KR102076855B1 - thermal polymerization type hole transport material with high molecular weight and organic light emitting diode using the same - Google Patents

Abstract

The present invention relates to a polymer type heat crosslinked hole transport material and a high efficiency organic light emitting diode for a solution process prepared through the same. When the hole transport layer is formed of the polymer type heat crosslinked hole transport material according to the present invention, the hole transport layer is heat After crosslinking, the interface is not dissolved because it is substantially insoluble in the solvent, and there is no intermixing even when the light emitting layer is laminated using a solution process on the top, so that an organic light emitting diode (OLED) having a multi-layer structure can be effectively produced and thermal crosslinking Since it is carried out at a relatively low temperature of 50 ~ 150 ℃, it can be used in the process of applying a plastic substrate with a low glass transition temperature in addition to the glass substrate.

Description

Thermopolymer type hole transport material with high molecular weight and organic light emitting diode using the same

The present invention relates to a hole transport thin film made of a heat crosslinkable hole transport material and an organic light emitting diode using the same, and more particularly, to a polymer type heat crosslinked hole transport material and a high efficiency organic light emitting diode for a solution process prepared therefrom.

 Organic light emitting diodes (OLEDs) have a simpler manufacturing process compared to displays such as LCDs and PDPs, have a wide viewing angle in high quality, high color purity, low power consumption, and low voltage driving. It has the advantages of being attracting attention as the next generation display.

 In general OLEDs, an anode is formed on a substrate, and an organic layer includes a hole transport layer, an electron transport layer, and the like on the anode, and may have a structure in which cathodes are sequentially formed thereon. However, existing processes for fabricating OLEDs use vacuum deposition of all layers. In the case of vacuum deposition, it is disadvantageous in that it is not suitable for mass production in terms of time, cost, and quantity, and has a large limitation in large area.

 Therefore, from this point of view, the vacuum deposition method needs to be improved, and the solution process is drawing attention as an alternative. However, when the OLED is manufactured using a solution process, intermixing occurs in the process of laminating the organic layer, the purity of the material, and deterioration of the other layer material due to a high temperature heat treatment (crosslinking reaction, etc.) process. Its characteristics are lower than that of the deposition method, and in particular, its life is low. Therefore, researches on various solution process materials and processes are being actively conducted, but the above problems have not been completely solved yet.

In general, a method of stacking organic materials using a solution process is divided into two types. The first method is to select the solvents used to dissolve the material to be laminated to the two layers as non-melting types. For example, when the lower layer is dissolved in water / alcohols to form a film, and the upper layer is melted and laminated in a general organic solvent, intermixing may be reduced. The second method is to crosslink the lower layer. Crosslinking significantly reduces the dissolution and melting properties, thus reducing the interaction with the solvent in the upper layer.

Currently developed organic light emitting diode materials using crosslinking are classified according to the type of crosslinking agent, such as siloxanes, styrenes, acrylates, and trifluorovinyl ethers. , Benzocyclobutenes, cinnamates / chalcones, and oxetanes. However, when fabricating an organic light emitting diode using a material containing these crosslinking agents, a process temperature is 200 ° C or higher or a long time is required, and a chemical structure that can act as a trap through unreacted and side reactions, or by using an initiator or the like is used. It has the disadvantage of leaving a substance which adversely affects the properties. If an unnecessary structure or material is included in the organic light emitting diode, the lifespan and efficiency characteristics are significantly reduced. If the process temperature is too high, it may also have a limited effect on the selection of the substrate material. Therefore, there is a need for an organic light emitting diode material using crosslinking to solve such problems.

1. Republic of Korea Patent Publication No. 10-2014-0069568 2. Republic of Korea Patent Publication No. 10-2013-0074815

The first problem to be solved by the present invention is to improve the disadvantages and problems of the prior art as described above, to provide a thermal crosslinkable hole transport material of a novel molecular structure.

Furthermore, a second object of the present invention is to provide an organic light emitting diode comprising the thermally crosslinkable hole transport material.

In addition, a third object of the present invention is to provide a method of manufacturing the organic light emitting diode.

However, the problem to be solved by the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the first object, the present invention comprises at least one polymer or a low molecular unit comprising an amine selected from the group consisting of the following formula (1), (2), and (3), (4), (5) and (6) At least one polymer or low molecular unit comprising a tertiary alcohol selected from the group is a condensation polymerization and crosslinked polymeric thermocrosslinked hole transport material, at least one of a compound comprising an amine or a compound comprising a tertiary alcohol Provides a polymer type heat crosslinkable hole transport material characterized in that the polymer.

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Formula 1 to Formula 6,

Ar ¹ to Ar ⁴ are independently a substituted or unsubstituted C ₃ -C ₃₀ aryl group, heteroaryl group, arylalkyl group or alkylaryl group,

R and R ¹ to R ⁶ are Independently of each other a substituted or unsubstituted C ₁ -C ₉ alkyl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C _6- C ₃₀ alkylaryl group, substituted or unsubstituted C ₆ -C ₃₀ arylalkyl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted From the group consisting of a substituted arylamine, a substituted or unsubstituted fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide and sulfone group Selected,

CoM is a comonomer,

A is carbon or silicon hybridizing with sp ³ ,

m and n are each an integer of 5 to 200,

o is an integer from 0 to 10,

p is an integer from 2 to 10,

x, y and z are each an integer from 0 to 10)

More preferably, Ar ¹ to Ar ⁴ are each independently a non-fused ring aromatic substituent consisting of benzene, pyridine, pyrrole, furan and thiophene; Hetero fused ring aromatic substituents; Fused ring aromatic substituents consisting of naphthalene, anthracene, triphenylene, pyrene and perylene; And a dibenzo type fused ring substituent consisting of carbazole, fluorene, dibenzofuran, dibenzothiophene and spirofluorene,

R and R ¹ to R ⁶ are each independently a substituted or unsubstituted C ₁ -C ₄ alkyl group, a substituted or unsubstituted C ₅ -C ₁₂ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl Group, substituted or unsubstituted C ₆ -C ₁₂ alkylaryl group, substituted or unsubstituted C ₆ -C ₁₂ arylalkyl group, substituted or unsubstituted C ₃ -C ₁₂ heteroaryl group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted arylamine, substituted or unsubstituted fused arylamine group, substituted or unsubstituted phosphine or phosphine oxide group, substituted or unsubstituted thiol group, substituted or unsubstituted Selected from the group consisting of sulfoxide and sulfone groups,

CoM is a comonomer,

A is carbon or silicon hybridizing with sp ³ ,

m and n are each an integer of 5 to 100,

o is an integer from 0 to 5,

p is an integer from 2 to 5,

x, y and z may each be an integer of 0-5.

More preferably, the compound comprising the amine of Formula 1 or Formula 2 has a reactive hydrogen at the ortho or para position of the benzene group, the reactive hydrogen being equal to or greater than the number of OH groups of the compound comprising the tertiary alcohol. There can be many.

More preferably, the heat crosslinkable hole transport material may be a polymer having a molecular weight of 2000 or more.

In order to achieve the second object, the present invention

Board;

A first electrode on the substrate;

A second electrode on the first electrode; And

An organic light emitting diode comprising: a first layer interposed between the first electrode and the second electrode and including the thermally crosslinkable hole transport material.

More preferably, the first layer may be a hole transport layer.

More preferably, the organic light emitting diode may further include a light emitting layer formed on the first layer.

In order to achieve the third object, the present invention

Forming a first electrode on the substrate;

At least one polymer or low molecular unit compound comprising an amine selected from the group consisting of Formula 1, Formula 2, and Formula 3 on the first electrode, and 3 selected from the group consisting of Formulas 4, 5 and 6 At least one polymer or low molecular unit compound containing a primary alcohol is placed in a solvent, the first layer-forming composition containing an acid catalyst is formed through a solution process, and thermally crosslinked by heat crosslinking under conditions capable of crosslinking. Forming a first layer comprising a hole transport material; And

Forming a second electrode on the first layer;

At least one of a compound containing an amine or a compound containing a tertiary alcohol provides a method for producing an organic light emitting diode, characterized in that the polymer.

More preferably, the solvent may be selected from the group consisting of chlorobenzene, toluene, xylene, chloroform and tetrahydrofuran.

More preferably, the acid catalyst is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, benzoic acid, benzoic acid, carbonic acid. , Fluoroacetic acid, Difluoroacetic acid, Trifluoroacetic acid, Trifluoroacetic acid, Chloroacetic acid, Dichloroacetic acid, Trichloroacetic acid, Iso It can be selected from the group consisting of isobutyric acid, HF, HCl, HBr, HI, sulfuric acid and Lewis acid.

More preferably, the solution process may be selected from the group consisting of spin coating, ink jet coating and nozzle jet coating.

More preferably, the thermal crosslinking may be performed at a low temperature of 50 ~ 150 ℃.

More preferably, the first layer may be a hole transport layer.

More preferably, the first layer may be substantially insoluble in a solvent after thermal crosslinking.

When the hole transport layer is formed of a heat crosslinkable hole transport material according to the present invention, the hole transport layer is substantially insoluble in a solvent after thermal crosslinking, so that the interface does not melt, and even though the light emitting layer is laminated using a solution process on the top, the interlayer mixing is performed. In this case, an organic light emitting diode (OLED) having a multilayer structure can be produced effectively. Therefore, instead of the OLED display process method that is currently limited to the vacuum deposition method, it is possible to implement a more stable multi-layer OLED by using an effective solution process in terms of time and cost.

Since the heat crosslinkable hole transport material according to the present invention performs heat crosslinking at a relatively low temperature of about 100 ° C., it may be used in a process of applying a plastic substrate having a low glass transition temperature in addition to the glass substrate. In addition, since the remaining by-products and additives are small after the film formation, it has the advantage of excellent life and efficiency.

Although the present invention focuses on the hole transport layer, there is a possibility of implementing a cross-linked light emitting layer and an electron transport layer through the change of the monomer in the chemical formula structure according to the present invention. Therefore, at present, it is partly a method of manufacturing OLED using a solution process, but through the future improvement will be able to implement the OLED using the entire process as a solution process.

The technical effects of the present invention are not limited to those mentioned above, and other technical effects which are not mentioned will be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view showing an organic light emitting diode according to an embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings in order to describe the present invention in more detail. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Like numbers refer to like elements throughout the specification.

When an element such as a layer, region or substrate is referred to as being on another component "on", it will be understood that it may be directly on another element or there may be an intermediate element in between. .

Although the terms first, second, etc. may be used to describe various elements, components, regions, layers, and / or regions, such elements, components, regions, layers, and / or regions It will be understood that it should not be limited by these terms.

Unless defined otherwise in the present specification, "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds. Alternatively, the alkyl group may be an "unsaturated alkyl group" containing at least one double bond or triple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight chain or cyclic. The alkyl group may be a C ₁ to C ₃₀ alkyl group. More specifically, the alkyl group may be a C ₁ to C ₁₀ alkyl group or a C ₁ to C ₆ alkyl group. For example, the C ₁ -C ₄ alkyl group can be selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl.

In addition, "cycloalkyl group" means a C3-C20 cyclic saturated hydrocarbon group unless it is specifically defined in this specification. Specifically, the cycloalkyl group includes a cycloalkyl group having 3 to 6 carbon atoms. As a specific example of the said cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned.

In addition, unless specifically defined herein, "aryl group (Ar)" means a carbocycle aromatic radical having 6 to 20 carbon atoms including at least one ring, and the rings are attached together by a pendant method or Or may be fused. Specifically, the aryl group includes an aryl group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group or a biphenyl group.

Moreover, unless specifically defined in this specification, an "arylalkyl group" means the functional group (Ar-Ra-) by which the linear or branched alkyl group (Ra) was substituted by the aryl group (Ar) which is an aromatic hydrocarbon group. Specifically, the arylalkyl group includes an arylalkyl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms. Specific examples of the arylalkyl group include benzyl group, phenethyl group and the like.

Moreover, unless specifically defined in this specification, an "alkylaryl group" means the functional group (Ra-Ar-) by which the aromatic hydrocarbon group (Ar) was substituted by the linear or branched alkyl group (Ra). Specifically, the alkylaryl group includes an alkylaryl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms.

In addition, unless specifically defined herein, "aryloxy group" means an aryl group (-OAr) bonded to oxygen, wherein the aryl group is as defined above. Specifically, the aryloxy group includes an aryloxy group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryloxy group include phenoxy and the like.

In addition, unless specifically defined herein, a "heteroaryl group" contains at least one hetero atom selected from the group consisting of N, O, S, Se, and P in at least one ring, and the remaining members It means a monocyclic aromatic compound which is carbon or a polycyclic aromatic compound consisting of fused aromatic rings.

In addition, when it is described in this specification as "C _x -C _y ", it should be interpreted that it also has the case where it has carbon number of the number corresponding to all the integers between carbon number x and carbon number y.

Thermal crosslinking  Hole transport material

The present invention is a material constituting the hole layer, comprising at least one polymer or low molecular unit comprising an amine selected from the group consisting of the following formula (1), (2) and (3), and (4), (5) and (6) At least one polymer or low molecular unit comprising a tertiary alcohol selected from the group provides a polymeric thermocrosslinked hole transport material condensation polymerization and crosslinking.

In this case, at least one of the compound containing the amine or the compound containing the tertiary alcohol is characterized in that the polymer.

(In Formula 1 to Formula 6,

Ar ¹ to Ar ⁴ are independently a substituted or unsubstituted C ₃ -C ₃₀ aryl group, heteroaryl group, arylalkyl group or alkylaryl group,

R and R ¹ to R ⁶ are Independently of each other a substituted or unsubstituted C ₁ -C ₉ alkyl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C _6- C ₃₀ alkylaryl group, substituted or unsubstituted C ₆ -C ₃₀ arylalkyl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted From the group consisting of a substituted arylamine, a substituted or unsubstituted fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide and sulfone group Selected,

CoM is a comonomer,

A is carbon or silicon hybridizing with sp ³ ,

m and n are each an integer of 5 to 200,

o is an integer from 0 to 10,

p is an integer from 2 to 10,

x, y and z are each an integer from 0 to 10)

Preferably,

Ar ¹ to Ar ⁴ are each independently a non-fused ring aromatic substituent consisting of benzene, pyridine, pyrrole, furan and thiophene; Hetero fused ring aromatic substituents; Fused ring aromatic substituents consisting of naphthalene, anthracene, triphenylene, pyrene and perylene; And a dibenzo type fused ring substituent consisting of carbazole, fluorene, dibenzofuran, dibenzothiophene and spirofluorene,

R and R ¹ to R ⁶ are each independently a substituted or unsubstituted C ₁ -C ₄ alkyl group, a substituted or unsubstituted C ₅ -C ₁₂ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl Group, substituted or unsubstituted C ₆ -C ₁₂ alkylaryl group, substituted or unsubstituted C ₆ -C ₁₂ arylalkyl group, substituted or unsubstituted C ₃ -C ₁₂ heteroaryl group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted arylamine, substituted or unsubstituted fused arylamine group, substituted or unsubstituted phosphine or phosphine oxide group, substituted or unsubstituted thiol group, substituted or unsubstituted Selected from the group consisting of sulfoxide and sulfone groups,

CoM is a comonomer,

A is carbon or silicon hybridizing with sp ³ ,

m and n are each an integer of 5 to 100,

o is an integer from 0 to 5,

p is an integer from 2 to 5,

x, y and z may each be an integer of 0-5.

In this case, the compound including the amine in at least one of Formula 1 to Formula 3 has a reactive hydrogen in the ortho or para position of the benzene group, the reactive hydrogen is equal to or greater than the number of OH groups of the compound containing tertiary alcohol There can be many.

More preferably, the heat crosslinkable hole transport material may be a polymer having a molecular weight of 2000 or more.

The structure of the amine monomer in the polymer of the general formula (1) of the present invention can be used as a specific example, the structures of the following formula 1-1 to formula 1-12, but is not limited thereto. In the polymer of Formula 1 according to the present invention, hydrogen capable of an electrophilic substitution reaction may be present at an ortho or para position of a benzene substituent.

The structure of the amine monomer in the polymer of the formula (2) of the present invention can be used as a specific example, the structure of formula 2-1 to formula 2-9, but is not limited thereto.

The structures of the comonomers (CoM) of Formula 1, Formula 2, Formula 4, and Formula 5 of the present invention may be, but are not limited to, the structures of Formulas CoM-1 to CoM-39.

The characteristics of the thermally crosslinkable hole transport material of the present invention include an aryl amine unit in which a substituent such as benzene is substituted for an amine having high hole transport ability to impart hole transport characteristics to hole injection or / and hole transport layer composition. It has a structure in which a tertiary alcohol unit which can be chemically condensed with an arylamine derivative through a condensation reaction and a crosslinking reaction is simultaneously contained in the molecule.

The compound including both arylamine and tertiary alcohol is in the form of a polymer having a molecular weight of 2000 or more, and may form a polymer through a crosslinking reaction after forming a thin film.

The polymer containing the arylamine and the tertiary alcohol is mixed at an appropriate ratio, and then an acid catalyst is added to dehydrate the condensation reaction between the polymer containing the arylamine and the polymer containing the tertiary alcohol, thereby connecting the two polymers. .

Therefore, the crosslinking reaction of the two polymers must have arylamine units and tertiary alcohol units in the polymer, and in the case of arylamines, hydrogen must be able to react at the reactive sites of the aromatic substituents (primarily, para positions of nitrogen). . Higher content of such arylamines and tertiary alcohols can yield highly crosslinked polymers.

In addition, the number of reactive hydrogens in the polymer containing arylamine is equal to or greater than the number of OH groups in the polymer containing tertiary alcohol in order to completely remove the OH group which may act as a trap of charge after the reaction or affect the stability of the device. Many are preferred.

The heat crosslinkable hole transport material according to the present invention can be prepared using an electrophilic substitution reaction of an aromatic compound as shown in Scheme 1 below.

Specifically, the method for preparing a thermally crosslinkable hole transport material according to the present invention includes at least one polymer or low molecular unit compound comprising an amine selected from the group consisting of Formula 1, Formula 2, and Formula 3, and Formula 4, Formula 5 And at least one polymer or low molecular unit compound comprising a tertiary alcohol selected from the group consisting of Chemical Formula 6 in a solvent, and thermally crosslinking hole transport material by thermal crosslinking under conditions capable of crosslinking the composition to which the acid catalyst is added. It comprises the step of preparing.

In this case, at least one of the compound containing the amine or the compound containing the tertiary alcohol is characterized in that the polymer.

According to the method it can be produced in a thin film comprising a heat crosslinkable hole transport material according to the present invention. After completion of the reaction, by-product water (H ₂ O) and the acid used as catalyst may remain in the thin film, but can be removed by an additional heating process.

Scheme 1

At this time, the acid catalyst used in the reaction is monoacid or diacid or higher polyacid, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, oxalic acid, benzoic acid ( Benzoic acid, Carbonic acid, Fluoroacetic acid, Difluoroacetic acid, Trifluoroacetic acid, Chloroacetic acid, Dichloroacetic acid Organic acids such as trichloroacetic acid and isobutyric acid, and inorganic acids such as HF, HCl, HBr, HI, and sulfuric acid may be used. In addition, Lewis acids such as trifluoroborane: THF can also be used. Such organic acids, inorganic acids, Lewis acids and the like are not particularly limited, but it is preferable to use an acid having a boiling point of 200 ° C. or less, which is good for device characteristics.

Organic light emitting diode

In addition, the present invention is a substrate; A first electrode; Second electrode; And a first layer interposed between the first electrode and the second electrode and including the thermally crosslinkable hole transport material.

Detailed description of the thermally crosslinkable hole transport material is described above.

The first layer may serve as a hole transport layer.

A light emitting layer may be further formed on the first layer of the organic light emitting diode. The light emitting layer may be formed based on a wet method.

The organic light emitting device may include a hole injection layer, an electron transport layer, and an electron injection layer in addition to the first layer (for example, may function as a hole transport layer) and the light emitting layer as described above between the first electrode and the second electrode. It may further comprise one or more layers selected from the group consisting of.

The manufacturing method of the organic light emitting diode,

Forming a first electrode on the substrate;

At least one polymer or low molecular unit compound comprising an amine selected from the group consisting of Formula 1, Formula 2, and Formula 3 on the first electrode, and 3 selected from the group consisting of Formulas 4, 5 and 6 The first layer-forming composition comprising the at least one polymer or the low molecular unit compound containing the primary alcohol in a solvent and added with an acid catalyst is formed through a solution process, and thermally crosslinked by heat crosslinking under conditions capable of crosslinking. Forming a first layer comprising a transfer material; And

And forming a second electrode on the first layer.

The solvent in the first layer forming step may be chlorobenzene, toluene, xylene, chloroform, tetrahydrofuran, and the like, but is not limited thereto.

The first layer-forming composition must include one polymer or low molecular weight unit containing an amine and one polymer or low molecular unit containing a tertiary alcohol, at least one of the amine compound and the tertiary alcohol compound It must be a polymer.

Therefore, the composition of the composition for forming the first layer is a method using two kinds of polymers of Formula 1 / Formula 4, Formula 1 / Formula 4, Formula 2 / Formula 4, Formula 2 / Formula 5, Formula 1 / Formula 4 / Formula 5, Formula 2 / Formula 4 / Formula 5, Formula 1 / Formula 2 / Formula 4, Formula 1 / Formula 2 / Method of using three kinds of Formula 5, and the formula 1 / Formula 2 / Formula 4 / Formula 5 A method using four kinds of polymers can be used.

In addition, the composition of the composition for forming the first layer may be a polymer and a single molecule (low molecular monomer), and the method of using the polymer and the low molecule, Formula 1 / Formula 6, Formula 2 / Formula 6, Formula 3 / Method of using one polymer and one single molecule of Formula 4, Formula 3 / Formula 5, Formula 1 / Formula 2 / Formula 6, Formula 3 / Formula 4 / Formula 5, Formula 1 / Formula 3 / Formula 4, Formula 1 / Formula 3 / Formula 5, Formula 2 / Formula 3 / Formula 4, Formula 2 / Formula 3 / Formula 5, Formula 1 / Formula 4 / Formula 6, Formula 1 / Formula 5 / Formula 6, Formula 2 / Formula 4 A method using two kinds of polymers such as / Formula 6, Formula 2 / Formula 5 / Formula 6 and a single molecule can be used. In this way, one polymer and two single molecules, two polymers and two single molecules, three polymers and one single molecule, three polymers and two single molecule, four polymers and one single molecule and A composition consisting of four polymers and two single molecules may be used. An example of one polymer and two single molecules is a composition of Formula 1 / Chemical Formula 3 / Formula 6, one example of two polymers and two single molecules is a composition of Formula 1 / Formula 3 / Formula 5 / Formula 6, a polymer 3 As an example of one species and a single molecule, the composition of Formula 1 / Chemical Formula 2 / Chemical Formula 3 / Chemical Formula 4, and one example of three polymers and one single molecule is the composition of Chemical Formula 1 / Formula 2 / Formula 3 / Formula 4 / Formula 5 For example, one of four polymers and one single molecule may be composed of the composition of Formula 1 / Formula 2 / Formula 3 / Formula 4 / Formula 5, but is not limited thereto. In the case of four polymers and two single molecules, it may be composed of a composition consisting of Formula 1 / Formula 2 / Formula 3 / Formula 4 / Formula 5 / Formula 6.

The composition for forming the first layer is preferably a composition capable of minimizing the amount of tertiary alcohol in consideration of the content of the unit in the composition of the solution.

The acid catalyst in the first layer forming step is formic acid, acetic acid, propionic acid, butyric acid, valeric acid, valeric acid, oxalic acid, benzoic acid, and carboxylic acid. ), Fluoroacetic acid, Difluoroacetic acid, Trifluoroacetic acid, Trifluoroacetic acid, Chloroacetic acid, Dichloroacetic acid, Trichloroacetic acid, Organic acids such as isobutyric acid and inorganic acids such as HF, HCl, HBr, HI and sulfuric acid may be used. In addition, Lewis acids of trifluoroborane: THF can be used.

The solution process may be selected from the group consisting of spin coating, ink jet coating and nozzle jet coating.

The thermal crosslinking conditions may be selected from conditions under which a crosslinking reaction may proceed between a polymer including arylamine and a polymer including tertiary alcohol. The thermal crosslinking conditions may be carried out at a low temperature of, for example, 50 ~ 150 ℃.

The thermally crosslinkable hole transport material formed by crosslinking between the polymer including the arylamine and the polymer including the tertiary alcohol may be substantially insoluble in a solvent after thermal crosslinking.

In the present specification, the meaning of “the heat crosslinkable hole transport material is substantially insoluble in a solvent” means that the heat crosslinkable hole transport material is dissolved in the solvent in a standard state (1 atm, 25 ° C.) only 10 wt% or less. When the organic light emitting diode further comprises a light emitting layer on the first layer (which may serve as a hole transport layer), substantially between the first layer and the light emitting layer comprising the heat crosslinkable hole transport material, This means that the intermixing layer in which the heat crosslinkable hole transport material and the light emitting layer forming material are mixed is not formed.

The intermediate mixed layer may be formed at an interface between the first layer and the light emitting layer by dissolving at least a portion of the first layer already formed by a solvent included in the light emitting layer forming composition when the light emitting layer is formed by a wet method. The performance of the organic light emitting device may be deteriorated, such that the thickness of the first layer formed by the intermediate mixed layer cannot be maintained.

However, the heat crosslinkable hole transport material included in the first layer is substantially insoluble with respect to a conventional organic solvent, for example, a solvent that may be included in the light emitting layer forming composition, and thus, an intermediate mixed layer between the first layer and the light emitting layer. Can be substantially not produced, and an organic light emitting device having excellent performance can be obtained.

1 is a cross-sectional view showing an organic light emitting diode according to an embodiment of the present invention.

Referring to FIG. 1, an organic light emitting diode includes an anode 10 as a first electrode and a cathode 70 as a second electrode, a light emitting layer 40 disposed between the two electrodes, and an anode 10 and a light emitting layer 40. A hole conductive layer 20 disposed in the upper portion and the electron conductive layer 50 disposed between the light emitting layer 40 and the cathode 70 may be provided. The hole conductive layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. In addition, the electron conductive layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating injection of electrons. In addition, a hole blocking layer (not shown) may be disposed between the light emitting layer 40 and the electron transport layer 55. In addition, an electron blocking layer (not shown) may be disposed between the light emitting layer 40 and the hole transport layer 25. However, the present invention is not limited thereto, and the electron transport layer 55 may serve as the hole blocking layer, or the hole transport layer 25 may serve as the electron blocking layer.

The anode 10 may be a conductive metal oxide, a metal, a metal alloy, or a carbon material. Conductive metal oxides include indium tin oxide (ITO), fluorine tin oxide (FTO), antimony tin oxide (ATO), fluorine-doped tin oxide (FTO), SnO ₂ , ZnO Or combinations thereof. Suitable metals or metal alloys as the anode 10 may be Au and CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

When forward bias is applied to the organic light emitting diode, holes are introduced into the light emitting layer 40 at the anode 10, and electrons are introduced into the light emitting layer 40 at the cathode 70. Electrons and holes introduced into the emission layer 40 combine to form excitons, and light is emitted as the excitons transition to the ground state.

The light emitting layer 40 may be made of a single light emitting material, or may include a light emitting host material and a light emitting dopant material.

Meanwhile, the hole injection layer 23 and / or the hole transport layer 25 are layers having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, and the light emitting layer 40 at the anode 10. It increases the efficiency of injection or transportation of holes into In addition, the electron injection layer 53 and / or the electron transport layer 55 are layers having an LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40, and the light emitting layer 40 at the cathode 70. ) To increase the injection or transport efficiency of electrons.

The hole injection layer 23 or / and the hole transport layer 25 is formed by applying a mixture of a polymer containing an amine according to the present invention and a polymer containing a tertiary alcohol and polymerization or crosslinking reaction through heat treatment. Can be. The polymerized or crosslinked hole transport material presented in the present invention may also serve as an electron blocking layer. In addition, the thin film made of a polymerization or crosslinking of the polymer containing the amine and the polymer containing the tertiary alcohol presented in the present invention may be used as one of the hole injection layer 23 or the hole transport layer 25, in this case As the hole injection layer 23 or the hole transport layer 25 other than the layer to which the material of the present invention is applied, a hole transport material generally used may be used.

Common hole transporters are, for example, mCP (N, N-dicarbazolyl-3,5-benzene); PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate); NPD (N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine); N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD); N, N'-diphenyl-N, N'- dinaphthyl-4,4'-diaminobiphenyl; N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl; N, N, N'N'-tetraphenyl-4,4'-diaminobiphenyl; Porphyrin compound derivatives such as copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; TAPC (1,1-Bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] Cyclohexane); Triarylamine derivatives such as N, N, N-tri (p-tolyl) amine, 4, 4 ', 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as metal-free phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamine stilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilanes and the like.

The method of forming the hole transport layer of the organic light emitting diode using the polymer comprising the amine and the tertiary alcohol of the present invention is to polymerize or crosslink after vacuum deposition, or to prepare a solution using a suitable solvent. After that, all methods of forming a thin film using a solution process may be used. Preferably, the hole transport layer according to the present invention may form a thin film using a solution process, and the solution process may use spin coating, inkjet coating, nozzle jet coating, and the like.

The hole blocking layer serves to prevent triplet excitons or holes from diffusing in the direction of the cathode 70 and may be arbitrarily selected from known hole blocking materials. For example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, etc. can be used.

The electron transport layer 55 is composed of TSPO1 (diphenylphosphine oxide-4- (triphenylsilyl) phenyl), tris (8-quinolinorate) aluminum (Alq ₃ ), 2,5-diaryl silol derivative (PyPySPyPy), perfluorinated compound (PF-6P), COTs (Octasubstituted cyclooctatetraene), TAZ (see formula below), Bphen (4,7-diphenyl-1,10-phenanthroline (4,7-diphenyl-1,10-phenanthroline)), BCP (see formula below), or BAlq (see formula below).

The electron injection layer 53 may be, for example, LiF, NaCl, CsF, Li ₂ O, BaO, BaF ₂ , or Liq (lithium quinolate).

The cathode 70 is a conductive film having a lower work function than the anode 70, for example, a metal such as aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, silver, lead, cesium, or the like. It can be formed using a combination of two or more kinds of.

The anode 10 and the cathode 70 may be formed using a sputtering method, vapor deposition method or ion beam deposition method. The hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the hole blocking layer, the electron transport layer 55, and the electron injection layer 53 irrespective of each other are deposited or coated, for example spraying And spin coating, dipping, printing, inkjet printing, nozzlejet printing, doctor blading, or electrophoresis.

The organic light emitting diode may be disposed on a substrate (not shown), which may be disposed under the anode 10 or may be disposed above the cathode 70. In other words, the anode 10 may be formed before the cathode 70 or the cathode 70 may be formed before the anode 10 on the substrate.

The substrate may be a light transmissive substrate as a flat member, in which case the substrate is glass; Ceramic materials; It may be made of a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP) and the like. However, the present invention is not limited thereto, and the substrate may be a metal substrate capable of light reflection.

Hereinafter, preferred synthesis examples and experimental examples are provided to help the understanding of the present invention. However, the following Synthesis Examples and Experimental Examples are only for better understanding of the present invention, and the present invention is not limited to the following Synthesis Examples and Experimental Examples.

< Synthesis Example  One : Amines  Preparation of Polymers Containing>

A polymer including an amine, which is one of the hole transport materials, was prepared in the following manner.

Specifically, one equivalent of 4-bromo-N- (4-bromophenyl) -N-phenylaniline and one equivalent of 9,9-dihexylfluorene-2,7-boronic acid and 0.02 After addition of Pd (PPh ₃ ) ₄ , 10 equivalents of K ₂ CO ₃ 2M aqueous solution and tetrahydrofuran were added as a solvent and reacted for 48 hours with vigorous stirring at 80 ° C. under a nitrogen atmosphere. Thereafter, after adding 0.005 equivalents of phenylboronic acid and reacting for 2 hours, the reaction was further performed after adding 0.005 equivalents of bromobenzene. After the reaction was completed, the reaction product was cooled to room temperature, the organic layer was separated, and poured into methanol (10 times to 20 times the volume of an organic solvent) to precipitate solids. The solid was filtered off, and the filtered solid was dissolved in dichloromethane and reprecipitated in methanol. The yellow solid obtained through filtration was vacuum dried to obtain a compound containing an amine.

Compound of Synthesis Example 1: yield 60%, number average molecular weight 17,200, polydispersity index = 2.0, glass transition temperature 70 ° C.

< Synthesis Example 2: 3rd  Preparation of Polymers Containing Alcohol>

A polymer including tertiary alcohol, which is one of the hole transport materials, was prepared in the following manner.

Specifically, 1 equivalent (based on fluorene residues) of poly (9,9-dimethylfluorene-co-fluorenone) was dissolved in 100 ml of water-depleted tetdahydrofuran, and then -78 with dry ice and acetone. The mixture was stirred in a nitrogen atmosphere while lowering to ℃. After sufficiently lowering the temperature, a phenylmagnesium bromide solution (1.2 equivalents) was added thereto, followed by stirring for 2 hours. Then, 9-fluorenone (2.83 g, 15.71 mmol) was added thereto, stirred at -78 ° C. for 2 hours, and reacted for 12 hours while gradually raising to room temperature. After the reaction was completed, 1.2 equivalents of sodium hydrogen carbonate solution was added to the reaction mixture, and the mixed solution was poured into methanol (10 times to 20 times the volume of the mixed solution) to precipitate solids. The solid was filtered off, and the filtered solid was dissolved in dichloromethane and reprecipitated in methanol. The white solid obtained through filtration was vacuum dried to obtain the title polymer compound containing tertiary alcohol.

Compound of Synthesis Example 2: yield 43%, number average molecular weight 25,000, polydispersity index = 1.8, glass transition temperature 82 ° C.

< Production Example  One: Of organic light emitting diode  Manufacture

The glass substrate on which the anode ITO (150 nm) was deposited was cleaned with isopropyl alcohol with a solvent for 30 minutes by ultrasonic waves. The cleaned ITO substrate was subjected to surface treatment using short-wave ultraviolet light, followed by spin coating a PEDOT: PSS solution and heat-treating at 110 ° C to form a hole injection layer. Next, the polymer prepared in Synthesis Example 1 and the polymer prepared in Synthesis Example 2 (the molar ratio of the amine group and the alcohol group are 1: 1) are dissolved at 0.5 wt% in an acetic acid and toluene mixed solvent (volume ratio 1: 3). The solution was spin coated at 2000 rpm for 30 seconds to form a hole transport layer. Thereafter, heat treatment was performed at 100 ° C. for 60 minutes to produce a heat-crosslinked hole transport layer.

Subsequently, the light emitting layer is a light emitting host material and a dopant material of mCP (N, N-dicarbazolyl-3,5-benzene) and 4Cz-IPN [2,4,5,6-tetra (9H-carbazol-9-yl) isophthalonitrile], respectively. Used as. The emission layer was formed by quantifying mCP and 4Cz-IPN in a weight ratio of 100: 10, dissolved in toluene, and spin-coated to form a 25 nm emission layer.

The process then used a deposition method. TPBi [1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene] was deposited at a rate of 0.1 nm / s under a pressure of 1 × 10 ⁻⁶ torr to form an electron transport layer of 30 nm. . Thereafter, LiF was deposited as an electron injection material at a rate of 0.01 nm / s under a pressure of 1 × 10 ⁻⁶ torr to form an electron injection layer of 1 nm. Thereafter, Al was deposited at a rate of 0.5 nm / sec under a pressure of 1 × 10 ⁻⁶ torr to form a cathode of 120 nm to form an organic light emitting diode. After the device was formed, the device was sealed using a CaO absorbent and a glass cover glass. As a result, the device structure was ITO / PEDOT: PSS / crosslinked thin film / mCP: 4Cz-IPN / TPBi / LiF / Al of the polymer of Synthesis Example 1 and the polymer of Synthesis Example 2.

< Production Example  2: Of organic light emitting diode  Manufacture

In Preparation Example 2, all of the devices were manufactured in the same manner as in Preparation Example 1 except that the polymer and the triphenylamine of Synthesis Example 2 were used to form the hole transport layer crosslinked thin film. As a result, the device structure was ITO / PEDOT: PSS / crosslinked thin film of polymer: triphenylamine of Synthesis Example 2 / mCP: 4Cz-IPN / TPBi / LiF / Al.

< Production Example  3: Of organic light emitting diode  Manufacture

In Preparation Example 3, the device was manufactured in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 1 and the following diol single molecule 1 were used to form the cross-linked thin film. As a result, the device structure was ITO / PEDOT: PSS / crosslinked thin film / mCP: 4Cz-IPN / TPBi / LiF / Al of polymer: diol single molecule 1 of Synthesis Example 1.

< Production Example  4: Of organic light emitting diode  Manufacture

In Preparation Example 4, a device was manufactured in the same manner as in Preparation Example 1 except that the polymer of Synthesis Example 1, the polymer of Synthesis Example 2, and triphenylamine were used to form the cross-linked thin film. As a result, the device structure was crosslinked thin film / mCP: 4Cz-IPN / TPBi / LiF / Al of ITO / PEDOT: PSS / polymer of Synthesis Example 1 polymer: Triphenylamine.

< Comparative example  One: Of organic light emitting diode  Manufacture

Comparative Example 1 was manufactured in the same manner as in Example 1 except that the polyvinylcarbazole (molecular weight of 1 million) was used instead of the crosslinked thin film of the polymer of Synthesis Example 1 used as the hole transport layer material in Synthesis Example 2. As a result, the device structure was ITO / PEDOT: PSS / polyvinylcarbazole / mCP: 4Cz-IPN / TPBi / LiF / Al.

Device performance data of the organic light emitting diodes prepared in Preparation Examples 1 to 4 and Comparative Example 1 are shown in Table 1 below.

As shown in Table 1, the organic light emitting diode including the hole transport layer made of the polymer type thermal polymerization hole transport material of the present invention is quantum efficiency, current efficiency and power efficiency compared to the organic light emitting diode made of the conventional hole transport material Since this exhibits an improved effect, it can be usefully used for organic light emitting diodes.

10: anode
20: hole conductive layer
23: hole injection layer
25: hole transport layer
40: light emitting layer
50: electron conductive layer
53: electron injection layer
55 electron transport layer
70: cathode

Claims (17)

At least one polymer or low molecular unit comprising an amine selected from the group consisting of Formulas 1, 2, and 3, and at least a tertiary alcohol selected from the group consisting of Formulas 4, 5 and 6 A polymer or a low molecular unit is a polymer type heat crosslinked hole transport material condensation polymerization and crosslinked under an acid catalyst, wherein at least one of a compound containing an amine or a compound containing a tertiary alcohol is a polymer Type heat crosslinkable hole transport material.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Formula 1 to Formula 6,
Ar ¹ to Ar ⁴ are independently a substituted or unsubstituted C ₃ -C ₃₀ aryl group, heteroaryl group, arylalkyl group or alkylaryl group,
R and R ¹ to R ⁶ are Independently of each other a substituted or unsubstituted C ₁ -C ₉ alkyl group, a substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C _6- C ₃₀ alkylaryl group, substituted or unsubstituted C ₆ -C ₃₀ arylalkyl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted From the group consisting of a substituted arylamine, a substituted or unsubstituted fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide and sulfone group Selected,
CoM is selected from the group consisting of Formula CoM-1 to Formula CoM-39,
A is carbon or silicon hybridizing with sp ³ ,
m and n are each an integer of 5 to 200,
o is an integer from 0 to 10,
p is an integer from 2 to 10,
x, y and z are each an integer from 0 to 10)

The method of claim 1,
Ar ¹ to Ar ⁴ are each independently a non-fused ring aromatic substituent consisting of benzene, pyridine, pyrrole, furan and thiophene; Hetero fused ring aromatic substituents; Fused ring aromatic substituents consisting of naphthalene, anthracene, triphenylene, pyrene and perylene; And a dibenzo type fused ring substituent consisting of carbazole, fluorene, dibenzofuran, dibenzothiophene and spirofluorene,
R and R ¹ to R ⁶ are each independently a substituted or unsubstituted C ₁ -C ₄ alkyl group, a substituted or unsubstituted C ₅ -C ₁₂ cycloalkyl group, a substituted or unsubstituted C ₆ -C ₁₂ aryl Group, substituted or unsubstituted C ₆ -C ₁₂ alkylaryl group, substituted or unsubstituted C ₆ -C ₁₂ arylalkyl group, substituted or unsubstituted C ₃ -C ₁₂ heteroaryl group, substituted or unsubstituted Aryloxy group, substituted or unsubstituted arylamine, substituted or unsubstituted fused arylamine group, substituted or unsubstituted phosphine or phosphine oxide group, substituted or unsubstituted thiol group, substituted or unsubstituted Selected from the group consisting of sulfoxide and sulfone groups,
CoM is selected from the group consisting of Formula CoM-1 to Formula CoM-39,
A is carbon or silicon hybridizing with sp ³ ,
m and n are each an integer of 5 to 100,
o is an integer from 0 to 5,
p is an integer from 2 to 5,
x, y and z are each an integer of 0 to 5, the polymer type heat crosslinked hole transport material.

The method of claim 1,
The structure of the amine monomer in the polymer of Formula 1 is a polymer type thermal crosslinked hole transport material, characterized in that selected from the group consisting of the formula (1-1) to (1-12).

The method of claim 1,
The structure of the amine monomer in the polymer of Formula 2 is a polymer type heat crosslinked hole transport material, characterized in that selected from the group consisting of the formula (2-1) to (2-9).

delete The method of claim 1,
Compounds containing an amine of Formula 1, Formula 2 or Formula 3 have a reactive hydrogen at the ortho or para position of the benzene group, the reactive hydrogen being equal to or greater than the number of OH groups of the compound comprising tertiary alcohol. Polymeric thermal crosslinkable hole transport material characterized in that.
The method of claim 1,
The thermally crosslinkable hole transport material is a polymer type heat crosslinkable hole transport material, characterized in that the polymer having a molecular weight of 2000 or more.
Board;
A first electrode on the substrate;
A second electrode on the first electrode; And
An organic light emitting diode comprising: a first layer interposed between the first electrode and the second electrode and comprising the thermally crosslinkable hole transport material of claim 1.
The method of claim 8,
The first layer is an organic light emitting diode, characterized in that the hole transport layer.
The method of claim 8,
The organic light emitting diode further comprises a light emitting layer formed on the first layer.
Forming a first electrode on the substrate;
At least one polymer or low molecular unit compound comprising an amine selected from the group consisting of Formula 1, Formula 2, and Formula 3 on the first electrode, and 3 selected from the group consisting of Formulas 4, 5 and 6 At least one polymer or low molecular unit compound containing a primary alcohol is placed in a solvent, and the composition for forming a first layer including an acid catalyst is formed through a solution process, and then thermally crosslinked by heat crosslinking under conditions capable of crosslinking. Forming a first layer comprising a hole transport material; And
Forming a second electrode on the first layer;
At least one of a compound containing an amine or a compound containing a tertiary alcohol is a method for producing the organic light emitting diode of claim 8, characterized in that the polymer.
[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

(In Formula 1 to Formula 6,
Ar ¹ to Ar ⁴ are independently a substituted or unsubstituted C ₃ -C ₃₀ aryl group, heteroaryl group, arylalkyl group or alkylaryl group,
R and R ¹ to R ⁶ are Independently substituted or unsubstituted C ₁ -C ₉ alkyl groups, substituted or unsubstituted C ₅ -C ₃₀ cycloalkyl groups, substituted or unsubstituted C ₆ -C ₃₀ aryl groups, substituted or unsubstituted C _6- C ₃₀ alkylaryl group, substituted or unsubstituted C ₆ -C ₃₀ arylalkyl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted From the group consisting of a substituted arylamine, a substituted or unsubstituted fused arylamine group, a substituted or unsubstituted phosphine or phosphine oxide group, a substituted or unsubstituted thiol group, a substituted or unsubstituted sulfoxide and sulfone group Selected,
CoM is selected from the group consisting of Formula CoM-1 to Formula CoM-39,
A is carbon or silicon hybridizing with sp ³ ,
m and n are each an integer of 5 to 200,
o is an integer from 0 to 10,
p is an integer from 2 to 10,
x, y and z are each an integer from 0 to 10)

The method of claim 11,
The solvent is a method of manufacturing an organic light emitting diode, characterized in that selected from the group consisting of chlorobenzene, toluene, xylene, chloroform and tetrahydrofuran.
The method of claim 11,
The acid catalyst is formic acid, acetic acid, propionic acid, butyric acid, butyric acid, valeric acid, oxalic acid, benzoic acid, benzoic acid, carbonic acid, fluoroacetic acid ( Fluoroacetic acid, Difluoroacetic acid, Trifluoroacetic acid, Chloroacetic acid, Dichloroacetic acid, Trichloroacetic acid, Isobutyric acid , HF, HCl, HBr, HI, sulfuric acid and Lewis acid method of manufacturing an organic light emitting diode, characterized in that selected from the group consisting of.
The method of claim 11,
The solution process is a method of manufacturing an organic light emitting diode, characterized in that selected from the group consisting of spin coating, ink jet coating and nozzle jet coating.
The method of claim 11,
The thermal crosslinking method of manufacturing an organic light emitting diode, characterized in that carried out at a low temperature of 50 ~ 150 ℃.
The method of claim 11,
The first layer is a method of manufacturing an organic light emitting diode, characterized in that the hole transport layer.
The method of claim 11,
The first layer is a method of manufacturing an organic light emitting diode, characterized in that insoluble in a solvent after thermal crosslinking.

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