KR20200003710A - Polymer and organic solar cell comprising the same - Google Patents

Abstract

The present specification provides: a polymer comprising a repeating unit represented by chemical formula 1 and a conjugated monomer; and an organic solar cell comprising the same. The polymer according to an embodiment of the present specification exhibits planarity, thereby having excellent aggregation characteristics and crystallinity, and having economical advantage in time and/or cost in manufacturing a device.

Description

POLYMER AND ORGANIC SOLAR CELL COMPRISING THE SAME

This application claims the benefit of the application date of Korean Patent Application No. 10-2018-0076380 filed with the Korea Intellectual Property Office on July 2, 2018, the entire contents of which are incorporated herein.

The present specification relates to a polymer and an organic solar cell including the same.

Organic solar cells are devices that can directly convert solar energy into electrical energy by applying the photovoltaic effect. Solar cells can be divided into inorganic solar cells and organic solar cells, depending on the material of the thin film. Typical solar cells are made of p-n junctions by doping crystalline silicon (Si), an inorganic semiconductor. Electrons and holes generated by absorbing light diffuse to the p-n junction and are accelerated by the electric field to move to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuits and the solar power into the solar cell, which is now up to 24% when measured under standardized virtual solar irradiation conditions. However, since the conventional inorganic solar cell has already shown a limitation in terms of economic and material supply and demand, organic semiconductor solar cells which are easy to process, inexpensive and have various functionalities are spotlighted as long-term alternative energy sources.

It is important to increase efficiency so that solar cells can output as much electrical energy as possible from solar energy. It is important to generate as much excitons as possible inside the semiconductor to increase the efficiency of such solar cells, but it is also important to draw the generated charges to the outside without loss. One of the causes of the loss of charge is that the generated electrons and holes disappear by recombination. Various methods have been proposed as methods for transferring the generated electrons or holes to the electrodes without losing the electrons or holes, but most of the additional processes are required and manufacturing costs may increase accordingly.

Two-layer organic photovoltaic cell (C.W.Tang, Appl. Phys. Lett., 48, 183. (1986)) Efficiencies via Network of Internal Donor-Acceptor Heterojunctions (G. Yu, J. Gao, J. C. Hummelen, F. Wudl, A. J. Heeger, Science, 270, 1789. (1995))

The present specification provides a polymer and an organic solar cell including the same.

The present specification is a repeating unit represented by the formula (1); And

Provided are polymers comprising conjugated monomers.

[Formula 1]

In Chemical Formula 1,

m1, m2, q1 and q2 are the same as or different from each other, and each independently an integer of 1 to 5,

When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

Z1 to Z6 are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',

R1 to R12, R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

Another embodiment of the present specification is a first compound represented by the following formula (2); And

It provides a polymer manufacturing method comprising the step of reacting a second compound represented by the formula (3).

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

m1, m2, q1 and q2 are the same as or different from each other, and each independently an integer of 1 to 5,

When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

A1, A1 ', A2 and A2' are the same as or different from each other, and each independently a halogen group; -BR _a R _b ; Or -SnR _a R _b R _c ,

E1 is the first conjugated monomer,

Z1 to Z6 are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',

R1 to R12, R _a , R _b , R _c , R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

Another embodiment of the present specification is a first electrode;

A second electrode provided to face the first electrode; And

At least one organic material layer provided between the first electrode and the second electrode, including a photoactive layer,

At least one layer of the organic material layer provides an organic solar cell comprising the polymer.

The polymer according to one embodiment of the present specification exhibits planarity, and is excellent in aggregation characteristics and crystallinity.

The polymer according to one embodiment of the present specification may have the effect of reducing the band gap and / or increasing the amount of light absorbed. Accordingly, when applied to an organic solar cell, as the high current value Isc is exhibited, excellent efficiency can be exhibited.

The polymer according to an exemplary embodiment of the present specification has a high solubility and at the same time has a suitable solubility, and thus has an economical time and / or cost in manufacturing the device.

The polymer according to one embodiment of the present specification may be used alone or in combination with other materials in an organic solar cell.

1 illustrates an organic solar cell according to an exemplary embodiment of the present specification.
2 is a diagram showing an MS measurement result of compound a-3.
3 is a diagram showing an NMR measurement result of compound a-3.
4 is a diagram showing an MS measurement result of compound a-4.
5 is a diagram showing a result of NMR measurement of compound a-4.
6 is a diagram showing an NMR measurement result of Compound A.
7 is a DSC measurement result of Polymer 1.
8 is a UV measurement result of Polymer 1.
9 is a diagram showing a result of MS measurement for compound b-2.
10 is a diagram showing an NMR measurement result of compound b-2.
11 is a DSC measurement result of Polymer 2.
12 is a UV measurement result of Polymer 2.
FIG. 13 is a DSC measurement result of Polymer 6. FIG.
14 is a result of UV measurement of polymer 6.

Hereinafter, the present specification will be described in detail.

An exemplary embodiment of the present specification includes a repeating unit represented by Chemical Formula 1; And a conjugated monomer.

The repeating unit represented by Chemical Formula 1 includes thiophene having electron donor properties and benzothiadiazole and diketopyrrolopyrrole structures having electron withdrawing properties. Therefore, the intermolecular interaction between the thiophene and the benzothiadiazole and the intramolecular interaction between the thiophene and the diketopyrrolopyrrole exhibit excellent planarity and agglomeration properties, thereby improving crystallinity. do.

In addition, the side chain of the repeating unit represented by the formula (1) has a certain orientation, it can improve the crystallinity. That is, R9 and R10 of the general formula (1) has a certain orientation can improve the crystallinity.

In one embodiment of the present specification, the polymer is a repeating unit represented by Formula 1; And conjugated monomers.

As used herein, the term "repeating unit" refers to a structure in which a monomer unit is repeatedly included in a polymer, and a plurality of monomers are bonded to the polymer by polymerization.

In one embodiment of the present specification, "the repeating unit represented by Chemical Formula 1" may include the following structure in the main chain.

In the above structure, m1, m2, q1, q2, Z1 to Z6 and R1 to R12 are the same as defined in the formula (1).

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.

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

In the present specification, "combination" means connecting a plurality of structures or connecting different types of structures.

Examples of substituents in the present specification are described below, but are not limited thereto.

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

Means a site bonded to another substituent, monomer or binding moiety.

In the present specification, the monomer may mean a repeating unit included in the polymer. For example, the conjugated monomer may mean a repeating unit derived from the conjugated monomer included in the polymer.

In the present specification, "derived" means that the bond between at least two adjacent elements in the compound is broken, or new bond is generated while hydrogen or a substituent is separated, and the repeating unit derived from the conjugated monomer is a main chain of the polymer. And a unit forming one or more of the side chains. The unit may be included in the main chain in the polymer to constitute the polymer.

Examples of substituents in the present specification are described below, but are not limited thereto.

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

In the present specification, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Carbonyl group; Ester group; Hydroxyl group; An alkyl group; Cycloalkyl group; An alkoxy group; Alkenyl groups; Silyl groups; Amine group; Aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group or substituted with a substituent to which two or more substituents in the above-described substituents are connected, or does not have any substituents. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.

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

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto. It is not.

In the present specification, the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heterocyclic group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Sleepyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C30. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the ester group may be substituted with oxygen or carbon of an ester group having 1 to 25 carbon atoms, a straight chain, branched chain or cyclic alkyl group or an aryl group having 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. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, carbon number 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, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-arylalkylamine group; Arylamine group; N-aryl heteroaryl amine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group and the like, but is not limited thereto.

In the present specification, the alkenyl group described above may be applied except that the alkenylene group is a divalent group.

In the present specification, the above description about the aryl group may be applied except that the arylene group is a divalent group.

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

In one embodiment of the present specification, the polymer includes a unit represented by the following Formula 1-1 or Formula 1-2.

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

m1, m2, m1 ', m2', q1, q2, q1 'and q2' are the same as or different from each other, and each independently an integer of 1 to 5,

When m1, m2, m1 ', m2', q1, q2, q1 'and q2' are each 2 or more, the structures in parentheses are the same or different from each other,

Z1 to Z6 and Z1 'to Z6' are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',

E1 is the first conjugated monomer,

E2 is the second conjugated monomer,

R1 to R12, R1 'to R12', R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

f is the mole fraction, which is a real number 0 <f <1,

g is the mole fraction, which is a real number 0 <g <1,

f + g = 1.

In one embodiment of the present specification, m1 and m2 are 1.

In one embodiment of the present specification, m1 'and m2' are 1.

In one embodiment of the present specification, q1 and q2 are two.

In one embodiment of the present specification, q1 'and q2' are two.

In one embodiment of the present specification, the polymer includes a unit represented by the following Formula 1-3 or 1-4.

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-3 and 1-4,

Z1 to Z6, Z1 'to Z6', Z3 '', Z4 '', Z3 '' ', and Z4' '' are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR ', PR or GeRR',

E1 is the first conjugated monomer,

E2 is the second conjugated monomer,

R1 to R12, R1 'to R12', R3 "to R6", and R3 '"to R6'", R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

f is the mole fraction, which is a real number 0 <f <1,

g is the mole fraction, which is a real number 0 <g <1,

f + g = 1.

In one embodiment of the present specification, Z1 to Z6 are each S.

In one embodiment of the present specification, Z1 'to Z6' are each S.

In one embodiment of the present specification, Z3 '', Z4 '', Z3 '' 'and Z4' '' are each S.

In one embodiment of the present specification, R1 to R12 and R3 ″ to R6 ″ are the same as or different from each other, and each independently hydrogen; Halogen group; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R1 and R8 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 and R8 are each hydrogen.

In one embodiment of the present specification, R1 and R8 are each a branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R2 to R7 are each hydrogen.

In one embodiment of the present specification, R9 and R10 are the same as or different from each other, and are each independently a halogen group.

In one embodiment of the present specification, R9 and R10 are fluorine, respectively.

In one embodiment of the present specification, R11 and R12 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R11 and R12 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R11 and R12 are the same as or different from each other, and each independently a branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R3 ″ to R6 ″ are each hydrogen.

In one embodiment of the present specification, R1 'to R12' and R3 '' 'to R6' '' are the same as or different from each other, and each independently hydrogen; Halogen group; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R1 'to R8' are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R1 'and R8' are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 'and R8' are each hydrogen.

In one embodiment of the present specification, R1 'and R8' are each a branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R2 'to R7' are each hydrogen.

In one embodiment of the present specification, R9 'and R10' are the same as or different from each other, and are each independently a halogen group.

In one embodiment of the present specification, R9 'and R10' are each fluorine.

In one embodiment of the present specification, R11 'and R12' are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R11 'and R12' are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R11 'and R12' are the same as or different from each other, and each independently a branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R3 '' 'to R6' '' are each hydrogen.

In one embodiment of the present specification, the conjugated monomer may be one conjugated monomer.

In one embodiment of the present specification, the conjugated monomer may be two kinds of conjugated monomers.

That is, in one embodiment of the present specification, the conjugated monomer may be one conjugated monomer or two conjugated monomers. For example, the conjugated monomer includes a first conjugated monomer and a second conjugated monomer different from the first conjugated monomer.

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

In one embodiment of the present specification, the conjugated monomer includes a combination of one or two or more groups of a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted divalent heterocyclic group. do.

According to an exemplary embodiment of the present specification, the conjugated monomer includes an electron donor structure or an electron acceptor structure.

In one embodiment of the present specification, the conjugated monomers each independently include any one or a combination of two or more of the following structures.

In the above structure,

a, a ', b and b' are each an integer of 1 to 5,

when a, a ', b and b' are each 2 or more, the substituents in parentheses are the same as or different from each other,

X10 to X24 and X27 to X41 are the same as or different from each other, and each independently S, O, Se, Te, NR _d , CR _d R _e , SiR _d R _e , PR _d or GeR _d R _e ,

X25 and X26 are the same as or different from each other, and each independently C, Si or Ge,

R110 to R135, R _d and R _e are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, the conjugated monomer is any one of the following structures.

In the above structure,

X14, X15 and X30 to X41 are the same as or different from each other, and each independently S, O, Se, Te, NR _d , CR _d R _e , SiR _d R _e , PR _d or GeR _d R _e ,

R110, R111, R124 to R135, R _d and R _e are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, X14, X15, X30, X31, X34, X35 X36 to X39 and X41 are each S.

In one embodiment of the present specification, X32 and X33 are the same as or different from each other, and each independently CR _d R _e , R _d and R _e is the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, X32 and X33 are the same as or different from each other, and each independently CR _d R _e , R _d and R _e is the same as or different from each other, and is each independently a substituted or unsubstituted aryl group.

In one embodiment of the present specification, X32 and X33 are the same as or different from each other, and each independently CR _d R _e , R _d and R _e is the same as or different from each other, and each independently a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, X32 and X33 are the same as each other, and each independently CR _d R _e , R _d and R _e are the same as each other, and are each independently a phenyl group substituted with an alkyl group.

In one embodiment of the present specification, X32 and X33 are the same as or different from each other, and each independently CR _d R _e , R _d and R _e is the same as or different from each other, and each independently a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, X32 and X33 are the same as or different from each other, and each independently CR _d R _e , R _d and R _e is the same as or different from each other, and each independently a substituted or unsubstituted thiophene group.

In one embodiment of the present specification, X32 and X33 are the same as each other, and each independently CR _d R _e , R _d and R _e are the same as each other, and are each independently a thiophene group substituted with an alkyl group.

In one embodiment of the present specification, X40 is NR _d , and R _d is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, X40 is NR _d , and R _d is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, X40 is NR _d , and R _d is a branched alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R110 and R111 are the same as or different from each other, and are each independently a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, R110 and R111 are the same as or different from each other, and are each independently a substituted or unsubstituted thiophene group.

In one embodiment of the present specification, R110 and R111 are the same as or different from each other, and each independently a thiophene group substituted with an alkyl group.

In one embodiment of the present specification, R124 and R125 are each hydrogen.

In one embodiment of the present specification, R126 to R131 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R126, R127, R130, and R131 are each hydrogen.

In one embodiment of the present specification, R128 and R129 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R128 and R129 are the same as or different from each other, and are each independently an alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R128 and R129 are the same as each other, and are each an alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R132 to R135 are each hydrogen.

In one embodiment of the present specification, the conjugated monomer is any one of the following structures.

In one embodiment of the present specification, the polymer includes any one of the following structures.

In the above structure,

n is an integer from 1 to 10,000.

In one embodiment of the present specification, n is an integer of 2 to 5,000.

In one embodiment of the present specification, n is an integer of 5 to 1,000.

In one embodiment of the present specification, the end group of the polymer is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, the end group of the polymer is an aryl group substituted with a halogen group.

In one embodiment of the present specification, the end group of the polymer is a benzotrifluoride group.

In one embodiment of the present specification, the polymer has a number average molecular weight of 2,000 g / mol to 30,000,000 g / mol. Preferably, the number average molecular weight of the polymer is from 5,000 g / mol to 10,000,000 g / mol. More preferably, the number average molecular weight of the polymer is 10,000 g / mol to 5,000,000 g / mol.

In one embodiment of the present specification, the polymer may have a molecular weight distribution (PDI) of 1 to 100. Preferably the polymer has a molecular weight distribution of 1-3.

In one embodiment of the present specification, the polymer is a random copolymer, an alternating copolymer or a block copolymer.

An exemplary embodiment of the present specification is a first compound represented by the formula (2); And

It provides a polymer manufacturing method comprising the step of reacting a second compound represented by the formula (3).

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

m1, m2, q1 and q2 are the same as or different from each other, and each independently an integer of 1 to 5,

When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,

A1, A1 ', A2 and A2' are the same as or different from each other, and each independently a halogen group; -BR _a R _b ; Or -SnR _a R _b R _c ,

E1 is the first conjugated monomer,

Z1 to Z6 are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',

R1 to R12, R _a , R _b , R _c , R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, the first compound represented by Formula 2; And

Reacting the second compound represented by Formula 3 is

First compound; Second compound; And reacting the third compound represented by Formula 4 below.

[Formula 4]

In Chemical Formula 4,

A3 and A3 'are the same as or different from each other, and each independently a halogen group; -BR _a R _b ; Or -SnR _a R _b R _c ,

R _a , R _b And R _c are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

E2 is a second conjugated monomer different from the first conjugated monomer.

That is, in one embodiment of the present specification, the method of preparing the polymer may include reacting two compounds, or may include reacting three compounds. At this time, the two compounds are the first compound represented by Formula 2; And a second compound represented by Chemical Formula 3, wherein the three compounds include a first compound; Second compound; And a third compound represented by Formula 4 above.

In one embodiment of the present specification, m1, m2, q1, q2, Z1 to Z6, and R1 to R12 of Chemical Formula 2 are the same as defined in Chemical Formula 1.

In one embodiment of the present specification, E1 of Formula 3 and E2 of Formula 4 are the same as defined in the polymer. For example, E1 and E2 are different from each other, and each has one of the following structures.

In one embodiment of the present specification, A1, A1 ', A2, A2', A3 and A3 'are the same as or different from each other, and each independently a halogen group; Or -SnR _a R _b R _c , wherein R _a , R _b , and R _c are as described above.

In one embodiment of the present specification, A1, A1 ', A2, A2', A3 and A3 'are the same as or different from each other, and are each independently bromine or -SnR _a R _b R _c , and R _a , R _b And R _c are substituted or unsubstituted alkyl groups.

In one embodiment of the present specification, A1, A1 ', A2, A2', A3 and A3 'are the same as or different from each other, and are each independently bromine or -SnR _a R _b R _c , and R _a , R _b And R _c are methyl groups.

In one embodiment of the present specification, the first compound represented by Formula 2; And reacting the second compound represented by Chemical Formula 3 includes refluxing a solution of the first compound and the second compound in a polymerization solvent at 90 ° C. to 150 ° C.

In one embodiment of the present specification, the polymer manufacturing method comprises a first compound in a solvent; Second compound; And dissolving the third compound.

In one embodiment of the present specification, the first compound; Second compound; And reacting the third compound represented by Chemical Formula 4 includes adding a third compound to a solution in which the first compound and the second compound are dissolved, and then refluxing at 90 ° C to 150 ° C.

In one embodiment of the present specification, after the refluxing step, one or more of passing through a silica column, filtering and extracting soxhlet may be further performed.

In one embodiment of the present specification, the solvent is a polymerization solvent.

In one embodiment of the present specification, the polymerization solvent may be toluene, dimethylformamide (DMF), chlorobenzene, dichlorobenzene and trichlorobenzene.

In one embodiment of the present specification, the content of the second compound in the solution is 0.3 mol to 1 mol relative to 1 mol of the first compound.

In one embodiment of the present specification, the content of the third compound in the solution is 0.3 mol to 1 mol relative to 1 mol of the first compound.

In one embodiment of the present specification, the solution means that each compound is dissolved in the polymerization solvent.

An exemplary embodiment of the present specification, the first electrode;

A second electrode provided to face the first electrode; And

It includes at least one organic material layer provided between the first electrode and the second electrode, including a photoactive layer,

At least one layer of the organic material layer provides an organic solar cell comprising the polymer.

In one embodiment of the present specification, the photoactive layer includes the polymer.

In one embodiment of the present specification, the photoactive layer includes an electron donor and an acceptor, and the electron donor includes the polymer.

In one embodiment of the present specification, the electron acceptor may be selected from the group consisting of fullerene, fullerene derivatives, vasocuproin, semiconducting elements, semiconducting compounds, and combinations thereof. Specifically, the electron acceptor may be PC ₆₀ BM (phenyl C ₆₀ -butyric acid methyl ester), PC ₆₁ BM (phenyl C ₆₁ -butyric acid methyl ester) or PC ₇₁ BM (phenyl C ₇₁ -butyric acid methyl ester) have.

In one embodiment of the present specification, the electron donor and the electron acceptor constitute a bulk hetero junction (BHJ).

In one embodiment of the present specification, the electron donor and the electron acceptor may be mixed in a ratio (w / w) of 1:10 to 10: 1. Specifically, the electron donor and the electron acceptor may be mixed in a ratio (w / w) of 1: 1 to 1:10, and more specifically, the electron donor and the electron acceptor may be mixed in a ratio of 1: 1 to 1: 5 (w). / w). If necessary, the electron donor and the electron acceptor may be mixed in a ratio (w / w) of 1: 1 to 1: 3.

In one embodiment of the present specification, the photoactive layer has a bilayer bilayer structure including an n-type organic compound layer and a p-type organic compound layer, and the p-type organic compound layer includes the polymer.

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

In one embodiment of the present specification, the organic solar cell is one or more organic material layer selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generating layer, an electron blocking layer, an electron injection layer and an electron transport layer. It includes more.

In one embodiment of the present specification, the organic material layer includes a hole transport layer, a hole injection layer, or a layer for simultaneously transporting holes and holes, and the hole transport layer, the hole injection layer, or a layer for simultaneously transporting holes and holes It includes the compound.

In another exemplary embodiment, the organic material layer includes an electron injection layer, an electron transport layer, or a layer for simultaneously injecting and transporting electrons, and the electron injection layer, the electron transport layer, or the layer for simultaneously transporting electrons and transporting electrons. It includes the compound.

In one embodiment of the present specification, the organic solar cell includes a first electrode, a photoactive layer, and a second electrode. The organic solar cell may further include a substrate, a hole transport layer, and / or an electron transport layer.

In one embodiment of the present specification, the organic solar cell further includes a substrate and a hole transport layer.

1 illustrates an organic solar cell according to an exemplary embodiment of the present specification including a first electrode 101, an electron transport layer 102, a photoactive layer 103, a hole transport layer 104, and a second electrode 105. It is also.

In one embodiment of the present specification, the organic solar cell further includes a substrate, a hole transport layer, and an electron transport layer.

In one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode. In another embodiment of the present specification, the first electrode is a cathode, and the second electrode is an anode.

In one embodiment of the present specification, the organic solar cell has a normal structure. In the normal structure, a substrate, a first electrode, a hole transport layer, an organic material layer including a photoactive layer, an electron transport layer, and a second electrode may be stacked in this order.

In one embodiment of the present specification, the organic solar cell has an inverted structure. In the inverted structure, a substrate, a first electrode, an electron transport layer, an organic material layer including a photoactive layer, a hole transport layer, and a second electrode may be stacked in this order.

In the present 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 the substrate may be any substrate that is commonly used in organic solar cells. Specifically, there are glass or polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polypropylene (PP), polyimide (PI), and triacetyl cellulose (TAC). It is not limited to this.

The first electrode may be a transparent and excellent conductive material, but is not limited thereto. Metals such as vanadium, chromium, copper, zinc, gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

The method of forming the first electrode is not particularly limited, but may be applied to one surface of the substrate or in the form of a film using, for example, sputtering, E-beam, thermal deposition, spin coating, screen printing, inkjet printing, doctor blade or gravure printing. It can be formed by coating.

When the first electrode is formed on the substrate, it may be subjected to cleaning, moisture removal, and hydrophilic modification.

For example, the patterned ITO substrate is sequentially cleaned with a detergent, acetone, and isopropyl alcohol (IPA), and then 1 to 30 minutes at 100 ° C. to 150 ° C., preferably at 120 ° C. for 10 minutes, on a heating plate to remove moisture. When the substrate is dried and thoroughly cleaned, the surface of the substrate is modified to be hydrophilic.

Through such surface modification, the bonding surface potential can be maintained at a level suitable for the surface potential of the photoactive layer. In addition, it is easy to form the polymer thin film on the first electrode during modification, the quality of the thin film may be improved.

Pretreatment techniques for the formation of the first electrode include a) surface oxidation using parallel plate discharge, b) oxidation of the surface through ozone generated using UV ultraviolet light in a vacuum state, and c) by plasma. And oxidation using the generated oxygen radicals.

One of the above methods can be selected according to the state of the first electrode or the substrate. In any case, however, it is preferable to prevent oxygen escape from the surface of the first electrode or the substrate and to minimize the residual of moisture and organic matter in common. At this time, the substantial effect of the pretreatment can be maximized.

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

However, the surface modification method of the patterned ITO substrate in this specification does not need to be specifically limited, Any method may be used as long as it is a method of oxidizing a substrate.

The second 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; LiF / Al, LiO ₂ / Al, LiF / Fe, Al: Li, Al: BaF ₂ , Al: BaF ₂ It may be a material of a multi-layer structure such as, but is not limited thereto.

The second electrode is 5x10 ^- may be formed is deposited on the internal heat evaporator showing a degree of vacuum of less than ⁷ torr, not limited to this method.

The hole transport layer and / or electron transport layer material plays a role of efficiently transferring electrons and holes separated in the photoactive layer to the electrode, and the material is not particularly limited.

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

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

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

The preparation method of the polymer and the preparation of the organic solar cell including the same will be described in detail in the following Preparation 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.

Preparation Example 1 Preparation of Polymer 1

(1) Preparation of Compound a-3

Compound a-1 (5.71 g, 5.60 mmol) and compound a-2 (7.19 g, 13 mmol) were dissolved in 120 mL toluene, and tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.25g, 0.22mmol) was added, and gradually heated to react at 90 ° C, 100 ° C, and 110 ° C for 48 hours. The resulting residue after cooling was precipitated in methanol, filtered and washed with water. The solvent is evaporated through drying, and the residual product is purified by flash chromatography using methylene chloride and chloroform, and then recrystallized from methylene chloride and methanol to obtain a solid. Got. Thereafter, the solid was washed with methanol, and dried in vacuo for 24 hours to obtain 4.13 g of compound a-3. (Yield 45%) (MALDI-TOF MS: 1636.5 g / mol)

2 is a diagram showing an MS measurement result of compound a-3.

3 is a diagram showing an NMR measurement result of compound a-3.

(2) Preparation of Compound a-4

Tetrahydrofuran solution (1.0M, in which compound a-3 (4.12 g, 2.52 mmol) was dissolved in 400 mL of tetrahydrofuran (THF) under nitrogen atmosphere at room temperature, and in which tetrabutylammonium fluoride (TBAF) was dissolved. 10 mL, 10 mmol, including 5% H ₂ O) was added dropwise and the resulting product was refluxed for 2 hours. Thereafter, 50 mL of ether and 10 mL of sodium bicarbonate (NaHCO ₃ ) aqueous solution were added and stirred for 10 minutes. Thereafter, the mixture was washed with an aqueous sodium chloride (NaCl) solution, and the solvent was evaporated under vacuum conditions. The residual product was purified by flash chromatography using chloroform and then recrystallized using chloroform to obtain a solid. Thereafter, the solid was washed with water, methanol, hexane, hexane, ethyl acetate, and acetone, and then dried under vacuum for 24 hours to obtain 1 g of compound a-4. (Yield 27%) (MALDI-TOF MS: 1492.7 g / mol)

4 is a diagram showing an MS measurement result of compound a-4.

5 is a diagram showing a result of NMR measurement of compound a-4.

(3) Preparation of Compound A

To 300 mL of chloroform (CHCl ₃ ) at 0 ° C., Compound a-4 (0.98 g, 0.66 mmol) and N-bromosuccinimide (NBS) (0.25 g, 1.40 mmol) were added and stirred at room temperature for 24 hours. It was. Thereafter, the solvent was evaporated and purified through flash chromatography (eluent (hexane to hexane: methylene chloride)) using the residue to obtain 0.881 g of Compound A. (Yield 81%) (MALDI-TOF MS: 1648.6 g / mol)

6 is a diagram showing an NMR measurement result of Compound A.

(4) Preparation of Polymer 1

In a 100 mL flask under nitrogen (N ₂ ) atmosphere, 12 mL of toluene, 3 mL of DMF, Compound A (0.25 mmol) and Compound C-1 (0.25 mmol) were added and bubbled with nitrogen for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain 137 mg of polymer 1. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 1 was prepared. (Yield 24%, Mn = 10,100 g / mol, PDI = 1.8)

7 is a DSC measurement result of Polymer 1.

It can be seen from FIG. 7 that Polymer 1 has crystalline properties.

8 is a UV measurement result of Polymer 1.

8 shows that the polymer 1 absorbs light in the visible and infrared regions.

In FIG. 8, (a) shows UV data in a solution state of polymer 1, (b) shows polymer 1 in a film state, and (c) measures polymer 1 after heat treatment at 110 ° C. for 10 minutes in a film state. UV data.

At this time, the solution state is a state in which polymer 1 is dissolved in a chlorobenzene solution, and a film is formed by spin coating the polymer 1 in solution state.

UV measurements were performed at room temperature using an Agilent Cary UV-vis-NIR spectrometer.

Preparation Example 2 Preparation of Polymer 2

(1) Preparation of Compound b-2

Compound b-1 (5.0 g, 9 mmol) was dissolved in 250 mL of THF, and 1 M lithium diisopropylamide (LDA) (15 mL, 15 mmol) was slowly injected at -78 ° C. After the reaction for 1 hour, trimethyltin chloride (trimethyltin chloride, Me ₃ SnCl) (1M, 15mmol) was slowly injected and raised to room temperature and stirred at room temperature for 5 hours. Thereafter, the mixture was washed with an aqueous sodium chloride (NaCl) solution, and the solvent was evaporated under vacuum to obtain 5.84 g of compound b-2. (Yield 90%)

9 is a diagram showing a result of MS measurement for compound b-2.

10 is a diagram showing an NMR measurement result of compound b-2.

(2) Preparation of Compound b-3

Dissolve compound a-1 (5.09 g, 5.00 mmol) and compound b-2 (8.66 g, 12 mmol) in 50 mL toluene, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (0.25g, 0.22mmol) was added, and gradually heated to react at 90 ° C, 100 ° C, and 110 ° C for 48 hours. The resulting residue on cooling was precipitated in methanol, filtered and washed with water. The solvent is then evaporated through drying, and the residual product is purified by flash chromatography using methylene chloride and chloroform, followed by recrystallization with methylene chloride and methanol. To obtain a solid. The solid was washed with methanol and dried in vacuo for 24 hours to obtain 7.41 g of compound b-3. (Yield 75%) (MALDI-TOF MS: 1973.0 g / mol)

(3) Preparation of Compound b-4

Tetrahydrofuran solution (1.0M, in which compound b-3 (7.31 g, 3.70 mmol) is dissolved in 150 mL of tetrahydrofuran (THF) under nitrogen atmosphere at room temperature, and in which tetrabutylammonium fluoride (TBAF) is dissolved. 8 mL, 8 mmol, including 5% H ₂ O) was added dropwise and the resulting product was refluxed for 2 hours. Thereafter, 50 mL of ether and 10 mL of sodium bicarbonate (NaHCO ₃ ) aqueous solution were added and stirred for 10 minutes. Thereafter, the mixture was washed with an aqueous sodium chloride (NaCl) solution, and the solvent was evaporated under vacuum conditions. The residual product was purified by flash chromatography using chloroform and then recrystallized using chloroform to give a dark purple solid. Thereafter, the solid was washed with water, methanol, hexane, ethyl acetate, and acetone, and then dried under vacuum for 24 hours to obtain 5.4 g of compound b-4. (Yield 80%) (MALDI-TOF MS: 1828.8 g / mol)

(4) Preparation of Compound B

Compound b-4 (4.57 g, 2.5 mmol) and N-bromosuccinimide (NBS) (1.07 g, 6.0 mmol) were added to 100 mL of chloroform at 0 ° C., and stirred at room temperature for 24 hours. Thereafter, the solvent was evaporated and purified through flash chromatography (eluent (hexane to hexane: methylene chloride)) using the residue to obtain 4.1 g of compound B. (Yield 82%) (MALDI-TOF MS: 1984.6 g / mol)

(5) Preparation of Polymer 2

12 mL of toluene, 3 mL of DMF, Compound B (0.25 mmol) and Compound C-1 (0.25 mmol) were added to a 100 mL flask under nitrogen (N ₂ ) atmosphere, and nitrogen bubbled for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain 452 mg of polymer 2. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 2 was prepared. (Yield 69%, Mn = 24,500 g / mol, PDI = 1.7)

11 is a DSC measurement result of Polymer 2.

It can be seen from FIG. 11 that the polymer 2 has crystallinity.

12 is a UV measurement result of Polymer 2.

12, it can be seen that the polymer 2 absorbs light in the visible and infrared regions.

In FIG. 12, (a) shows UV data in a solution state of polymer 2, (b) shows polymer 2 in a film state, and (c) measures polymer 2 after heat treatment at 110 ° C. for 10 minutes in a film state. UV data.

In this case, the solution state is a state in which polymer 2 is dissolved in a chlorobenzene solution, and a film is formed by spin coating the polymer 2 in solution state.

Preparation Example 3 Preparation of Polymer 3

In a 100 mL flask under nitrogen (N ₂ ) atmosphere, 12 mL of toluene, 3 mL of DMF, Compound B (0.25 mmol) and Compound C-2 (0.25 mmol) were added and bubbled with nitrogen for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain 580 mg of polymer 3. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 3 was prepared. (Yield 81%, Mn = 31,200 g / mol, PDI = 1.5)

Preparation Example 4 Preparation of Polymer 4

12 mL of toluene, 3 mL of DMF, Compound B (0.25 mmol) and Compound C-3 (0.25 mmol) were added to a 100 mL flask under nitrogen (N ₂ ) atmosphere, and nitrogen bubbled for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected, purified, and dried under vacuum to yield 657 mg of polymer 4. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 4 was prepared. (Yield 62%, Mn = 20,300 g / mol, PDI = 1.8)

 Preparation Example 5 Preparation of Polymer 5

12 mL of toluene, 3 mL of DMF, Compound B (0.25 mmol) and Compound C-4 (0.25 mmol) were added to a 100 mL flask under nitrogen (N ₂ ) atmosphere, and nitrogen bubbled for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected, purified, and dried under vacuum to give 618 mg of polymer 5. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 5 was prepared. (Yield 87%, Mn = 31,800 g / mol, PDI = 2.2)

Preparation Example 6 Preparation of Polymer 6

12 mL of toluene, 3 mL of DMF, Compound B (0.3 mmol), and Compound C-5 (0.3 mmol) were added to a 100 mL flask under nitrogen (N ₂ ) atmosphere, and nitrogen bubbled for 30 minutes. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected and purified, and dried under vacuum to obtain 434 mg of polymer 6. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer 6 was produced. (Yield 60%, Mn = 29,000 g / mol, PDI = 1.4)

FIG. 13 is a DSC measurement result of Polymer 6. FIG.

It can be seen from FIG. 13 that Polymer 6 has crystalline properties.

14 is a result of UV measurement of polymer 6.

14 shows that the polymer 6 absorbs light in the visible and infrared regions.

In FIG. 14, (a) shows UV data in a solution state of polymer 6, (b) shows polymer 6 in film state, and (c) measures polymer 6 after heat treatment at 110 ° C. for 10 minutes in film state. UV data.

At this time, the solution state is a state in which the polymer 6 is dissolved in a chlorobenzene solution, and the film was formed by the spin coating method of the polymer 6 in solution.

Comparative Preparation Example. Preparation of Polymer D

In a 100 mL flask under nitrogen (N2) atmosphere, add 12 mL of toluene, 3 mL of DMF, compound a-1 (0.15 mmol), compound c-1 (0.15 mmol) and compound d-1 (0.30 mmol) in a nitrogen bubble for 30 minutes. Ring. Then, tetrakis (triphenylphosphine) palladium (0) catalyst (Pd (PPh ₃ ) ₄ ) (2 mol%) was added thereto, and the mixture was stirred at 110 ° C. for 72 hours. 0.5 mL of Br-Benzotrifluoride was added and stirred for 24 hours, and cooled to room temperature. The product was then poured into chloroform, passed through a short column with silica and poured into a mixed solution (180 mL methanol + 20 mL HCl (2M concentration)) to filter the precipitate. The product was then subjected to soxhlet extraction in the order of methanol, acetone, hexane, methylene chloride and chloroform. The extract extracted with chloroform was put into methanol to form a precipitate. The resulting precipitate was collected, purified, and dried under vacuum to obtain Comparative Polymer D. At this time, the number average molecular weight (Mn) was measured to confirm that Polymer D was prepared. (Mn = 41,500 g / mol, PDI = 3.7)

Example.

Polymer 1 prepared in Preparation Example 1 was used as a donor, and PCBM was used as an acceptor to dissolve in chlorobenzene (Chlorobenzene, CB) in a 1: 2 ratio to prepare a composite solution. At this time, the concentration was adjusted to 2.0 wt%, the organic solar cell was ITO / ZnO / photoactive layer / MoO ₃ / Ag structure.

The glass substrate coated with ITO was ultrasonically cleaned with distilled water, acetone, and 2-propanol, ozonated the surface of ITO for 10 minutes, and then heat-coated at 120 ° C. for 10 minutes by spin coating a ZnO precursor solution. The composite solution was then filtered through a 0.45 μm PTFE syringe filter and then spin coated to form a photoactive layer. Thereafter, MoO ₃ was deposited on the photoactive layer at a thickness of 5 nm to 20 nm at a rate of 0.4 dl / s in a thermal evaporator to prepare a hole transport layer. Thereafter, Ag was deposited at 10 nm on the hole transport layer at a rate of 1 dB / s in the thermal evaporator to manufacture an organic solar cell.

Example 2.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer 2 was used instead of Polymer 1.

Example 3.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer 3 was used instead of Polymer 1.

Example 4.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer 4 was used instead of Polymer 1.

Example 5.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer 5 was used instead of Polymer 1.

Example 6.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer 6 was used instead of Polymer 1.

Comparative Example 1.

In Example 1, an organic solar cell was manufactured in the same manner as in Example 1, except that Polymer D was used instead of Polymer 1.

Comparative Example 2.

In Example 1, an organic solar cell was fabricated using the following Compound A instead of Polymer 1, but the solubility of Compound A was low and device fabrication was impossible.

[Compound A]

The photoelectric conversion characteristics of the organic solar cells prepared in Examples 1 to 6 and Comparative Example 1 were measured under 100 mW / cm ² (AM 1.5), and the results are shown in Table 1 below.

V _oc
(V) J _sc
(mA / cm ² ) FF η
(%) Example 1 0.81 12.14 0.48 4.72 Example 2 0.80 14.27 0.55 6.27 Example 3 0.85 13.54 0.53 6.09 Example 4 0.83 15.17 0.60 7.55 Example 5 0.84 13.21 0.53 5.88 Example 6 0.88 16.07 0.58 8.20 Comparative Example 1 0.84 10.50 0.37 3.26

In Table 1, Voc represents an open voltage, Jsc represents a short circuit current, FF represents a fill factor, and η represents an energy conversion efficiency. The open-circuit and short-circuit currents are the X- and Y-axis intercepts in the four quadrants of the voltage-current density curve, respectively. The higher these two values, the higher the efficiency of the solar cell. Also, the fill factor is the area of the rectangle drawn inside the curve divided by the product of the short circuit current and the open voltage. By dividing these three values by the intensity of the emitted light, the energy conversion efficiency can be obtained, and higher values are preferable.

From Table 1, it can be seen that the organic solar cells (Examples 1 to 6) according to an exemplary embodiment of the present specification is superior to Comparative Example 1.

101: first electrode
102: electron transport layer
103: photoactive layer
104: hole transport layer
105: second electrode

Claims (12)

A repeating unit represented by Formula 1 below; And
Polymers Containing Conjugated Monomers:
[Formula 1]

In Chemical Formula 1,
m1, m2, q1 and q2 are the same as or different from each other, and each independently an integer of 1 to 5,
When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,
Z1 to Z6 are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',
R1 to R12, R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group. The method according to claim 1,
Wherein said conjugated monomer comprises a first conjugated monomer and a second conjugated monomer different from said first conjugated monomer. The method according to claim 1,
Wherein said conjugated monomer comprises a combination of one or more groups of a substituted or unsubstituted alkenylene group, a substituted or unsubstituted arylene group, and a substituted or unsubstituted divalent heterocyclic group. The method according to claim 1,
Wherein said conjugated monomer comprises any one or a combination of two or more of the following structures:

In the above structure,
a, a ', b and b' are each an integer of 1 to 5,
when a, a ', b and b' are each 2 or more, the substituents in parentheses are the same as or different from each other,
X10 to X24 and X27 to X41 are the same as or different from each other, and each independently S, O, Se, Te, NR _d , CR _d R _e , SiR _d R _e , PR _d or GeR _d R _e ,
X25 and X26 are the same as or different from each other, and each independently C, Si or Ge,
R110 to R135, R _d and R _e are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group. The method according to claim 1,
The polymer is a polymer comprising a unit represented by the following formula 1-1 or formula 1-2:
[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,
m1, m2, m1 ', m2', q1, q2, q1 'and q2' are the same as or different from each other, and each independently an integer of 1 to 5,
When m1, m2, m1 ', m2', q1, q2, q1 'and q2' are each 2 or more, the structures in parentheses are the same or different from each other,
Z1 to Z6 and Z1 'to Z6' are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',
E1 is the first conjugated monomer,
E2 is the second conjugated monomer,
R1 to R12, R1 'to R12', R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
f is the mole fraction, which is a real number 0 <f <1,
g is the mole fraction, which is a real number 0 <g <1,
f + g = 1. The method according to claim 1,
Wherein said polymer comprises any of the following structures:

In the above structure,
n is an integer from 1 to 10,000. A first compound represented by Formula 2; And
A method for preparing a polymer comprising reacting a second compound represented by Formula 3 below:
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,
m1, m2, q1 and q2 are the same as or different from each other, and each independently an integer of 1 to 5,
When m1, m2, q1 and q2 are each 2 or more, the structures in parentheses are the same or different from each other,
A1, A1 ', A2 and A2' are the same as or different from each other, and each independently a halogen group; -BR _a R _b ; Or -SnR _a R _b R _c ,
E1 is the first conjugated monomer,
Z1 to Z6 are the same as or different from each other, and each independently S, O, Se, Te, NR, CRR ', SiRR', PR or GeRR ',
R1 to R12, R _a , R _b , R _c , R and R 'are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group. The method according to claim 7,
A first compound represented by Formula 2; And
Reacting the second compound represented by Formula 3 is
First compound; Second compound; And reacting a third compound represented by Chemical Formula 4 below:
[Formula 4]

In Chemical Formula 4,
A3 and A3 'are the same as or different from each other, and each independently a halogen group; -BR _a R _b ; Or -SnR _a R _b R _c ,
R _a , R _b And R _c are the same as or different from each other, and each independently hydrogen; Halogen group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
E2 is a second conjugated monomer different from the first conjugated monomer. The method according to claim 8,
The polymer production method may include a first compound in a solvent; Second compound; And dissolving the third compound. A first electrode;
A second electrode provided to face the first electrode; And
At least one organic material layer provided between the first electrode and the second electrode, including a photoactive layer,
At least one layer of the organic material layer is an organic solar cell comprising a polymer according to any one of claims 1 to 6. The method according to claim 10,
The photoactive layer includes an electron donor and an electron acceptor,
The electron donor is an organic solar cell comprising the polymer. The method according to claim 10,
The organic solar cell further comprises one or more organic material layers selected from the group consisting of a hole injection layer, a hole transport layer, a hole blocking layer, a charge generating layer, an electron blocking layer, an electron injection layer and an electron transport layer. .

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