KR20180034936A - Composition and organic electronic device comprising same - Google Patents

Abstract

The present invention provides a composition comprising a compound represented by the chemical formula 1, a film formed using the same, and an organic electronic device comprising the same. The organic electronic device comprising the composition according to one embodiment of the present disclosure may exhibit excellent characteristics in terms of an increase in open-circuit voltage, short-circuit current and/or an increase in efficiency.

Description

Technical Field [0001] The present invention relates to a composition and an organic electronic device including the composition.

The present invention relates to a composition, a film comprising the crosslinked product of the composition, and an organic electronic device comprising the same.

An organic electronic device means an element requiring charge exchange between an electrode and an organic material using holes and / or electrons. The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electric device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor that interfaces with an electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of organic electronic devices include organic light emitting devices, organic solar cells, and organic transistors, all of which require hole injecting or transporting materials, electron injecting or transporting materials, or light emitting materials for driving the devices. Hereinafter, the organic solar cell will be described in detail. However, in the above organic electronic devices, a hole injecting or transporting material, an electron injecting or transporting material, or a light emitting material acts on a similar principle.

The possibility of organic solar cells was first suggested in the 1970s, but efficiency was too low to be practical.

However, in 1986, Eastman Kodak's CWTang showed a possibility of practical use as various solar cells with a double layer structure using copper phthalocyanine (CuPc) and perylene tetracarboxylic acid derivatives , Interest and interest in organic solar cells and research have been rapidly increasing and have brought many improvements.

In 1995, Yu et al. Introduced the concept of bulk heterojunction (BHJ), and developed fullerene derivatives such as PCBM, which have improved solubility, as n-type semiconductors. there was.

Since then, research has been continuously carried out to increase the efficiency of organic solar cells.

Two-layer organic photovoltaic cells (C. W. Tang, Appl. Phys. Lett., 48, 183. (1996)

It is an object of the present invention to provide a composition, a film comprising the crosslinked product of the composition, and an organic electronic device including the same.

The present invention provides a composition comprising a compound represented by the following general formula (1) and a crosslinking agent.

[Chemical Formula 1]

In Formula 1,

R1 to R4 are the same or different from each other and each independently represents a halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Amide group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted amine group; Or a substituted or unsubstituted sulfonyl group,

R5 and R6 are the same or different and each independently O or S,

R7 and R8 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

n and m are each an integer of 1 to 4,

When n and m are each 2 or more, the structures in parentheses are the same or different from each other,

L is a conjugated structure-containing group.

The present disclosure also provides a film comprising a crosslinked product of the composition.

Further, the present specification provides an organic electronic device including the film.

An organic electronic device including a composition according to one embodiment of the present invention can exhibit excellent characteristics in terms of an increase in open-circuit voltage and short-circuit current and / or an increase in efficiency.

The composition according to one embodiment of the present invention can be used alone or in combination with other materials in an organic electronic device, and it is expected that the lifetime of the device can be improved by improving the efficiency and the thermal stability of the compound.

1 is a view illustrating an organic solar cell according to an embodiment of the present invention.
2 is a view illustrating an organic light emitting device according to an embodiment of the present invention.
3 illustrates an organic transistor according to an embodiment of the present invention.
4 shows the MS spectrum of Compound 1. Fig.
FIG. 5 is a graph showing the MS spectrum of the compound prepared in Production Example 1. FIG.
6 is a graph showing the MS spectrum of the compound prepared in Preparation Example 2. Fig.
7 is a graph showing the MS spectrum of the compound prepared in Preparation Example 3. FIG.
8 is a graph showing the MS spectrum of Compound 2-B.
9 is a graph showing the MS spectrum of Compound 2-E.
FIGS. 10 and 11 show current densities according to the voltages of the organic solar cells manufactured in Examples 1 to 4 and Comparative Examples 1 to 4.
12 is a graph showing the stability evaluation results of the organic solar cell prepared in Example 5 and Comparative Example 5. Fig.

Hereinafter, the present specification will be described in detail.

One embodiment of the present invention provides a composition comprising the compound represented by Formula 1 and a crosslinking agent.

In this specification, when a part is referred to as "including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

는 다른 치환기, 단량체 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; means a moiety bonded to another substituent, monomer, or binding site.

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" A halogen group; A nitrile group; A nitro group; Imide; Amide group; Carbonyl group; An ester group; A hydroxy group; An alkyl group; A cycloalkyl group; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; An alkenyl group; Silyl group; Siloxyl group; Boron group; An amine group; Arylphosphine groups; Phosphine oxide groups; An aryl group; And a heterocyclic group, or that two or more of the substituents in the above-exemplified substituents are substituted with a substituent to which they are linked, or have no substituent. For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the amide group may be substituted with nitrogen of the amide group by hydrogen, a straight chain, branched chain or cyclic alkyl group of 1 to 30 carbon atoms or an aryl group of 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, But is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In this specification, the amine group is -NH ₂ ; An alkylamine group; N-alkylarylamine groups; An arylamine group; An N-arylheteroarylamine group; An N-alkylheteroarylamine group, and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, N-9- An amine group, a diphenylamine group, an N-phenylnaphthylamine group, a ditolylamine group, an N-phenyltolylamine group, a triphenylamine group, an N-biphenylfluorenylamine group, An N-phenylpiperazinylamine group, an N-phenyl spirobifluorenylamine group, an N-biphenyl spirobifluorenylamine group, an N-biphenyldibenzofuranylamine group, Phenylbenzopyranylamine group, an N-phenyldibenzofurylamine group, an N-phenylbiphenylamine group, an N-phenylcarbazolylamine group, an N-biphenylcarbazolylamine group, , N-phenyldibenzothiophenylamine group, N-biphenylnaphthylamine group, N-biphenylterphenylamine group, N-phenylphenylamine group, N-phenylnaphthylamine group, A perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, a perfluorenylamine group, And the like, but the present invention is not limited thereto.

In the present specification, the sulfonyl group is -SO ₂ R, and R is a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRR'R ", wherein R, R 'and R" are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include, but are not limited to, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, triphenylsilyl, diphenylsilyl and phenylsilyl groups. Do not.

In the present specification, the boron group may be represented by the formula of -BRR ', wherein R and R' are each hydrogen; A substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert- But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert- But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methylphenylamine, 4-methyl-naphthylamine, 2-methyl- But are not limited to, cenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, carbazole and triphenylamine groups.

In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group, a fluorenyl group and a triphenylene group.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

,

,

,

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group and is a heterocyclic group containing at least one of N, O, S, Si and Se. The number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, a thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenoxazinyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto. The heterocyclic group may be monocyclic or polycyclic, and includes an aliphatic heterocyclic group and an aromatic heterocyclic group.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heteroaryl group.

In the present specification, the aromatic ring group may be monocyclic or polycyclic, and examples of the aryl group may be selected.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the arylphosphine group, the aralkyl group, the aralkylamine group, the aralkenyl group, the alkylaryl group, the arylamine group and the arylheteroarylamine group, The description of one aryl group may be applied.

In the present specification, the alkyl group in the alkylthio group, the alkylsulfoxy group, the aralkyl group, the aralkylamine group, the alkylaryl group and the alkylamine group can be applied to the alkyl group described above.

In the present specification, the heteroaryl group, the heteroarylamine group, and the heteroaryl group in the arylheteroarylamine group may be aromatic, but the description of the above-mentioned heterocyclic group may be applied.

In this specification, a conjugated structure means that two or more multiple bonds are present in the structure of a compound with one single bond sandwiched therebetween and exhibit an interaction.

In the present specification, a conjugated structure-containing group means a functional group containing the conjugated structure.

In one embodiment of the present specification, the conjugated structure-containing group may be a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted divalent heterocyclic group in combination of one or two or more groups .

As used herein, " combination " means connecting several structures or connecting different types of structures.

In the present specification, the description of the aforementioned alkenyl group can be applied except that the alkenylene group is divalent.

In the present specification, the description of the aryl group described above can be applied, except that the arylene group is divalent.

In the present specification, the description of the aforementioned heterocyclic group can be applied, except that the divalent heterocyclic group is a divalent group.

In this specification, the conjugated structure-containing group includes any one or two or more of the following structures.

In the above structure,

a, e, f, g, g ', h, h', i, i ', j and j'

In the case where a, e, f, g, g ', h, h', i, i ', j and j' are 2 or more, the structures in parentheses are the same or different,

b and b 'are each an integer of 1 to 3,

b and b 'are 2 or more, the structures in parentheses are the same or different from each other,

c and d are each 1 or 2,

When c and d are each 2 or more, the structures in parentheses are the same or different from each other,

X11 to X47, X50 to X56, X59, X60 and Y1 to Y6 are the same as or different from each other, each independently S, O, Se, Te, NR _a, CR _a R _b, SiR _a R _b, PR _a, or GeR _a R _b ,

X48, X49, X57 and X58 are the same or different and each independently C, Si or Ge,

R101 to R104 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R _a and R _b are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the present specification, L may include any one or a combination of two or more of the following structures.

In the above structure, X15 to X20, X24 to X42, X55 to X60, R101, R102, R105 to R124, R137 to R140, a, b, b ', c, d, e, f, i, And j 'are as described above.

In the present specification, L may include any one or a combination of two or more of the following structures.

In the above structure, X19, X20, X24, X29 to X35, X39 to X42, X55 to X60, R101, R102, R105, R106, R109 to R112, R115, R116, R123, R124, R137 to R140, , b ', c, d, e, f, i, i', j and j 'are as described above.

In the present specification, L may include any one or a combination of two or more of the following structures.

In the above structure, X24, X31, X39 to X42, X55 to X60, R105, R106, R111, R112, R123, R124, R137 to R140, a, b, b ', e, f, i, And j 'are as described above.

In the present specification, L has the following structure.

In the above structure, X24 '', X39 '' to X42 '' are the same or different and each is independently selected from S, O, Se, Te, NR _a, CR _a R _b, SiR _a R _b, PR _a, or GeR _a R _b ,

R105 ", R106 ", R123 " and R124 " are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a ", e" and f "are each an integer of 1 to 5,

When a ", e", and f "are two or more, the structures in parentheses are the same or different,

X24, X31, X39 to X42, R105, R106, R111, R112, R123, R124, a, b, b ', e, f, R _a and R _b are as described above.

In the present specification, L has the following structure.

In the above structures, X55 to X60, R137 to R140, i, i ', j and j' are as described above.

In the present specification, X11 to X47, X50 to X56, X59, X60 and Y1 to Y6 are the same or different from each other and are each independently S, O, NR _a , CR _a R _b or SiR _a R _b .

In the present specification, X11 to X47, X50 to X56, X59, X60 and Y1 to Y6 are the same or different and each independently represents S, NR _a Or CR _a R _b .

In the present specification, R 101 to R 140 are the same or different and each independently hydrogen; A halogen group; A nitrile group; A nitro group; Carbonyl group; An ester group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the present specification, R 101 to R 140 are the same or different and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In the present specification, R 101 to R 140 are the same or different and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In the present specification, the crosslinking agent may be a diol compound or a diamine compound.

In the present specification, the diol compound is a compound containing two hydroxy groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30 carbon atoms. Examples of the diol compound include, but are not limited to, methanediol, ethylene glycol, propanediol, butanediol, and benzenediol.

In the present specification, the diamine compound is a functional group containing two amino groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Examples of the diamine compound include ethylenediamine, diaminopropane, putrescine, cadaverine, hexamethylenediamine, piperazine, and 4,4'-bipiperidine (4,4 ' -bipiperidine, and the like, but the present invention is not limited thereto.

Specifically, the diamine compound may be piperazine and 4,4'-bipiperidine.

In the present specification, the crosslinking agent in the composition may be contained in an amount of 0.0001 wt% to 10 wt% with respect to the compound. Specifically, the crosslinking agent may be contained in an amount of 0.001 wt% to 8 wt% relative to the compound. More specifically, the cross-linking agent may be contained in an amount of 0.1 wt% to 5 wt% with respect to the compound.

One embodiment of the present disclosure provides a film formed comprising a crosslinked product of the composition.

The method of forming the film is not particularly limited, and may be formed, for example, by dissolving a crosslinked material in a solvent and then using spin coating, screen printing, bar coating or slot die coating.

In the present specification, the crosslinked product of the composition means that the compound contained in the composition is crosslinked by the crosslinking agent contained in the composition.

In the present specification, the crosslinked product of the composition may include at least one of the following formulas.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 through 1-3,

And X1 and X2 are groups in which at least one hydrogen is removed from the crosslinking agent.

In this specification, the termination of at least one hydrogen means that at least one hydrogen is dropped so that the crosslinking agent binds to the compound. For example, the removal of hydrogen from piperazine may be of the following structure.

In the present specification, the crosslinked product of the composition is not limited to the above-mentioned formulas 1-1 to 1-3, but further crosslinking may occur.

In the present specification, the solvent includes, for example, chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and dichlorobenzene; Ether solvents such as tetrahydrofuran and dioxane; Aromatic hydrocarbon solvents such as toluene, xylene, trimethylbenzene and mesitylene; Aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, isophorone, tetralone, decalone, and acetylacetone; Ester solvents such as ethyl acetate, butyl acetate and ethyl cellosolve acetate; Examples of polyhydric alcohols such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, Alcohol-based solvents and derivatives thereof; Alcohol solvents such as methanol, ethanol, propanol, isopropanol, and cyclohexanol; Sulfoxide-based solvents such as dimethylsulfoxide; And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. However, a solvent capable of dissolving and film-coating the composition according to the embodiment of the present invention is sufficient, and is not limited thereto.

In this specification, the film can be used as an electron acceptor material.

In this specification, the film may further include an electron donor material.

The electron donor material is pentacene, Coumarin 6, ZnPc, CuPc, TiOPc, Spiro-MeOTAD, F ₁₆ CuPc, SubPc, P3HT, P3KT, P3OT, PCPDTBT, PCDTBT, PFDTBT, MEH-PPV, MDMO-PPV, PFO and PFO -DMP, but is not limited thereto.

When the electron donor material is further included, the electron donor material may further include a ratio of 1: 0.1 to 1: 5 by mass relative to the cured material of the composition.

In this specification, the film may be used as a dopant.

In this specification, the film may further include a hole injecting material or a hole transmitting material.

The hole injecting material may be at least one selected from the group consisting of metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene- , Anthraquinone, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto.

When the film further contains a hole injecting material, the hole injecting material may further include 0.001 wt% to 10 wt% of the composition relative to the hardening amount.

The hole transporting material may be an arylamine-based organic material, a conductive polymer, or a block copolymer having a conjugated portion and a non-conjugated portion together, but the present invention is not limited thereto.

When the hole transfer material is further contained in the film, the hole transfer material may further include 0.001 wt% to 10 wt% of the composition relative to the hard coating.

One embodiment of the present invention provides an organic electronic device to which the film is applied.

In one embodiment of the present invention, the organic electronic device includes an organic light emitting device; Organic solar cell; And an organic transistor.

In one embodiment of the present invention, the organic electronic device may further include an additional organic layer. Also, the organic electronic device can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present invention, the organic electronic device may be an organic solar cell.

In one embodiment of the present invention, the organic electronic device includes a first electrode; A second electrode; And a photoactive layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes the film.

The principle of an organic solar cell is that a p-type semiconductor forms an exciton paired with electrons and holes, and the exciton is separated into an electron and a hole at a p-n junction. The separated electrons and holes migrate to the n-type semiconductor thin film and the p-type semiconductor thin film, respectively, and they are collected in the first electrode and the second electrode, respectively, so that they can be used as electric energy from the outside.

1 is a view illustrating an organic solar cell according to an embodiment of the present invention. 1 illustrates an organic solar cell including a substrate 101, a first electrode 102, a hole transport layer 103, a photoactive layer 104, and a second electrode 105.

However, the organic solar cell according to one embodiment of the present invention is not limited to the structure and material of FIG. 1, but may be provided with additional layers, and various layers may be formed using various materials.

In one embodiment of the present disclosure, the photoactive layer may be a bulk heterojunction structure including an electron donor material and an electron acceptor material. At this time, the electron acceptor material may be the film.

Bulk heterojunction means that the electron donor material and the electron acceptor material are mixed in the photoactive layer.

The bulk heterojunctions in which the electron donor material and the electron acceptor material are mixed are mainly composed of a donor-rich portion, an acceptor-rich portion of the electron acceptor, and an electron donor- mixed phase. The excitons formed in the photoactive layer are dissociated into holes and electrons at portions where the electron carriers and the electron acceptors coexist and at portions where the electron carriers and the electron acceptors contact each other, The molecules of the donor material are moved to the first electrode or the second electrode, respectively.

In one embodiment of the present disclosure, the organic layer includes an additional organic layer disposed between the photoactive layer and the first electrode or between the photoactive layer and the first electrode or between the second electrode and the photoactive layer. May further comprise the film.

In one embodiment of the present invention, the organic material layer includes a hole transport layer, a hole injection layer, or a layer that simultaneously transports holes and holes, and the hole transport layer, the hole injection layer, And may include the film.

In one embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, And may include the film.

In one embodiment of the present invention, the organic solar battery may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

In one embodiment of the present invention, the organic solar cell may have a normal structure. The normal structure may mean that the anode is formed on the substrate. More specifically, according to one embodiment of the present invention, when the organic solar cell has a normal structure, the first electrode formed on the substrate may be an anode, and the second electrode may be a cathode.

In one embodiment of the present invention, the organic solar cell may have an inverted structure. The inverted structure may mean that the cathode is formed on the substrate. Specifically, according to an embodiment of the present invention, when the organic solar cell is an inverted structure, the first electrode formed on the substrate may be a cathode, and the second electrode may be an anode.

In this specification, the substrate may be a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness, but is not limited thereto, and is not limited as long as it is a substrate commonly used in organic solar cells. Specific examples include glass or polyethylene terephthalate, polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC) But is not limited thereto.

The anode electrode may be a transparent material having excellent conductivity. Specifically, the anode electrode may be formed of a metal such as vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The method of forming the anode electrode is not particularly limited and may be applied to one surface of the substrate or may be coated in a film form using, for example, sputtering, E-beam, thermal evaporation, spin coating, screen printing, inkjet printing, doctor blade or gravure printing . ≪ / RTI >

When the anode electrode is formed on a substrate, it may undergo cleaning, moisture removal and hydrophilic reforming processes.

For example, the patterned ITO substrate is sequentially washed with a cleaning agent, acetone, and isopropyl alcohol (IPA), and then dried on a heating plate at 100 to 150 ° C for 1 to 30 minutes, preferably 120 ° C for 10 minutes If the substrate is completely cleaned, the surface of the substrate may be modified to be hydrophilic.

Through such surface modification, the junction surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. Further, in the modification, the formation of the polymer thin film on the anode electrode is facilitated, and the quality of the thin film may be improved.

The pretreatment techniques for the anode electrode include a) surface oxidation using a parallel plate discharge, b) a method of oxidizing the surface through ozone generated using UV ultraviolet radiation in vacuum, and c) oxygen generated by the plasma And a method of oxidizing using a radical.

One of the above methods can be selected depending on the state of the anode electrode or the substrate. However, whichever method is used, it is preferable to prevent oxygen from escaping from the surface of the anode electrode or the substrate and to suppress the residual of moisture and organic matter as much as possible. At this time, the substantial effect of the preprocessing can be maximized.

As a specific example, a method of oxidizing the surface through ozone generated using UV can be used. At this time, the ITO substrate patterned after the ultrasonic cleaning is baked on a hot plate, dried well, then put into a chamber, and is irradiated with ozone generated by reaction of oxygen gas with UV light by operating a UV lamp The patterned ITO substrate can be cleaned.

However, the method of modifying the surface of the patterned ITO substrate in the present specification is not particularly limited, and any method may be used as long as it is a method of oxidizing the substrate.

The cathode electrode may be a metal having a small work function. Specifically, the cathode may be formed of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or an alloy thereof; Layer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The cathode may be deposited in a thermal evaporator having a degree of vacuum of 5 x 10 ^{< -7} > torr or less, but the method is not limited thereto.

The hole transporting layer and / or the electron transporting layer material efficiently transfer electrons and holes separated from the photoactive layer to the electrode, and the material is not particularly limited.

The hole transport layer material may include poly (3,4-ethylenediocythiophene) doped with poly (styrenesulfonic acid) (PEDOT: PSS), molybdenum oxide (MoO _x ); Vanadium oxide (V ₂ O ₅ ); Nickel oxide (NiO); And tungsten oxide (WO _x ), but the present invention is not limited thereto.

The electron transport layer material may be electron-extracting metal oxides, specifically a metal complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Metal complexes including Liq; LiF; Ca; Titanium oxide (TiO _x ); Zinc oxide (ZnO); And cesium carbonate (Cs ₂ CO ₃ ), but the present invention is not limited thereto.

The photoactive layer can be formed by dissolving a photoactive material such as an electron donor and / or an electron acceptor in an organic solvent, and then applying the solution by spin coating, dip coating, screen printing, spray coating, doctor blade, brush painting, But is not limited to the method.

In one embodiment of the present invention, the organic electronic device may be an organic light emitting device.

In one embodiment of the present invention, the organic light emitting device includes a first electrode, a second electrode, and at least one organic layer provided between the first electrode and the second electrode, and at least one of the organic layers includes And may include the film.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

In one embodiment of the present invention, the organic material layer of the organic light emitting device includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, May comprise the film.

In another embodiment, the organic material layer of the organic light emitting element may include a light emitting layer, and the light emitting layer may include the film.

In one embodiment of the present invention, the organic material layer of the organic light emitting device includes an electron transport layer, an electron injection layer, or a layer that simultaneously transports electrons and electron, and the electron transport layer, the electron injection layer, The layer that is to be made at the same time may comprise said film.

2 is a diagram illustrating an organic light emitting device according to an embodiment of the present invention. 2, the organic light emitting device includes a substrate 101, a first electrode 102, a light emitting layer 106, and a second electrode 105. In such a structure, the film may be included in the light emitting layer.

However, the organic light emitting device according to one embodiment of the present invention is not limited to the structure and material of FIG. 2, but may include additional layers and may be formed of various layers using various materials.

In one embodiment of the present specification, the light emitting layer may include a host material and a dopant material.

In one embodiment of the present invention, the host material includes a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds and pyrimidine derivatives, but are not limited thereto.

In one embodiment of the present invention, the dopant material includes an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamine groups, such as pyrene, anthracene, chrysene, and ferriflantene having an arylamine group. Examples of the styrylamine compound include substituted or unsubstituted Substituted arylamine in which at least one aryl vinyl group is substituted, wherein at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamine group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

In one embodiment of the present invention, the electron transport layer, the electron injection layer, the hole transport layer, and the hole injection layer of the organic light emitting device are not particularly limited as long as they are materials used in the art.

In one embodiment of the present disclosure, the organic electronic device may be an organic transistor.

In one embodiment of the present invention, the organic transistor includes a gate electrode, a source electrode, a drain electrode, an insulating layer, and at least one organic layer, and at least one of the organic layers includes an organic electronic element do.

In this specification, the organic transistor may be a top gate structure. Specifically, the source electrode 108 and the drain electrode 107 may be formed first on the substrate 101, and then the organic layer 109, the insulating layer 110, and the gate electrode 111 may be sequentially formed. Figure 3 shows the structure of the organic transistor accordingly.

In this specification, the organic transistor may be a bottom contact structure of a bottom gate structure. Specifically, a gate electrode and an insulating layer are sequentially formed on the substrate, a source electrode and a drain electrode are formed on the insulating layer, and finally, an organic semiconductor layer is formed on the source electrode and the drain electrode.

In this specification, the organic transistor may be a top contact structure of a bottom gate structure. Specifically, a gate electrode and an insulating layer are sequentially formed on a substrate, an organic semiconductor layer is formed on an insulating layer, and finally, a source electrode and a drain electrode are formed on the organic semiconductor layer.

Further, HMDS (1,1,1,3,3,3-hexamethyldisilazane), octyltrichlorosilane (OTS), and octadecyltrichlorosilane (OTDS) may be coated between the source electrode and the drain electrode and the organic semiconductor layer.

In this specification, the gate electrode, the source electrode, and the drain electrode are not particularly limited as long as they are materials used in the art. For example, it may be a conductive material. Specifically, it may be a material selected from the group consisting of Au, Ag, Al, Ni, Cr, and ITO.

In this specification, the source electrode and the drain electrode may be manufactured using an E-beam photolithography method, but the present invention is not limited thereto.

In the present specification, the insulating layer is not particularly limited as long as it is a material used in the art. For example, silicon dioxide (SiO ₂ ), which has a high insulation rate and can be easily formed on the gate electrode, can be used.

In this specification, the method of manufacturing the insulating layer is not particularly limited as long as it is a method used in the related art. For example, the insulating layer may be manufactured using an E-beam or photolithography method, but the present invention is not limited thereto.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present specification is not construed as being limited to the embodiments described below. Embodiments of the present disclosure are provided to more fully describe the present disclosure to those of ordinary skill in the art.

Manufacturing example  One.

(1) Preparation of Compound (1)

Compound A (0.7 g, 0.42 mmol), Compound B (0.4 g, 2.1 mmol) and 2 mL of pyridine were added to 70 mL of chloroform (CHCl ₃ ) in a nitrogen atmosphere, and the mixture was stirred under a nitrogen atmosphere for 24 hours . After the reaction, the reaction product was extracted with methylene chloride (CH ₂ Cl ₂ ) and washed with water. The solvent was then removed and the residual product was recrystallized using methylene chloride and methanol and chromatographed on silica gel column using chloroform (CHCl ₃ ) as the eluent Respectively. Recrystallization twice with chloroform and ethylacetate, and filtration gave a black solid. The solid was then washed with methanol and dried under vacuum for 24 hours to give 0.595 g of a black solid (Compound 1). (Yield: 70%).

Fig. 4 shows the MS spectrum of Compound 1. Fig.

(2) Crosslinking of Compound 1

Compound 1 and 4,4'-bipiperidine were mixed at a weight ratio of 10: 1 and reacted at room temperature for 30 minutes to obtain Compound 1-A, Compound 1-B and Compound 1 C was obtained.

FIG. 5 is a graph showing the MS spectrum of the compound prepared in Production Example 1. FIG.

Manufacturing example  2.

Compound 1-A, Compound 1-B and Compound 1-B were prepared in the same manner as in Production Example 1 except that Compound 1 and 4,4'-bipiperidine were reacted at room temperature for 1 hour. Compound 1-C was obtained.

6 is a graph showing the MS spectrum of the compound prepared in Preparation Example 2. Fig.

Manufacturing example  3.

Compound 1-A, Compound 1 (Compound 1), Compound 1-A and compound 4-Bipiperidine were prepared in the same manner as in Preparation Example 1, except that Compound 1 and 4,4'-bipiperidine were reacted at 80 ° C for 30 minutes at room temperature. -B and compound 1-C.

7 is a graph showing the MS spectrum of the compound prepared in Preparation Example 3. FIG.

In FIGS. 5 to 7, the compound 1-A is shown in a circle, the compound 1-B is shown in square, and the compound 1-C is shown in triplicate.

Manufacturing example  4.

Compound 2 (ITIC, Solarmer) and piperazine were mixed in a weight ratio of 10: 1 and reacted at room temperature for 30 minutes to obtain Compound 2-A, Compound 2-B and Compound 2-C as described below.

8 is a graph showing the MS spectrum of Compound 2-B.

Manufacturing example  5.

Compound 2 (ITIC, Solarmer) and bi-piperazine were mixed at a weight ratio of 10: 1 and reacted at room temperature for 30 minutes to obtain Compound 2-D, Compound 2-E and Compound 2-F .

9 is a graph showing the MS spectrum of Compound 2-E.

Example  One.

(1) Preparation of complex solution 1

Compound 2 and Compound 10 were dissolved in chlorobenzene (CB) at a weight ratio of 1: 1.3 to prepare a composite solution 1. At this time, the concentration was adjusted to 2.5 wt%.

(2) Preparation of complex solution 2 and production of organic solar cell

The complex solution 1 and the piperazine were mixed in a volume ratio of 1: 1 to prepare a complex solution 2. The organic solar cell has a structure of ITO / PEDOT: PSS / photoactive layer / Al. PEDOT: PSS (AI4083) was prepared by ozone treatment of the ITO surface for 10 min. The glass substrate coated with 1.5 × 1.5 cm ² of ITO in bar type was ultrasonically cleaned using distilled water, acetone and 2-propanol. Was spin coated at 4000 rpm for 40 seconds and heat treated at 235 캜 for 10 minutes to form a 45 nm thick PEDOT: PSS layer. Thereafter, the composite solution 2 was spin-coated at 1,000 rpm for 20 seconds to form a film having a thickness of 158 nm. The formed film was dried through heat treatment to form a photoactive layer. Finally, 3x10 ^- under ⁸ torr vacuum using a thermal evaporator (thermal evaporator) the organic solar battery was produced by depositing Al by 1Å / s speed to 100nm thick.

Example  2.

In Example 1, the composite solution 2 was spin-coated at 1,000 rpm for 20 seconds to form a photoactive layer, and then heat-treated at 100 ° C to prepare a photoactive layer.

Example  3.

In Example 1, the complex solution 2 was spin-coated at 800 rpm for 20 seconds to form a photoactive layer.

Example  4.

In Example 1, the complex solution 2 was spin-coated at 1200 rpm for 20 seconds to form a photoactive layer, and the same procedure as in Example 1 was conducted.

Comparative Example  One.

An organic solar cell was prepared in the same manner as in Example 1, except that the complex solution 1 was spin-coated at 1,000 rpm for 20 seconds to form a photoactive layer.

Comparative Example  2.

An organic solar cell was prepared in the same manner as in Example 1, except that the composite solution 1 was spin-coated at 1,000 rpm for 20 seconds and then heat-treated at 100 ° C to form a photoactive layer.

Comparative Example  3.

An organic solar cell was prepared in the same manner as in Example 1, except that the complex solution 1 was spin-coated at 800 rpm for 20 seconds to form a photoactive layer.

Comparative Example  4.

An organic solar cell was prepared in the same manner as in Example 1, except that the complex solution 1 was spin-coated at 1,200 rpm for 20 seconds to form a photoactive layer.

The performance of the organic solar cell prepared in Examples 1 to 4 and Comparative Examples 1 to 4 was measured under the condition of ¹ sun (100 mW / cm ² ), which is a reference light quantity of a solar simulator.

FIGS. 10 and 11 show current densities according to the voltages of the organic solar cells manufactured in Examples 1 to 4 and Comparative Examples 1 to 4. The higher the X-axis and Y-axis intercepts in the fourth quadrant of the current density curve according to the voltage, the higher the efficiency of the solar cell is, and the fill factor is a rectangular width that can be drawn inside the curve. The energy conversion efficiency can be obtained by dividing the value (open-circuit voltage, short-circuit current, charge rate) by the intensity of the irradiated light.

10 and 11, it can be confirmed that Examples 1 to 4, in which the complex solution 1 and piperazine were mixed, were superior in performance to Comparative Examples 1 to 4 in which the complex solution 1 was used alone. This is because the use of piperazine reduces the aggregation phenomenon of the compound 2 and improves the stability of the solution.

Example  5.

(1) Preparation of complex solution 3

Compound 2 and Compound 10 were dissolved in dichlorobenzene at a weight ratio of 1: 1.3 to prepare a composite solution 3. At this time, the concentration was adjusted to 2.5 wt%.

(2) Preparation of complex solution 4 and production of organic solar cell

The complex solution 3 and 4,4'-bipiperidine were mixed in a volume ratio of 1: 1 to prepare a complex solution 4. The organic solar cell has a structure of ITO / PEDOT: PSS / photoactive layer / Al. PEDOT: PSS (AI4083) was prepared by ozone treatment of the ITO surface for 10 min. The glass substrate coated with 1.5 × 1.5 cm ² of ITO in bar type was ultrasonically cleaned using distilled water, acetone and 2-propanol. Was spin coated at 4000 rpm for 40 seconds and heat treated at 235 캜 for 10 minutes to form a 45 nm thick PEDOT: PSS layer. Thereafter, the composite solution 2 was spin-coated at 1,000 rpm for 20 seconds to form a film having a thickness of 158 nm. The formed film was dried through heat treatment to form a photoactive layer. Lastly, Al was deposited at a rate of 1 Å / s with a thickness of 100 nm using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr to produce an organic solar cell.

Comparative Example  5.

An organic solar cell was prepared in the same manner as in Example 5 except that the complex solution 3 was spin-coated at 1,000 rpm for 20 seconds to form a photoactive layer.

The organic solar cells prepared in Example 5 and Comparative Example 5 were stored in a vacuum oven at 120 ° C for 1 hour, and then the performance was measured under the condition of ¹ Sun (100 mW / cm ² ) as a reference light quantity of a solar simulator.

12 shows the results of the stability evaluation of the organic solar cell prepared in Example 5 and Comparative Example 5. Fig. According to Fig. 12, it can be confirmed that Example 5 in which the complex solution 3 and non-piperazine were mixed had better stability than Comparative Example 5 in which the complex solution 3 was used alone.

101: substrate
102: first electrode
103: Hole transport layer
104: photoactive layer
105: second electrode
106: light emitting layer
107: drain electrode
108: source electrode
109: organic layer
110: insulating layer
111: gate electrode

Claims (13)

A composition comprising a compound of formula (1) and a crosslinking agent:
[Chemical Formula 1]

In Formula 1,
R1 to R4 are the same or different from each other and each independently represents a halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Amide group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted amine group; Or a substituted or unsubstituted sulfonyl group,
R5 and R6 are the same or different and each independently O or S,
R7 and R8 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
n and m are each an integer of 1 to 4,
When n and m are each 2 or more, the structures in parentheses are the same or different from each other,
L is a conjugated structure-containing group. The method according to claim 1,
Wherein the conjugated structure-containing group comprises a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a combination of one or two or more groups of a substituted or unsubstituted divalent heterocyclic group. The method according to claim 1,
Wherein the conjugated structure-containing group comprises any one or combination of two or more of the following structures:

In the above structure,
a, e, f, g, g ', h, h', i, i ', j and j'
In the case where a, e, f, g, g ', h, h', i, i ', j and j' are 2 or more, the structures in parentheses are the same or different,
b and b 'are each an integer of 1 to 3,
b and b 'are 2 or more, the structures in parentheses are the same or different from each other,
c and d are each 1 or 2,
When c and d are each 2 or more, the structures in parentheses are the same or different from each other
X11 to X47, X50 to X56, X59, X60 and Y1 to Y6 are the same as or different from each other, each independently S, O, Se, Te, NR _a, CR _a R _b, SiR _a R _b, PR _a, or GeR _a R _b ,
X48, X49, X57 and X58 are the same or different and each independently C, Si or Ge,
R101 to R104 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R _a and R _b are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; A hydroxy group; Carbonyl group; An ester group; Imide; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkylsulfoxy group; A substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1,
Wherein the crosslinking agent is a diol compound or a diamine compound. The method according to claim 1,
Wherein the composition comprises 0.0001 wt% to 10 wt% of the crosslinking agent relative to the compound. A film comprising a crosslinked product of the composition of any one of claims 1 to 5. 7. An organic electronic device comprising the film of claim 6. The method of claim 7,
The organic electronic device may include an organic light emitting device; Organic solar cell; And an organic transistor. The method of claim 7,
The organic electronic device includes a first electrode; A second electrode; And a photoactive layer provided between the first electrode and the second electrode, the organic solar cell comprising:
Wherein at least one of the organic material layers comprises the film. The method of claim 9,
Wherein the organic material layer includes a hole transporting layer, a hole injecting layer, or a layer simultaneously transporting holes and injecting holes,
Wherein the hole transport layer, the hole injection layer, or the layer that simultaneously transports the hole and the hole injects the film. The method of claim 9,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport,
Wherein the electron injecting layer, the electron transporting layer, or the layer simultaneously injecting electrons and transporting electrons comprises the film. The method of claim 7,
The organic electronic device includes a first electrode; A second electrode; And at least one organic compound layer provided between the first electrode and the second electrode,
Wherein at least one of the organic material layers comprises the film. The method of claim 7,
The organic electronic device is an organic transistor including a gate electrode, a source electrode, a drain electrode, an insulating layer, and at least one organic layer,
Wherein at least one of the organic material layers comprises the film.

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