KR20150009127A - Polymer and organic solar cell comprising the same - Google Patents

Abstract

Provided are a polymer and an organic solar cell including the polymer. According to an embodiment of the specification, the polymer can be used as a material of an organic material layer of the organic solar cell. Also, the organic solar cell includes a substrate, a first electrode, a hole transport layer, a light activation layer, and a second electrode, thereby showing excellent properties in increase of open voltage and short current, and/or efficiency.

Description

POLYMER AND ORGANIC SOLAR CELL COMPRISING THE SAME [0002]

The present invention relates to polymers and organic solar cells comprising them.

Organic solar cells are devices that can convert solar energy directly into electric energy by applying photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells depending on the material constituting the thin film. A typical solar cell is made of p-n junction by doping crystalline silicon (Si), which is an inorganic semiconductor. Electrons and holes generated by absorption of light are diffused to the p-n junction, accelerated by the electric field, and moved to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit to the solar power entering the solar cell, and is achieved up to 24% when measured under the current standardized virtual solar irradiation conditions. However, since conventional inorganic solar cells have already been limited in economic efficiency and supply / demand of materials, organic semiconductor solar cells, which are easy to process, have various functions and are inexpensive, are seen as long-term alternative energy sources.

Solar cells are important to increase efficiency so that they can output as much electrical energy as possible from solar energy. In order to increase the efficiency of such a solar cell, it is also important to generate as much excitons as possible in the semiconductor, but it is also important to draw out generated charges without loss. One of the causes of loss of charge is that the generated electrons and holes are destroyed by recombination. Various methods have been proposed as methods for transferring generated electrons and holes to electrodes without loss, but most of them require additional processing, which may increase the manufacturing cost.

US 5331183 US 5454880

Two-layer organic photovoltaic cells (C. W. Tang, Appl. Phys. Lett., 48, 183. (1996) Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995)).

It is an object of the present invention to provide a polymer and an organic solar cell including the same.

In one embodiment of the present invention, there is provided a polymer comprising a first unit represented by the following general formula (1).

[Chemical Formula 1]

In formula (1)

a is an integer of 1 to 2,

when a is 2, R is the same as or different from each other,

R is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

 In another embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic layer provided between the first electrode and the second electrode and including a photoactive layer, wherein at least one of the organic layers includes the above-described polymer.

The polymer of the present invention can be used as a material for an organic solar cell organic material layer, and an organic solar cell using the polymer can exhibit excellent characteristics in terms of an increase in open circuit voltage and short circuit current and / or an increase in efficiency.

In particular, polymers according to one embodiment of the present disclosure may exhibit superior properties with deep HOMO levels, small bandgaps, and high charge mobilities. The polymer according to one embodiment of the present invention can be used alone or in combination with other materials in an organic solar cell, and can improve the efficiency and improve the lifetime characteristics of the device by the thermal stability of the compound.

1 shows an organic solar cell according to one embodiment.

Hereinafter, the present invention will be described in detail.

As used herein, the term "unit" means a repeating structure contained in a monomer of a polymer, wherein the monomer is bonded to the polymer by polymerization.

In one embodiment of the present invention, there is provided a polymer comprising a first unit represented by the general formula (1).

Polymers according to one embodiment of the present disclosure have asymmetric positions where N is not symmetric. In this case, the organic solar cell including the polymer absorbs solar light of a long wavelength and can realize a high efficiency, and the polymer has an electron attracting effect of -3.3 eV to -3.7 eV It has the appropriate LUMO energy level.

In one embodiment of the present specification, a is 1.

In one embodiment of the present disclosure, R is located next to N, not between N and N in formula (1).

In another embodiment, the first unit represented by the formula (1) is represented by the following formula (2).

(2)

In formula (2)

R is the same as defined in formula (1).

In one embodiment of the present specification, R is a substituted or unsubstituted alkoxy group. In this case, the solubility can be increased.

In one embodiment of the present specification, R is a substituted or unsubstituted C1-C30 alkoxy group.

In one embodiment of the present specification, the polymer is a monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; And a second unit comprising at least one member selected from the group consisting of a monocyclic or polycyclic heterocyclic group and a condensed divalent condensed ring in which a monocyclic or polycyclic aromatic ring is substituted or unsubstituted.

In the present specification, the meaning of "including a second unit" in the polymer is meant to be included in the main chain or side chain in the polymer. In one embodiment of the present disclosure, the second unit is included in the main chain of the polymer.

In one embodiment of the present specification, the second unit is any one of the following formulas.

b is an integer of 1 to 4,

c is an integer of 1 to 6,

d is an integer of 1 to 8,

e and f are each an integer of 1 to 3,

R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,

X1 to X3 are the same or different and each independently selected from the group consisting of CR'R ", NR ', O, SiR'R", PR', S, GeR'R ", Se and Te,

Y1 to Y4 are the same or different from each other and each independently selected from the group consisting of CR ', N, SiR', P and GeR '

R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, Dog It is selected from the group consisting of a substituted or unsubstituted heterocyclic group containing a.

In one embodiment of the present invention, the polymer includes those represented by the following general formula (3).

(3)

In formula (3)

R is the same as defined in formula (1)

p is an integer of 1 to 10,000,

1 is a molar fraction, 0? 1 < 1,

m is a mole fraction, 0? m < 1,

o is the molar fraction, 0 < o &lt; = 1,

n is a molar fraction, 0? n <1,

l + m + n + o = 1,

M1 to M3 are the same or different and are each independently a direct bond; A monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; Or a condensed divalent condensed ring in which a monocyclic or polycyclic heterocyclic group and a monocyclic or polycyclic aromatic ring are substituted or unsubstituted.

In one embodiment of the present invention, each of M1 to M3 is represented by any one of the following formulas.

b is an integer of 1 to 4,

c is an integer of 1 to 6,

d is an integer of 1 to 8,

e and f are each an integer of 1 to 3,

R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,

X1 to X3 are the same or different and each independently selected from the group consisting of CR'R ", NR ', O, SiR'R", PR', S, GeR'R ", Se and Te,

Y1 to Y4 are the same or different from each other and each independently selected from the group consisting of CR ', N, SiR', P and GeR '

R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, Dog It is selected from the group consisting of a substituted or unsubstituted heterocyclic group containing a.

Examples of such substituents are described below, but are not limited thereto.

As used herein, the term " substituted or unsubstituted " A halogen group; An alkyl group; An alkenyl group; An alkoxy group; A cycloalkyl group; Silyl group; An arylalkenyl group; An aryl group; An aryloxy group; An alkyloxy group; An alkylsulfoxy group; Arylsulfoxy group; Boron group; An alkylamine group; An aralkylamine group; An arylamine group; A heteroaryl group; Carbazole group; An arylamine group; An aryl group; A fluorenyl group; A nitrile group; A nitro group; Means a substituted or unsubstituted group selected from the group consisting of a hydroxyl group and a heterocyclic group containing at least one of N, O and S atoms.

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 amide group may be mono- or di-substituted by nitrogen of the amide group with hydrogen, a straight-chain, branched-chain or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, N-octyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

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 20 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 straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. 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 the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group, and includes a case where an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms is substituted. In addition, an aryl group in the present specification may mean an aromatic ring.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 carbon atoms. Specific examples of the monocyclic aryl group include, but are not limited to, a phenyl group, a biphenyl group, a terphenyl group, and a stilbenyl group.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, a fluorenyl group is a structure in which two cyclic organic compounds are connected through one atom.

The fluorenyl group includes a structure of an open fluorenyl group, wherein the open fluorenyl group is a structure in which one ring compound is disconnected in a structure in which two ring organic compounds are connected through one atom.

,

,

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 silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, But are not limited thereto.

In the present specification, the number of carbon atoms of the amine group 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, a 9- , A diphenylamine group, a phenylnaphthylamine group, a ditolylamine group, a phenyltolylamine group, a triphenylamine group, and the like, but are not limited thereto.

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 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.

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, the heterocyclic group is a heterocyclic group containing at least one of O, N and S as a heteroatom. 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, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolinyl group, an isoquinolyl group, A benzothiazole group, a benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group and aralkylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include phenoxy, p-tolyloxy, m-tolyloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, Naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl Phenanthryloxy, 9-phenanthryloxy and the like. Examples of the arylthioxy group include phenylthio group, 2-methylphenylthio group, 4-tert-butylphenyl And the like. Examples of the aryl sulfoxy group include a benzene sulfoxy group and a p-toluenesulfoxy group, but the present invention is not limited thereto.

In the present specification, the heteroaryl group in the heteroarylamine group can be selected from the examples of the above-mentioned heterocyclic group.

In the present specification, the alkyl group in the alkylthio group and the alkylsulfoxy group is the same as the alkyl group described above. Specific examples of the alkyloxy group include a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group and an octylthio group. Examples of the alkylsulfoxy group include a mesyl group, an ethylsulfoxy group, a propylsulfoxy group, But are not limited thereto.

In one embodiment of the present specification, R is a substituted or unsubstituted alkoxy group.

In one embodiment of the present disclosure, R is an octoxy group.

를 포함한다. In one embodiment of the present disclosure, the second unit is

.

를 포함한다. In one embodiment of the present disclosure, the second unit is

.

를 포함한다. In one embodiment of the present disclosure, the second unit is

.

를 포함한다. In one embodiment of the present disclosure, the second unit is

.

In one embodiment of the present invention, the polymer includes the copolymer represented by the following general formulas (1-1) to (1-5).

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

In Formulas 1-1 to 1-5,

a, e, f, R, R1, R2, X1, X2, X3, Y1 and Y2 are as defined above,

R1 'and R1 "are the same as or different from each other, and each independently is the same as defined in R1,

X1 'and X1 "are the same as or different from each other, and each independently represents the same definition as X1,

Y1 'and Y1' 'are the same as or different from each other, and each independently is the same as Y1.

In one embodiment of the present disclosure, X1 is S, SiR'R "or NR '.

In one embodiment of the present disclosure, X1 is S.

In one embodiment of the present disclosure, X1 is SiR'R ".

In one embodiment of the present disclosure, X1 is NR '.

In one embodiment of the present disclosure, X2 is S.

In one embodiment of the present disclosure, X3 is S.

In one embodiment of the present disclosure, Y1 is CR '.

In one embodiment of the present specification, Y2 is CR '.

In one embodiment of the present disclosure, R1 is hydrogen.

In one embodiment of the present disclosure, R 2 is hydrogen.

In one embodiment of the present invention, R 'and R "are the same or different from each other, and each independently hydrogen, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted alkyl group.

In one embodiment of the present disclosure, R 'is hydrogen.

In one embodiment of the present invention, R 'is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted branched alkyl group.

In one embodiment of the present specification, R 'is a 2-ethyl-hexyl group.

In one embodiment of the present specification, R is a 9-heptadecanyl group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted alkoxy group.

In one embodiment of the present specification, R 'is a substituted or unsubstituted alkoxy group of a branched chain.

In one embodiment of the present disclosure, R 'is a 2-ethylheptoxy group.

In one embodiment of the present specification, R "is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R "is a substituted or unsubstituted branched alkyl group.

In one embodiment of the present specification, R "is a 2-ethyl-hexyl group.

를 포함하고, 상기 X1은 S이고, Y1은 CR'이다. In one embodiment of the present disclosure, the second unit is

, X1 is S, and Y1 is CR '.

를 포함하고, 상기 X1은 S이고, Y1은 CR'이며, R' 및 R1은 수소이다. In one embodiment of the present disclosure, the second unit is

, X1 is S, Y1 is CR ', and R' and R1 are hydrogen.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, and each independently CR '.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 치환 또는 비치환된 알콕시기이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, each independently CR ', and R' is a substituted or unsubstituted alkoxy group.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 분지쇄의 알콕시기이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, and each independently CR 'and R' is an alkoxy group of a branched chain.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 분지쇄의 알콕시기이고, R1 및 R2는 수소이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, and each independently CR ', R' is a branched chain alkoxy group, and R1 and R2 are hydrogen.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 알킬기가 치환된 알콕시기이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, each independently CR ', and R' is an alkoxy group substituted with an alkyl group.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 2-에틸헥톡시기이다. In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, and each independently CR 'and R' is a 2-ethylheptoxy group.

를 포함하고, X1는 S, X2는 S이고, Y1 및 Y2는 서로 동일하거나 상이하고, 각각 독립적으로 CR'이며, R'는 2-에틸헥톡시기이고, R1 및 R2는 수소이다.In one embodiment of the present disclosure, the second unit is

X1 is S, X2 is S, Y1 and Y2 are the same as or different from each other, and each independently CR ', R' is a 2-ethylheptoxy group, and R1 and R2 are hydrogen.

를 포함하고, X1은 SiR'R"이다. In one embodiment of the present disclosure, the second unit is

X1 is SiR'R &quot;.

를 포함하고, X1은 SiR'R"이며, R' 및 R"은 치환 또는 비치환된 알킬기이다. In one embodiment of the present disclosure, the second unit is

, X1 is SiR'R &quot;, and R 'and R "are substituted or unsubstituted alkyl groups.

를 포함하고, X1은 SiR'R"이며, S2 및 S3는 S이다. In one embodiment of the present disclosure, the second unit is

X1 is SiR'R &quot;, and S2 and S3 are S.

를 포함하고, X1은 SiR'R"이며, R' 및 R"은 분지쇄의 알킬기이며, S2 및 S3는 S이고, R1 및 R2는 수소이다. In one embodiment of the present disclosure, the second unit is

, X1 is SiR'R &quot;, R 'and R "are a branched chain alkyl group, S2 and S3 are S, and R1 and R2 are hydrogen.

를 포함하고, X1은 SiR'R"이며, R' 및 R"은 2-에틸-헥실기이고, S2 및 S3는 S이고, R1 및 R2는 수소이다. In one embodiment of the present disclosure, the second unit is

X1 is SiR'R ", R 'and R" are 2-ethylhexyl groups, S2 and S3 are S, and R1 and R2 are hydrogen.

를 포함하고, X1은 NR'이고, R'는 치환 또는 비치환된 알킬기이다. In one embodiment of the present disclosure, the second unit is

, X1 is NR ', and R' is a substituted or unsubstituted alkyl group.

를 포함하고, X1은 NR'이고, R'는 분지쇄의 알킬기이다. In one embodiment of the present disclosure, the second unit is

, X1 is NR ', and R' is an alkyl group of a branched chain.

를 포함하고, X1은 NR'이고, R'는 9-헵타데카닐기이다. In one embodiment of the present disclosure, the second unit is

, X1 is NR ', and R' is a 9-heptadecanyl group.

In one embodiment of the present disclosure, M1 is a direct bond.

In one embodiment of the present disclosure, M2 is a direct bond.

In one embodiment of the present disclosure, M3 is a direct bond.

이다. In one embodiment of the present disclosure,

to be.

이다. In one embodiment of the present disclosure,

to be.

이다. In one embodiment of the present disclosure,

to be.

이다. In one embodiment of the present disclosure,

to be.

이다. In one embodiment of the present disclosure, M2 is

to be.

이다. In one embodiment of the present disclosure, M2 is

to be.

이다. In one embodiment of the present disclosure, M2 is

to be.

이다. In one embodiment of the present disclosure,

to be.

In one embodiment of the present disclosure, the polymer comprises any one of the following copolymers 1 to 5:

[Copolymer 1]

[Copolymer 2]

[Copolymer 3]

[Copolymer 4]

[Copolymer 5]

In the copolymers 1 to 5, p is the same as defined above.

In one embodiment of the present disclosure, the polymer is selected from the group consisting of random copolymers, alternative copolymers, block copolymers, graft copolymers, star copolymers, starblock copolymer).

In another embodiment, the polymer comprises an alternative copolymer.

In one embodiment of the present disclosure, the terminal group of the copolymer is selected from the group consisting of hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms.

In one embodiment of the present invention, the terminal group of the copolymer is a heterocyclic group or an aryl group.

In one embodiment of the present invention, the terminal group of the copolymer is a 4- (trifluoromethyl) phenyl group.

In one embodiment of the present disclosure, the first unit is from 1 mole% to 100 mole% of the total content of polymer.

In one embodiment of the present invention, the first unit of the total polymer content is from 1 mol% to 100 mol%, and the second unit has a total content of from 0 mol% to 99 mol%.

According to one embodiment of the present disclosure, the number average molecular weight of the polymer is preferably from 500 g / mol to 1,000,000 g / mol. Preferably, the number average molecular weight of the polymer is 10,000 to 100,000. In one embodiment of the present disclosure, the number average molecular weight of the polymer is from 30,000 to 70,000.

According to one embodiment of the present disclosure, the polymer may have a molecular weight distribution of from 1 to 100. Preferably, the polymer has a molecular weight distribution of from 1 to 3.

The lower the molecular weight distribution and the higher the number average molecular weight, the better the electrical and mechanical properties.

In addition, the number-average molecular weight is preferably 100,000 or less in order to have a solubility of more than a certain level and to be advantageous in application of a solution coating method.

The polymer can be produced on the basis of the following production example.

Polymers according to the present disclosure can be prepared by a multistage chemical reaction. The monomers are produced through an alkylation reaction, a Grignard reaction, a Suzuki coupling reaction, a Stille coupling reaction, and the like, followed by a carbon-carbon coupling reaction such as a steel coupling reaction, . &Lt; / RTI &gt; When the substituent to be introduced is a boronic acid or a boronic ester compound, it can be prepared through a Suzuki coupling reaction. When the substituent to be introduced is a tributyltin compound, But it is not limited thereto.

In one embodiment of the present disclosure, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer including a photoactive layer, wherein at least one of the organic compound layers includes the polymer.

An organic solar cell according to an embodiment of the present invention includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transporting layer, and / or an electron transporting layer.

In one embodiment of the present invention, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron beams and the electron acceptors. The generated holes are transported to the anode through the electron donor layer.

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, Lt; RTI ID = 0.0 &gt; polymer. &Lt; / RTI &gt;

In another embodiment, the organic material layer may include 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 the polymer.

In one embodiment of the present invention, when the organic solar cell receives photons from an external light source, electrons and holes are generated between the electron beams and the electron acceptors. The generated holes are transported to the anode through the electron donor layer.

In one embodiment of the present disclosure, the organic solar cell may further include an additional organic layer. The organic solar cell can reduce the number of organic layers by using organic materials having various functions at the same time.

In one embodiment of the present disclosure, the organic solar cell may be arranged in the order of the cathode, the photoactive layer, and the anode, and may be arranged in the order of the anode, the photoactive layer, and the cathode, but is not limited thereto.

In another embodiment, the organic solar cell may be arranged in the order of an anode, a hole transporting layer, a photoactive layer, an electron transporting layer and a cathode, and may be arranged in the order of a cathode, an electron transporting layer, a photoactive layer, a hole transporting layer, , But is not limited thereto.

In another embodiment, a buffer layer may be provided between the photoactive layer and the hole transporting layer or between the photoactive layer and the electron transporting layer. At this time, a hole injection layer may be further provided between the anode and the hole transport layer. Further, an electron injecting layer may be further provided between the cathode and the electron transporting layer.

In one embodiment of the present invention, the photoactive layer includes one or two or more selected from the group consisting of an electron donor and a donor, and the electron donor material includes the polymer.

In one embodiment of the present disclosure, the electron acceptor material may be selected from the group consisting of fullerene, fullerene derivatives, vicoprofoins, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, there can be a _{PC 61 BM (phenyl C 61 -butyric} acid methyl ester) or _{PC 71 BM (phenyl C 71 -butyric} acid methyl ester).

In one embodiment of the present invention, the mixing ratio between the polymer and the electron acceptor is from 1: 0.5 to 1: 4.

In one embodiment of the present disclosure, the electron donor and the electron acceptor are bulk heterojunction (BHJ). The electron donor material and the electron acceptor material are mixed in a ratio (w / w) of 1:10 to 10: 1.

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, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, and gold, or alloys 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 . &Lt; / RTI &gt;

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 detergent, 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 , And the substrate surface is hydrophilically reformed when the substrate is completely cleaned.

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, but is not limited thereto. Specifically, metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure such as LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ and Al: BaF ₂ : Ba.

The cathode electrode may be formed by depositing in a thermal evaporator having a degree of vacuum of 5 x 10 &lt; ^-7 &gt; 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.

The production method of the polymer and the production of the organic solar battery including the same will be described in detail in the following Production Examples and Examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

Example  One. Monomer  Synthesis-1 ( Thieno [3,4-d] pyrimidine 4-ol ( thieno [3,4-d] pyrimidin-4-ol)

In the present specification, formamidine acetate was prepared by referring to the prior literature. (Krechl, Jiri, Boehm, Stanislav; Smrckova, Svatava; Kuthan, Josef, Collection of Czechoslovak Chemical Communications 54, 1989, 673-683)

In this specification, ethyl 4-aminothiophene-3-carboxylate hydrochloride was prepared by referring to the prior literature. (Shinkwin, Anne E .; Whish, William J. D .; Threadgill, Michael D., Bioorganic and Medicinal Chemistry 7, 1999, 297-308)

(Ethyl 4-aminothiophene-3-carboxylate hydrochloride (10 g, 40.0 mmol) and formamidine acetate (16.1 g, 40.0 mmol) were added to 100 ml of ethanol. , 155 mmol), and the mixture was stirred under reflux for 24 hours. After that, the reaction mixture was poured into ice water and the precipitated solid was filtered out, and then this was poured into 150 ml of water and washed again. After 5 minutes, the solids were filtered off again and the water and the remaining solvent were removed under vacuum to recover the solids.

Yield: 73.1%

MS: 152.01

Example  2. Monomer  Synthesis-2 (4- ( Octyloxy ) Cyeno Synthesis of [3,4-d] pyrimidine (4- (octyloxy) thieno [3,4-d] pyrimidine)

Thieno [3,4-d] pyrimidin-4-ol (1 g, 6.57 mmol) was added to 30 ml of dimethylformamide (DMF) Then, potassium hydroxide (3.68 g, 65.7 mmol) was added thereto and stirred for 30 minutes. Then, 1-bromooctane (1.52 g, 7.89 mmol) was added thereto and stirred for 24 hours. After the reaction, the mixture was poured into water, extracted three times with methylene chloride, washed three times with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The remaining solution was distilled under reduced pressure to remove the solvent and purified by column chromatography.

Yield: 53.5%

MS: 264.10

Example  3. Monomer  Synthesis of 3 (5,7- Dive Lomo -4-( Octyloxy ) Cyeno [3,4-d] pyrimidine (5,7- dibromo -4-( octyloxy ) thieno [3,4-d] 피리 미딘 ))

(Octyloxy) thieno [3,4-d] pyrimidine (1 g, 3.78 mmol) in 20 ml of dimethylformamide (DMF) And N-bromosuccinimide (0.808 g, 4.54 mmol) was added thereto, followed by stirring for 12 hours. Then, the mixture was poured into water, extracted three times with methylene chloride, washed three times with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The remaining solution was distilled under reduced pressure to remove the solvent and purified by column chromatography.

Yield: 78.2%

MS: 419.9

Example  4. Monomer  Synthesis-4 (4- ( Octyloxy ) -5,7-di ( Thiophene -2 days) Cyeno [3,4-d] pyrimidine) (4- ( octyloxy ) -5,7-di ( thiophen -2- yl ) thieno [3,4-d] pyrimidine

A microwave reactor vial was charged with 15 ml of chlorobenzene, 2-tributylstannyl thiophene (1.56 g, 4.17 mmol), 5,7-dibromo-4- ( (Octyloxy) thieno [3,4-d] pyrimidine, 0.8 g, 1.89 mmol), Pd ₂ (dba) _{3 (} O-tolyl) phosphine (70 mg), and the mixture was reacted at 170 ° C for 1 hour. The mixture was cooled to room temperature, poured into water, extracted three times with methylene chloride, washed three times with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The remaining solution was distilled under reduced pressure to remove the solvent and purified by column chromatography.

Yield: 63.0%

MS: 428.1

Example  5. Monomer  Synthesis 5 (4- ( Octyloxy ) -5,7-di ( Thiophene -2 days) Cyeno [3,4-d] pyrimidine (5,7- bis (5- bromothiophen -2- yl )-4-( octyloxy ) thieno [3,4-d] pyrimidine)))

(Octyloxy) -5,7-di (thiophen-2-yl) thieno [3,4-d] pyrimidine) (4- (octyloxy) Thiophen-2-yl) thieno [3,4-d] pyrimidine (0.7 g, 1.63 mmol) was dissolved in N, N-Bromosuccinimide (0.639 g, 3.59 mmol) were added and stirred for 12 hours. Then, the mixture was poured into water, extracted three times with methylene chloride, washed three times with water, and the residue was removed with magnesium sulfate (MgSO ₄ ). The remaining solution was distilled under reduced pressure to remove the solvent and purified by column chromatography.

Yield: 60.1%

MS: 583.9

Example  6. Polymer Polymerization (Polymerization of Copolymer 1)

15 ml of chlorobenzene and 2.5-bis (trimethylstannyl) thiophene (1.2 g, 2.93 mmol) were added to a microwave reactor vial, 5 , 5-dibromo-4- (octyloxy) thieno [3,4-d] pyrimidine, 1.2364 g, 2.93 mmol), Pd ₂ (dba) _{3 (} Tris (dibenzylideneacetone) dipalladium (0), 80 mg) and tri- (o-tolyl) phosphine Lt; / RTI &gt; for 1 hour. The mixture was cooled to room temperature, poured into methanol, and the solids were filtered through Soxhlet extraction with methanol, acetone, hexane and chloroform. The chloroform portion was again precipitated in methanol to remove the solid.

Yield: 58%

Number average molecular weight: 41,400 g / mol

Weight average molecular weight: 82,500 g / mol

Example  7. Polymer Polymerization (Polymerization of Copolymer 2)

In the present specification, the term "2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4,5-b '] dithiophene (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4,5- b '] dithiophene) was prepared by referring to the previous literatures. (P. Morvillo, F. Parenti, R. Diana, C. Fontanesi, A. Mucci, F.Tassinari, L.Schenetti, Solar Energy Materials & Solar Cells 104, 2012, 45-52)

A microwave reactor vial was charged with 15 ml of chlorobenzene, 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4 , 5-b '] dithiophene, 1.2 g, 1.55 (2-ethylhexyloxy) benzo [1,2- mmol, 5,7-dibromo-4- (octyloxy) thieno [3,4-dlpyrimidine (5,7-dibromo-4- (octyloxy) thieno [ 0.656 g and 1.55 mmol), Pd ₂ (dba) _{3 (} Tris (dibenzylideneacetone) dipalladium (0), 43 mg) and tri- (o-tolyl) phosphine And the reaction was allowed to proceed at 170 ° C for 1 hour. The mixture was cooled to room temperature, poured into methanol, and the solids were filtered through Soxhlet extraction with methanol, acetone, hexane and chloroform. The chloroform portion was again precipitated in methanol to remove the solid.

Yield: 68%

Number average molecular weight: 19,800 g / mol

Weight average molecular weight: 33,900 g / mol

Example  8. Polymer Polymerization (Polymerization of Copolymer 3)

As used herein, 4,4'-bis (2-ethyl-hexyl) -5,5'-bis (trimethyltin) -dithiano [3,2-b: 2 ', 3'- 4'-Bis (2-ethyl-hexyl) -5,5'-bis (trimethyltin) -dithieno [3,2-b: 2 ', 3'-d] silole) Respectively. (J. Hou, H. Chen, S. Zhang, G. Li, Y. Yang, J.Am.Chem.Soc. 130, 2008, 16144-16145)

A microwave reactor vial was charged with 15 ml of chlorobenzene, 4,4'-bis (2-ethyl-hexyl) -5,5'-bis (trimethyltin) -dithiano [3 Bis (2-ethyl-hexyl) -5,5'-bis (trimethyltin) -dithieno [3,2-b: 2 ', 3'- 3'-d] silole, 1.2 g, 1.61 mmol), 5,7-dibromo-4- (octyloxy) thieno [3,4- dibromo-4- ) thieno [3,4-d] pyrimidine, 0.681 g, 1.61 mmol), Pd ₂ (dba) _{3 (} Tris (dibenzylideneacetone) dipalladium (0), 44 mg) (o-tolyl) phosphine, 59 mg) was added thereto and reacted at 170 ° C for 1 hour. The mixture was cooled to room temperature, poured into methanol, and the solids were filtered through Soxhlet extraction with methanol, acetone, hexane and chloroform. The chloroform portion was again precipitated in methanol to remove the solid.

Yield: 49%

Number average molecular weight: 15,000 g / mol

Weight average molecular weight: 21,600 g / mol

Example  9. Polymer Polymerization (Polymerization of Copolymer 4)

As used herein, the term 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -N, 9-heptadecanylcarbazole Bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -N, 9-heptadecanylcarbazole) was prepared by referring to the previous literatures. (N.Blouin, A. Michaud, M. Leclerc, Adv. Mater. 19, 2007, 2295-2300)

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -N, 9-heptadecanylcarbazole (2,7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -N, 9-heptadecanylcarbazole, 500 mg, 0.760 mmol), 4- (octyloxy) -5,7- 5-bromothiophen-2-yl) -4- (octyloxy) thieno [3,4-d] pyrimidine, , 6 ml of a 20 wt% aqueous solution of Et ₄ NOH and 26 mg of Pd (PPh ₃ ) ₄ were added and dissolved, and the mixture was stirred under reflux. After 72 hours, the mixture was cooled to room temperature, poured into methanol, and the solids were filtered through Soxhlet extraction with methanol, acetone, hexane and chloroform. The chloroform portion was again precipitated in methanol to remove solids.

Yield: 43%

Number average molecular weight: 27.600 g / mol

Weight average molecular weight: 78,000 g / mol

Example  10. Polymer Polymerization (Polymerization of Copolymer 5)

A microwave reactor vial was charged with 15 ml of chlorobenzene, 2,6-bis (trimethyltin) -4,8-bis (2-ethylhexyloxy) benzo [1,2-b: 4 , 5-b '] dithiophene, 1.2 g, 1.55 (2-ethylhexyloxy) benzo [1,2- 5-bromothiophen-2-yl) thiophene-2-yl) thiophene- (Octyloxy) thieno [3,4-d] pyrimidine, 911 mg, 1.55 mmol), Pd ₂ (dba) _{3 (} Tris (dibenzylideneacetone) dipalladium Phosphine (Tri- (o-tolyl) phosphine, 57 mg) was added thereto and reacted at 170 ° C for 1 hour. The mixture was cooled to room temperature, poured into methanol, and the solids were filtered through Soxhlet extraction with methanol, acetone, hexane and chloroform. The chloroform portion was again precipitated in methanol to remove the solid.

Yield: 50%

Number average molecular weight: 32,200 g / mol

Weight average molecular weight: 66,900 g / mol

Preparation and characterization of organic solar cell

Manufacturing example  1. Manufacture of organic solar cell -1

Copolymer 1 prepared in Example 6 and PCBM were dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the copolymer 1-PCBM complex solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. Using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr, Al was deposited to produce an organic solar cell.

Manufacturing example  2. Manufacture of organic solar cell -2

The copolymer 2 prepared in Example 7 and PCBM were dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the copolymer 2-PCBM complex solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. Using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr, Al was deposited to produce an organic solar cell.

Manufacturing example  3. Manufacturing of Organic Solar Cells -3

Copolymer 3 and PCBM prepared in Example 8 were dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the copolymer 3-PCBM complex solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. The resultant was filtered using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr to a thickness of 200 nm Al was deposited to produce an organic solar cell.

Manufacturing example  4. Manufacture of organic solar cell -4

Copolymer 4 and PCBM prepared in Example 9 were dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the copolymer 4-PCBM composite solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. Using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr, Al was deposited to produce an organic solar cell.

Manufacturing example  5. Manufacture of organic solar cell -5

Copolymer 5 and PCBM prepared in Example 10 were dissolved in chlorobenzene (CB) at a ratio of 1: 2 to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, and the organic solar cell had the structure of ITO / PEDOT: PSS / photoactive layer / Al. The glass substrate coated with ITO was ultrasonically cleaned using distilled water, acetone, and 2-propanol, and the ITO surface was ozone-treated for 10 minutes and spin coated with PEDOT: PSS (baytrom P) Min. For the coating of the photoactive layer, the copolymer 5-PCBM complex solution was filtered with a 0.45 μm PP syringe filter, and then spin-coated. The resultant was filtered using a thermal evaporator under a vacuum of 3 × 10 ^-8 torr to a thickness of 200 nm Al was deposited to produce an organic solar cell.

< Test Example  1>

The photoelectric conversion characteristics of the organic solar cells prepared in Production Examples 1 to 5 and Comparative Example 1 were measured under the conditions of 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

Active layer V _OC (V) J _SC (mA / cm ² ) FF PCE (%) Production Example 1 Copolymer 1 / PC ₆₁ BM = 1: 2 0.87 7.65 59.3 3.94 Production Example 2 Copolymer 2 / PC ₆₁ BM = 1: 2 0.75 3.28 54.3 1.33 Production Example 3 Copolymer 3 / PC ₆₁ BM = 1: 2 0.62 8.01 56.7 2.81 Production Example 4 Copolymer 4 / PC ₆₁ BM = 1: 2 0.89 1.26 30.9 0.35 Production Example 5 Copolymer 5 / PC ₆₁ BM = 1: 2 0.76 5.02 50.5 1.92 Comparative Example 1 P3HT / PC ₆₁ BM = 1: 1 0.64 8.30 55.5 2.94

In Table 1, the total thickness means the thickness of the active layer in the organic solar cell, V _oc is the open voltage, J _sc is the short-circuit current, FF is the fill factor, and PCE is the energy conversion efficiency. The open-circuit voltage and the short-circuit current are the X-axis and Y-axis intercepts in the fourth quadrant of the voltage-current density curve, respectively. The higher the two values, the higher the efficiency of the solar cell. The fill factor is the width of the rectangle that can be drawn inside the curve divided by the product of the short-circuit current and the open-circuit voltage. The energy conversion efficiency can be obtained by dividing these three values by the intensity of the irradiated light, and a higher value is preferable.

101: substrate
102: first electrode
103: Hole transport layer
104: photoactive layer
105: second electrode

Claims (16)

1. A polymer comprising a first unit represented by the following formula (1): &lt; EMI ID =
[Chemical Formula 1]

In formula (1)
a is an integer of 1 to 2,
when a is 2, R is the same as or different from each other,
R is hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms. The method according to claim 1,
Wherein the first unit represented by the formula (1) is represented by the following formula (2):
(2)

In formula (2)
R is the same as defined in formula (1). The method according to claim 1,
Wherein R is a substituted or unsubstituted alkoxy group. The method according to claim 1,
The polymer may be a monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; And a second unit comprising at least one member selected from the group consisting of a monocyclic or polycyclic heterocyclic group and a condensed divalent condensed ring in which a monocyclic or polycyclic aromatic ring is substituted or unsubstituted. The method of claim 4,
Wherein the second unit is represented by any one of the following formulas:

b is an integer of 1 to 4,
c is an integer of 1 to 6,
d is an integer of 1 to 8,
e and f are each an integer of 1 to 3,
R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,
X1 to X3 are the same or different and each independently selected from the group consisting of CR'R ", NR ', O, SiR'R", PR', S, GeR'R ", Se and Te,
Y1 to Y4 are the same or different from each other and each independently selected from the group consisting of CR ', N, SiR', P and GeR '
R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, Dog It is selected from the group consisting of a substituted or unsubstituted heterocyclic group containing a. The method according to claim 1,
Wherein the polymer comprises a polymer represented by the following Formula 3:
(3)

In formula (3)
R is the same as defined in formula (1)
p is an integer of 1 to 10,000,
1 is a molar fraction, 0? 1 < 1,
m is a mole fraction, 0? m < 1,
o is the mole fraction, 0 < o < = 1,
n is a molar fraction, 0? n <1,
l + m + n + o = 1,
M1 to M3 are the same or different and are each independently a direct bond; A monocyclic or polycyclic substituted or unsubstituted divalent heterocyclic group; A monocyclic or polycyclic substituted or unsubstituted divalent aromatic ring group; Or a condensed divalent condensed ring in which a monocyclic or polycyclic heterocyclic group and a monocyclic or polycyclic aromatic ring are substituted or unsubstituted. The method of claim 6,
Wherein each of M1 to M3 is represented by any one of the following formulas:

b is an integer of 1 to 4,
c is an integer of 1 to 6,
d is an integer of 1 to 8,
e and f are each an integer of 1 to 3,
R1 to R4 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A nitro group; Imide; Amide group; A hydroxy 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 alkylamine group; A substituted or unsubstituted aralkylamine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted heteroarylamine group; A substituted or unsubstituted aryl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; And a substituted or unsubstituted heterocyclic group containing at least one of N, O and S atoms, or two adjacent substituents may form a condensed ring,
X1 to X3 are the same or different and each independently selected from the group consisting of CR'R ", NR ', O, SiR'R", PR', S, GeR'R ", Se and Te,
Y1 to Y4 are the same or different from each other and each independently selected from the group consisting of CR ', N, SiR', P and GeR '
R 'and R "are the same or different from each other and each independently represents hydrogen, deuterium, halogen, nitrile, nitro, imide, amide, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthioxy group, a substituted or unsubstituted arylthioxy group, a substituted or unsubstituted alkylsulfoxy group, a substituted or unsubstituted aryloxy group, A substituted or unsubstituted alkenyl group, a substituted or unsubstituted silyl group, a substituted or unsubstituted boron group, a substituted or unsubstituted alkylamine group, a substituted or unsubstituted aralkylamine group, a substituted or unsubstituted aryl group, A substituted or unsubstituted aryl group, a substituted or unsubstituted arylamine group, a substituted or unsubstituted heteroarylamine group, a substituted or unsubstituted aryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazole group, Dog It is selected from the group consisting of a substituted or unsubstituted heterocyclic group containing a. The method according to any one of claims 1 to 7,
Wherein the number average molecular weight of the polymer is from 500 / mol to 1,000,000 g / mol. The method according to any one of claims 1 to 7,
Wherein the polymer has a molecular weight distribution of 1 to 100. A first electrode; A second electrode facing the first electrode; And at least one organic layer provided between the first electrode and the second electrode and including a photoactive layer, wherein at least one of the organic layers includes a polymer according to any one of claims 1 to 7 The organic solar cell will be. The method of claim 10,
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 transporting layer, the hole injecting layer, or the layer simultaneously transporting the holes and the hole injecting layer comprises the polymer. The method of claim 10,
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 copolymer. The method of claim 10,
Wherein the photoactive layer comprises one or more selected from the group consisting of an electron donor and an electron donor,
Wherein the electron donor comprises the polymer. 14. The method of claim 13,
Wherein the electron acceptor is selected from the group consisting of fullerene, a fullerene derivative, a carbon nanotube, a carbon nanotube derivative, a subcomplex, a semiconductor element, a semiconducting compound, and a combination thereof. 14. The method of claim 13,
Wherein the mixing ratio of the polymer to the electron acceptor is 1: 0.5 to 1: 4. 15. The method of claim 14,
Wherein the electron donor and the electron acceptor are bulk heterojunction (BHJ).

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