as described in connection with R1.
* and *′ in the present specification each indicate a binding site to a neighboring atom, unless otherwise stated.
In one or more embodiments, in Formula 1, n1 may not be 0, n4 may be 0, and a group represented by
may be a group represented by one of Formulae CY1(1) to CY1(23):
wherein, in Formulae CY1(1) to CY1(23),
In one or more embodiments, in Formula 1, n1 may be 1, n4 may be 0, and a group represented by
may be a group represented by one of Formulae CY1-1 to CY1-18:
wherein, in Formulae CY1-1 to CY1-18,
In one or more embodiments, in Formula 1, n1 and n2 may each be 1, and ring CY2 may be a group represented by Formula CY2A or CY2B:
wherein, in Formulae CY2A and CY2B,
In one or more embodiments, in Formula 1, each of n1 and n2 may not be 0, and a group represented by
may be a group represented by one of Formulae CY2(1) to CY2(21):
wherein, in Formulae CY2(1) to CY2(21),
In one or more embodiments, in Formula 1, each of n1 and n2 may be 1, and a group represented by
may be a group represented by one of Formulae CY2-1 to CY2-16:
wherein, in Formulae CY2-1 to CY2-16,
In one or more embodiments, in Formula 1,
In one or more embodiments, in Formula 1, each of n2 and n3 may not be 0, and a group represented by
may be a group represented by one of Formulae CY3(1) to CY3(15):
wherein, in Formulae CY3(1) to CY3(15),
In one or more embodiments, in Formula 1, each of n2 and n3 may be 1, and a group represented by
may be a group represented by one of Formulae CY3-1 to CY3-13:
wherein, in Formulae CY3-1 to CY3-31,
In one or more embodiments, in Formula 1, n3 may not be 0, n4 may be 0, and a group represented by
may be a group represented by one of Formulae CY4(1) to CY4(20):
wherein, in Formulae CY4(1) to CY4(20),
In one or more embodiments, in Formula 1, n3 may be 1, n4 may be 0, and a group represented by
may be a group represented by one of Formulae CY4-1 to CY4-16:
wherein, in Formulae CY4-1 to CY4-16,
In one or more embodiments, the platinum-containing organometallic compound may be a compound represented by one of Formulae 1-1 to 1-3:
wherein, in Formulae 1-1 to 1-3,
In one or more embodiments,
wherein, in Formulae A1-1 to A1-3,
For example, Z14 in Formulae A1-1 to A1-3 may be a deuterated C1-C20 alkyl group, —Si(Q3)(Q4)(Q5), or —Ge(Q3)(Q4)(Q5).
In one or more embodiments,
in Formula 2-2 may be a group represented by one of Formulae NR1 to NR48:
wherein, in Formulae NR1 to NR48,
In one or more embodiments,
wherein, in Formulae CR1 to CR29,
In one or more embodiments,
wherein, in Formulae CR(1) to CR(13),
In one or more embodiments, the platinum-containing organometallic compound may include at least one deuterium.
In one or more embodiments, the iridium-containing organometallic compound may include at least one deuterium.
For example, the platinum-containing organometallic compound may be selected from compounds of [Group 1-1] to [Group 1-4]:
In one or more embodiments, the iridium-containing organometallic compound may be selected from compounds of [Group 2-1] to [Group 2-6]:
In the present specification, “Ome” refers to a methoxy group, “TMS” refers to a trimethylsilyl group, and “TMG” refers to a trimethylgermyl group.
In one or more embodiments, the iridium-containing organometallic compound may not be a compound of [Group B]:
wherein R′ and R″ of [Group B] may each be an alkyl group.
The fluorescent compound
In one or more embodiments, the fluorescent compound may include at least one 6-membered ring including at least one N and at least one B.
In one or more embodiments, the fluorescent compound may be a compound represented by Formula 3 or a compound represented by Formula 4:
wherein, in Formulae 3 and 4,
For example, ring A31 to ring A33, ring A41, and ring A42 are each as described in connection with ring A1.
In one or more embodiments, in Formula 3, ring A31 and ring A32 may each be a benzene group, and ring A33 may be a benzene group, a quinoline group, or an isoquinoline group.
In one or more embodiments, T34 in Formula 3 may be N—[W34—(Z34)e34].
In one or more embodiments, T34 in Formula 3 may be N—[W34—(Z34)e34], and Z34 and ring A31 and/or Z34 and Z31 may be bonded to each other via a single bond, or a linking group including O, S, N, B, C, or a combination thereof.
In one or more embodiments, T35 in Formula 3 may be N—[W35—(Z35)e35].
In one or more embodiments, T35 in Formula 3 may be N—[W35—(Z35)e35], and Z35 and ring A32 and/or Z35 and Z32 may be bonded to each other via a single bond, or a linking group including O, S, N, B, C, or a combination thereof.
In one or more embodiments, ring A41 and ring A42 in Formula 4 may each be a pyrrole group. For example, T41 and T42 may each be N.
For example, the fluorescent compound may be selected from compounds of [Group 3] and [Group 4]:
A weight ratio of the first compound to the second compound in the composition of the first compound and the second compound may be in range of about 90:10 to about 10:90, about 80:20 to about 20:80, about 70:30 to about 30:70, or about 60:40 to about 40:60.
The matrix material may be, for example, a host of an emission layer among materials for an organic light-emitting device.
In one or more embodiments, the matrix material may consist of only one compound (for example, a hole-transporting compound, an electron-transporting compound, or a bipolar compound).
In one or more embodiments, the matrix material may include a first host and a second host, and the first host and the second host may be different from each other.
The first host and the second host may each include a hole-transporting compound, an electron-transporting compound, a bipolar compound, or a combination thereof.
For example, the first host and the second host may each include a hole-transporting compound and an electron-transporting compound, and the hole-transporting compound and the electron-transporting compound may be different from each other.
In one or more embodiments, the hole-transporting compound may include at least one π electron-rich C3-C60 cyclic group (for example, a carbazole group, an indolocarbazole group, a benzene group, or the like), and may not include an electron-transporting group. Examples of the electron-transporting group may include a cyano group, a fluoro group, a π electron-deficient nitrogen-containing C1-C60 cyclic group, a phosphine oxide group, a sulfoxide group, and the like.
In one or more embodiments, the electron-transporting compound may be a compound including at least one electron-transporting group. The electron-transporting group may be a cyano group, a fluoro group, a π electron-deficient nitrogen-containing C1-C60 cyclic group, a phosphine oxide group, a sulfoxide group, or a combination thereof.
In one or more embodiments, the hole-transporting compound may be at least one of Compounds H1-1 to H1-72 of Group 5-1 and Compounds H1-1 to H1-20 of Group 5-2:
In one or more embodiments, the electron-transporting compound may be at least one of Compounds E1-1 to E1-62:
In one or more embodiments, the bipolar compound may be at least one of Compounds BP1-1 to BP1-17:
Meanwhile, the mixed layer 15 may not include compounds of Group A:
A substrate may be additionally arranged under the first electrode 110 or above the second electrode 190. For use as the substrate, any substrate that is used in light-emitting devices of the related art may be used, and the substrate may be a glass substrate or a transparent plastic substrate, each having excellent mechanical strength, thermal stability, transparency, surface smoothness, ease of handling, and water resistance.
The first electrode 110 may be formed by providing, on the substrate, a material for forming the first electrode 110, by using a deposition or sputtering method. The first electrode 110 may be an anode. The material for forming the first electrode 110 may include materials with a high work function to facilitate hole injection. The first electrode 110 may be a reflective electrode. The material for forming the first electrode 110 may be indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), or zinc oxide (ZnO). In one or more embodiments, the material for forming the first electrode 110 may be metal, such as magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), or magnesium-silver (Mg—Ag).
The first electrode 110 may have a single-layered structure or a multi-layered structure including two or more layers. For example, the first electrode 110 may have a three-layered structure of ITO/Ag/ITO.
The hole transport region 120 may be arranged between the first electrode 110 and the emission layer 150.
The hole transport region 120 may include a hole injection layer, a hole transport layer, an electron blocking layer, a buffer layer, or a combination thereof.
The hole transport region 120 may include only a hole injection layer or only a hole transport layer. In one or more embodiments, the hole transport region 120 may have a hole injection layer/hole transport layer structure or a hole injection layer/hole transport layer/electron blocking layer structure, which are sequentially stacked in this stated order from the first electrode 110.
When the hole transport region 120 includes a hole injection layer, the hole injection layer may be formed on the first electrode 110 by using one or more suitable methods, for example, a vacuum deposition method, a spin coating method, a casting method, a Langmuir-Blodgett (LB) method, and/or an ink-jet printing method.
When a hole injection layer is formed by vacuum deposition, the deposition conditions may vary depending on a material that is used to form the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the deposition conditions may include a deposition temperature of about 100° C. to about 500° C., a vacuum pressure of about 10−8 torr to about 10−3 torr, and a deposition rate of about 0.01 angstroms per second (Å/sec) to about 100 Å/sec.
When the hole injection layer is formed by spin coating, the coating conditions may vary depending on a material for forming the hole injection layer, and the structure and thermal characteristics of the hole injection layer. For example, the coating conditions may include a coating speed in a range of about 2,000 revolutions per minute (rpm) to about 5,000 rpm and a heat treatment temperature in a range of about 80° C. to about 200° C. for removing a solvent after coating.
The conditions for forming the hole transport layer and the electron blocking layer may be as the conditions for forming the hole injection layer.
The hole transport region 120 may include, for example, 4,4′,4″-tris(3-methylphenylphenylamino)triphenylamine (m-MTDATA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (TDATA), 4,4′,4″-tris{N-(2-naphthyl)-N-phenylamino}-triphenylamine (2-TNATA), N,N′-di(1-naphthyl)-N,N′-diphenylbenzidine (NPB), p-NPB, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1-biphenyl]-4,4′-diamine (TPD), spiro-TPD, spiro-NPB, methylated NPB, 4,4′-cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine] (TAPC), 4,4′-bis[N,N′-(3-tolyl)amino]-3,3′-dimethylbiphenyl (HMTPD), 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), a compound represented by Formula 201, a compound represented by Formula 202, or a combination thereof:
Ar101 and Ar102 in Formula 201 may each independently be a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptalenylene group, an acenaphthylene group, a fluorenylene group, a phenalenylene group, a phenanthrenylene group, an anthracenylene group, a fluoranthenylene group, a triphenylenylene group, a pyrenylene group, a chrysenylenylene group, a naphthacenylene group, a picenylene group, a perylenylene group, or a pentacenylene group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, an amino group, an amidino group, a hydrazine group, a hydrazone group, a carboxylic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a C1-C60 alkyl group, a C2-C60 alkenyl group, a C2-C60 alkynyl group, a C1-C60 alkoxy group, a C1-C60 alkylthio group, a C3-C10 cycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C7-C60 alkyl aryl group, a C7-C60 aryl alkyl group, a C6-C60 aryloxy group, a C6-C60 arylthio group, a C1-C60 heteroaryl group, a C2-C60 alkyl heteroaryl group, a C2-C60 heteroaryl alkyl group, a C1-C60 heteroaryloxy group, a C1-C60 heteroarylthio group, a monovalent non-aromatic condensed polycyclic group, a monovalent non-aromatic condensed heteropolycyclic group, or a combination thereof.
xa and xb in Formula 201 may each independently be an integer from 0 to 5, or may each independently be 0, 1, or 2. For example, xa may be 1 and xb may be 0.
R101 to R108, R111 to R119, and R121 to R124 in Formulae 201 and 202 may each independently be:
R109 in Formula 201 may be a phenyl group, a naphthyl group, an anthracenyl group, or a pyridinyl group, each unsubstituted or substituted with deuterium, —F, —Cl, —Br, —I, —SF5, a hydroxyl group, a cyano group, a nitro group, an amino group, a C1-C20 alkyl group, a C1-C20 alkoxy group, a C1-C20 alkylthio group, a phenyl group, a naphthyl group, an anthracenyl group, a pyridinyl group, or a combination thereof.
In one or more embodiments, the compound represented by Formula 201 may be represented by Formula 201A:
wherein, in Formula 201A, R101, R111, R112, and R109 are respectively as those described herein.
For example, the hole transport region 120 may include one of Compounds HT1 to HT20 or a combination thereof:
A thickness of the hole transport region 120 may be in a range of about 100 angstroms (Å) to about 10,000 Å, for example, about 100 Å to about 1,000 Å. When the hole transport region 120 includes a hole injection layer, a hole transport layer, an electron blocking layer, or a combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 10,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region 120, the hole injection layer, and the hole transport layer are within these ranges, satisfactory hole transporting characteristics may be obtained without a substantial increase in driving voltage.
In addition to the above-described materials, the hole transport region 120 may further include a charge-generation material to improve conductivity. The charge-generation material may be homogeneously or non-homogeneously dispersed in the hole transport region 120.
The charge-generation material may be, for example, a p-dopant. The p-dopant may be a quinone derivative, a metal oxide, a cyano group-containing compound, or a combination thereof. For example, the p-dopant may be a quinone derivative such as tetracyanoquinodimethane (TCNQ), 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane (F4-TCNQ), or F6-TCNNQ; metal oxide, such as tungsten oxide or molybdenum oxide; a cyano group-containing compound, such as Compound HT-D1; or a combination thereof:
The hole transport region 120 may further include a buffer layer.
The buffer layer may compensate for an optical resonance distance according to a wavelength of light emitted from the emission layer to increase efficiency.
Meanwhile, when the hole transport region 120 includes an electron blocking layer, the material for the electron blocking layer may include a material that may be used in the hole transport region 120 as described above, a host material, or a combination thereof. For example, when the hole transport region 120 includes an electron blocking layer, the material for the electron blocking layer may be mCP or the like.
The emission layer 150 may be formed on the hole transport region 120 by using, for example, a vacuum deposition method, a spin coating method, a cast method, an LB method, and/or an ink-jet printing method.
The emission layer 150 may be as described in connection with the mixed layer 15.
A thickness of the emission layer 150 may be in a range of about 100 Å to about 1,000 Å, for example, about 200 Å to about 600 Å. When the thickness of the emission layer 150 is within these ranges, excellent light-emission characteristics may be obtained without a substantial increase in driving voltage.
When the light-emitting device is a full-color light-emitting device, the emission layer 150 may be patterned into a red emission layer, a green emission layer, and/or a blue emission layer.
Next, the electron transport region 170 may be arranged on the emission layer 150.
The electron transport region 170 may include a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof.
For example, the electron transport region 170 may have a hole blocking layer/electron transport layer/electron injection layer structure or an electron transport layer/electron injection layer structure. The electron transport layer may have a single-layered structure or a multi-layered structure including two or more different materials.
The conditions for the forming the hole blocking layer, the electron transport layer, and the electron injection layer in the electron transport region 170 are as the conditions for the forming the hole injection layer.
When the electron transport region 170 includes a hole blocking layer, the hole blocking layer may include, for example, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen),bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq), or a combination thereof:
In one or more embodiments, the hole blocking layer may include any host material, and a material for an electron transport layer, a material for an electron injection layer, or a combination thereof, which will be described later.
A thickness of the hole blocking layer may be in a range of about 20 Å to about 1,000 Å, for example, about 30 Å to about 600 Å. When the thickness of the hole block layer is within these ranges, excellent hole blocking characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may include BCP, Bphen, 1,3,5-tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl (TPBi), tris(8-hydroxy-quinolinato)aluminum (Alq3), bis(2-methyl-8-quinolinolato-N1,O8)-(1,1′-biphenyl-4-olato)aluminum (BAlq), 3-(4-biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2,4-triazole (TAZ), 4-(naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole (NTAZ), or a combination thereof:
In one or more embodiments, the electron transport layer may include one of Compounds ET1 to ET25 or a combination thereof:
A thickness of the electron transport layer may be in a range of about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layer is within these ranges, satisfactory electron transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport layer may include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 or ET-D2:
In one or more embodiments, the electron transport region 170 may include an electron injection layer that facilitates injection of electrons from the second electrode 190.
The electron injection layer may include LiF, NaCl, CsF, Li2O, BaO, Yb, Compound ET-D1, Compound ET-D2, or a combination thereof.
A thickness of the electron injection layer may be in a range of about 1 Å to about 100 Å, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within these ranges, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 190 may be arranged on the electron transport region 170. The second electrode 190 may be a cathode. A material for forming the second electrode 190 may be metal, an alloy, an electrically conductive compound, or a combination thereof, which have a relatively low work function. For example, lithium (Li), magnesium (Mg), aluminum (Al), silver (Ag), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or the like may be used as the material for forming the second electrode 190. In one or more embodiments, to manufacture a top-emission type light-emitting device, a transparent or semi-transparent electrode formed using ITO or IZO may be used as the second electrode 190.
The light-emitting device 100 in
The first light-emitting unit 151 may include a first emission layer 151-EM, and the second light-emitting unit 152 may include a second emission layer 152-EM. At least one of the first emission layer 151-EM and the second emission layer 152-EM may be the mixed layer 15 described herein.
A hole transport region 120 is arranged between the first light-emitting unit 151 and the first electrode 110, and the second light-emitting unit 152 includes a second hole transport region 122 arranged on the side of the first electrode 110.
An electron transport region 170 is arranged between the second light-emitting unit 152 and the second electrode 190, and the first light-emitting unit 151 includes a first electron transport region 171 arranged between the charge generation layer 141 and the first emission layer 151-EM.
The first electrode 110 and the second electrode 190 in
The hole transport region 120 and the second hole transport region 122 in
The electron transport region 170 and the first electron transport region 171 in
Hereinbefore, one or more embodiments of a tandem light-emitting device has been described with reference to
The term “C1-C60 alkyl group” as used herein refers to a linear or branched saturated aliphatic hydrocarbons monovalent group having 1 to 60 carbon atoms, and the term “C1-C60 alkylene group” as used here refers to a divalent group having the same structure as the C1-C60 alkyl group.
Examples of the C1-C60 alkyl group, the C1-C20 alkyl group, and/or the C1-C10 alkyl group may include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, or a tert-decyl group, each unsubstituted or substituted with a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, a tert-decyl group, or a combination thereof. For example, Formula 9-33 is a branched C6 alkyl group, for example, a tert-butyl group that is substituted with two methyl groups.
The term “C1-C60 alkoxy group” as used herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a pentoxy group.
The term “C1-C60 alkylthio group” as used herein refers to a monovalent group having the formula of —SA1,1 (wherein A101 is the C1-C60 alkyl group).
The term “C2-C60 alkenyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as used herein refers to a hydrocarbon group formed by substituting at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group, and a propynyl group. The term “C2-C60 alkynylene group” as used herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C3-C10 cycloalkyl group” as used herein refers to a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and the term “C3-C10 cycloalkylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
Examples of the C3-C10 cycloalkyl group may include a cyclopropyl group, a cyclobutyl group, a cyclopentyl, cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantanyl group, a norbornanyl group (or a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1]hexyl group, and a bicyclo[2.2.2]octyl group.
The term “C1-C10 heterocycloalkyl group” as used herein refers to a monovalent saturated cyclic group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and 1 to 10 carbon atoms, and the term “C1-C10 heterocycloalkylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
Examples of the C1-C10 heterocycloalkyl group may include a silolanyl group, a silinanyl group, tetrahydrofuranyl group, a tetrahydro-2H-pyranyl group, and a tetrahydrothiophenyl group.
The term “C3-C10 cycloalkenyl group” as used herein refers to a monovalent monocyclic group that has 3 to 10 carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as used herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as used herein refers to a monovalent monocyclic group that has at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom, 1 to 10 carbon atoms, and at least one double bond in its ring. Examples of the C1-C10 heterocycloalkenyl group include a 2,3-dihydrofuranyl group and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as used herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as used herein refers to a monovalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms, and the term “C6-C60 arylene group” as used herein refers to a divalent group having a carbocyclic aromatic system having 6 to 60 carbon atoms. Examples of the C6-C60 aryl group include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a pyrenyl group, and a chrysenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the two or more rings may be fused to each other.
The term “C7-C60 alkyl aryl group” as used herein refers to a C6-C60 aryl group substituted with at least one C1-C60 alkyl group.
The term “C7-C60 aryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C6-C60 aryl group.
The term “C1-C60 heteroaryl group” as used herein refers to a monovalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a cyclic aromatic system having 1 to 60 carbon atoms, and the term “C1-C60 heteroarylene group” as used herein refers to a divalent group that includes at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B as a ring-forming atom and a carbocyclic aromatic system having 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, and an isoquinolinyl group. When the C6-C60 heteroaryl group and the C6-C60 heteroarylene group each include two or more rings, the two or more rings may be fused to each other.
The term “C2-C60 alkyl heteroaryl group” as used herein refers to a C1-C60 heteroaryl group substituted with at least one C1-C60 alkyl group.
The term “C2-C60 heteroaryl alkyl group” as used herein refers to a C1-C60 alkyl group substituted with at least one C1-C60 heteroaryl group.
The term “C6-C60 aryloxy group” as used herein indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as used herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “monovalent non-aromatic condensed polycyclic group” as used herein refers to a monovalent group (for example, having 8 to 60 carbon atoms) having two or more rings condensed to each other, only carbon atoms as ring-forming atoms, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed polycyclic group include a fluorenyl group. The term “divalent non-aromatic condensed polycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as used herein refers to a monovalent group (for example, having 1 to 60 carbon atoms) having two or more rings condensed to each other, at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B, other than carbon atoms, as a ring-forming atom, and no aromaticity in its entire molecular structure. Examples of the monovalent non-aromatic condensed heteropolycyclic group include a carbazolyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as used herein refers to a divalent group having the same structure as the monovalent non-aromatic condensed heteropolycyclic group.
The term “C5-C30 carbocyclic group” as used herein refers to a saturated or unsaturated cyclic group including 5 to 30 carbon atoms only as ring-forming atoms. The C5-C30 carbocyclic group may be a monocyclic group or a polycyclic group. Examples of the “C5-C30 carbocyclic group (unsubstituted or substituted with at least one R10a)” as used herein may include an adamantane group, a norbornene group, a bicyclo[1.1.1]pentane group, a bicyclo[2.1.1]hexane group, a bicyclo[2.2.1]heptane(norbornane) group, a bicyclo[2.2.2]octane group, a cyclopentane group, a cyclohexane group, a cyclohexene group, a benzene group, a naphthalene group, an anthracene group, a phenanthrene group, a triphenylene group, a pyrene group, a chrysene group, a 1,2,3,4-tetrahydronaphthalene group, a cyclopentadiene group, and a fluorene group (each unsubstituted or substituted with at least one R10a).
The term “C1-C30 heterocyclic group” as used herein refers to a saturated or unsaturated cyclic group having, as a ring-forming atom, at least one heteroatom selected from N, O, P, Si, S, Se, Ge, and B other than 1 to 30 carbon atoms. The C1-C30 heterocyclic group may be a monocyclic group or a polycyclic group. Examples of the “C1-C30 heterocyclic group (unsubstituted or substituted with at least one R10a)” as used herein may include a thiophene group, a furan group, a pyrrole group, a silole group, borole group, a phosphole group, a selenophene group, a germole group, a benzothiophene group, a benzofuran group, an indole group, a benzosilole group, a benzoborole group, a benzophosphole group, a benzoselenophene group, a benzogermole group, a dibenzothiophene group, a dibenzofuran group, a carbazole group, a dibenzosilole group, a dibenzoborole group, a dibenzophosphole group, a dibenzoselenophene group, a dibenzogermole group, a dibenzothiophene 5-oxide group, a 9H-fluoren-9-one group, a dibenzothiophene 5,5-dioxide group, an azabenzothiophene group, an azabenzofuran group, an azaindole group, an azaindene group, an azabenzosilole group, an azabenzoborole group, an azabenzophosphole group, an azabenzoselenophene group, an azabenzogermole group, an azadibenzothiophene group, an azadibenzofuran group, an azacarbazole group, an azafluorene group, an azadibenzosilole group, an azadibenzoborole group, an azadibenzophosphole group, an azadibenzoselenophene group, an azadibenzogermole group, an azadibenzothiophene 5-oxide group, an aza-9H-fluoren-9-one group, an azadibenzothiophene 5,5-dioxide group, a pyridine group, a pyrimidine group, a pyrazine group, a pyridazine group, a triazine group, a quinoline group, an isoquinoline group, a quinoxaline group, a quinazoline group, a phenanthroline group, a pyrazole group, an imidazole group, a triazole group, an oxazole group, an isooxazole group, a thiazole group, an isothiazole group, an oxadiazole group, a thiadiazole group, a benzopyrazole group, a benzimidazole group, a benzoxazole group, a benzothiazole group, a benzoxadiazole group, a benzothiadiazole group, a 5,6,7,8-tetrahydroisoquinoline group, and a 5,6,7,8-tetrahydroquinoline group (each unsubstituted or substituted with at least one R10a).
In one or more embodiments, examples of the “C5-C30 carbocyclic group” and “C1-C30 heterocyclic group” as used herein include i) a first ring, ii) a second ring, iii) a condensed ring in which two or more first rings are condensed with each other, iv) a condensed ring in which two or more second rings are condensed with each other, or v) a condensed ring in which at least one first ring and at least one second ring are condensed with each other,
The terms “fluorinated C1-C60 alkyl group (or, a fluorinated C1-C20 alkyl group or the like)”, “fluorinated C3-C10 cycloalkyl group”, “fluorinated C1-C10 heterocycloalkyl group,” and “fluorinated phenyl group” as used herein respectively refer to a C1-C60 alkyl group (or, a C1-C20 alkyl group or the like), a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, and a phenyl group, each substituted with at least one fluoro group. For example, the term “fluorinated C1 alkyl group (that is, a fluorinated methyl group)” includes —CF3, —CF2H, and —CFH2. The “fluorinated C1-C60 alkyl group (or, a fluorinated C1-C20 alkyl group or the like)”, “the fluorinated C3-C10 cycloalkyl group”, “the fluorinated C1-C10 heterocycloalkyl group”, or “the fluorinated a phenyl group” may be i) a fully fluorinated C1-C60 alkyl group (or, a fully fluorinated C1-C20 alkyl group or the like), a fully fluorinated C3-C10 cycloalkyl group, a fully fluorinated C1-C10 heterocycloalkyl group, or a fully fluorinated phenyl group, wherein, in each group, all hydrogen included therein is substituted with a fluoro group, or ii) a partially fluorinated C1-C60 alkyl group (or, a partially fluorinated C1-C20 alkyl group or the like), a partially fluorinated C3-C10 cycloalkyl group, a partially fluorinated C1-C10 heterocycloalkyl group, or a partially fluorinated phenyl group, wherein, in each group, not all hydrogen included therein is substituted with a fluoro group.
The terms “deuterated C1-C60 alkyl group (or, a deuterated C1-C20 alkyl group or the like)”, “deuterated C3-C10 cycloalkyl group”, “deuterated C1-C10 heterocycloalkyl group,” and “deuterated phenyl group” as used herein respectively refer to a C1-C60 alkyl group (or, a C1-C20 alkyl group or the like), a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, and a phenyl group, each substituted with at least one deuterium. For example, the “deuterated C1 alkyl group (that is, a deuterated methyl group)” may include —CD3, —CD2H, and —CDH2, and examples of the “deuterated C3-C10 cycloalkyl group” are, for example, Formula 10-501 and the like. The “deuterated C1-C60 alkyl group (or, the deuterated C1-C20 alkyl group or the like)”, “the deuterated C3-C10 cycloalkyl group”, “the deuterated C1-C10 heterocycloalkyl group”, or “the deuterated phenyl group” may be i) a fully deuterated C1-C60 alkyl group (or, a fully deuterated C1-C20 alkyl group or the like), a fully deuterated C3-C10 cycloalkyl group, a fully deuterated C1-C10 heterocycloalkyl group, or a fully deuterated phenyl group, in which, in each group, all hydrogen included therein are substituted with deuterium, or ii) a partially deuterated C1-C60 alkyl group (or, a partially deuterated C1-C20 alkyl group or the like), a partially deuterated C3-C10 cycloalkyl group, a partially deuterated C1-C10 heterocycloalkyl group, or a partially deuterated phenyl group, in which, in each group, not all hydrogen included therein are substituted with deuterium.
The term “(C1-C20 alkyl) ‘X’ group” as used herein refers to a ‘X’ group that is substituted with at least one C1-C20 alkyl group. For example, the term “(C1-C20 alkyl)C3-C10 cycloalkyl group” as used herein refers to a C3-C10 cycloalkyl group substituted with at least one C1-C20 alkyl group, and the term “(C1-C20 alkyl)phenyl group” as used herein refers to a phenyl group substituted with at least one C1-C20 alkyl group. An example of the term “(C1 alkyl)phenyl group” is a toluyl group.
The terms “an azaindole group, an azabenzoborole group, an azabenzophosphole group, an azaindene group, an azabenzosilole group, an azabenzogermole group, an azabenzothiophene group, an azabenzoselenophene group, an azabenzofuran group, an azacarbazole group, an azadibenzoborole group, an azadibenzophosphole group, an azafluorene group, an azadibenzosilole group, an azadibenzogermole group, an azadibenzothiophene group, an azadibenzoselenophene group, an azadibenzofuran group, an azadibenzothiophene 5-oxide group, an aza-9H-fluoren-9-one group, and an azadibenzothiophene 5,5-dioxide group” respectively refer to heterocyclic groups having the same backbones as “an indole group, a benzoborole group, a benzophosphole group, an indene group, a benzosilole group, a benzogermole group, a benzothiophene group, a benzoselenophene group, a benzofuran group, a carbazole group, a dibenzoborole group, a dibenzophosphole group, a fluorene group, a dibenzosilole group, a dibenzogermole group, a dibenzothiophene group, a dibenzoselenophene group, a dibenzofuran group, a dibenzothiophene 5-oxide group, a 9H-fluoren-9-one group, and a dibenzothiophene 5,5-dioxide group,” in which, in each group, at least one carbon selected from ring-forming carbons is substituted with nitrogen.
At least one substituent of the substituted C5-C30 carbocyclic group, the substituted C1-C30 heterocyclic group, the substituted C1-C60 alkyl group, the substituted C2-C60 alkenyl group, the substituted C2-C60 alkynyl group, the substituted C1-C60 alkoxy group, the substituted C1-C60 alkylthio group, the substituted C3-C10 cycloalkyl group, the substituted C1-C10 heterocycloalkyl group, the substituted C3-C10 cycloalkenyl group, the substituted C1-C10 heterocycloalkenyl group, the substituted C6-C60 aryl group, the substituted C7-C60 alkyl aryl group, the substituted C7-C60 aryl alkyl group, the substituted C6-C60 aryloxy group, the substituted C6-C60 arylthio group, the substituted C1-C60 heteroaryl group, the substituted C2-C60 alkyl heteroaryl group, the substituted C2-C60 heteroaryl alkyl group, the substituted C1-C60 heteroaryloxy group, the substituted C1-C60 heteroarylthio group, the substituted monovalent non-aromatic condensed polycyclic group, and the substituted monovalent non-aromatic condensed heteropolycyclic group may be:
Q1 to Q9, Q11 to Q19, Q21 to Q29, and Q31 to Q39 as used herein may each independently be:
For example, Q1 to Q, Q11 to Q19, Q21 to Q29, and Q31 to Q39 as used herein may each independently be:
an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, a phenyl group, a biphenyl group, or a naphthyl group, each unsubstituted or substituted with at least one of deuterium, a C1-C10 alkyl group, a phenyl group, or a combination thereof.
The melting point and/or fusion temperature of each of Pre-mixed composition A1, Pre-mixed composition A2, Ir-1, and Pt-1 were evaluated, and the results thereof are summarized in Table 1. Pre-mixed composition A1 is a composition prepared by physically mixing Ir-1 and Pt-1 at a weight ratio of 1:1, and pre-mixed composition A2 is a composition prepared by solidifying Ir-1 and Pt-1 after sublimation and purification at a weight ratio of 1:1. The melting point was measured using a DSC evaluation device of TA Instruments Inc., and the fusion temperature was measured using a melting point measuring device of BUCHI Inc.
Referring to Table 1, it was confirmed that the melting point of Pre-mixed composition A1 and the fusion temperature of Pre-mixed composition A2 were lower than the melting points of Ir-1 and Pt-1, respectively.
The purity of each of Pre-mixed composition A1, Ir-1, and Pt-1 was evaluated using high performance liquid chromatography (HPLC), and the results thereof are summarized in Table 2.
Next, each of Pre-mixed composition A1, Ir-1, and Pt-1 was heated for 300 hours in a chamber maintained at a vacuum degree of 1.2×10−2 torr and an internal temperature of 310° C., and then collected and subjected again to purity evaluation using the HPLC. The results thereof are summarized in Table 2.
Referring to Table 2, it was confirmed that Pt-1 and Ir-1, which have melting points higher than 310° C., showed little change in purity before and after heating, and thus were substantially free from thermal denaturation due to heating at 310° C. for 300 hours.
However, pre-mixed composition A1, which has a melting point lower than 310° C., showed a significant change in purity before and after heating, and thus, it was confirmed that a significant amount of Pt-1 and/or Ir-1 included in pre-mixed composition A1 was decomposed due to thermal denaturation due to heating at 310° C. for 300 hours.
As an anode, an ITO-patterned glass substrate was cut to a size of 50 millimeters (mm)×50 mm×0.5 mm, sonicated with isopropyl alcohol and pure water, each for 5 minutes, and then cleaned by exposure to ultraviolet rays and ozone for 30 minutes. The resultant glass substrate was loaded onto a vacuum deposition apparatus.
HT3 and F6-TCNNQ were vacuum-co-deposited on the anode at a weight ratio of 98:2 to form a hole injection layer having a thickness of 100 Å, and HT3 was vacuum-deposited on the hole injection layer to form a hole transport layer having a thickness of 1,350 Å. H-H1 was vacuum-deposited on the hole transport layer to form an electron blocking layer having a thickness of 300 Å.
Next, a host and a dopant were co-deposited at a weight ratio of 88:12 on the electron blocking layer to form an emission layer having a thickness of 400 Å. As the host, H-H1 and H-H2 were used at a weight ratio of 5:5, and as the dopant, Pt-1 and Ir-1 were used at a weight ratio of 1:1.
The emission layer was formed by performing the reciprocating process of the deposition source moving unit 350 described with reference to
Then, ET3 and ET-D1 were co-deposited at a volume ratio of 50:50 on the emission layer to form an electron transport layer having a thickness of 350 Å, ET-D1 was vacuum-deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and A1 was vacuum-deposited on the electron injection layer to form a cathode having a thickness of 1,000 Å, thereby completing the manufacture of a light-emitting device.
OLED A was manufactured in a similar manner as used to manufacture OLED 1, except that, in forming an emission layer, Pre-mixed composition A1 collected after the heat resistance evaluation of Evaluation Example 2 was used instead of Pt-1 and Ir-1 collected after the heat resistance evaluation of Evaluation Example 2.
OLED B was manufactured in a similar manner as used to manufacture OLED 1, except that, in forming an emission layer, the deposition source B1 loaded with Pt-1 and the deposition source B2 loaded with Ir-1 were each used instead of the first deposition source 300 in which Pt-1 and Ir-1 are not mixed with each other.
The driving voltage (Volts, V), the external quantum luminescence efficiency (EQE, %), and the lifespan (T97, %) of each of OLED 1, OLED A, and OLED B were evaluated, and the results thereof are shown in Table 3. As evaluation devices, a current-voltmeter (Keithley 2400) and a luminance meter (Minolta Cs-1000A) were used, and the lifespan (T97) (at 16,000 candela per square meter, or nits) was evaluated as the time taken for luminance to be reduced to 97% of the initial luminance of 100%.
Referring to Table 3, it was confirmed that OLED 1 had a driving voltage equal to or higher than those of OLED A and OLED B, and showed improved external quantum luminescence efficiency and lifetime characteristics compared to those of OLED A and OLED B. In detail, from the device data of OLED A, it is determined that when the heating conditions of 310° C. for 300 hours are the desired deposition temperature and deposition time conditions, it is not suitable to use Pre-mixed composition A1 as a deposition object, and, in order to perform a deposition process without thermal denaturation of Pt-1 and Ir-1 while using Pre-mixed composition A1 as the deposition object, it is necessary to select a deposition temperature that is lower than the melting point of Pre-mixed composition A1.
In the mixed layer as described above, a first dopant and a second dopant are effectively doped at substantially the same time (e.g., at the same time) without thermal denaturation. Accordingly, a light-emitting device including the mixed layer may have excellent luminescence efficiency and/or a long lifespan. By using the light-emitting device, a high-quality electronic apparatus may be manufactured. In addition, the method of preparing a mixed layer as described above may provide excellent process stability and reduction of manufacturing costs. Accordingly, by using the method of preparing a mixed layer, high-quality light-emitting devices and electronic apparatuses may be economically manufactured in large quantities.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the figures, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2021-0181735 | Dec 2021 | KR | national |
