KR20190026496A - A Coating Solution For Forming A Thin Film Of An Organic Photo diode, Its Manufacturing Method And An Organic Photo diode Manufactured Thereby - Google Patents

Abstract

The present invention relates to a coating liquid for forming an organic photodiode thin film, a production method thereof, and an organic photodiode produced thereby. The coating liquid for forming an organic photodiode thin film. The coating liquid for forming an organic photodiode thin film is easily cured at the low temperature to form a thin film by cross-linking between an amine group and an epoxy group when applying heat energy when forming a thin film after producing a monomolecular compound including the amine group and a monomolecular compound including the epoxy group as a coating liquid for an organic photodiode solution process, and is capable of forming a stable multilayered organic photodiode without the phenomenon that an adjacent layer is dissolved by a solution even when a thin film having a multilayered structure is produced.

Description

[0001] The present invention relates to a coating solution for forming an organic photodiode thin film, a method for manufacturing the same, and an organic photodiode made by the method.

The present invention relates to a coating liquid for forming an organic photodiode thin film, a method for producing the same, and an organic photodiode produced thereby. More particularly, the present invention relates to a coating liquid for forming an organic photodiode thin film, To an organic photodiode having a stable multilayer structure by forming a crosslinking bond between an amine group and an epoxy group.

Generally, in an organic device, particularly an organic photodiode, an organic thin film is inserted between a pair of electrodes. The organic thin film is used as a constituent, and a low molecular organic thin film or a polymer organic thin film is used.

According to Japanese Laid-Open Patent Application No. 2006-156847 (hereinafter referred to as Conventional Technique 1), an organic compound and a technique for depositing it on a substrate by a vacuum deposition method to manufacture an organic photodiode including a single-layer organic film are disclosed.

The vacuum deposition method is a principle in which a thin film is formed by heating a sample in a high-temperature vacuum atmosphere to sublimate it, and the sublimed sample is grown to a solid at a relatively low temperature.

However, when an expensive vacuum deposition ratio is required, it may be difficult to manufacture a photodiode with a large area. In the case of forming a polymer organic thin film, an organic photodiode including only a polymer organic thin film having a single-layer structure can be manufactured However, in the case of the single-layer structure, the driving voltage, luminance, and luminous efficiency of the organic photodiodes are lower than in the case of using the multi-layered organic thin film.

In addition, since a monomolecular compound for an organic photodiode used in a conventional evaporation method has a low solubility in a solvent, a polymer material capable of forming a thin film by itself can be additionally added to a solvent, There is a problem in that the solution can dissolve the other layers in the organic photodiode. To solve this problem, it is necessary to perform additional insolubilization treatment, which is costly There was a problem of inefficiency.

Japanese Patent Application Laid-Open No. 2006-156847

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide an organic photodiode and a method for fabricating the organic photodiode, in which the adjacent layer is dissolved by the solution and the organic photodiode thin film is formed by the solution process, And the organic photodiode has been developed.

More specifically, when a compound containing an amine group and a compound containing an epoxy group are prepared from a coating solution for an organic photodiode solution process and heat energy is applied when a thin film is formed, crosslinking between the amine group and the epoxy group results in easy It is an object of the present invention to provide an organic photodiode capable of forming a stable multi-layered organic photodiode without the phenomenon that adjacent layers are dissolved by a solution even when a thin film of a multilayer structure is produced through a solution process .

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

In order to accomplish the above object, an embodiment of the present invention relates to a method for preparing a composition comprising a first organic monomolecular compound in which two or more amine crosslinking groups are substituted, a second organic monomolecular compound in which two or more epoxy crosslinking groups are substituted, Wherein the amine crosslinking group and the epoxy crosslinking group form a three-dimensional network structure by cross-linking between the amine crosslinking group and the epoxy crosslinking group. The present invention also provides a coating liquid for forming an organic photodiode thin film.

In an embodiment of the present invention, a first organic monomolecular compound in which two or more amine crosslinking groups are substituted, a second organic monomolecular compound in which two or more epoxy crosslinking groups are substituted, and a second organic monomolecular compound in which the second organic monomolecular compound and the second organic The organic solvent for dissolving the monomolecular compound, and forming a three-dimensional network structure by crosslinking between the amine crosslinking group and the epoxy crosslinking group.

According to an embodiment of the present invention, the first organic monomolecular compound is a compound represented by the following general formula (1), (2) or (3).

[Chemical Formula 1]

(Wherein X ₁ and X ₂ are each independently NR ₁₁ or CR ₁₁ but not simultaneously NR ₁₁ , R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

At least any one of R ₁ to R ₅ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₆ to R ₁₀ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group)

(2)

(Wherein at least any one of R ₁₂ to R ₁₆ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R < ₁₇ > to R < ₂₁ > is a crosslinking group containing an amine group and the remainder is hydrogen or a pyridine group,

At least any one of R ₂₂ to R ₂₆ is a crosslinking group containing an amine group, and the remainder is a hydrogen or a pyridine group).

(3)

(Wherein at least any one of R ₂₇ to R ₃₁ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₃₂ to R ₃₆ is a crosslinking group containing an amine group and the other is a hydrogen or a pyridine group).

,

또는

인 것을 특징으로 하는 유기 포토다이오드 박막 형성용 코팅액일 수 있다.In an embodiment of the present invention, the crosslinking group containing the amine group

,

or

The organic photodiode thin film may be a coating liquid for forming an organic photodiode thin film.

In an embodiment of the present invention, the second organic monomolecular compound is a compound represented by the following general formula (4), (5) or (6).

  [Chemical Formula 4]

(Wherein X ₃ and X ₄ are independently NR ₄₇ or CR _47, but not simultaneously NR ₄₇ , R ₄₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

At least any one of R ₃₇ to R ₄₁ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₄₂ to R ₄₆ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group)

[Chemical Formula 5]

(Wherein at least one of R ₄₈ to R ₅₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least one of R ₅₃ to R ₅₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₅₈ to R ₆₂ is a crosslinking group containing an epoxy group and the other is a hydrogen or a pyridine group).

[Chemical Formula 6]

(Wherein at least one of R ₆₃ to R ₆₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₆₈ to R ₇₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group).

,

또는

인 것을 특징으로 하는 유기 포토다이오드 박막 형성용 코팅액일 수 있다.In the embodiment of the present invention, the crosslinking group containing the epoxy group is preferably a crosslinking group containing the epoxy group

,

or

The organic photodiode thin film may be a coating liquid for forming an organic photodiode thin film.

In another embodiment of the present invention, there is provided a process for preparing a compound, which comprises preparing a first organic monomolecular compound substituted with two or more amine crosslinking groups, preparing a second organic monomolecular compound substituted with two or more epoxy crosslinking groups, Preparing a coating solution by dissolving the organic monomolecular compound and the second organic monomolecular compound in an organic solvent, and applying the coating solution for thin film formation to a substrate, followed by heat treatment to prepare a thin film And may be a thin film production method for an organic photodiode.

The step of preparing the first organic monomolecular compound in which the amine crosslinking group is substituted with two or more groups,

Reacting the solvent with a precursor and a crosslinking compound to produce a first organic monomolecular compound in which the amine crosslinking group is substituted with two or more of the amine crosslinking groups, thereby forming a coating liquid for forming an organic photodiode thin film.

The step of preparing the second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more,

Reacting a solvent with a precursor and a crosslinking compound to produce a second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more epoxy crosslinking groups to form a coating solution for forming an organic photodiode thin film.

According to another aspect of the present invention, there is provided an organic light emitting display comprising a first electrode, a second electrode facing the first electrode, and a second electrode disposed between the first electrode and the second electrode, Preparing a substituted first organic monomolecular compound, preparing a second organic monomolecular compound substituted with two or more epoxy crosslinking groups, and mixing the first organic monomolecular compound and the second organic monomolecular compound in an organic solvent And a step of coating the coating liquid for forming a thin film on a substrate and then heat-treating the thin film to prepare a thin film. The organic photodiode manufactured by the method for producing a thin film for an organic photodiode And the organic photodiode may include a thin film.

According to the embodiment of the present invention, when two or more organic monomers having at least two amine crosslinking groups are substituted and at least two organic monomers having at least two epoxy crosslinking groups are substituted, cross-linking between the amine crosslinking group and the epoxy crosslinking group A first effect that a stable organic thin film can be formed,

In order to overcome the problem of poor planarity in the prior art, the deposition process used can be used for only a single molecule and is used only in a high-temperature process. However, even if an organic thin film of a multi- A second effect that a photodiode having a stable multi-layer structure can be manufactured without a phenomenon that a photodiode

It is possible to make the organic photodiode large in size and low in cost by using a solution process.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

1 is a flowchart illustrating a method for forming an organic photodiode thin film according to an embodiment of the present invention
2 is a graph showing the voltage (V) -current (I) of Production Example 1 according to an embodiment of the present invention.
FIG. 3 is a graph showing current efficiency according to a change in current density in Production Example 1 according to an embodiment of the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Hereinafter, the coating liquid for forming an organic photodiode thin film will be described.

Wherein the coating solution for forming an organic photodiode thin film comprises an organic solvent for dissolving a first organic monomolecular compound substituted with two or more amine crosslinking groups and a second organic monomolecular compound substituted with two or more epoxy crosslinking groups, And a crosslinking group between the epoxy crosslinking group and the epoxy crosslinking group to form a three-dimensional network structure.

The cross-linking between the amine crosslinking group and the epoxy crosslinking group may be a coating solution for forming an organic photodiode thin film, which is formed by applying a solution on a substrate after solution mixing and forming by heat treatment.

The organic monomolecular compound of the organic photodiode organic monomolecular compound may be a compound represented by Chemical Formula 1, Chemical Formula 2 or Chemical Formula 3.

 [Chemical Formula 1]

(Wherein X ₁ and X ₂ are each independently NR ₁₁ or CR ₁₁ but not simultaneously NR ₁₁ , R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

At least any one of R ₁ to R ₅ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₆ to R ₁₀ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group)

(2)

(Wherein at least any one of R ₁₂ to R ₁₆ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R < ₁₇ > to R < ₂₁ > is a crosslinking group containing an amine group and the remainder is hydrogen or a pyridine group,

At least any one of R ₂₂ to R ₂₆ is a crosslinking group containing an amine group, and the remainder is a hydrogen or a pyridine group).

(3)

(Wherein at least any one of R ₂₇ to R ₃₁ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₃₂ to R ₃₆ is a crosslinking group containing an amine group and the other is a hydrogen or a pyridine group).

The position where the two or more crosslinking groups are substituted can be anywhere on the end of the compound, and the term " terminal " means that the compound is not chemically bonded to the compound except that two or more crosslinking groups are located at adjacent positions And the amine crosslinking group may be represented by the following formula.

The amine crosslinking group contained in the first organic monomolecular compound:

,

또는

,

or

The organic monomolecular compound of the organic photodiode organic monomolecular compound may be a compound represented by the following general formula (4), (5) or (6).

[Chemical Formula 4]

(Wherein X ₃ and X ₄ are independently NR ₄₇ or CR _47, but not simultaneously NR ₄₇ , R ₄₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms,

At least any one of R ₃₇ to R ₄₁ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₄₂ to R ₄₆ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group)

[Chemical Formula 5]

(Wherein at least one of R ₄₈ to R ₅₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least one of R ₅₃ to R ₅₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₅₈ to R ₆₂ is a crosslinking group containing an epoxy group and the other is a hydrogen or a pyridine group).

[Chemical Formula 6]

(Wherein at least one of R ₆₃ to R ₆₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,

At least any one of R ₆₈ to R ₇₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group).

The position where the two or more crosslinking groups are substituted can be anywhere on the end of the compound, and the term " terminal " means that the compound is not chemically bonded to the compound except that two or more crosslinking groups are located at adjacent positions And the epoxy crosslinking group may be represented by the following formula.

The epoxy crosslinking group contained in the second organic monomolecular compound:

,

또는

,

or

In order to form each organic thin film constituting the conventional organic photodiodes, a vapor deposition process is generally used. In the case of a vapor deposition process, however, it is difficult to make a large-sized organic photodiode. Thus, application to organic photodiodes having various shapes and sizes It was difficult. In order to solve this problem, a solution process in which a thin film is formed by dissolving a compound forming a thin film in a solution is introduced. However, in the solution process, in order to form an organic thin film in a multilayer, a solution process for continuously forming a thin film after forming an organic thin film must be performed. In such a case, the organic thin film already formed is dissolved again, There is a problem that it can not be formed.

The present invention provides a coating liquid for forming an organic photodiode thin film which can be used in a solution process that solves the above problems, wherein a thin film is formed from the coating liquid for forming an organic photodiode thin film, Even when the coating liquid for forming a thin film is applied to the surface of the thin film, it can be maintained in a constant shape without dissolving again.

This is because two or more crosslinking groups located at the end portions of the organic monomolecular compound are cross-linked between the crosslinking groups by the heat treatment reaction, so that the phenomenon of dissolution between the compounds forming the thin film does not occur.

The organic monomolecular compound may have hole transporting properties. A hole is a virtual particle that has a positive (+) charge and behaves like an electron, and means to carry an electric current. Hole Injection Layer (HIL) is a layer that moves when a positive voltage is applied to both ends of a hole from a hole injection layer.

In an embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound having the hole transporting property may be represented by the following formula.

[화학식 7]

(7)

[화학식 8]

[Chemical Formula 8]

[화학식 9]

[Chemical Formula 9]

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 10과 같이 표시할 수 있다. As an example of this, the end of the first organic monomolecular compound represented by the general formula (7)

The organic monomolecular compound in which the crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented by the following chemical formula (10).

[화학식 10]

[Chemical formula 10]

Further, as another example, it is preferable that the terminal of the first organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기 화학식 11과 같이 표시 될 수 있다.

The organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following Chemical Formula 11.

[화학식 11]

(11)

Further, as another example, it is preferable that the terminal of the first organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기 화학식 12과 같이 표시 될 수 있다.

The organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (12).

[화학식 12]

[Chemical Formula 12]

Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기 화학식 13과 같이 표시 될 수 있다.

The organic monomolecular compound in which the crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented as shown in the following Chemical Formula 13.

[화학식 13]

[Chemical Formula 13]

Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기 화학식 14과 같이 표시 될 수 있다.

The organic monomolecular compound in which the crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented by the following Chemical Formula 14.

[화학식 14]

[Chemical Formula 14]

In another embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound may be represented by the following formula:

Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기 화학식 15과 같이 표시 될 수 있다.

The organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (15).

[화학식 15]

[Chemical Formula 15]

In an embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound having the hole transporting property may be represented by the following formula.

[화학식 16]

[Chemical Formula 16]

[화학식 17]

[Chemical Formula 17]

[화학식 18]

[Chemical Formula 18]

[화학식 19]

[Chemical Formula 19]

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 20과 같이 표시될 수 있다. As an example of this, the end of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (20).

[화학식 20]

[Chemical Formula 20]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 21과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (21).

[화학식 21]

[Chemical Formula 21]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 22과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (22).

[화학식 22]

[Chemical Formula 22]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 23과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (23).

[화학식 23]

(23)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 24과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (19)

The organic monomolecular compound in which a crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented by the following Chemical Formula 24.

[화학식 24]

≪ EMI ID =

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 25과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (19)

The organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (25).

[화학식 25]

(25)

In an embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound having the hole transporting property may be represented by the following formula.

[화학식 26]

(26)

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 27과 같이 표시될 수 있다. As an example of this, the end of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (27).

[화학식 27]

(27)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 28과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (28).

[화학식 28]

(28)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 29과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (29).

[화학식 29]

[Chemical Formula 29]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 30과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (30).

[화학식 30]

(30)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 31과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the formula (26)

The organic monomolecular compound in which a crosslinking group is substituted at a terminal where a crosslinking group is substituted can be represented by the following chemical formula (31).

[화학식 31]

(31)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 32과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the formula (26)

The organic monomolecular compound in which the crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented by the following chemical formula (32).

[화학식 32]

(32)

 The organic monomolecular compound may have hole transporting properties. Electron Injection Layer (EIL) and Electron Transfer Layer (ETL) are known as thin film layers having an electron transporting property in an organic photodiode. The electron injection layer is a layer that allows electrons to easily enter the light emitting layer as a layer closest to a cathode in a positive charge OLED laminated light emitting structure. The electron transport layer is a layer that moves when electrons entered from the electron injection layer are applied with DC voltage at both extremes.

In an embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound having the electron transporting property may be represented by the following formula.

[화학식 7]

(7)

[화학식 8]

[Chemical Formula 8]

[화학식 9]

[Chemical Formula 9]

The organic monomolecular compound may have hole blocking properties. A hole blocking layer (HBL) is a thin film layer having a hole blocking property in an organic photodiode. The hole blocking layer may be positioned between the light emitting layer and the cathode.

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 10 같이 표시할 수 있다. As an example of this, the end of the organic monomolecular compound represented by the general formula (7)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following general formula (10).

[화학식 10]

[Chemical formula 10]

Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기 화학식 11과 같이 표시 될 수 있다.

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following general formula (11).

[화학식 11]

(11)

Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기 화학식 12과 같이 표시 될 수 있다.

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following general formula (12).

[화학식 12]

[Chemical Formula 12]

Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기 화학식 13과 같이 표시 될 수 있다.

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (13).

[화학식 13]

[Chemical Formula 13]

Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기 화학식 14과 같이 표시 될 수 있다.

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following general formula (14).

[화학식 14]

[Chemical Formula 14]

Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (7)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기 화학식 15과 같이 표시 될 수 있다.

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following general formula (15).

[화학식 15]

[Chemical Formula 15]

In another embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound may be represented by the following formula:

[화학식 16]

[Chemical Formula 16]

[화학식 17]

[Chemical Formula 17]

[화학식 18]

[Chemical Formula 18]

[화학식 19]

[Chemical Formula 19]

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제 1유기 단분자 화합물은 하기의 화학식 20과 같이 표시될 수 있다. As an example of this, the end of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (20).

[화학식 20]

[Chemical Formula 20]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 21과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (21).

[화학식 21]

[Chemical Formula 21]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 22과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (22).

[화학식 22]

[Chemical Formula 22]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 23과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the general formula (19)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (23).

[화학식 23]

(23)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 24과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (19)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following Chemical Formula 24.

[화학식 24]

≪ EMI ID =

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 25과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the general formula (19)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (25).

[화학식 25]

(25)

In an embodiment of the present invention, the first organic monomolecular compound or the second organic monomolecular compound having the electron transporting property may be represented by the following formula.

[화학식 26]

(26)

At least two of the crosslinking groups represented by the following formulas may be substituted at the end of any of the benzenes constituting the first organic monomolecular compound or the second organic monomolecular compound.

The amine bridging group contained in the first organic monomolecular compound:

,

또는

,

or

The epoxy crosslinker contained in the second organic monomolecular compound:

,

또는

,

or

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 27과 같이 표시될 수 있다. As an example of this, the end of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (27).

[화학식 27]

(27)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 28과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (28).

[화학식 28]

(28)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제1 유기 단분자 화합물은 하기의 화학식 29과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The first organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following formula (29).

[화학식 29]

[Chemical Formula 29]

가교기가 치환되어 형성되는 말단에 가교기가 치환된 제2 유기 단분자 화합물은 하기의 화학식 30과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the organic monomolecular compound represented by the formula (26)

The second organic monomolecular compound in which a crosslinking group is substituted with a crosslinking group may be represented by the following chemical formula (30).

[화학식 30]

(30)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 31과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the formula (26)

The organic monomolecular compound in which a crosslinking group is substituted at a terminal where a crosslinking group is substituted can be represented by the following chemical formula (31).

[화학식 31]

(31)

가교기가 치환되어 형성되는 말단에 가교기가 치환된 유기 단분자 화합물은 하기의 화학식 32과 같이 표시될 수 있다.Further, as another example, it is preferable that the terminal of the second organic monomolecular compound represented by the formula (26)

The organic monomolecular compound in which the crosslinking group is substituted at the terminal where the crosslinking group is substituted can be represented by the following chemical formula (32).

[화학식 32]

(32)

The first organic monomolecular compound or the second organic monomolecular compound may have luminescent properties. A light emitting layer (EML) is a thin film layer having a light emitting property in an organic photodiode. The light emitting layer is a layer in which holes and electrons are combined and converted into quantum and thermal energy to emit light of various wavelengths depending on the kind of the material.

The light emitting layer is a layer in which both electrons and holes exist and is composed of a compound having an electron donating functional group and an electron withdrawing functional group in one molecule. However, if the scientific band gap energy is sufficient, the light emitting layer can emit light, Transportation type, electronic transportation type, and bipolar transportation type. Accordingly, the organic thin film forming compound for forming the light emitting layer may be a compound selected from a hole transporting type compound, an electron transporting type compound and a bipolar transporting type compound.

In an embodiment of the present invention, the organic solvent is selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec- butyl alchol, tert- butyl alcohol, dimethyl formamide, dimethylacetamide, ketone, acetone, diacetone alcohol, keto-alcohol, dioxane, ether, polyethylene glycol, polypropylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, triethylene glycol , Hexylene glycol, diethylene glycol, glycerol, ethylene glycol monomethyl ether, diethylene glycol methyl ether, triethylene glycol monomethyl ether, 2-pyrrolidone, toluene, xylene, chlorobenzene, dichlorobenzene, chloroform, dichloromethane , Dichloroethane, gamma butyl lactone, butyl cellosolve, cyclohexane, N-methyl-2-pyrrolidone, cyclohexanone, tetrahydrofuran, (2-heptanone), benzene, terpinelol, butyl carbitol acetate, and ion-exchanged water (such as benzene, toluene, xylene, Pure water). ≪ / RTI >

However, the present invention is not limited to the solvents listed above, and any solvent may be used for the solvent used in the solution process. These solvents are different from the vapor deposition process. According to the conventional solution process, the organic thin film already formed by the organic solvent can be dissolved. However, according to the present invention, when the thin film is crosslinked by two or more substituted crosslinking groups It is not easily dissolved and a uniform shape is maintained. As a solution process, it is also possible to laminate two or more organic thin films.

Hereinafter, a method of manufacturing a coating liquid for forming an organic photodiode thin film according to an embodiment of the present invention will be described.

1 is a flow chart showing a method of manufacturing a coating liquid for forming an organic photodiode thin film.

Referring to FIG. 1, the coating liquid for forming an organic photodiode thin film includes a step (S100) of preparing a first organic monomolecular compound having two or more amine crosslinking groups substituted, a second organic monomolecular molecule having two or more epoxy crosslinking groups (S300) of preparing a coating liquid for forming a thin film by dissolving the first organic monomolecular compound and the second organic monomolecular compound in an organic solvent (S300), the step Wherein the first organic monomolecular compound in which the amine crosslinking group is substituted with two or more is crosslinked and the second organic monomolecular compound in which the epoxy crosslinking group is substituted in two or more positions, A method for producing a coating liquid for forming a diode thin film.

Hereinafter, a step (S100) of preparing a first organic monomolecular compound in which two or more amine crosslinking groups are substituted will be described.

In an embodiment of the present invention, the step of preparing the first organic monomolecular compound having two or more amine bridging groups substituted,

Reacting the solvent with a precursor and a crosslinking compound to produce a first organic monomolecular compound in which the amine crosslinking group is substituted with two or more of the amine crosslinking groups, thereby forming a coating liquid for forming an organic photodiode thin film.

The crosslinkable compound may be at least one compound selected from the group consisting of bromamine, N-phenyl-p-phenylenediamine, and 5-bromopyridin-3-amine. .

As an example, it may be 5-bromopyridin-3-amine.

Wherein the solvent comprises at least one selected from the group consisting of benzene, toluene, 1,4-dioxane, tetrahydrofuran, acetonitrile, 1,2-dimethoxyethane and N, N- Wherein the organic photodiode thin film is formed on the substrate.

As an example, it may be tetrahydrofuran.

Wherein the precursor comprises at least one selected from the group consisting of 1,3-di (phenyl) benzene, 4,4-diiodobiphenyl, and Tris (4-bromophenyl) amine. Way.

For example, it may be 1,3-di (phenyl) benzene.

Hereinafter, a step (S200) of preparing a second organic monomolecular compound in which two or more epoxy crosslinking groups are substituted will be described.

According to an embodiment of the present invention, the step of preparing the second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more,

Reacting a solvent with a precursor and a crosslinking compound to produce a second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more epoxy crosslinking groups to form a coating solution for forming an organic photodiode thin film.

The crosslinkable compound may be at least one selected from the group consisting of epichlorohydrin, 9H-cabazole-3-ethyloxiran, and 4-epoxypropanoxycarbazole.

As an example, it may be 4-Epoxypropanoxycarbazol.

Wherein the solvent comprises at least one selected from the group consisting of benzene, toluene, 1,4-dioxane, tetrahydrofuran, acetonitrile, 1,2-dimethoxyethane and N, N- Wherein the organic photodiode thin film is formed on the substrate.

An example is 1,4-dioxane.

Wherein the precursor comprises at least one selected from the group consisting of 1,3-di (phenyl) benzene, 4,4-diiodobiphenyl, and Tris (4-bromophenyl) amine. Way.

As an example, it may be Tris (4-bromophenyl) amine.

According to an embodiment of the present invention, there is provided a method of preparing a first organic monomolecular compound in which at least two amine crosslinking groups are substituted (S100), a step of preparing a second organic monomolecular compound substituted with two or more epoxy crosslinking groups S200), the reaction may be a Suzuki coupling reaction.

The Suzuki coupling reaction requires a substance to make the base condition to be carried out in the base condition. In making the base condition, an inorganic base can be used, and a potassium-based inorganic base, a cesium-based inorganic base and a sodium- But it should be understood that the present invention is not limited thereto.

In one example, the inorganic base may be potassium acetate.

A substance capable of promoting a Suzuki coupling reaction is required, and a substance promoting the reaction may include a transition metal-based catalyst. Particularly, a palladium catalyst in the transition metal catalyst may be used. Since the palladium catalyst has excellent chemoselectivity and regioselectivity, the palladium catalyst can be used as a catalyst for the Suzuki coupling reaction.

In one embodiment, the palladium catalyst is palladium (Ⅱ) acetate (Pd ( OAc) 2), Tris (dibenzylideneacetone) dipalladium (O) (Pd-2 (dba) 3), Palladium-tetrakis (triphenylphosphine) (Pd (PPh 3) ₄ ) and [1,1'-Bis (diphenylphosphino) ferrocene] dichloropalladium (II) (PdCl ₂ (dppf)).

Hereinafter, a step (S300) of preparing a coating liquid for forming a thin film by dissolving the first organic monomolecular compound and the second organic monomolecular compound in an organic solvent will be described.

In the exemplary embodiment of the present invention, when the coating solution is coated on a substrate and then heat-treated, the first organic monomolecular compound in which the amine crosslinking group is substituted by two or more and the second organic monomolecular compound in which the epoxy crosslinking group is substituted in two or more Wherein the cross-linking is performed between the molecular compound and the molecular compound.

Hereinafter, a method of forming a thin film for an organic photodiode will be described.

The method for forming a thin film for an organic photodiode includes the steps of preparing a first organic monomolecular compound substituted with two or more amine crosslinking groups, preparing a second organic monomolecular compound substituted with two or more epoxy crosslinking groups, Preparing a coating liquid for forming a thin film by dissolving the organic monomolecular compound and the second organic monomolecular compound in an organic solvent, and applying the coating liquid for forming a thin film to a substrate, followed by heat treatment to form a thin film for an organic photodiode And forming the organic photodiode thin film, wherein the crosslinking group forms a three-dimensional network structure by crosslinking between the amine crosslinking group and the epoxy crosslinking group.

 In an embodiment of the present invention, the organic monomolecular compound is used in a solution process

When a thin film is formed using the coating liquid for forming an organic photodiode thin film and then a coating liquid for forming a thin film containing an organic solvent is applied on the surface of the thin film, It can be maintained in a constant shape without being dissolved again.

This is because the first organic monomolecular compound in which at least two of the amine crosslinking groups located at the end of the organic monomolecular compound are substituted and the second organic monomolecular compound in which the epoxy crosslinking group is substituted in two or more are crosslinked Crosslinking is carried out, and the phenomenon of dissolution between the compounds forming the thin film does not occur.

In an embodiment of the present invention, it may further comprise the step of purifying the compound substituted with the two or more crosslinking groups.

In order to purify the compounds substituted with two or more crosslinking groups, purification can be carried out using column chromatography.

Column chromatography is a purification method in which a tube is filled with an adsorbent or other suitable solid material as a filler, the material is injected thereinto, and the mixture is passed through a tube. This is referred to as a chromatographic column or simply a column. As the filling material, alumina, starch, cellulose and the like can be generally used.

In the present invention, a compound in which at least two crosslinking groups are substituted can be injected into a column, and then purified through passing through a column.

In the exemplary embodiments of the present invention, the organic monomolecular compound may have at least one property selected from the group consisting of hole transporting property, electron transporting property, hole blocking property, and light emitting property. Accordingly, the organic monomolecular compound may form a thin film layer for an organic photodiode selected from a hole transporting layer, an electron transporting layer, a hole blocking layer, and a light emitting layer of an organic photodiode.

The light emitting layer is a layer in which both an electron and a hole layer are present, and is generally composed of a compound having an electron donating functional group and an electron withdrawing functional group in one molecule. However, if the optical band gap energy is sufficient, Hole transport type, electron transport type, and bipolar transport type. Accordingly, the organic thin film forming compound for forming the light emitting layer may be a compound selected from a hole transporting type compound, an electron transporting type compound and a bipolar transporting type compound.

In the exemplary embodiment of the present invention, the cross-linking between the crosslinking groups may be performed due to the heat treatment in the step of forming the thin film for organic photodiodes, and the temperature during the heat treatment may be 50 ° C to 400 ° C.

When the reaction proceeds in the above-mentioned temperature range, cross-linking between the compounds substituted with the two or more crosslinking groups can occur well, and a thin film can be easily formed.

Hereinafter, a thin film for an organic photodiode formed by a thin film forming method for an organic photodiode will be described.

When the organic photodiode thin film is formed by the above-described method for forming an organic photodiode, it is difficult for the organic photodiode thin film to be deformed by external stimuli due to crosslinking between the compounds substituted with two or more crosslinking groups . Therefore, even if a thin film for other types of organic photodiodes is formed on the surface of the thin film for organic photodiodes, the organic thin film for organic photodiodes formed before is not dissolved by the organic solvent and a thin film for organic photodiodes of two or more layers is formed can do.

Hereinafter, the organic photodiode will be described.

The organic photodiode includes a first electrode, a second electrode positioned to face the first electrode, and a first organic monomolecular compound provided between the first electrode and the second electrode, the first organic monomolecular compound having two or more amine bridging groups, And a second organic monomolecular compound in which at least two crosslinking groups are substituted, wherein the organic photodiode thin film is formed by coating an organic solvent on the thin film by cross-linking between the crosslinking groups And the thin film is not dissolved.

 In an embodiment of the present invention, the thin film for organic photodiodes may be any one of a hole transporting layer, an electron transporting layer, a hole blocking layer, and a light emitting layer. However, the present invention is not limited to this, and all the organic thin films used for the organic photodiodes may be included in the organic photodiode thin film.

Hereinafter, Preparation Examples and Experimental Examples of the present invention will be described. However, these production examples and experimental examples are intended to explain the constitution and effects of the present invention more specifically, and the scope of the present invention is not limited thereto.

[Production Example 1]

1. Preparation of first organic monomolecular compound

(1) The first organic monomolecular compound SMH-C1

In an atmosphere of nitrogen, 250ml 3-bromopyridien the tow neck flask (3g, 0.02mol) , Bis (pinacolato) diboron (4.8g, 0.02mol), Pd (pph 3) 4 (0.2g, 0.0002mol), potassium acetate (4g , 0.04 mol) were added, and 1,4-dioxane (100 ml) was added thereto. The mixture was stirred, and the reaction was allowed to proceed at 80 ° C for 12 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, washed with ethyl acetate, and then purified by column chromatography (EA: Hx = 1: 8) to prepare a pure first intermediate.

Next, the first intermediate (2.5 g, 0.012 mol), 1,3,5-tribromobenzene (1.3 g, 0.004 mol), Pd (pph ₃ ) ₄ (0.7 g, 0.0006 mol) and THF (Tetrahydrofuran) (80 ml) were added and stirred. If all the substances in the flask are dissolved, add potassium carbonate solution (2N, 150 ml) and proceed at 80 ℃ for 12 hours. After completion of the reaction, the reaction mixture was purified by column chromatography (EA: Hx = 1: 10) to obtain a pure second intermediate.

Followed by, in an atmosphere of nitrogen, the second intermediate in 500ml tow neck flask (3g, 0.0096mol) , 1,4-benzenediboronic acid (6.3g, 0.019mol), Pd (pph 3) 4 (0.55g, 0.00048mol ), THF (Tetrahydrofuran) (100 ml) was added and the mixture was stirred. If all the substances in the flask are dissolved, add potassium carbonate solution (2N, 100 ml) and proceed at 80 ℃ for 12 hours. After completion of the reaction, the reaction product was purified by column chromatography (EA: Hx = 1: 7) to obtain a pure third intermediate.

(3 g, 0.0055 mol), Bis (pinacolato) diboron (2.8 g, 0.01 mol) and Pd (pph ₃ ) ₄ (0.3 g, 0.00027 mol) were added to a 250 ml tow neck flask in a nitrogen atmosphere. , and potassium acetate (1.1 g, 0.011 mol) were added, and 1,4-dioxane (100 ml) was added thereto, followed by stirring for 12 hours at 80 ° C. After completion of the reaction, the reaction mixture was cooled at room temperature, washed with ethyl acetate, and then purified by column chromatography (EA: Hx = 1: 20) to obtain a pure fourth intermediate.

Then, a fourth intermediate (2 g, 0.003 mol), 5-bromopyridin-3-amine (1.1 g, 0.006 mol) and Pd (pph ₃ ) ₄ (0.17 g , 0.00015 mol) was added, and THF (50 ml) was added thereto and stirred. If all the substances in the flask are dissolved, add potassium carbonate solution (2N, 50 ml) and proceed at 80 ℃ for 12 hours. After completion of the reaction, the product was purified by column chromatography (MC: Hx = 1: 5) to prepare the first organic monomolecular compound SMH-C1.

(2) The first organic monomolecular compound CJC-1

4-Diiodobiphenyl (1.5 g, 0.003695 mol), 4-Nitrodiphenylamine (1.98 g, 0.009236 mol), potassium phosphate (2.35 g, 0.0111 mol) and Cuprous iodide were added to a 500 mL round bottom flask under nitrogen atmosphere. 1,4-dioxane (35 mL) is added to the reaction mixture, and the mixture is refluxed at 110 ° C. for 24 hours. After completion of the reaction, the reaction mixture was cooled at room temperature and washed with EA. The filtrate was subjected to solvent filtration and column chromatography (MC: Hx = 1: 2) yielded intermediate (1).

Subsequently, intermediate (1) (1 g, 0.001728 mol) and SnCl ₂ (3.9 g, 0.01728 mol) were added to a 250 mL two-neck flask under nitrogen atmosphere, and ethanol (20 mL) The reaction is carried out by refluxing at 80 DEG C for 12 hours.

After completion of the reaction, the ethanol was removed under reduced pressure, the precipitated solid was poured into distilled water, neutralized with NaHCO ₃ solution, and extracted with EA / distilled water to separate the organic layer.

After the solvent of the separated organic layer is completely blown off, the product is purified by column chromatography (MC: Hx = 1: 10) to obtain the first organic monomolecular compound CJC-1.

(3) The first organic monomolecular compound CJC-2

4-Diiodobiphenyl (1.5 g, 0.003695 mol), 4-Nitrodiphenylamine (1.98 g, 0.009236 mol), potassium phosphate (2.35 g, 0.0111 mol) and Cuprous iodide were added to a 500 mL round bottom flask under nitrogen atmosphere. 1,4-dioxane (35 mL) is added to the reaction mixture, and the mixture is refluxed at 110 ° C. for 24 hours.

After completion of the reaction, the reaction mixture was cooled at room temperature and washed with EA. The filtrate was subjected to solvent filtration and column chromatography (MC: Hx = 1: 2) yielded intermediate (1).

Then, the intermediate (1) (1 g, 0.001728 mol) and SnCl2 (3.9 g, 0.01728 mol) were added to a 250 mL two-neck flask under a nitrogen atmosphere and ethanol (20 mL) At reflux for 12 hours.

After completion of the reaction, the ethanol was removed under reduced pressure, and the precipitated solid was poured into distilled water, neutralized with NaHCO 3 solution, and extracted with EA / distilled water to separate the organic layer.

After the solvent of the separated organic layer was completely blown off, the product was purified by column chromatography (MC: Hx = 1: 10) to obtain the first organic monomolecular compound CJC-2.

2. Organic photodiode manufacturing

After the ITO substrate was ultrasonically washed with distilled water and acetone, poly (3,4-ethylenedioxythiophene) (poly (4-styrenesulfonate)) was spin-coated on the ITO substrate and vacuum And dried in an oven for 30 minutes to form a hole injection layer having a thickness of 30 nm. VNPB was dissolved in chlorobenzene on the hole injection layer, and spin-coated water was dried in a vacuum oven at a temperature of 180 ° C to form a hole transport layer 8 wt% of DV-CBP and Ir (mppy) ₃ are dissolved in chlorobenzene, spin-coated on the hole transport layer, and dried in a vacuum oven at a temperature of 180 ° C to form an electron transport layer having a thickness of 30 nm. LiF and Al are vacuum-deposited on the electron transport layer to form an electrode to produce an organic photodiode.

[Production Example 2]

2. Preparation of second organic monomolecular compound

(1) Second organic monomolecular compound SMH-C2

(1 g, 3.4 mol), Epichlorohydrin (0.69 g, 3.4 mmol), and N, N'-tetramethyl-1,3,2-dioxaborolan- Pd (pph ₃ ) ₄ (0.19 g, 0.17 mmol) and THF (80 ml) were added and stirred. If all the substances in the flask are dissolved, add potassium carbonate solution (2N, 10 ml) and proceed at 80 ℃ for 12 hours. After completion of the reaction, the reaction mixture was cooled at room temperature, washed with ethyl acetate and H2O, and then the organic layer was separated. The solvent of the organic layer was removed under reduced pressure, and purified by column chromatography (ethylene: hexane = 1: 5) to prepare a pure first intermediate.

Subsequently, a first intermediate (1.34 g, 6 mmol), tris (4-bromophenyl) amine (1 g, 0.002 mol), potassium phosphate (5 g, 0.024 mol) and CuI , 0.001 mol), trans-1,2-diaminocyclohexane (0.68 ml, 0.006 mol) and 1,4-dioxane (100 ml) were added. After completion of the reaction, the reaction mixture is heat-treated and the organic solvent is removed under reduced pressure.

The solid mixture was purified by column chromatography (MC: Hx = 1: 7) to prepare the second organic monomolecular compound SMH-C2.

(2) The second organic monomolecular compound CJC-3

(5 g, 0.027291 mol), Di-tert-butyl dicarbonate (5.33 mL, 0.023197 mol) and 4-dimethylaminopyridine (0.47 g, 0.003821 mol) were placed in a 500 mL round bottom flask under a nitrogen atmosphere and THF mL), stirred, and refluxed at R / T for 24 hours to conduct the reaction.

After completion of the reaction, the reaction mixture was cooled at room temperature and washed with EA. The filtrate was subjected to filtration to remove all of the solvent, followed by column chromatography (MC: Hx = 1: 5) to obtain intermediate (1).

Then, the intermediate (1) (5.64 g, 0.02 mol) and NaH (1.433 g, 0.059718 mol) were added to a 250 mL two-neck flask under a nitrogen atmosphere, THF (50 mL) T, Epichlorohydrin (7.79 mL, 0.1 mol) is dropwise added, and the reaction is carried out by refluxing at 70 ° C for 12 hours.

After completion of the reaction, the mixture is cooled at room temperature and extracted with EA / distilled water to separate the organic layer.

After the solvent of the separated organic layer was completely blown off, the product was purified by column chromatography (MC: Hx = 1: 1) to obtain intermediate (2).

Then, the intermediate (2) is added to a 500 mL round-bottomed flask under nitrogen atmosphere with stirring in Trifluoroacetic acid (TFA, 30 mL) / DMF (100 mL) and refluxed at 110 ° C for 48 hours.

After completion of the reaction, the reaction mixture is cooled at room temperature, and the solvent is removed under reduced pressure.

Add NaOH (200 mL, 1 N aqueous solution).

The reaction mixture is washed with EA, the filtrate is subjected to filtration, and the solvent is blown, followed by column chromatography to obtain intermediate (3).

Next, 4,4-Diiodobiphenyl, intermediate (3), potassium phosphate, Cuprous iodide, and Trans-1,2-cyclohexane diamine were placed in a 250 mL two-neck flask under nitrogen atmosphere and 1,4- And the reaction is carried out by refluxing at 110 DEG C for 24 hours.

After completion of the reaction, cool at room temperature and wash with EA.

The filtrate is filtered to remove all of the solvent and then purified by column chromatography to obtain a second organic monomolecular compound CJC-3.

(3) Second organic monomolecular compound CJC-4

(5 g, 0.027291 mol), Di-tert-butyl dicarbonate (5.33 mL, 0.023197 mol) and 4-dimethylaminopyridine (0.47 g, 0.003821 mol) were placed in a 500 mL round bottom flask under a nitrogen atmosphere and THF mL), stirred, and refluxed at R / T for 24 hours to conduct the reaction.

After completion of the reaction, cool at room temperature and wash with EA.

After the filtrate was filtered off, the solvent was completely blown off, followed by column chromatography (MC: Hx = 1: 5) to obtain intermediate (1).

Then, the intermediate (1) (5.64 g, 0.02 mol) and NaH (1.433 g, 0.059718 mol) were added to a 250 mL two-neck flask under a nitrogen atmosphere, THF (50 mL) T and dropwise with Epichlorohydrin (7.79 mL, 0.1 mol).

The reaction is carried out by refluxing at 70 DEG C for 12 hours.

After completion of the reaction, the mixture is cooled at room temperature and extracted with EA / distilled water to separate the organic layer.

After the solvent of the separated organic layer was completely blown off, the product was purified by column chromatography (MC: Hx = 1: 1) to obtain intermediate (2).

Then, the intermediate (2) is added to a 500 mL round-bottomed flask under nitrogen atmosphere with stirring in Trifluoroacetic acid (TFA, 30 mL) / DMF (100 mL) and refluxed at 110 ° C for 48 hours.

After completion of the reaction, the reaction mixture is cooled at room temperature, and the solvent is removed under reduced pressure.

Add NaOH (200 mL, 1 N aqueous solution).

The reaction mixture is washed with EA, the filtrate is subjected to filtration, and the solvent is blown, followed by column chromatography to obtain intermediate (3).

Tris (4-bromophenyl) amine, intermediate (3), potassium phosphate, Cuprous iodide and Trans-1,2-cyclohexane diamine were placed in a 250 mL two-neck flask under nitrogen atmosphere. 1,4- The reaction is carried out by refluxing at 110 DEG C for 24 hours.

After completion of the reaction, cool at room temperature and wash with EA.

After the filtrate was filtered, the solvent was completely blown and then purified by column chromatography to obtain a second organic monomolecular compound CJC-4.

[Experimental Example 1]

Energy level analysis of organic photodiodes (voltage-current analysis)

4 is a graph showing the voltage (V) -current (I) of Production Example 1. Fig.

FIG. 4 shows that the current increases sharply when the voltage increases by a certain level or more. This shows that the organic photodiode composed of the organic thin film manufactured by the solution process operates at a constant yield or more.

The photophysical and electrochemical characteristics of Production Example 1 are shown in Table 1 below.

Example abs E _T1 HOMO E _g LUMO Production Example 1 310 nm 2.87 eV 6.48 eV 3.29 eV 3.19 eV

[Experimental Example 2]

5 is a graph showing the current efficiency according to the variation of the current density in Production Example 1. FIG. Referring to FIG. 5, when the current density is 0 mA / cm ² to 10 mA / cm ² , the current efficiency shows a maximum value of about 45 cd / A. It can be confirmed that the current efficiency is improved as compared with the conventional organic photodiodes which do not use a compound in which two or more crosslinking groups are substituted.

In addition, it can be confirmed that the current efficiency decreases as the current density increases. If the current density is increased to a certain level or more, the efficiency of the current decreases, It can be confirmed that the result is that the diode operates normally at a constant current level.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (25)

A first organic monomolecular compound in which two or more amine bridging groups are substituted;
A second organic monomolecular compound in which two or more epoxy crosslinking groups are substituted; And
And an organic solvent for dissolving the first organic monomolecular compound and the second organic monomolecular compound,
Wherein a thin film having a three-dimensional network structure is formed by crosslinking between the amine crosslinking group and the epoxy crosslinking group.
The method according to claim 1,
Wherein the first organic monomolecular compound is a compound represented by Formula 1, Formula 2 or Formula 3:
[Chemical Formula 1]

(Wherein X ₁ and X ₂ are each independently NR ₁₁ or CR ₁₁ but not simultaneously NR ₁₁ , R ₁₁ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
At least any one of R ₁ to R ₅ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,
At least any one of R ₆ to R ₁₀ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group)

(2)

(Wherein at least any one of R ₁₂ to R ₁₆ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,
At least any one of R < ₁₇ > to R < ₂₁ > is a crosslinking group containing an amine group and the remainder is hydrogen or a pyridine group,
At least any one of R ₂₂ to R ₂₆ is a crosslinking group containing an amine group, and the remainder is a hydrogen or a pyridine group).

(3)

(Wherein at least any one of R ₂₇ to R ₃₁ is a crosslinking group containing an amine group and the remainder is a hydrogen or a pyridine group,
At least any one of R ₃₂ to R ₃₆ is a crosslinking group containing an amine group and the other is a hydrogen or a pyridine group). 3. The method of claim 2,
The crosslinking group containing the amine group

,

or

Wherein the organic photodiode thin film is formed on the substrate.
The method according to claim 1,
Wherein the second organic monomolecular compound is a compound represented by the following Chemical Formula 4, Chemical Formula 5 or Chemical Formula 6:
[Chemical Formula 4]

(Wherein X ₃ and X ₄ are independently NR ₄₇ or CR _47, but not simultaneously NR ₄₇ , R ₄₇ is hydrogen or an alkyl group having 1 to 10 carbon atoms,
At least any one of R ₃₇ to R ₄₁ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,
At least any one of R ₄₂ to R ₄₆ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group)

[Chemical Formula 5]

(Wherein at least one of R ₄₈ to R ₅₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,
At least one of R ₅₃ to R ₅₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,
At least any one of R ₅₈ to R ₆₂ is a crosslinking group containing an epoxy group and the other is a hydrogen or a pyridine group).
[Chemical Formula 6]

(Wherein at least one of R ₆₃ to R ₆₇ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group,
At least any one of R ₆₈ to R ₇₂ is a crosslinking group containing an epoxy group and the remainder is a hydrogen or a pyridine group). 5. The method of claim 4,
The crosslinking group containing the epoxy group

,

or

Wherein the organic photodiode thin film is formed on the substrate.
The method according to claim 1,
Wherein the first organic monomolecular compound or the second organic monomolecular compound has at least one property selected from the group consisting of a hole transporting property, an electron transporting property, a major blocking property, and a light emitting property.
The method according to claim 1,
The organic solvent may be selected from the group consisting of methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alchol, tert-butyl alcohol, But are not limited to, dimethyl acetamide, ketone, acetone, diacetone alcohol, keto-alcohol, dioxane, ether, polyethylene glycol, polypropylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, triethylene glycol, hexylene glycol, , Glycerol, ethylene glycol monomethyl ether, diethylene glycol methyl ether, triethylene glycol monomethyl ether, 2-pyrrolidone, toluene, xylene, chlorobenzene, dichlorobenzene, chloroform, dichloromethane, dichloroethane, Butyl cellosolve, cyclohexane, N-methyl-2-pyrrolidone, cyclohexanone, tetrahydrofuran, carbon tetrachloride, tetrachloroethane, (1) selected from among benzene, dodecylbenzene, quinoline, trichlorobenzene, nitrobenzaldehyde, nitrobenzene, carbon disulfide, 2-heptanone, benzene, terpinelol, butylcarbitol acetate and ion- Or more of a solvent for forming an organic photodiode thin film. The method according to claim 1,
Wherein the thin film is formed by the coating liquid for forming an organic photodiode thin film and then the organic thin film is formed by applying an organic solvent on the thin film without the organic thin film being dissolved by the crosslinking. Coating liquid for forming a thin film.
9. The method of claim 8,
Wherein the organic monomolecular compound comprises at least one compound selected from the group consisting of a hole transporting compound, an electron transporting compound and a bipolar transporting compound, when the organic monomolecular compound has luminescence properties. Coating liquid for forming. An organic photodiode produced by using the coating solution for forming an organic photodiode thin film according to claim 1. Preparing a first organic monomolecular compound in which two or more amine crosslinking groups are substituted;
Preparing a second organic monomolecular compound in which two or more epoxy crosslinking groups are substituted; And
And dissolving the first organic monomolecular compound and the second organic monomolecular compound in an organic solvent to prepare a coating solution,
When the coating solution is coated on a substrate and then heat-treated, cross-linking is performed between the first organic monomolecular compound substituted with two or more amine crosslinking groups and the second organic monomolecular compound substituted with two or more epoxy crosslinking groups Wherein the organic photodiode thin film is formed on the substrate. 12. The method of claim 11,
The step of preparing the first organic monomolecular compound in which the amine crosslinking group is substituted with two or more groups,
Wherein the solvent is reacted with a precursor and a crosslinking compound to produce a first organic monomolecular compound in which the amine crosslinking group is substituted with two or more of the amine crosslinking groups. 13. The method of claim 12,
Wherein the crosslinkable compound comprises at least one selected from the group consisting of bromamine, N-phenyl-p-phenylenediamine, and 5-bromopyridin-3-amine.
12. The method of claim 11,
The step of preparing the second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more,
Reacting a solvent with a precursor and a crosslinking compound to produce a second organic monomolecular compound in which the epoxy crosslinking group is substituted with two or more of the epoxy crosslinking groups.
15. The method of claim 14,
Wherein the crosslinking compound comprises at least one selected from the group consisting of epichlorohydrin, 9H-cabazole-3-ethyloxiran, and 4-epoxypropanoxycarbazole. 15. The method according to claim 12 or 14,
Wherein the reaction in each step is a Suzuki coupling reaction. ≪ RTI ID = 0.0 > 11. < / RTI > 15. The method according to claim 12 or 14,
Wherein the precursor comprises at least one selected from the group consisting of 1,3-di (phenyl) benzene, 4,4-diiodobiphenyl, and Tris (4-bromophenyl) amine. Way. 15. The method according to claim 12 or 14,
Wherein the solvent comprises at least one selected from the group consisting of benzene, toluene, 1,4-dioxane, tetrahydrofuran, acetonitrile, 1,2-dimethoxyethane and N, N- Wherein the organic photodiode thin film is formed on the substrate.
Preparing a coating liquid for forming an organic photodiode thin film produced by the manufacturing method of claim 11; And
And applying a coating liquid for forming a thin film on a substrate, followed by heat treatment to produce a thin film.
20. The method of claim 19,
Wherein crosslinking is carried out between the first organic monomolecular compound in which the amine crosslinking group is substituted by 2 or more and the second organic monomolecular compound in which the epoxy crosslinking group is substituted by 2 or more owing to the heat treatment in the step of forming the thin film (JP) METHOD FOR PRODUCING THIN FILM FOR ORGANIC PHOTODIODE
20. The method of claim 19,
Wherein the organic thin film is formed on the organic thin film, and the organic thin film is formed on the organic thin film.
20. The method of claim 19,
Wherein the annealing temperature in the step of forming the organic photodiode thin film is 50 to 400 ° C.
A thin film for an organic photodiode according to claim 19, which is produced by the method for producing a thin film for an organic photodiode.
A first electrode;
A second electrode positioned to face the first electrode; And
The organic photodiode according to claim 19, wherein the organic photodiode thin film is formed between the first electrode and the second electrode.
25. The method of claim 24,
Wherein the thin film for an organic photodiode is any one of a hole transporting layer, an electron transporting layer, a hole blocking layer, and a light emitting layer.

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