KR20150066479A - A composition of hole transporting layer comprising crosslinkable double-bond and crosslinking agent comprising 2 or more thiol groups and use thereof - Google Patents

Abstract

Provided are a hole transporting material, which comprises a first unit comprising a first hole transporting fragment and a second unit comprising a second hole transporting fragment having one or more crosslinkable double bonds, and a hole transporting layer (HTL) composition, which comprises crosslinking agents containing two or more thiol groups. Also provided is a method of preparing an organic semiconductor device having one or more an organic layer, comprising: a first step which coats a first organic semiconductor material comprising two or more crosslinkable double bonds and a second organic layer composition comprising crosslinking agents containing two or more thiol groups; a second step which crosslinks by application of light or heat; and a third step which coats a second organic layer composition with liquid form on the formed first organic layer.

Description

TECHNICAL FIELD [0001] The present invention relates to a polymeric hole transporting material comprising a double bond capable of crosslinking and a hole transporting layer composition comprising a cross-linking agent containing two or more thiol groups and a use thereof for a hole transporting layer comprising a crosslinkable double- thiol groups and use thereof.

The present invention relates to a hole transporting layer (HTL) composition and a method of manufacturing an organic semiconductor device including the stacked one or more organic layers.

Organic light-emitting diodes (OLEDs) have received strong interest as next-generation displays since Tang first disclosed them in 1987 at Eastman Kodak. Early OLEDs have several features: multilayer thin film structure (about 100 nm thick), the use of small organic molecules, film formation by thermal vacuum evaporation, and so on.

Three years later, PLED (Polymer Organic Light Emitting Diode) was reported by Burroughes et al in Cambridge. Both OLED and PLED have the same mechanism of operation, but the main difference between them is the film formation method. In the case of PLED, an organic thin film is prepared by a solution process (spin coating) of a conjugated polymer compound, which opens up the possibility of manufacturing an electronic device through a simple and inexpensive solution process. However, while OLEDs in the form of vacuum deposition are currently being commercialized, OLEDs due to solution processes remain a challenge.

From the point of view of materials and device structures, HTLs are particularly important for OLEDs by solution processes. A multilayer structure with a separate charge transport layer and a light emitting layer is essential to have high efficiency of the OLED. However, due to the erosion of the basal layer, it is not easy to implement a multilayer structure by a simple solution process. In addition, HTL is the starting point of the multilayer structure in OLED structures (from the ITO anode to the low work function metal cathode) by conventional solution processes. Therefore, HTL should have good solvent resistance, which can generally be achieved by introducing a cross-linking unit.

The crosslinking units can be generally classified into two types of thermal crosslinking and photo crosslinking based on the method of starting the crosslinking reaction. Thermal crosslinking is relatively simple and requires no complicated equipment. This is why many cross-linkable HTL materials take heat crosslinking units. Among the various thermo-crosslinking units, the use of styrene, benzocyclobutenes (BCBs), trifluorovinlyether (TFVEs), ethynyl groups and sol for gel reaction Reactive silanes have been introduced into OLED HTL materials. On the other hand, photocrosslinking units are relatively uncommon, but they have advantages such as fast reaction times, low thermal stress on the base layer, and fine patterning availability. Also, when a plurality of organic layers are laminated, if a single layer is photocured in this manner, even if a new solution layer is introduced on the upper layer, the photocured lower layer can be maintained without dissolving the form or pattern by the solvent, There are advantages. Therefore, in order to utilize the advantages of such photo-crosslinking in the production of an organic semiconductor device requiring a process such as the production of a fine pattern and / or a lamination of an organic layer in the form of a solution, a new photo-crosslinkable monomer unit and a photo- .

Therefore, the inventors of the present invention have focused on the fact that the thiol group and the carbon-carbon double bond can cause effective photo-crosslinking, and accordingly, a polymer hole-transporting material is modified so that a crosslinking-capable hole transport material into which a double bond is introduced and a cross- , The hole transporting layer composition formed by the photo-crosslinking is dissolved in the solvent so that the pattern is disrupted and the surface is not unevenly dispersed even if the process using the solution is further proceeded by curing and / or patterning by irradiation with UV light It is possible to introduce an additional organic layer while maintaining the above-mentioned properties, thus completing the present invention. In addition, this reaction can be used for introducing a new layer in a solution state while maintaining the substructure without the influence of the solvent of the solution layer introduced at the top in the production of the organic semiconductor device requiring the lamination and / or fine patterning of a plurality of organic layers .

One object of the present invention is to provide a process for producing a polymeric material comprising a first monomer unit containing 0 to 99 mol% of a first monomer unit containing a first hole transporting fragment and a second monomer unit containing a second hole transporting moiety and containing at least one crosslinkable double bond, A polymeric hole transporting material comprising 1 to 100 mol% of monomer units; And a hole transporting layer (HTL) composition comprising a cross-linking agent containing two or more thiol groups.

It is another object of the present invention to provide an organic semiconductor device comprising at least one organic layer stacked, wherein the first organic semiconductor material includes two or more double bonds capable of crosslinking, and the cross- A first step of applying a first organic layer composition containing A second step of applying light or heat to crosslink; And a third step of applying a second organic layer composition in the form of a solution on the formed first organic layer.

According to one aspect of the present invention, there is provided an organic electroluminescent device comprising 0 to 99 mol% of a first unit element including a first hole transporting fragment and a second hole transporting moiety, And 1 to 100% by mole of a second monomer unit containing at least one monomer unit; And a hole transporting layer (HTL) composition comprising a cross-linking agent containing two or more thiol groups.

Preferably, the first hole transporting region and the second hole transporting region may be the same, but are not limited thereto.

The first monomer unit and the second monomer unit may form a polymer skeleton in addition to the hole transporting site and may be independently substituted or unsubstituted arylene such as phenylene or fluorene, Or a hydrocarbon chain with or without a heteroatom, but is not limited thereto.

Preferably, the first monomer is derived from a first monomer, the second monomer is derived from a second monomer, and the second monomer may be a modification of the first monomer to include a crosslinkable double bond, But is not limited thereto. The modification to include the crosslinkable double bond may be accomplished by introducing styrene (-Ph-CHCH ₂ ), allyloxy (-O-CHCH ₂ ), or allyloxyalkyl group (RO-CHCH ₂ ; R is C 1 to C 8 alkyl) But is not limited thereto.

Preferably, the first hole transporting moiety and the second hole transporting moiety may each independently include a tertiary amine structure substituted with at least one aryl group. Specifically, triazole or triarylamine in which three aryl groups are substituted with each other or two aryl groups substituted in an amine group form a ring containing a single bond or a heteroatom to each other, a carbazole group such as phenothiazine but are not limited to, fused arylamines such as phenothiazine, phenoxazine, and the like.

The first monomer may be derived from a first monomer, and non-limiting examples of the first monomer include

One)

,2)

,

,3)

,

,4)

,

,5)

,

,6)

,

,7)

,

,8)

,

,9)

,

,10)

,

및11)

And

일 수 있다.
12)

Lt; / RTI >

The polymer hole transport material and the cross-linking agent of the HTL composition of the present invention can be bonded to each other by light or heat through a thiol-ene reaction using a double bond capable of crosslinking of the second unit and a thiol group, The polymer hole transport material includes a second monomer having a double bond capable of cross-linking at a molar ratio of 1 to 100% as described above. Since the cross-linking agent includes two or more thiol groups, the cross- Can be formed.

,

,

,

,

,

,

및

로 구성된 군으로부터 선택되는 것일 수 있으나, 이에 제한되지 않는다.Preferably, the crosslinking agent is

,

,

,

,

,

,

And

≪ / RTI > but are not limited thereto.

Preferably, the composition may further comprise a radical initiator to initiate a thiol-ene reaction. The radical initiator may be 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl- 369), 1-hydroxycyclohexyl phenyl ketone, Irgacure 184, 2,2-dimethoxy-2-phenyl-acetophenone, Irgacure 651 ), 2-isopropoxy-2-phenylacetophenone (Vicure 30), diphenyl- (2,4,6-trimethylbenzoyl) -phosphinic oxide , 6-trimethylbenzoyl) -phosphine oxide, Chivacure TPO), benzophenone, 4'-tertiarybutyl-2,2,2-trichloroacetophenone (4 ' 2-trichloroacetophenone, Trigonal P1), 2-isopropylthioxanthone, Genocure ITX, 2,2'-azobis (2-methylpropionitrile) And benzoyl peroxide, but it may be selected from the group consisting of It is not.

Preferably, the composition of the present invention may be a solution-state composition further comprising a solvent so as to perform a solution process having advantages of economic efficiency, enlargement and high resolution of the process.

The solvent may be selected from the group consisting of chlorobenzene, dichlorobenzene, trichlorobenzene, chloroform, dichloroethane, methoxybenzene, toluene, xylene, trimethylbenzene and tetrahydronaphthalene.

According to another aspect of the present invention, there is provided a method of manufacturing an organic semiconductor device including one or more organic layers stacked, the method comprising: forming a first organic semiconductor material including two or more crosslinkable double bonds, A first step of applying a first organic layer composition comprising a cross-linking agent; A second step of applying light or heat to crosslink; And a third step of applying a second organic layer composition in the form of a solution on the formed first organic layer.

In the second step, light may be applied through the photoresist to selectively crosslink the desired pattern. The organic semiconductor device may also comprise a finely patterned organic layer if desired. Such fine patterning is hardly achieved by heat curing. The production method according to the present invention can be cured by light as well as heat, and therefore can be used not only for the lamination of an organic layer by a solution process, but also for the production of an organic semiconductor device requiring fine patterning in the case of photocuring using a photoresistor of a desired pattern Can be usefully used.

In addition, the manufacturing method according to the present invention may further include removing unreacted sites by washing with a solvent prior to the third step.

Preferably, the organic semiconductor device is an organic light emitting device, and each of the first and second organic layers includes a hole injecting layer (HIL), a hole transporting layer, an emitting layer (EML), and an electron transporting layer a transporting layer (ETL) and an electron injection layer (EIL). The organic light emitting device may further include a substrate, a cathode, and a cathode. The substrate, the anode, and the cathode may be made of a material used in a conventional organic light emitting device.

Preferably, each of the first organic layer compositions independently has two double bonds capable of crosslinking to an organic semiconductor material selected from the group consisting of a hole injecting material, a hole transporting material, an organic light emitting material, an electron transporting material and an electron injecting material Or more.

There are a number of compounds that can act as the hole injection, hole transport, luminescence, electron transport, electron injection, etc., and generally include substituted or unsubstituted aromatic or heteroaromatic groups.

The hole injection material, which is an organic material capable of injecting holes, facilitates injection of holes from the anode, and has an appropriate ionization potential for injecting holes from the anode, a high interfacial adhesion to the anode, Absorptivity of the organic compound, and examples of the substituent capable of injecting holes include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, Perylene-based organic materials, and anthraquinone, but are not limited thereto.

The hole transporting material, which is an organic material capable of transferring holes, has a high hole mobility and preferably has a high LUMO level for electron blocking. For example, as substituents capable of transferring holes, arylamine- But are not limited to these. More specific examples include triarylamine derivatives, amines having a bulky aromatic group, starburst aromatic amines, amines having spirofluorene, cross-linked amines (e.g., crosslinked amine compounds.

The electron transferring material, which is an organic substance capable of electron transferring, is a compound having an electron withdrawing group, and examples of the substituent capable of electron transfer include a functional group which attracts electrons by resonance such as a cyano group, oxadiazole, And the like, but the present invention is not limited thereto.

Preferably, the second organic layer composition is an organic semiconductor material independently selected from the group consisting of a hole injecting material, a hole transporting material, an organic light emitting material, an electron transporting material and an electron injecting material, or a double bond capable of cross- Or more.

The hole injecting material may be at least one selected from the group consisting of 1,3-bis (triphenylsilyl) benzene, polyaniline (emeraldine salt) (3,4-ethylenedioxythiophene), bis (poly (ethyleneglycol)), poly (3,4-ethylenedioxythiophene), bis (N, N'-bis [4- [bis (3-methylphenyl) amino] phenyl] -block-poly (ethylene glycol) N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine, poly (3,4-ethylenedioxythiophene- ethylenedioxythiophene) -poly (styrenesulfonate), tetramethacrylate end-capped poly (3,4-ethylenedioxythiophene), tetracyanoethylene, Sulfonated poly (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2,5-di ) sulfonated poly (thiophene-3- [2- (2-methoxyethoxy) ethoxy] -2,5-diyl), 7,7,8,8-tetracyanoquinodimethane (7,7,8,8 tetracyanoquinodimethane), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane ), 4,4 ', 4 "-tris [phenyl (m-tolyl) amino] triphenylamine, However, the present invention is not limited thereto.

The hole transport material may be a polymer or a vacuum deposition type low molecular weight material without limitation.

,

또는

의 구조를 갖는 것일 수 있다. 상기 각 고리 상의 결합자리는 각각 독립적으로 수소원자이거나, C1 내지 C6 알킬, C1 내지 C6 알킬에테르가 결합된 것일 수 있으며, X₁ 및 X₂는 각각 독립적으로 단일결합, S, O, NR₁ 및 CR₂R₃일 수 있고, 이때 R₁ 내지 R₃은 임의의 치환기일 수 있다.As described above, the polymer hole transport material may be a polymer including a tertiary amine structure substituted with at least one aryl group serving as a hole transport site. Or a copolymer including a moiety that does not include the hole transporting moiety and forms a skeleton structure. However, the present invention is not limited thereto. The moiety that does not include the hole transporting moiety and forms a skeleton structure

,

or

. ≪ / RTI > And X ₁ and X ₂ are each independently a single bond, S, O, NR _1, and / or R ₁ and R ₂ are each independently a hydrogen atom or a C 1 to C 6 alkyl, CR ₂ R ₃ , wherein R ₁ to R ₃ may be any substituent.

Non-limiting examples of the polymeric hole transport material include

,One)

,

,2)

,

,3)

,

,4)

,

,5)

,

,6)

,

,7)

,

,8)

,

,9)

,

,10)

,

및11)

And

이 있다.
12)

.

Non-limiting examples of vacuum deposition type low molecular weight hole transport materials include

1) 4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine (4,4', 4"

2) Preparation of 1,1-bis (4- (N, N'-di (p-tolyl) amino) phenyl) cyclohexane ) phenyl cyclohexane; TAPC),

3) 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), 4,4'

4) DATA,

5) TFV-TCTA,

6) 1,3-bis (N-carbazolyl) benzene,

7) 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (4,4'-bis

8) 1,4-bis (diphenylamino) benzene, 1,4-bis

9) Synthesis of 4,4'-bis (3-ethyl-N-carbazolyl) -1,1'-biphenyl ,

10) N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine,

11) N, N'-bis (phenanthren-9-yl) -N, N'-bis (phenyl) phenyl) -benzidine),

12) Copper (II) phthalocyanine (copper (II) phthalocyanine),

13) 4- (dibenzylamino) benzaldehyde-N, N-diphenylhydrazone,

14) 4- (Dimethylamino) benzaldehyde diphenylhydrazone (4- (dimethylamino) benzaldehyde diphenylhydrazone),

15) Synthesis of 2,2'-dimethyl-N, N'-di - [(1-naphthyl) -N, N'-diphenyl] -1,1'- 2'-dimethyl-N, N'-di - [(1-naphthyl) -N, N'- diphenyl] -1,1'-biphenyl-4,4'-

16) Synthesis of 9,9-dimethyl-N, N'-di (1-naphthyl) -N, N'-diphenyl-9H-fluorene- -di (1-naphthyl) -N, N'-diphenyl-9H-fluorene-2,7-diamine),

17) Synthesis of N, N'-di- [(1-naphthyl) -N, N'-diphenyl] (1-naphthyl) -N, N'-diphenyl] -1,1'-biphenyl) -4,4'-diamine),

18) 4- (diphenylamino) benzaldehyde diphenylhydrazone, 4- (diphenylamino) benzaldehyde diphenylhydrazone,

19) N, N'-diphenyl-N, N'-di-p-tolylbenzene-1,4- diamine),

20) Diffie la Gino [2,3- f: 2 ', 3' -h] quinoxaline -2,3,6,7,10,11- hexahydro-carbonitrile saline (dipyrazino [2,3- f: 2' , 3'-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile),

N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (N, N'- N'-bis [4- [bis (3-methylphenyl) amino] phenyl] -N, N'- diphenyl- [1,1'-biphenyl] -4,4'-

22) N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine,

23) N, N, N ', N'-tetrakis (3-methylphenyl) -3,3'-dimethylbenzidine dimethylbenzidine),

24) N, N, N ', N'-tetrakis (2-naphthyl) benzidine,

25) tetra-N-phenylbenzidine,

26) N, N, N ', N'-tetraphenylnaphthalene-2,6-diamine,

27) Tin (IV) 2,3-naphthalocyanine dichloride (tin (IV) 2,3-naphthalocyanine dichloride)

28) titanyl phthalocyanine,

29) tris [4- (diethylamino) phenyl] amine, tris [4-

30) 1,3,5-tris (diphenylamino) benzene, 1,3,5-tris (diphenylamino) benzene,

31) 1,3,5-tris (2- (9-ethylcarbazyl-3) ethylene) benzene), 1,3,5-

32) 1,3,5-tris [(3-methylphenyl) phenylamino] benzene, 1,3,5-tris [

33) 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine), 4,4'

34) 4,4 ', 4 "-tris [phenyl (m-tolyl) amino] triphenylamine and 4,4'

35) tri-p-tolylamine.

The organic light emitting material may be a light emitting material, a host material, or a dopant material. Specific examples thereof include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorene, perylene, phthaloperylene, perrinone, phthaloperenone, naphthaloperenerone, A quinoline metal complex, an aminoquinoline metal complex, a benzoquinoline metal complex, an imine, a quinoline metal complex, a quinoline metal complex, a quinoline quinoline metal complex, a quinoline quinoline metal complex, Although there can be mentioned diphenylethylene, vinyl anthracene, diaminocarbazole, pyran, thiopyran, polymethine, melocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, fluorescent dyes and mixtures thereof, But are not limited thereto. When a dopant material is selected, it is preferable to select a dopant having a bandgap equal to or less than the bandgap of the host material while having high efficiency of fluorescence or phosphorescence.

The electron transport material may be selected from the group consisting of bathocuproine, bathophenanthroline, 3- (biphenyl-4-yl) -5- (4-tert- 4-phenyl-4H-1,2,4-triazole), 2- (4-biphenyl- 4-biphenylyl-5-phenyl-1,3,4-oxadiazole, 3,5-bis (4-tert-butylphenyl) 4-phenyl-4H-1,2,4-triazole, 3,5-bis (4-tert-butylphenyl) Bis (8-hydroxy-2-methylquinoline) - (4-phenylphenoxy) aluminum, 2,5-bis (1-naphthyl) -1 , 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, 2- (4-tert-butylphenyl) (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4-oxadiazole, 3,5-diphenyl- (1-naphthyl) -1H-1,2,4-triazole), tris- (8-hydroxyquinoline) aluminum tris- (8-hydroxyquinoline) aluminu m), but the present invention is not limited thereto.

Examples of the electron injecting material include, but are not limited to, LiF, CsF, and Cs ₂ CO ₃ .

The hole transport layer composition comprising the crosslinkable polymeric hole transport material and the crosslinking agent containing two or more thiol groups of the present invention may be cured by crosslinking a double bond and a thiol group by applying heat or light, It is possible to provide a hole transport layer that is not crushed or damaged even when the organic layer composition including the organic layer composition is applied. Therefore, it is possible to economically produce a solution process capable of producing a large-sized, high-resolution OLED. In addition, the photo-curing method using a bond between a double bond and thiol can be used for manufacturing an organic semiconductor device including a fine pattern because fine patterning can be performed using a photoresist.

1 is a ¹ H NMR spectrum of Compound 2. Fig.
2 is a ¹ H NMR spectrum of Compound 3. Fig.
3 is a ¹ H NMR spectrum of Compound 4. Fig.
4 is a ¹ H NMR spectrum of Compound 5. Fig.
5 is a ¹ H NMR spectrum of Compound 6.
6 is a ¹³ C NMR spectrum of Compound 4. Fig.
Figure 7 is the ¹³ NMR spectrum of compound 6.
8 is a ¹ H NMR spectrum of allyl-TFBO5 (Allyl-TFB05) containing 5 wt% of cross-linkable allyl-TFB. At this time, the insertion degree is an enlarged image of approximately 3.5 ppm.
9 is a ¹ H NMR spectrum of allyl-TFB08 (Allyl-TFB08) containing 8 wt% of cross-linkable allyl-TFB. At this time, the insertion degree is an enlarged image of approximately 3.5 ppm.
10 is a thermogravimetric analysis (TGA) thermogram of allyl-TFB05.
11 is a differential scanning calorimetry (DSC) thermogram of allyl-TFB05.
12 (a) shows the UV-Vis absorption spectrum of the photo-crosslinked allyl-TFBO5 film having a UV irradiation time of 30 seconds before and after solvent rinsing.
12 (b) shows the UV-Vis absorption spectrum of the photo-crosslinked allyl-TFBO5 film having a UV irradiation time of 180 seconds before and after solvent rinsing.
Figure 12 (c) shows a plot of solvent resistance with different UV irradiation times.
13 shows the UV-Vis absorption spectrum of the photocrosslinked allyl-TFBO5 film before and after solvent rinsing with different UV irradiation times.
14 shows the UV-Vis absorption spectrum before and after the solvent rinsing of the photo-crosslinked allyl-PTPA12 film with different UV irradiation times.
15 (a) shows an optical microscope image of a patterned allyl-TFB05 film.
FIG. 15B is an enlarged image of the same sample as FIG. 13A. At this time, the bright line pattern is crosslinked allyl-TFBO5 and the other region is the substrate.
16 is a cyclic voltammogram of allyl-TFBO5 and TPD.
17 is an energy level diagram of an OLED device comprising photocrosslinked allyl-TFB05.
Figure 18 (a) shows the current density-voltage characteristics of an OLED device comprising photo-crosslinked allyl-TFB05.
Fig. 18 (b) shows the brightness-voltage characteristics of an OLED device comprising photolyzed allyl-TFB05.
FIG. 18 (c) shows the power efficiency-brightness-brightness efficiency characteristics of an OLED device including photocrosslinked allyl-TFB05.
19 shows the results of atmospheric photoelectron spectroscopy (Riken AC-2) measurement of an HTL film containing photo-crosslinked allyl-TFB05 with different UV irradiation times.
Figure 20 shows the current density (J) - electric field (F) characteristics of a hole-only device of an HTL film comprising photo-crosslinked allyl-TFB05 with different UV irradiation times.
Figure 21 (a) shows the current density-voltage characteristics of an OLED device comprising photo-crosslinked allyl-PTPA12.
Figure 21 (b) shows the brightness-voltage characteristics of an OLED device comprising photocrosslinked allyl-PTPA12.
Figure 21 (c) shows the power efficiency-voltage characteristics of an OLED device comprising photocrosslinked allyl-PTPA12.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited by these examples.

Example  1: Materials and Methods

N-bromosuccinimide (NBS), 1-bromo-4-butylbenzene, trans-1,2-dichloroethylene ) Was purchased from TCI Co., Ltd. Tri-tert-butylphosphine P (t-Bu) ₃ was obtained from Kanto Chemical Co., Inc., tetrakis (triphenylphosphine) palladium (0) (0); Pd (pph ₃ ) ₄ ) was purchased from Strem Chemicals Inc. Irgacure 369 was purchased from Ciba Specialty Chemicals Inc. All other reagents were purchased from Sigma-Aldrich Co. LLC, all reagents were used without further purification.

^{The 1} H and ¹³ C NMR spectra were measured using a Bruker DPX-300 and 500 NMR spectrometer. Thermogravimetric analysis (TGA) was performed with TA instruments TGA Q 500 and differential scanning calorimetry (DSC) was performed with a Mettler Toledo DSC 1. The number average molecular weight and weight average molecular weight of the polymer were confirmed using gas permeation chromatography (GPC) with a Waters 2690 separation module. The UV-vis absorption spectrum was measured using SHIMADZU UV-2550, and the cyclic voltammetry was measured using WonATech BAS 100B. The thickness of the film was confirmed using a KLA Tencor Alpha Step IQ surface profiler. The emission and emission spectra of the OLED devices were confirmed with a Konica-Minolta CS-100A luminance meter and a CS-1000 spectroradiometer, respectively. The electrical properties of the device were measured with a Kiethley 2400.

Example  2: Preparation of monomer A

Step 1: Tri (4-bromophenyl) Min tri (4- bromophenyl ) amine ; 1)

A solution of triphenylamine (10 g, 40.76 mmol) dissolved in DMF (N, N-dimethylformamide; 100 ml) was added to a 250 ml two-necked round bottom flask and stirred under a nitrogen atmosphere. After 10 minutes, a solution of NBS (N-bromosuccinimide; 23.21 g, 130.44 mmol) dissolved in DMF (40 mL) was added dropwise to the triphenylamine solution. After addition of NBS, the reaction mixture turned green. The reaction mixture was stirred overnight at room temperature and then extracted with ether and brine water. The organic layer was dried over anhydrous MgSO ₄ , filtered and the solvent was evaporated. The crude product was washed with MeOH to give a white solid product 1 (16.36 g, 83.3%).

¹ H-NMR (CDCl ₃ , 300 MHz)? = 7.39 (d, 6H), 6.96 (d, 6H).

Step 2: 4- ( Bis (4-bromophenyl) amino ) Benzaldehyde (4- (bis (4-bromophenyl) amino) benzaldehyde; 2)

A solution of compound 1 (16 g, 33.2 mmol) dissolved in anhydrous THF (tetrahydrofuran; 88 ml) was added to a 250 ml two-necked round bottom flask, and n-butyllithium (n-BuLi , 17.26 mL, 2.5 M hexane solution) was slowly added dropwise. After stirring at -78 占 폚 for 1 hour, DMF (16 ml) was added. The reaction mixture was stirred at -78 ° C for 1 hour, and further stirred for 1 hour while cooling slowly at room temperature. After it was confirmed that the product was caused from TLC, extracted with ether and brine, the organic layer was dried over anhydrous MgSO _4. The solvent was evaporated and the residue was purified by silica gel column chromatography with ethyl acetate / hexane = 1/15 to give a yellow solid product 2 (4.2 g, 29.3%).

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 9.86 (s, 1H), 7.72 (d, 2H), 7.48 (d, 4H), 7.07-7.02 (m, 6H).

Step 3: (4- ( Bis (4-bromophenyl) amino ) Phenyl ) Preparation of methanol ((4- (bis (4-bromophenyl) amino) phenyl) methanol 3)

A solution of the compound 2 (3.84 g, 8.9 mmol) dissolved in ethanol (30 ml) and ether (30 ml) were mixed in a 250 ml two-neck round bottom flask. After sufficient stirring, a 0.1 M aqueous NaOH solution (9 ml) of sodium borohydride (0.17 g, 4.45 mmol) was slowly added dropwise to the mixture. After 4 hours at room temperature, the reaction mixture was extracted with dichloromethane (dichloromethane) and brine, dried over anhydrous MgSO _4. After filtration, the solvent was evaporated to give a white solid product 3 (3.8 g, 98.8%).

¹ H-NMR (CDCl ₃ , 300 MHz)? = 7.37-7.28 (m, 6H), 7.08 (d, 2H), 6.96 (d, 4H), 4.67 (s, 2H).

Step 4: 4 - (( Allyloxy ) methyl ) -N, N- Bis (4-bromophenyl) Preparation of 4 - ((allyloxy) methyl) -N, N-bis (4-bromophenyl) aniline 4)

Compound 3 (3.55 g, 8.21 mmol), tetrabutylammonium hydrogen sulphate (0.14 g, 0.41 mmol) and 50% aqueous NaOH solution (1.97 g) were added to a 50 mL two- Was added to 10 ml of trans-1,2-dichloroethylene, and allyl bromide (0.91 ml, 9.86 mmol) was added dropwise to the mixed solution. The reaction mixture was then stirred vigorously at 50 < 0 > C for 12 hours under reflux. After completion of the reaction, extracting the reaction with ethyl acetate and brine and dried over anhydrous MgSO _4. After evaporation of the solvent, the residue was purified by column chromatography with ethyl acetate / hexane = 1/10 to give product 4 (2.87 g, 73.8%) as colorless oil in the form of monomer A.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 7.37-6.93 (m, 12H), 6.03 (m, 1H), 5.37 (d, 1H), 5.27 (d, 1H), 4.48 (s, 2H), 4.09 (d, 2 H).

¹³ C-NMR (CDCl ₃ , 500 MHz): 146.67, 144.34, 138.85, 132.19, 129.48, 124.95, 123.20, 114.92, 35.04, 33.61, 22.65, 14.13.

Example  3: Preparation of monomer B

Step 1: 4-Butyl-N, N-diphenylalanine (4- butyl -N, N- diphenylaniline ;  5) of  Produce

(1 g, 5.9 mmol), 1-bromo-4-butylbenzene (1.26 g, 5.9 mmol) and sodium tert-arabide in a 50 mL two- Tris (dibenzylideneacetone) dipalladium (0); 0.108 g, 0.118 mmol), and tri-tert-butyl (0) Tri-tert-butylphosphine (0.047 g, 0.236 mmol) were mixed. To maintain the nitrogen atmosphere, anhydrous toluene was added to the flask. Was heated at 95 < 0 > C for 12 hours to reflux. After cooling to room temperature, the reaction mixture was extracted with ethyl acetate and brine and dried over anhydrous MgSO _4. After evaporation of the solvent, the residue was purified by column chromatography with ethyl acetate / hexane = 1/30 to give product 5 (1.2 g, 67.5%) as a colorless oil.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 7.30 (t, 4H), 7.14 (d, 2H), 7.08 (m, 8H), 2.65 (t, 2H), 1.68 (m, 2H), 1.47 ( m, 2 H), 1.02 (t, 3 H).

Step 2: 4-Butyl-N, N- Bis (4- Bromophenyl ) -Aniline (4- butyl -N, N-bis (4-bromophenyl) -aniline; 6)

NBS (1.085 g, 6.1 mmol) was added to a solution of compound 5 (0.91 g, 3.02 mmol) dissolved in DMF (8 mL) in a 50 mL 2-necked round bottom flask. The reaction mixture was stirred at room temperature for 20 hours. The reaction mixture was extracted with ethyl acetate and brine and dried over anhydrous MgSO _4. The residue was purified by column chromatography with ethyl acetate / hexane = 1/30 to give product 6 (0.74 g, 53.36%) as monomer B in the form of a colorless oil.

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 7.36 (d, 4H), 7.13 (d, 2H), 6.96 (q, 6H), 2.60 (t, 2H), 1.63 (m, 2H), 1.42 ( m, 2 H), 0.97 (t, 3 H).

¹³ C-NMR (CDCl ₃ , 500 MHz): 146.67, 144.34, 138.85, 132.19, 129.48, 124.95, 123.20, 114.92, 35.04, 33.61, 22.40, 13.98.

Example  4: Allyl- TFB05 ( Allyl - TFB05 ; 7)

Compound 4 (0.0149, 0.03 mmol), Compound 6 (0.2767 g, 0.6 mmol) and 9,9-dioctylfluorene-2,7-diboronic acid bis (1,3-propanediol (9,9-dioctylfluroene-2,7-diboronic acid bis (1,3-propanediol) ester; 0.3527 g, 0.63 mmol) were mixed. Tetrakis (triphenylphosphine) palladium (0) (0.007 g, 0.0063 mmol) was then added to the mixture in a glove box. Next, tetraethyl ammonium hydroxide (1.45 ml) and anhydrous toluene (10 ml) were added to the flask under a nitrogen atmosphere. The reaction mixture was heated and refluxed at 95 < 0 > C for 72 h under a nitrogen atmosphere. The terminal functional group was capped with phenyl boronic acid and bromobenzene. After completion of the reaction, the catalyst was deactivated with a small amount of HCl, and then the reaction product was slowly added dropwise to MeOH to precipitate the resulting polymer. After stirring for 4 hours, the precipitated polymer was filtered and extracted with soxhlet for 24 hours in MeOH to obtain a yellow solid product 7 (0.4 g, 91.9%).

_{^{1 H-NMR (CDCl 3,}} 300 MHz) δ = 7.74-7.12 (m, 19H), 6.02 (m, 0.05H), 5.28 (m, 0.11H), 4.51 (s, 0.11H), 4.08 (d, 3H), 0.78 (t, 6H), 1.61 (m, 2H), 2.61 (t, 2H) ).

Example  5: Allyl- TFB08 ( Allyl - TFB08 )

Except that a mixture of 0.03 mmol of compound 4 and 0.60 mmol of compound 6 in Example 4 was used instead of 0.05 mmol of compound 4 and 0.58 mmol of compound 6 to obtain 8 mol% Of allyl-TFB08 containing TFB comprising a crosslinkable allyl group.

Example  6: Allyl- PTPA12 ( Allyl - PTPA12 )

Compound 4 (0.0283, 0.06 mmol) and Compound 6 (0.2472 g, 0.54 mmol) were mixed in a 25 ml two-necked round bottom flask (Flask 1) and subjected to vacuum and nitrogen purging three times. Anhydrous tetrahydrofuran ML) was added. Then, another 2,2'-bipyridine (0.1874 g, 1.2 mmol) and bis (1,5-cyclooctadiene) nickel (0) (0.20 g) were added to another 50 mL 2-necked round bottom flask (flask 2) 0.3301 g, 1.2 mmol) were mixed and anhydrous tetrahydrofuran (10 mL) was added.

The flask 2 was heated at 60 캜 for 30 minutes under a nitrogen atmosphere, and then a mixed solution of the flask 1 was added to the flask 2. Lt; RTI ID = 0.0 > 60 C < / RTI > for an additional 24 hours under a nitrogen atmosphere, and finally terminal functional groups were capped with bromobenzene. After completion of the reaction, the catalyst was deactivated with a small amount of HCl, and the reaction product was slowly added dropwise to MeOH to precipitate the resulting polymer. After stirring for 4 hours, the precipitated polymer was filtered off and Soxhlet extraction was carried out with MeOH for 24 hours to obtain a yellow solid product allyl-PTPA12 (0.15 g, 83.3%).

¹ H-NMR (CDCl ₃ , 300 MHz)? = 7.50-7.30 (m, 4.5H), 7.20-7.00 (m, 9.1H), 5.98 (s, 0.28H), 4.07 (d, 0.28H), 2.57 (t, 2H), 1.59 (m, 2H), 1.45-1.00 (m, 4H), 0.95 (t, 3H).

Comparative Example  One: TFB Manufacturing

In Example 4, instead of using 0.03 mmol of the compound 4 and 0.60 mmol of the compound 6 as a reactant, 0.63 mmol of the compound 6 was used as a reactant to carry out the same reaction to synthesize TFB containing no allyl group.

Experimental Example  1: Compound structure analysis

The structures of the compounds prepared according to Examples 2 to 4 were confirmed by ¹ H NMR and ¹³ C NMR spectra (Figs. 1 to 7).

In an embodiment of the present invention, an allyl ether group was introduced into the polymer as a crosslinking unit capable of participating in thiol-ene photopolymerization. The feed rate of triphenylamine comonomer (compound 4 ) containing allyl was 5 mol% based on the polymer of Example 4, and its substantial content in the polymer was confirmed by ¹ H NMR measurement. 4.49 ppm (singlet) and 2.56 ppm (triplet), ¹ H NMR peaks are distinct in the spectrum is -C ₆ H ₅ -C ₆ of the -C H ₂ O-, and compounds 6 of each of the two comonomers (compound 4 H ₅ -CH ₂ C ₃ H ₇ ) (FIG. 8). Comparing the integral values of proton peaks including two benzyl groups, the substantial content of triphenylamine comonomer units containing allyl groups was calculated to be 5.2 mol% based on the polymer, ). The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the allyl-TFB05 polymer were confirmed by gel permeation chromatography (GPC), and Mn and Mw were 31,400 g / mol and 171,300 g / mol, respectively. On the other hand, Mn and Mw of allyl-TFB08 measured by the same method were 15,000 g / mol and 78,700 g / mol, respectively, and Mn and Mw of allyl-free TFB were 16,600 g / mol and 83,700 g / mol, respectively.

On the other hand, the feed rate of the allyl-containing triphenylamine comonomer (compound 4 ) to the polymer of Example 6 was 10 mol%, and the substantial content thereof in the polymer was confirmed by ¹ H NMR measurement. 4.46 ppm (singlet) and 2.57 ppm (triplet), ¹ H NMR peaks are distinct in the spectrum is -C ₆ H ₅ -C ₆ of the -C H ₂ O-, and compounds 6 of each of the two comonomers (compound 4 H ₅ - CH ₂ C ₃ H ₇ ). Comparing the integral values of proton peaks including two benzyl groups, the substantial content of triphenylamine comonomer units containing allyl groups was calculated to be 12.3 mol% based on the polymer, and the ratio of the supplied monomers (10 mol% ). The number average molecular weight (Mn) and weight average molecular weight (Mw) of the allyl-PTPA12 polymer were confirmed by gel permeation chromatography (GPC), and Mn and Mw were 9,300 g / mol and 45,000 g / mol, respectively.

Experimental Example  2: Polymeric Thermal stability  analysis

The thermal stability of the polymers synthesized according to Examples 2 to 4 was evaluated using thermal gravity analysis (TGA) under a nitrogen atmosphere. Allyl-TFB05 showed excellent thermal stability showing a mass loss of less than 5% up to 400 ° C. The TGA thermogram of allyl-TFB05 is shown in Fig. In addition to thermal stability, thermal properties of allyl-TFB05 were confirmed using DSC. The measurement was carried out at 30 DEG C to 250 DEG C at a heating or cooling rate of 10 DEG C / min. The procedure was repeated twice, and the results are shown in Fig.

As shown in Fig. 11, no special heat transfer or thermal reaction was observed during the measurement. These thermal characterization results show that allyl-TFB05 is thermally stable and does not involve thermal crosslinking up to 250 ° C.

Example  7: Allyl- TFB05 of Light bridging

Allyl-TFBO5 synthesized in Examples 2 to 4 and pentaerythritol tetrakis (3-mercaptopropionate) as a crosslinking agent were prepared in the same manner as in Example 2, -mercaptopropionate) and Irgacure 369 as an initiator were dissolved in chlorobenzene to a total concentration of 0.5% by weight at a weight ratio of 100: 0.94: 0.056. The HTL solution was spin-coated at 2500 rpm for 30 seconds and irradiated with UV (intensity> 20 mW / cm ² at 254 nm) for a certain period of time.

Example  8: Allyl- PTPA12 of Light bridging

Containing allyl-PTPA12 To prepare the photocrosslinkable HTL solution, allyl-PTPA12 synthesized in accordance with Example 6 above was used in place of allyl-TFB05, and pentaerythritol tetrakis (3 (mercaptopropionate) (3 -mercaptopropionate) as a polymerization initiator and Irgacure 369 as an initiator in a weight ratio of 100: 4.87: 0.29 so as to have a total concentration of 0.5% by weight, to prepare photolyzed allyl-PTPA12.

Experimental Example  3: Photocrosslinked  Allyl- TFB05 Solvent resistance

For multi-layer OLED manufacturing by solution process, it is particularly important that the HTL material is solvent resistant. Therefore, in this Experimental Example, a novel photo-crosslinkable allyl-TFB05 polymer containing an allyl group containing an allyl group was synthesized, and after the photo-crosslinking of the polymer, solvent resistance was confirmed by UV-Vis absorption spectroscopy. In this experiment, the solvent resistance was defined as the ratio of the maximum absorbance of the film after solvent rinsing to the maximum absorbance of the photo-crosslinked film before solvent rinse.

First, the present inventors confirmed the dependence of the solvent resistance of the photopolymerizable HTL film containing allyl-TFB05 on the UV irradiation time. A film for analysis was prepared by spin-coating an HTL solution composed of the novel photo-crosslinkable allyl-TFBO5, pentaerythritol tetrakis (3-mercaptopropionate) and Irgacure 369 synthesized according to Examples 2 to 4 in chlorobenzene . After irradiating UV and measuring the maximum absorbance before solvent rinse, the irradiated film was soaked in chlorobenzene and the soluble portion of the film was washed away. At this time, solvent resistance was confirmed by the above-described method while changing the UV irradiation time to 240 seconds (5, 10, 30, 60, 120, 180 and 240 seconds). 12A to 12C show the result of solvent resistance measurement according to the UV irradiation time.

As shown in Figs. 12A and 12B, when the film was irradiated with UV for 30 seconds, the solvent resistance was about 70%. However, when the film was irradiated with UV for 180 seconds, the solvent resistance exceeded 95%. The absorption spectrum of the film irradiated for 180 seconds showed almost no change even after rinsing with the solvent chlorobenzene (Fig. 12B). Figure 12C shows solvent resistance plots for different UV exposure times from 0 to 240 seconds each. As the irradiation time increased from 0 to 120 seconds, the solvent resistance increased sharply. On the other hand, after 120 seconds, it gradually increased until the maximum value was reached. The absorption spectrum before and after rinsing of the HTL film containing allyl-TFBO5 irradiated with UV for different times is shown in Fig.

Experimental Example  4: Photocrosslinked  Allyl- PTPA12 Solvent resistance

An HTL film containing allyl-PTPA12 photocrosslinked was prepared in the same manner as in Experimental Example 3, except that allyl-TFB05 was used instead of allyl-TFB05. The HTL film was irradiated with ultraviolet rays for 30 seconds and 180 seconds, The absorption spectrum measured before and after rinsing is shown in Fig. As shown in FIGS. 14A and 14B, the solvent resistance of the HTL film comprising photo-crosslinked allyl-PTPA12 prepared by UV irradiation for 30 seconds was about 88%, the solvent resistance of the film prepared by UV irradiation for 180 seconds Was 93%. This indicates that allyl-PTPA12 is also photo-crosslinkable and thus solvent resistant.

Experimental Example  5: Allyl- TFB05 On by Optical patterning

Photocrosslinkable materials can also be used for fine patterning, which is usually difficult to achieve with thermally crosslinked materials. Thus, in this Experimental Example, the optical patterning ability of the photo-crosslinkable allyl-TFB05 synthesized according to Examples 2 to 4 was confirmed. The photocrosslinkable HTL system of the present invention acted as a negative photoresist, leaving the irradiated areas of the film after development (developing a.k.a. solvent rinsing) and the unirradiated areas removed. An example of such optical patterning is shown in Fig.

15A is an optical microscope image of allyl-TFBO5 film photopatterned using a line-patterned photo-mask, and Fig. 15B is an enlarged image of the same specimen. A fine line pattern having a narrow line width of about 5 mu m was successfully formed by optical patterning. This result indicates that allyl-TFB05 can be easily patterned by photo-crosslinking, which is an additional advantage of the novel photo-crosslinked HTL system of the present invention.

Experimental Example  6: Allyl- TFB05 Electrochemical characteristics of

The electrochemical properties of allyl-TFB05 newly synthesized according to Examples 2 to 4 were confirmed by cyclic voltammetry (CV). Allyl-TFB05 was dissolved in a 0.1 M methylene chloride (MC) solution containing tetrabutylammonium hexafluorophosphate as a supporting electrolyte. Two platinum electrodes were used as the working electrode and the counter electrode, respectively, and Ag / Ag ⁺ was used as the reference electrode. Dislocations were calibrated against the primary oxidation potential of ferrocene. In order to calculate the highest occupied molecular orbital (HOMO) energy level of allyl-TFBO5, N, N'-bis (3-methylphenyl) -bis (N, N'-bis (3-methylphenyl) -bis (phenyl) -benzidine (TPD) was used. The cyclic voltammogram of allyl-TFBO5 and TPD is shown in Fig.

In the cyclic voltammetry experiment, TPD showed two distinct reversible oxidation peaks during the oxidation scan, and the primary oxidation potential of TPD was 280 mV for Fc / Fc ⁺ . In addition, the newly synthesized allyl-TFB05 of the present invention exhibited a pronounced reversible oxidation peak with a primary oxidation potential of 353 mV with respect to Fc / Fc ⁺ . This is very similar to TPD, a typical HTL material in OLEDs. From the difference of 73 mV, the HOMO energy level of allyl-TFB05 was calculated to be -5.47 eV. The optical bandgap of the allyl-TFB05 of the present invention was calculated to be 2.88 eV from the starting value (431 nm) of the UV-Vis absorption spectrum of the film state (Fig. 12). Next, the lowest unoccupied molecular orbital (LUMO) energy level of allyl-TFBO5 was calculated to be -2.59 eV based on the HOMO energy level and the optical band-gap. Thus, the HOMO and LUMO energy levels of the allyl-TFBO5 very close to the value of TPD indicate that the allyl-TFBO5 of the present invention can act as a potential HTL material in OLEDs.

Example  8: Photocrosslinked  Allyl- TFB05 Containing OLED  Device fabrication

First, ITO (indium tin oxide; In 2 O 3 / SnO 2) was further processed to a substrate by UV / ozone-washed, each for 30 minutes with acetone and isopropanol. PEDOT: PSS (Clevios AI4083) solution was spin-coated on the ITO substrate at 4000 rpm for 30 seconds and then treated at 150 ° C for 30 minutes to remove residual moisture to obtain a 30 nm thick layer. In the case of an HTL-containing device, an HTL solution containing allyl-TFBO5 was prepared, spin-coated, and irradiated with UV for a certain period of time to prepare HTL as in the above-mentioned method of producing a crosslinked HTL. And washed with chlorobenzene before performing the next step. The light emitting layer (EML) solution was prepared by dissolving Ir (mppy) ₃ and 26DCzPPy (weight ratio of 7: 93, respectively) in 1,2-dichloroethane to a total concentration of 0.64 wt%. The EML was spin coated with the EML solution at 1800 rpm for 30 seconds and baked at 60 DEG C for 30 minutes to give a thickness of 40 nm. TPBi, CsF and aluminum electrodes were deposited by vacuum thermal evaporation to a thickness of 57 nm, 1 nm and 150 nm, respectively. The deposition rates were 0.5 Å / sec, 0.1 Å / sec and 5 Å / sec, respectively. After the vacuum deposition was completed, the OLED device was finally encapsulated with a cover glass in a glove box in a nitrogen atmosphere.

Experimental Example  7: Photocrosslinked  Allyl- TFB05 Containing OLED  Features of the device

The arrangement of [ITO / PEDOT: PSS / (crosslinked allyl-TFB05) / 26DCzPPy: Ir (mppy) ₃ / TPBi / CsF / Al] was used to verify the usefulness of the novel photo- Were fabricated and evaluated.

First, an HTL solution containing allyl-TFBO5, pentaerythritol tetrakis (3-mercaptopropionate) and Irgacure 369 was spin-coated on a pre-coated PEDOT: PSS layer and irradiated with UV light. To investigate the effect of UV irradiation time on the final OLED device performance, different UV exposure times of 30 and 180 seconds, respectively, were applied. (9H-carbazol-9-yl) pyridine (2,6-bis (3- (9H- phenyl) pyridine (26DCzPPy) and Ir (mppy) ₃ as a dopant were also spin-coated onto the previously coated HTL. An electron transport layer (ETL), an electron injection layer (EIL) and a cathode were successively formed by vacuum thermal deposition. Hereinafter, an OLED device including HTL photocrosslinked by UV irradiation for 30 seconds is referred to as " Device-1 ", and another device manufactured by irradiation for 180 seconds is referred to as "Device-2 ". The energy level diagram of the OLED devices of the present invention having the above arrangement is shown in Fig.

The current density-voltage (J-V) and brightness-voltage (L-V) characteristics of the devices are shown in FIGS. 18A and 18B, respectively. Table 1 summarizes the characteristics of the OLED device.

On voltage
(V) Driving voltage
(V) Luminous efficiency
(cd / A) Power efficiency
(lm / W) Luminous efficiency
(cd / A) Power efficiency
(lm / W) at 1 nit at 1000 nit at Max Device-1 3.1 5.3 29.9 19.3 31.4 21.8 Device-2 3.7 7.4 25.0 11.8 27.6 15.6 Device-3 4.1 6.4 18.6 10.0 19.8 12.2 Device-4 4.0 5.6 23.4 14.5 23.5 14.8

As shown in Table 1, there was a large difference in device characteristics depending on the UV irradiation time of the HTL. Device-1 with shorter UV exposure times exhibited lower operating voltages and higher brightness than Device-2 with longer UV exposure times. In the case of the device-1, the maximum brightness efficiency (31.4 cd / A) and the power efficiency (21.8 lm / W) were also higher (Fig. 18C). To investigate the cause of this difference, we first measured the work-function of the HTL film with atmospheric photoelectron spectroscopy using Riken AC-2 (FIG. 19). All of the HTL films exhibited almost the same work function values. Specifically, it was 5.39 eV for 30 second UV irradiation and 5.41 eV for 180 second UV irradiation, and this difference can be regarded as being within the measurement error range. From this, it was confirmed that the hole injection barrier from the anode side to HTL and EML was the same for the two HTLs. Next, the present inventors investigated the hole transporting property of the HTL film through hole-only device characteristic analysis (FIG. 20). In contrast to the two HTLs having similar work function values, the current-voltage characteristics were significantly different. In the case of UV irradiation for 30 seconds, more current was passed through the HTL film in the same applied electric field, and these results were similar for the J-V characteristics of OLED devices. This shows that the hole transporting property of the photo-crosslinked HTL film of the present invention can be changed according to the UV irradiation time. In fact, when the UV irradiation time increased from 30 seconds to 180 seconds, the hole transporting properties were somewhat deteriorated. It is believed that such a change in the hole transporting property causes a difference in the device characteristics of the final OLED device.

In addition to the OLED devices (device-1 and device-2) containing the above-mentioned photo-crosslinked HTL, an OLED device containing no HTL was prepared and used as a negative control group. In addition, an OLED device including an HTL composed only of TFB without an allyl group instead of allyl-TFB05 was prepared and used as a positive control group, which was named "Device-4 ".

As shown in Figure 18, Device-1 exhibited reduced operating voltage and improved device performance as compared to the negative control device (Device-3) that did not contain HTL. In addition, it was confirmed that the performance of the device 1 of the present invention in which the photocrosslinking was also superior to the device 4 which is a positive control group including HTL not crosslinked. All four devices exhibited the same electroluminescence (EL) spectrum independent of HTL, indicating that exciton formation only occurs within the EML. These OLED device results for Device-1 through Device-4 demonstrate the superior device performance of Device-1 comprising the novel photo-crosslinked HTL of the present invention. Further, the driving voltage (5.3 V) and the device efficiency (19.3 lm / W) of device-1 at a brightness of 1,000 cd / m ² were compared with the recent results 5.2 V and 16.0 lm / W; Org. Electron., 2009, 10: 189). Specifically, it has been confirmed that higher drive efficiency can be achieved with a similar drive voltage. From this, it has been confirmed that "thiol-ene" photo-crosslinking is a feasible way of implementing a multilayer structure in an OLED produced by a solution process.

Example  9: Photocrosslinked  Allyl- PTPA12 Containing OLED  Device fabrication

(ITO / PEDOT: PSS / (crosslinked allyl-PTPA12) / 26DCzPPy: Ir (mppy) ₃ (Tyr) was prepared in the same manner as in Example 8, except that allyl-PTPA12 was used instead of allyl- / TPBi / CsF / Al] was fabricated.

Experimental Example  8: Photocrosslinked  Allyl- PTPA12 Containing OLED  Features of the device

(ITO / PEDOT: PSS / (crosslinked allyl-PTPA12) / 26DCzPPy: Ir (mppy) ₃ prepared according to the above Example 9 to confirm the usefulness of the photocrosslinked HTL system containing allyl- / TPBi / CsF / Al]. ≪ / RTI >

OLED devices including allyl-PTPA12 photocrosslinked by UV irradiation for 30 seconds were called "Device-5 ", OLED devices including allyl-TFB05 prepared in the same manner as" OLED device was manufactured in the same way except that it was referred to as "device-3 ".

The current density-voltage (J-V), brightness-voltage (L-V) and power efficiency-voltage (P-V) characteristics of the devices are measured and shown in FIGS. 21A, B and C, respectively.

Further, the characteristics of the OLED device are compared and analyzed and are shown in Table 2 below.

On voltage
(V) Driving voltage
(V) Luminous efficiency
(cd / A) Power efficiency
(lm / W) Luminous efficiency
(cd / A) Power efficiency
(lm / W) at 1 nit at 1000 nit at Max Device-1 ' 3.7 6.9 26.1 13.2 28.1 16.2 Device-3 ' 4.4 8.6 18.1 7.4 21.3 11.3 Device-5 3.3 5.9 21.1 12.5 23.5 17.7

As shown in Table 2 above, Device-5, which is an OLED device including photolyzed allyl-PTPA12 according to Example 6, has a hole transporting site according to Example 4, 1 ', which is an OLED device including a crosslinked allyl-TFB05, and thus the maximum luminous efficiency of the device-5 is somewhat lower than that of the device-1' And that it was further improved in terms of power efficiency. This indicates that the performance of the HTL-equipped OLED, which is finally manufactured, can be controlled by controlling the presence, type, and content of the skeleton forming portion to constitute the HTL.

Claims (19)

From 0 to 99 mol% of a first unit material comprising a first hole transporting fragment and from 1 to 100 mol% of a second unit material comprising at least one double bond capable of crosslinking including a second hole transporting moiety, A hole transporting material comprising a polymer; And a crosslinking agent containing at least two thiol groups. The hole transporting layer (HTL)
The method according to claim 1,
Wherein the first hole transporting moiety and the second hole transporting moiety are the same.
The method according to claim 1,
Wherein the first monomer unit is derived from a first monomer, the second monomer unit is derived from a second monomer,
Wherein the second monomer is modified to include a cross-linkable double bond.
The method according to claim 1,
Wherein the first hole transporting moiety and the second hole transporting moiety each independently comprise a tertiary amine structure substituted with at least one aryl group.
The method according to claim 1,
Wherein the composition is cross-linked by light or heat.
The method according to claim 1,
Wherein the composition further comprises a radical initiator.
The method according to claim 6,
The radical initiator may be 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl- 369), 1-hydroxycyclohexyl phenyl ketone, Irgacure 184, 2,2-dimethoxy-2-phenyl-acetophenone, Irgacure 651 ), 2-isopropoxy-2-phenylacetophenone (Vicure 30), diphenyl- (2,4,6-trimethylbenzoyl) -phosphinic oxide , 6-trimethylbenzoyl) -phosphine oxide, Chivacure TPO), benzophenone, 4'-tertiarybutyl-2,2,2-trichloroacetophenone (4 ' 2-trichloroacetophenone, Trigonal P1), 2-isopropylthioxanthone, Genocure ITX, 2,2'-azobis (2-methylpropionitrile) ≪ / RTI > and benzoyl peroxide.
The method according to claim 1,
The cross-

,

,

,

,

,

,

And

≪ / RTI >
The method according to claim 1,
Wherein the composition further comprises a solvent.
10. The method of claim 9,
Wherein the solvent is selected from the group consisting of chlorobenzene, dichlorobenzene, trichlorobenzene, chloroform, dichloroethane, methoxybenzene, toluene, xylene, trimethylbenzene and tetrahydronaphthalene.
A method of manufacturing an organic semiconductor device comprising at least one organic layer stacked,
A first step of applying a first organic layer comprising a first organic semiconductor material containing two or more crosslinkable double bonds and a crosslinking agent containing two or more thiol groups;
A second step of applying light or heat to crosslink;
And a third step of applying a second organic layer composition in a solution form onto the formed first organic layer.
A method of manufacturing an organic semiconductor device.
12. The method of claim 11,
And light is applied through the photomask in the second step to selectively crosslink the desired pattern.
13. The method of claim 12,
Further comprising the step of removing the unreacted sites by washing with a solvent prior to the third step.
12. The method of claim 11,
The organic semiconductor device is an organic light emitting device,
The first and second organic layers may each independently have a hole injection layer (HIL), a hole transport layer, an emission layer (EML), an electron transport layer (ETL), and an electron injection layer ; EIL). ≪ / RTI >
12. The method of claim 11,
The first organic layer composition may be formed by independently introducing two or more double bonds capable of crosslinking into an organic semiconductor material selected from the group consisting of a hole injecting material, a hole transporting material, an organic light emitting material, an electron transporting material and an electron injecting material ≪ / RTI > material.
12. The method of claim 11,
Wherein the second organic layer composition independently comprises at least two organic semiconductor materials selected from the group consisting of a hole injecting material, a hole transporting material, an organic light emitting material, an electron transporting material and an electron injecting material or a double bond capable of crosslinking thereto Lt; RTI ID = 0.0 > 1, < / RTI >
17. The method according to claim 15 or 16,
Wherein the hole transport material is a polymer or a vacuum deposition type low molecular material.
18. The method of claim 17,
Wherein the polymer hole transport material is a polymer comprising a tertiary amine structure substituted with at least one aryl group acting as a hole transport site.
18. The method of claim 17,
The vacuum deposition type low molecular weight hole transport material
1) 4,4 ', 4 "-tris (N-carbazolyl) -triphenylamine (4,4', 4"
2) Preparation of 1,1-bis (4- (N, N'-di (p-tolyl) amino) phenyl) cyclohexane ) phenyl cyclohexane; TAPC),
3) 4,4 ', 4 "-tris (3-methylphenylphenylamino) triphenylamine (m-MTDATA), 4,4'
4) DATA,
5) TFV-TCTA,
6) 1,3-bis (N-carbazolyl) benzene,
7) 4,4'-bis (N-carbazolyl) -1,1'-biphenyl (4,4'-bis
8) 1,4-bis (diphenylamino) benzene, 1,4-bis
9) Synthesis of 4,4'-bis (3-ethyl-N-carbazolyl) -1,1'-biphenyl ,
10) N, N'-bis (3-methylphenyl) -N, N'-diphenylbenzidine,
11) N, N'-bis (phenanthren-9-yl) -N, N'-bis (phenyl) phenyl) -benzidine),
12) Copper (II) phthalocyanine (copper (II) phthalocyanine),
13) 4- (dibenzylamino) benzaldehyde-N, N-diphenylhydrazone,
14) 4- (Dimethylamino) benzaldehyde diphenylhydrazone (4- (dimethylamino) benzaldehyde diphenylhydrazone),
15) Synthesis of 2,2'-dimethyl-N, N'-di - [(1-naphthyl) -N, N'-diphenyl] -1,1'- 2'-dimethyl-N, N'-di - [(1-naphthyl) -N, N'- diphenyl] -1,1'-biphenyl-4,4'-
16) Synthesis of 9,9-dimethyl-N, N'-di (1-naphthyl) -N, N'-diphenyl-9H-fluorene- -di (1-naphthyl) -N, N'-diphenyl-9H-fluorene-2,7-diamine),
17) Synthesis of N, N'-di- [(1-naphthyl) -N, N'-diphenyl] (1-naphthyl) -N, N'-diphenyl] -1,1'-biphenyl) -4,4'-diamine),
18) 4- (diphenylamino) benzaldehyde diphenylhydrazone, 4- (diphenylamino) benzaldehyde diphenylhydrazone,
19) N, N'-diphenyl-N, N'-di-p-tolylbenzene-1,4- diamine),
20) Diffie la Gino [2,3- f: 2 ', 3' -h] quinoxaline -2,3,6,7,10,11- hexahydro-carbonitrile saline (dipyrazino [2,3- f: 2' , 3'-h] quinoxaline-2,3,6,7,10,11-hexacarbonitrile),
N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (N, N'- N'-bis [4- [bis (3-methylphenyl) amino] phenyl] -N, N'- diphenyl- [1,1'-biphenyl] -4,4'-
22) N, N, N ', N'-tetrakis (4-methoxyphenyl) benzidine,
23) N, N, N ', N'-tetrakis (3-methylphenyl) -3,3'-dimethylbenzidine dimethylbenzidine),
24) N, N, N ', N'-tetrakis (2-naphthyl) benzidine,
25) tetra-N-phenylbenzidine,
26) N, N, N ', N'-tetraphenylnaphthalene-2,6-diamine,
27) Tin (IV) 2,3-naphthalocyanine dichloride (tin (IV) 2,3-naphthalocyanine dichloride)
28) titanyl phthalocyanine,
29) tris [4- (diethylamino) phenyl] amine, tris [4-
30) 1,3,5-tris (diphenylamino) benzene, 1,3,5-tris (diphenylamino) benzene,
31) 1,3,5-tris (2- (9-ethylcarbazyl-3) ethylene) benzene), 1,3,5-
32) 1,3,5-tris [(3-methylphenyl) phenylamino] benzene, 1,3,5-tris [
33) 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine), 4,4'
34) 4,4 ', 4 "-tris [phenyl (m-tolyl) amino] triphenylamine and 4,4'
35) tri-p-tolylamine. ≪ / RTI >

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