JP2013140923A - Organic semiconductor thin film and organic thin-film solar cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a highly functional organic thin-film solar cell.SOLUTION: An n-type semiconductor represented by formula (1) and a p-type semiconductor of a polythiophene derivative form a bulk heterojunction.

Description

  The present invention relates to a power generation layer composed of an organic semiconductor thin film and an organic thin film solar cell.

  An organic thin film solar cell is formed by using an organic compound as a light conversion material by a coating method from a solution. 1) Low cost for creating a device 2) Easy to enlarge 3) Compared to inorganic materials such as silicon, it is flexible and has a wider range of usable locations. 4) It has various advantages such as less concern about resource depletion. For this reason, in recent years, organic thin film solar cells have been developed, and in particular, conversion efficiency can be greatly improved by employing a bulk heterojunction structure, which has attracted widespread attention.

  Among the power generation layers used in organic thin film solar cells, for p-type semiconductors, in particular, poly-3-hexylthiophene (P3HT) is known as a p-type semiconductor material having excellent performance. Recently, with the aim of higher functionality, compounds having a structure capable of absorbing a wide range of wavelengths of sunlight and a structure in which the energy level is adjusted have been developed and have greatly contributed to performance improvement (Non-Patent Document 1).

On the other hand, for an n-type semiconductor, various fullerene derivatives are known as n-type semiconductor materials. Among them, PCBM (phenyl C61 butyric acid methyl ester) has the most reported examples (Non-patent Document 2). On the other hand, there are very few fullerene derivatives for organic thin-film solar cells that surpass PCBM (Non-Patent Documents 3 and 4), and the development of highly functional fullerene derivatives is desired.
As an n-type semiconductor function, it has been reported that a fullerene derivative having a perfluoroalkyl group in a molecule achieves high electron mobility in a FET and operates under the atmosphere (Non-patent Document 5). The reason why the high function is expressed here is that fullerenes are highly arranged due to the cohesiveness of the perfluoroalkyl group because a part of the molecule is substituted with a perfluoroalkyl group.
In addition, it has been reported that fluorine-containing polythiophene, which is a p-type semiconductor, has improved durability by having a perfluoroalkyl group in the molecule (Non-patent Document 6). Introduction of a fluoroalkyl group has been studied. As an example aimed at improving the efficiency of recent solar cells, taking advantage of the cohesiveness of perfluoroalkyl groups, interface control using fluorinated fullerene (Non-patent Document 7) and improvement of open circuit voltage using fluorinated polythiophene It has been reported (Non-patent Document 8).

  However, efforts have not yet been made for the development of highly functional materials that take advantage of the high carrier mobility and high durability of semiconductors having perfluoroalkyl groups. In particular, even when a solar cell is manufactured using the above-described fluorine-containing fullerene derivative as an n-type semiconductor, the conversion efficiency is very low. This is because the perfluoroalkyl group has an agglomeration property and has a poor affinity with the p-type semiconductor material, and a bulk heterojunction structure can be formed in the organic power generation layer originally formed from these n-type semiconductor and p-type semiconductor. Not to mention.

  In order to improve this, it has been reported that an alkyl group chain is introduced into the molecule or the chain length of the perfluoroalkyl group is shortened (Patent Document 1, Non-Patent Document 9).

That is, in Patent Document 1, the following formula:
And a fullerene derivative having a high affinity for a p-type semiconductor and capable of forming a favorable organic power generation layer by a coating method is disclosed.

JP 2011-140480 A

Yu, L. P. et al., Journal of American Chemical Society, American Chemical Society, 2011, 133, 1885. Hummelen, J. C. et al., The Journal of Organic Chemistry, American Chemical Society, 1995, 60, 532. Ito et al., Journal of Materials Chemistry, 2010, 20, pp. 9226 Li, Y. et al. Journal of American Chemical Society, American Chemical Society, 2010, 132, 1377. Chikamatsu et al., Chemistry of Materials, American Chemical Society, 2008, 20, 7365 Zhang, J. et al., Chinese Journal of Polymer Science, 1996, 14, p. 330 Tajima et al., Advanced Materials, 2008, 20, 2211 Tajima et al., Nature Materials, 2011, 10, pp. 450 Nagai et al., Abstract of the 34th Fluorine Chemistry Conference, Lecture No. O-4, Fluorine Chemistry Study Group, October 18, 2010

However, further development of semiconductor materials and organic power generation layers formed from these materials is desired for improving the conversion efficiency of organic thin-film solar cells.
Therefore, an object of the present invention is to provide a highly functional organic thin-film solar cell by developing a new semiconductor material.

According to the study by the present inventors, in order to easily form a bulk heterojunction structure having excellent photoelectric conversion performance, each of the p-type semiconductor material and the n-type semiconductor material is improved, or other conditions are optimized. It turns out that alone is not always enough.
Based on such knowledge, the present inventors have searched for a suitable combination of a p-type semiconductor material and an n-type semiconductor material,
Formula (1):
[Where:
Ring A represents a 3- or 5-membered ring optionally having a nitrogen atom in addition to a carbon atom as a ring-constituting atom,
R ^a represents an organic group substituted with one or more substituents (at least one of the substituents is a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group);
R ^b is the same or different at each occurrence and represents a hydrocarbon group;
na represents 1 or 2,
Ring B represents fullerene.
An n-type semiconductor compound which is a fullerene derivative represented by:
Formula (2a):
[Where:
R ^5a represents a perfluoroalkyl group or a perfluoropolyether group,
R ^{5a ′} represents hydrogen or a hydrocarbon group, and L ^5a represents — (CH ₂ ) _n2 —, or —CH ₂ —O— (CH ₂ ) _n2 — (wherein n2 represents 1 to 3) Integer). ]
And having the repeating unit represented by formula (2b):
[Where:
R ^{5a ′} represents hydrogen or a hydrocarbon group, and R ^5b represents an alkyl group. Or a polythiophene derivative A that may further have a repeating unit represented by formula (3):
[Where:
R ^6a , R ^6b , R ^6c , and R ^6d each independently represents a perfluoroalkyl group, and L ^6a , L ^6b , L ^6c , and L ^6d each independently represent a bond or an alkylene chain. R ^7a and R ^7b are the same or different, and are the same or different at each occurrence, represent hydrogen or an alkyl group, and n3 represents the number of repetitions. ]
The present inventors have found that an excellent organic power generation layer can be obtained by a combination with a p-type semiconductor compound that is a polythiophene derivative B represented by the following. As a result of further studies, the present invention has been completed.

  That is, the present invention includes the following aspects.

Item 1.
Formula (1):
[Where:
Ring A represents a 3- or 5-membered ring optionally having a nitrogen atom in addition to a carbon atom as a ring-constituting atom,
R ^a represents an organic group substituted with one or more substituents (at least one of the substituents is a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group);
R ^b is the same or different at each occurrence and represents a hydrocarbon group;
na represents 1 or 2,
Ring B represents fullerene. ]
And a fullerene derivative represented by formula (2a):
[Where:
R ^5a represents a perfluoroalkyl group or a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and L ^5a represents a linker having 1 to 5 atoms in the main chain. ]
And having the repeating unit represented by formula (2b):
[Where:
R ^{5a ′} represents hydrogen or an alkyl group, and R ^5b represents an alkyl group. ]
Or a polythiophene derivative A which may further have a repeating unit represented by formula (3):
[Where:
R ^6a , R ^6b , R ^6c , and R ^6d each independently represent a perfluoroalkyl group,
L ^6a , L ^6b , L ^6c and L ^6d each independently represent a bond or an alkylene chain;
R ^7a and R ^7b are the same or different and are the same or different at each occurrence,
Hydrogen and an alkyl group are represented, and n3 represents a repeating number. ]
A p-type semiconductor compound which is a polythiophene derivative B represented by:
An organic power generation layer formed of the n-type semiconductor compound and the p-type semiconductor compound.
Item 2.
The fullerene derivative is
Formula (1a):
[Where:
R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group,
R ^3a represents an alkyl group,
R ^4a represents hydrogen or an alkyl group,
n1 represents an integer of 0 to 2,
Ring B represents fullerene. ]
Item 2. The organic power generation layer according to Item 1, which is a compound represented by:
Item 3.
The fullerene derivative is
Formula (1a ′):
[Where:
R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group,
R ^3a represents an alkyl group,
R ^4a represents hydrogen or an alkyl group,
n1 represents the integer of 0-2. ]
Item 3. The organic power generation layer according to Item 2, which is an n-type semiconductor compound that is a fullerene derivative represented by:
Item 4.
Item 4. The organic power generation layer according to Item 2 or 3, wherein R ^1a is a perfluoroalkyl group.
Item 5.
In formula (1a) or formula (1a ′),
The part represented by
[The symbols in the formula are as defined above. ]
Item 5. The organic power generation layer according to any one of Items 2 to 4.
Item 6.
Item 6. The organic power generation layer according to any one of Items 2 to 5, wherein R ^4a is an alkyl group.
Item 7.
Item 6. The organic power generation layer according to any one of Items 2 to 5, wherein R ^4a is hydrogen.
Item 8.
The fullerene derivative is
Formula (1b):
[Where:
R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
L ^b represents a linker having 1 to 5 atoms in the main chain;
R ^2b represents an optionally substituted aromatic group,
nb represents an integer of 1 to 20,
Ring B represents fullerene. ]
Item 2. The organic power generation layer according to Item 1, which is a compound represented by:
Item 9.
The fullerene derivative is
Formula (1b ′):
[Where:
R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
L ^b represents a linker;
R ^2b represents an optionally substituted aromatic group,
nb represents an integer of 1 to 20. ]
Item 9. The organic power generation layer according to Item 8, which is a compound represented by:
Item 10.
Item 10. The organic power generation layer according to Item 8 or 9, wherein R ^1b is a perfluoropolyether group.
Item 11.
The p-type semiconductor compound is polythiophene derivative A;
R ^5a is a C 4-12 perfluoroalkyl group or a C 4-18 perfluoropolyether group, and L ^5a is — (CH ₂ ) _n2 —, or —CH ₂ —O— (CH ₂ ) The organic power generation layer according to any one of Items 1 to 10, wherein _n2 − (wherein n2 is an integer of 1 to 3).
Item 12.
The p-type semiconductor compound is a polythiophene derivative B;
R ^6a , R ^6b , R ^6c , and R ^6d are the same or different and are a C 4-12 perfluoroalkyl group or a C 4-18 perfluoropolyether group,
L ^6a , L ^6b , L ^6c , and L ^6d are the same or different and each is an alkylene chain having 1 to 5 carbon atoms,
R ^7a and R ^7b are the same or different and are the same or different at each occurrence,
Item 12. The organic power generation layer according to any one of Items 1 to 11, which is hydrogen or a carbon number of 4 to 12, and n3 is an integer of 6 to 20.
Item 13.
The organic thin-film solar cell containing the organic electric power generation layer of any one of claim | item 1 -12.
Item 14.
formula:
[Where:
R ^5a represents a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and n2 represents an integer of 1 to 3. ]
A compound represented by

  ADVANTAGE OF THE INVENTION According to this invention, the electric power generation layer for organic thin film solar cells which can be manufactured easily and has the outstanding photoelectric conversion performance is provided.

It is general | schematic sectional drawing of the solar cell of this invention. It is the schematic of a field effect transistor.

  1. the term

In the present specification, “perfluoroalkyl group” means a group in which all hydrogen atoms of an alkyl group are substituted with fluorine atoms, or all hydrogen atoms other than one hydrogen atom at the end of the alkyl group are fluorine atoms. Means a substituted group.
In the present specification, examples of the “alkyl group” include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, 1-ethylpropyl, hexyl, isohexyl, 1 , 1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, and 2-ethylbutyl.
In the present specification, the term “perfluoroalkoxy group” means a group in which all hydrogen atoms of an alkoxy group are substituted with fluorine atoms, or all hydrogen atoms other than one hydrogen atom at the terminal of an alkoxy group are fluorine atoms. Means a substituted group.
In the present specification, examples of the “alkoxy group” include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, and tert-butoxy.

In the present specification, the “perfluoropolyether group” means a perfluoroalkyl group in which one etheric oxygen atom is inserted into each of two or more carbon-carbon bonds. Therefore, the “perfluoropolyether group” is a monovalent group having a plurality of perfluoroalkylene oxide chains and having a perfluoroalkyl group at the terminal.
In the present specification, the “perfluoroalkylene oxide chain” means a perfluoroalkylene-O-chain.
In the present specification, the “perfluoroalkylene chain” means a divalent group in which all hydrogen atoms of the alkylene chain are substituted with fluorine atoms.
In the present specification, “alkylene (chain)” means a divalent group formed by removing one hydrogen atom from an alkyl group. Examples thereof include methylene, methylmethylene, ethylene, methylethylene, trimethylene, methylmethylene, tetramethylene, methyltetramethylene, pentamethylene and hexamethylene.

  2. Organic power generation layer

  The power generation layer for an organic thin film solar cell of the present invention is formed from a semiconductor thin film in which an n-type semiconductor compound and the p-type semiconductor compound described below form a bulk heterojunction.

  2.1. n-type semiconductor compound

The n-type semiconductor compound contained in the organic power generation layer of the present invention has the formula (1):
It is a fullerene derivative represented by these.

  Hereinafter, symbols in the formula (1) will be described.

Ring A represents a 3- or 5-membered ring which may have a nitrogen atom in addition to a carbon atom as a ring-constituting atom.
Ring A is preferably
It is.

R ^a represents an organic group substituted with one or more substituents (at least one of the substituents is a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group).
R ^a is preferably
formula:
[Where:
R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group,
n1 represents the integer of 0-2. ]
Or a group represented by
formula:
[Where:
R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
L ^b represents a linker having 1 to 5 atoms in the main chain;
nb represents an integer of 1 to 20. ]
It is group represented by these.

L ^b is preferably —O— (CH ₂ ) _nc —, —S— (CH ₂ ) _nc —, —C (═O) —O— (CH ₂ ) _nc —, —C (═O) —. (CH ₂ ) _nc —, or —N (—R ^d ) — (CH ₂ ) _nc —. nc is preferably an integer of 1 to 4 (provided that the number of atoms in the main chain of the linker represented by Lb is 1 to 5). R ^d represents hydrogen or an alkyl group. The “alkyl group” represented by R ^d is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, particularly preferably 8 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear. L ^b is preferably —C (═O) —O— (CH ₂ ) _nc —.

R ^b is the same or different at each occurrence and represents a hydrocarbon group.
R ^b is preferably an alkyl group or an optionally substituted aromatic group. The “aromatic group” of the “optionally substituted aromatic group” represented by R ^b is preferably an aryl group having 6 to 14 carbon atoms such as phenyl, naphthyl, and anthryl. The “aromatic group” may be substituted with one or more (eg, 1 to 5) substituents. The “substituent” includes a halogen atom, an alkyl group which may be substituted with one or more (eg, 1 to 3) halogen atoms.

  na represents 1 or 2.

Ring B, ie the moiety in the formula:
Represents fullerene.
The fullerene represented by ring B is preferably fullerene C60 or fullerene C70, more preferably fullerene C60.

In the present specification, fullerene C60 may be expressed as follows.

  The n-type semiconductor compound which is a fullerene derivative represented by the formula (1) is preferably a fullerene derivative represented by the following formula (1a) or a fullerene derivative represented by the following formula (1b), more preferably Is a fullerene derivative represented by the following formula (1a ′) or a fullerene derivative represented by the following formula (1b ′). The fullerene derivative represented by the formula (1b) is a novel compound.

Formula (1a):

  Hereinafter, symbols in formula (1a) and formula (1a ′) will be described.

R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group.
The “perfluoroalkyl group” represented by R ^1a is preferably a perfluoroalkyl group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkyl group” may be linear or branched, but is preferably linear.

The “perfluoroalkoxy group” represented by R ^1a is preferably a perfluoroalkoxy group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkoxy group” may be linear or branched, but is preferably linear.

The “perfluoropolyether group” represented by R ^1a is preferably a perfluoropolyether group having 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms). The “perfluoropolyether group” may be linear or branched, but is preferably linear.

R ^1a is preferably a perfluoroalkyl group, more preferably a perfluoroalkyl group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms).

R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group.
The “perfluoroalkyl group” represented by R ^2a is preferably a perfluoroalkyl group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkyl group” may be linear or branched, but is preferably linear.
The “perfluoroalkoxy group” represented by R ^2a is preferably a perfluoroalkoxy group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkoxy group” may be linear or branched, but is preferably linear.
The “perfluoropolyether group” represented by R ^2a is preferably a perfluoropolyether group having 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms). The “perfluoropolyether group” may be linear or branched.
The “alkyl group” represented by R ^2a is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, and particularly preferably 8 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear.

n1 represents the integer of 0-2.
n1 is preferably 0. That is, R ^2a is preferably absent.

In formula (1),
The part represented by
[The symbols in the formula are as defined above. ]

R ^3a represents an alkyl group.
Preferably, alkyl having 1 to 12 carbons (more preferably 1 to 8 carbons, more preferably 1 to 2 carbons (that is, methyl or ethyl), particularly preferably 1 carbon (that is, methyl)). It is a group.

R ^4a represents hydrogen or an alkyl group.
The “alkyl group” represented by R ^4a is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, particularly preferably 8 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear.

In a preferred embodiment of the present invention,
R ^1a is a perfluoroalkyl group,
In formula (1),
The part represented by
And
R ^3a is an alkyl group and R ^4a is hydrogen.

  Hereinafter, symbols in the formula (1b) and the formula (1b ′) will be described.

R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group.

The “perfluoroalkyl group” represented by R ^1b is preferably a perfluoroalkyl group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkyl group” may be linear or branched, but is preferably linear.

The “perfluoroalkoxy group” represented by R ^1b is preferably a perfluoroalkoxy group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkoxy group” may be linear or branched, but is preferably linear.

The “perfluoropolyether group” represented by R ^1b is preferably a perfluoropolyether group having 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms). The “perfluoropolyether group” may be linear or branched.

R ^1b is preferably a perfluoropolyether group, more preferably a perfluoroalkyl group having 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms).

L ^b represents a linker having 1 to 5 atoms in the main chain.

L ^b is preferably —O— (CH ₂ ) _nc —, —S— (CH ₂ ) _nc —, —C (═O) —O— (CH ₂ ) _nc —, —C (═O) —. (CH ₂ ) _nc —, or —N (—R ^d ) —C (═O) — (CH ₂ ) _nc —. nc is preferably an integer of 1 to 4 (provided that the number of atoms in the main chain of the linker represented by Lb is 1 to 5). R ^d represents hydrogen, hydrogen or an alkyl group. The “alkyl group” represented by R ^d is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, particularly preferably 8 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear. L ^b is preferably —C (═O) —O— (CH ₂ ) _nc —.

R ^2b represents an optionally substituted aromatic group. The “aromatic group” of the “optionally substituted aromatic group” represented by R ^2b is preferably an aryl group having 6 to 14 carbon atoms such as phenyl, naphthyl and anthryl. The “aromatic group” may be substituted with one or more (eg, 1 to 5) substituents. The “substituent” includes a halogen atom, an alkyl group which may be substituted with one or more (eg, 1 to 3) halogen atoms.

  nb represents an integer of 1 to 20.

  2.2. p-type semiconductor compound

  The p-type semiconductor compound contained in the semiconductor thin film of the present invention is polythiophene derivative A or polythiophene derivative B described below.

  2.2.1. Polythiophene derivative A

The polythiophene derivative A as a p-type semiconductor compound contained in the organic power generation layer of the present invention has the formula (2a):
[Where:
R ^5a represents a perfluoroalkyl group or a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and L ^5a represents — (CH ₂ ) _n2 —, or —CH ₂ —O— (CH ₂ ) _n2 — (wherein n2 represents 1 to 3) Integer). ]
And a repeating unit represented by the following formula (2b):
[Where:
R ^{5a ′} represents hydrogen or an alkyl group, and R ^5b represents an alkyl group. ]
It may further have a repeating unit represented by (hereinafter sometimes referred to as repeating unit 2b).

  Hereinafter, symbols in the formulas (2a) and (2b) will be described.

R ^5a represents a perfluoroalkyl group or a perfluoropolyether group.
The “perfluoroalkyl group” represented by R ^5a is preferably a perfluoroalkyl group having 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). The “perfluoroalkyl group” may be linear or branched, but is preferably linear.
The “perfluoropolyether group” represented by R ^5a is preferably a perfluoropolyether group having 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms).
R ^5a is preferably a C 4-10 perfluoroalkyl group or a C 4-15 perfluoropolyether group, more preferably a C 4-8 perfluoroalkyl group, or a C 4-4 carbon atom. 12 perfluoropolyether groups.

L ^5a represents a linker having 1 to 5 atoms in the main chain.
L ^5a is preferably — (CH ₂ ) _n2 — or —CH ₂ —O— (CH ₂ ) _n2 — (wherein n2 is an integer of 1 to 3). Here, the formula: —CH ₂ —O— (CH ₂ ) _n2 — is represented such that the left methylene bonds to thiophene.
n2 is preferably 1 or 2.
L ^5a is preferably ethylene (—CH ₂ —CH ₂ —), or methyleneoxymethylene (—CH ₂ —O—CH ₂ —) and methyleneoxyethylene (—CH ₂ —O—CH ₂ —CH ₂ —). ).

R ^5b represents an alkyl group. R ^5b is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, particularly preferably 6 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear.

  In the polythiophene derivative A, the repeating unit 2a and the repeating unit 2b may each form a block or may be bonded at random.

In a preferred embodiment of the present invention, the polythiophene derivative A has a repeating unit 2b.
In this case, the molar ratio of the repeating unit 2a and the repeating unit 2b is preferably 1:50 to 50: 1, more preferably 1:30 to 1: 1.

The polythiophene derivative A preferably has a high regioregularity. Specifically, the polythiophene derivative A particularly preferably has a structure in which the repeating units 2a and 2b are alternately connected, that is, the following structure.
[Wherein x represents the number of repetitions. Other symbols are as defined above. ]
Here particularly preferably, R5 a ^'are both hydrogen.

  In another preferred embodiment of the present invention, the polythiophene derivative A does not have the repeating unit 2b.

  2.2.2. Polythiophene derivative B

The polythiophene derivative B as a p-type semiconductor compound contained in the organic power generation layer of the present invention has the formula (3):
It is represented by

  Hereinafter, symbols in the formula (3) will be described.

R ^6a , R ^6b , R ^6c and R ^6d each independently represent a perfluoroalkyl group or a perfluoropolyether group.
The “perfluoroalkyl group” represented by each of R ^6a , R ^6b , R ^6c , and R ^6d is preferably 4 to 12 carbon atoms (more preferably 4 to 10 carbon atoms, particularly preferably 4 to 8 carbon atoms). ) Perfluoroalkyl group. The “perfluoroalkyl group” may be linear or branched, but is preferably linear.
The “perfluoropolyether group” represented by R ^6a , R ^6b , R ^6c and R ^6d is preferably 4 to 18 carbon atoms (more preferably 4 to 15 carbon atoms, particularly preferably 4 to 12 carbon atoms). ) Perfluoropolyether group.
R ^6a , R ^6b , R ^6c , and R ^6d are preferably the same.

L ^6a , L ^6b , L ^6c , and L ^6d each independently represent a linker having 1 to 5 atoms in the main chain.
The linker represented by each of L ^6a , L ^6b , L ^6c , and L ^6d is preferably — (CH ₂ ) _n2 —, or —CH ₂ —O— (CH ₂ ) _n2 — (wherein n 2 Is an integer of 1 to 3. Here, the formula: —CH ₂ —O— (CH ₂ ) _n2 — is represented such that the left methylene bonds to the benzene ring. n2 is preferably 1 or 2.
These linkers are preferably ethylene (—CH ₂ —CH ₂ —), or methyleneoxymethylene (—CH ₂ —O—CH ₂ —) and methyleneoxyethylene (—CH ₂ —O—CH ₂ —CH ₂ —). ).
L ^6a , L ^6b , L ^6c , and L ^6d are preferably the same.

R ^7a and R ^7b are the same or different and are the same or different at each occurrence and represent hydrogen or an alkyl group.
n3 represents the number of repetitions.
The alkyl group represented by each of R ^7a and R ^7b is preferably an alkyl group having 4 to 12 carbon atoms (more preferably 6 to 10 carbon atoms, particularly preferably 6 carbon atoms). The “alkyl group” may be linear or branched, but is preferably linear.
R ^7a and R ^7b are preferably the same.

  n3 is preferably an integer of 6 to 20, particularly preferably 8 to 20.

  3. Manufacturing method of organic power generation layer

  The organic power generation layer of the present invention includes, for example, the n-type semiconductor compound and the p-type semiconductor compound dissolved in an organic solvent, and a spin coating method, a casting method, a dipping method, an inkjet method, and screen printing from the obtained solution. By forming a thin film on a substrate by a known thin film forming method such as a method, an organic power generation layer including a p-type semiconductor compound and an n-type semiconductor compound and having a bulk heterojunction structure can be obtained.

As the organic solvent, for example, chloroform, dichloromethane, carbon disulfide, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, and trichlorobenzene can be used. The said solvent may be used individually by 1 type, and may be used in combination of 2 or more type.
As the substrate, for example, a silicon substrate, a glass substrate, or a plastic substrate (eg, polyethylene terephthalate (PET) substrate) can be used.

  3.1. Preparation of n-type semiconductor compounds

The n-type semiconductor compound used in the present invention is synthesized by, for example, a known method such as the method described in Japanese Patent Application Laid-Open No. 2011-140480 and Japanese Patent Application Laid-Open No. 2007-251086, or a method analogous thereto. Can do.
Specifically, for example, when the n-type semiconductor compound is a fullerene derivative represented by the formula (1a), the compound may be synthesized according to the method of the following scheme or a method analogous thereto.

(In the formula, X represents a leaving group, and C60 represents fullerene C60.)

In step A, compound (iii) is obtained by reacting compound (i) with compound (ii).
In step B, compound (iv) is obtained by ester hydrolysis of compound (iii).
In step C, fullerene derivative (1a ′) is obtained by reacting compound (iv) with compound (v) and fullerene C60.

  Further, for example, when the n-type semiconductor compound is a compound represented by the formula (1b), the compound may be synthesized according to the following method or a method based thereon.

The fullerene derivative represented by the formula (1b) includes, for example, a fullerene derivative represented by the following formula (1b-a) (hereinafter sometimes referred to as a fullerene derivative (1b-a)) and a formula (b) : Obtained by reacting with an alcohol represented by R ^1b —CH ₂ OH (the symbols in the formula are as defined above) (hereinafter sometimes referred to as alcohol (1b-b)). it can.
[Where:
L ^c represents a carboxyl group [—COOH] or a carboxylic acid halide group [—C (═O) —X ^h (X ^h represents chlorine, bromine, or iodine)], and the other symbols are as defined above. Represents the same significance. ]

(i) When L ^c is a carboxylic acid halide group [—C (═O) —X ^h ]

The reaction can be performed in the presence of a base. Bases include sodium hydride, sodium hydroxide, potassium hydride, sodium carbonate, potassium carbonate, triethylamine, diisopropylethylamine, tributylamine, cyclohexyldimethylamine, pyridine, lutidine, 4-dimethylaminopyridine, N, N-dimethylaniline. N-methylpiperidine, N-methylpyrrolidine, N-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] octane, 1,8 Organic bases such as -diazabicyclo [5.4.0] -7-undecene can be used. These bases may be used alone or in combination of two or more. Such a base is generally used in an amount of about 0.5 to 10 mol, preferably about 0.5 to 6.0 mol, per 1 mol of fullerene derivative (1b-a).
The reaction can be performed without solvent or in a solvent. As the solvent, carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, bromobenzene and the like can be used. In particular, toluene, chlorobenzene, bromobenzene and the like are preferable. These solvents may be used alone or in combination of two or more.
The reaction can be performed in an inert gas (eg, nitrogen gas) atmosphere.
The reaction temperature is usually about −78 ° C. to 150 ° C., preferably about 0 ° C. to 50 ° C.
The reaction time is usually about 1 to 72 hours.

In addition, the fullerene derivative (1b-a) in which L ^c is a carboxylic acid halide group [—C (═O) —X ^h ] is obtained by, for example, converting a fullerene derivative (1b-a) in which L ^c is a carboxyl group to thionyl chloride. , Oxalyl chloride, phosphorus oxychloride, or phosphorus pentachloride.
The reaction can be performed without solvent or in a solvent.
As a solvent, the thing similar to what was illustrated about reaction of the said fullerene derivative (1b-a) and alcohol (1b-b) can be used.
The reaction can be suitably performed in an inert gas (eg, nitrogen gas) atmosphere.
The reaction temperature may usually be about room temperature to about 100 ° C.
The reaction time is usually about 1 to 72 hours.

(ii) When L ^c is a carboxyl group

This reaction can be carried out by superheated dehydration in the presence of an acid catalyst. In this case, sulfonic acids such as sulfuric acid, alkylsulfonic acid, and arylsulfonic acid are preferably used as the acid. Usually, the acid is used in an amount of 0.0001 to 1 mol, preferably about 0.01 to 0.1 mol, per 1 mol of the fullerene derivative (1b-a).
The reaction can be performed without solvent or in a solvent. As the solvent, carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, bromobenzene and the like can be used. In particular, toluene, chlorobenzene, bromobenzene and the like are preferable. These solvents may be used alone or in combination of two or more.
The reaction temperature is usually about room temperature to about 150 ° C, preferably about 80 to 120 ° C. For example, when a solvent is used, the reaction may be performed at about the boiling point of the solvent used.
The reaction can be performed in an inert gas (eg, nitrogen gas) atmosphere.
The reaction time is usually about 1 to 72 hours.

Alternatively, the reaction can be performed under a suitable condensing agent.
As the condensing agent in this case, N, N′-dicyclohexylcarbodiimide (DCC), 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide (WSCI), diphenylphosphoric acid amide (DPPA), benzotriazole-1 -Iloxytridimethylaminophosphonium salt (Castro reagent), 2-chloro-4,6-dimethoxy-1,3,5-triazine-N-methylmorpholine (DMT-MM) and the like are preferably used.
In this case, the amount of the condensing agent used is 0.1 to 10 mol, preferably 1 to 2 mol, relative to 1 mol of the fullerene derivative (1b-a). The reaction temperature is usually about −78 ° C. to 150 ° C., preferably about 0 ° C. to 50 ° C.
The reaction can be performed without solvent or in a solvent. As the solvent, carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene, bromobenzene and the like can be used. In particular, toluene, chlorobenzene, bromobenzene and the like are preferable. These solvents may be used alone or in combination of two or more.

  The reaction can be performed in an inert gas (eg, nitrogen gas) atmosphere.

  The mixing ratio of the fullerene derivative (1b-a) and the alcohol (1b-b) is not particularly limited, but from the viewpoint of increasing the yield, the amount of the alcohol (1b-b) is determined based on the fullerene derivative (1b-b). a) It is preferable to set it as about 0.1-10 mol with respect to 1 mol, and it is more preferable to set it as about 0.5-2 mol.

  The reaction time is usually about 1 to 48 hours, preferably about 10 to 36 hours.

  The fullerene derivative (1b) obtained by the reaction can be purified by a known purification method as necessary. Specifically, for example, after purification by silica gel column chromatography, it can be further purified by HPLC. At this time, hexane-chloroform, hexane-toluene, hexane-carbon disulfide, or the like can be used as a developing solvent for silica gel column chromatography, and chloroform, toluene, or the like can be used as a developing solvent for HPLC.

The fullerene derivative (1b-a) in which L ^c is a carboxyl group is, for example, the formula (1b-c):
[Where:
L ^b represents -C (= O) -O-,
R ^3b represents an alkyl group,
Other symbols are as defined above. ]
It can obtain by hydrolyzing the compound (henceforth a fullerene derivative (1b-c)). A fullerene derivative (1b-c) can be manufactured by the manufacturing method of a well-known fullerene derivative, or the method according to this, and can also be obtained commercially.

  The reaction can be performed in the presence of an acid. As the acid, mineral acids such as hydrochloric acid and sulfuric acid can be used. These acids may be used singly or in combination of two or more. Such an acid is generally used in an amount of about 0.5 to 10 mol, preferably about 0.5 to 6.0 mol, per 1 mol of the fullerene derivative (1b-c).

  The reaction can be performed without solvent or in a solvent. As the solvent, carbon disulfide, chloroform, dichloroethane, toluene, xylene, chlorobenzene, dichlorobenzene and the like can be used. In particular, toluene, chlorobenzene and the like are preferable. These solvents may be used alone or in combination of two or more.

  The reaction can be suitably performed in an inert gas (eg, nitrogen gas) atmosphere.

  The reaction temperature is usually about room temperature to about 150 ° C, preferably about 80 to 120 ° C. For example, when a solvent is used, the reaction may be performed at about the boiling point of the solvent used.

  The reaction time is usually about 1 to 48 hours, preferably about 10 to 36 hours.

  The fullerene derivative (1b-a) obtained by the reaction may be purified by a known purification method such as concentration, solvent extraction, or phase transfer, if necessary, before being subjected to the next reaction.

3.2. Preparation of p-type semiconductor compound (polythiophene derivative A) The polythiophene derivative A as a p-type semiconductor compound used in the present invention is prepared by Wang et al., Macromolecules 2008, 41, 5156-5165; Synthetic Metals 111-112 2000, pp.433- 436; and Geng et al., Macromol. Rapid Commun. 2011, 32, pp. 1478-1483, and the like, or a method analogous thereto.

Specifically, for example, by a cross-coupling polymerization method using a nickel catalyst such as 1,3-bis (diphenylphosphino) propane] nickel (II) dichloride complex [Ni (dppp) Cl ₂ ], the formula:
[The symbols in the formula are as defined above. ]
Or a compound of the formula:
[The symbols in the formula are as defined above. ]
It can synthesize | combine by superposing | polymerizing with the compound represented by these.

formula:
[The symbols in the formula are as defined above. ]
Can be produced, for example, as follows.

(i) Compound (a) (compound (a ′)) in which L ^5a is — (CH ₂ ) _n2 — (where n2 is an integer of 1 to 3) can be produced, for example, according to the following scheme .
In the first stage of the scheme, the compound (a-1) is prepared according to a known method such as a known method such as the method described in Chemical reviews. 1995, vol. 95, issue. 7, pp. 2457-2483. And compound (a-2) are coupled.
In the second step of the scheme, compound (a-3) is brominated using a bromination reagent such as N-bromosuccinimide (sometimes abbreviated as NBS in this specification), and compound (a )

(ii) Compound (a) (compound (a ″)) in which L ^5a is —CH ₂ —O— (CH ₂ ) _n2 — can be produced, for example, according to the following scheme.

  In the reaction of the scheme, compound (a ″) is obtained by reacting compound (b-1) with compound (b-2) in the presence of a base such as sodium hydride.

The formula:
[Where:
R ^5a represents a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and n2 represents an integer of 1 to 3. ]
A compound represented by
Is a novel compound.

Polythiophene derivative A is
formula:
[Wherein x represents the number of repetitions. Other symbols are as defined above. ]
Such a polythiophene derivative A has, for example, a structure represented by
(1) Formula:
[The symbols in the formula are as defined above. ]
A compound represented by the formula:
[Wherein n-Bu represents an n-butyl group. Other symbols have the same meaning as described above. In the presence of a palladium catalyst such as tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ )
[The symbols in the formula are as defined above. A step of preparing a compound represented by formula (2):
[The symbols in the formula are as defined above. And a compound represented by the formula: N-bromosuccinimide
[The symbols in the formula are as defined above. ]
Can be prepared by a method comprising a step of preparing
Polymerization of the dibromo compound thus obtained can be performed by a cross-coupling polymerization method using a nickel catalyst such as Ni (dppp) Cl ₂ .

  3.3. Preparation of p-type semiconductor compound (polythiophene derivative B)

  The polythiophene derivative B as a p-type semiconductor compound used in the present invention is, for example, Yuan et al., Chem. Mater. 2008, 20, 2763-2772; Kim et al., Journal of Polymer Science Part A: Polymer Chemistry, 2002, Volume 40. Issue 8, pp.1173-1183; AM Assaka et al., Polymer, 2004, 45, pp.7071-7081; Tang et al., Chem. Mater., 2006, 18, pp.6250-6257; Ventelon et al., Synthetic Metals, 2002 , 127, pp. 17-21; Odobel et al., Chem. Eur. J., 2002, 8, No. 13, pp. 3027-3046; Cremer et al., Chem. Mater., 2007, Vol. 19, No. 17 , pp.4155-4165; and Krebs et al., Solar Energy Materials & Solar Cells, 2005, 88, pp.363-37, etc. it can.

  Such an organic semiconductor thin film formed of a semiconductor can be used for a field effect capacitor (eg, an organic thin film transistor (TFT)), a photoelectric conversion element (eg, an organic thin film solar cell), or the like.

  4). Organic thin film solar cell

With reference to FIG. 1, the organic thin-film solar cell of this invention is demonstrated. The organic thin film solar cell 100 of the present invention has an organic power generation layer 3. Between the pair of electrodes 1 and 2, the electrodes 1 and 2 are disposed in an electrically bonded state. The organic power generation layer 3 includes a semiconductor thin film layer including a p-type semiconductor compound and an n-type semiconductor compound and having a bulk heterojunction structure.
Examples of the material for the electrodes 1 and 2 include gold, platinum, and indium oxide (ITO).

  The organic thin film solar cell 100 of the present invention can be manufactured, for example, by forming the organic power generation layer 3 on the electrode 1 as described above and forming the electrode 2 thereon.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

The symbols in the examples are used in the following meanings.
s: singlet bs: broad singlet t: triplet m: multiplet THF: tetrahydrofuran DMF: N, N-dimethylformamide DME: dimethoxyethane Pd (PPh ₃ ) ₄ : tetrakis (triphenylphosphine) palladium (0)

Synthesis Example 1 Synthesis of raw thiophene monomer 1

2,5-Dibromo-3-bromomethylthiophene is in accordance with the previous report (Hsu, SL .; Chen, CM .; Cheng, YH .; Wei, KH., Journal of Polymer Science, 2011, 49, 603). Synthesized from 3-methylthiophene.

A DMF solution (50 mL) of C ₄ F ₉ CH ₂ OH 12.5 g (50 mmol) was added dropwise at 0 ° C. to a DMF suspension of 2.00 g (60 wt%, 50 mmol) of sodium hydride. After the addition, this suspension was stirred at room temperature for 30 minutes. A DMF solution (50 mL) of 14.85 g (49 mmol) of 2,5-dibromo-3-bromomethylthiophene was added dropwise thereto at 0 ° C. The reaction solution was stirred at room temperature for 15 hours, then opened in ice water and extracted with diisopropyl ether. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain 17.6 g (63%) of the desired product.

2,5-Dibromo-3- [perfluoro (1,1,3,3, -tetrahydro-2-oxo) heptyl] thiophene
¹ H-NMR (CDCl ₃ ): δ 3.93 (2H, t, J = 13.7 Hz), 4.55 (2H, s), 6.95 (1H, s).
¹⁹ F-NMR (CDCl ₃ ): ppm -80.86 (3F, tt, J = 9.8, 2.6 Hz), -119.46--119.67 (2F, m), -124.06--124.24 (2F, m), -126.19- -126.36 (2F, m).

Synthesis Example 2 Synthesis of raw thiophene monomer 2

A DMF solution (10 mL) of 2.82 g (10 mmol) of CF ₃ OCF ₂ CF ₂ OCF ₂ CH ₂ OH was added dropwise at 0 ° C. to a DMF suspension of 400 mg (60 wt%, 10 mmol) of sodium hydride. After the addition, this suspension was stirred at room temperature for 30 minutes. A DMF solution (10 mL) of 3.02 g (10 mmol) of 2,5-dibromo-3-bromomethylthiophene was added dropwise thereto at 0 ° C. The reaction solution was stirred at room temperature for 15 hours, then opened in ice water and extracted with diisopropyl ether. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain 2.02 g (38%) of the desired product.

2,5-Dibromo-3- [perfluoro (1,1,3,3, -tetrahydro-2,5,8-trioxo) nonyl] thiophene
¹ H-NMR (CDCl ₃ ): δ 3.82 (2H, t, J = 9.6 Hz), 4.55 (2H, s), 6.96 (1H, s).
¹⁹ F-NMR (CDCl ₃ ): ppm -55.01 (3F, t, J = 8.7Hz), -77.23 (2F, tt, J = 13.3, 9.6Hz), -88.40 (2F, tt, J = 13.3, 8.7 Hz), -90.66 (2F, tt, J = 8.7, 8.7Hz).

Synthesis Example 3 Synthesis of raw thiophene monomer 3

Nonafluorohexyl iodide (12.2 g, 32.6 mmol), 3-thienylboronic acid (3.8 g, 29.6 mmol) Pd (PPh ₃ ) ₄ (684 mg, 0.59 mmol), NaHCO ₃ (6.2 g, 74 mmol) in DME (160 m The L) -H ₂ O (80 mL) solution was stirred at reflux for 5 hours. After cooling, the reaction solution was extracted with ether. The ether phase was concentrated under reduced pressure, and the resulting product was distilled under reduced pressure (Bp 60 ° C. 7 mmHg) to give 3-[(perfluorobutyl) ethyl] thiophene (7.6 g, 69%).

3-[(Perfluorobutyl) ethyl] thiophene
¹ H-NMR (CDCl ₃ ): δ 2.32-2.46 (2H, m), 2.93-2.97 (2H, m), 6.94-9.69 1H, m), 7.01-7.02 (1H, m), 7.28-7.30 (1H , m).

3-[(Perfluorobutyl) ethyl] thiophene (1.0 g, 3.0 mmol) purified above was dissolved in 20 mL of chloroform, and bromine (0.31 mL, 6.02 mmol) was added dropwise thereto at 0 ° C. The mixture was stirred for 30 minutes, and the reaction solution was poured into saturated sodium sulfite water. After the reaction product was extracted with chloroform and the solvent was concentrated under reduced pressure, the resulting reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain monomer 3 (1.17 g, 80%). .

2,5-Dibromo-3-[(perfluorobutyl) ethyl] thiophene
¹ H-NMR (CDCl ₃ ): δ 2.24-2.37 (2H, m), 2.82-2.86 (2H, m), 7.25 (1H, s).

  Example 1

  2,5-Dibromo-3-hexylthiophene was synthesized according to a previous report (Loewe, R. S .; Ewbank, P. C .; Liu, J .; Zhai, L. L .; McCullough, R. D., Macromolecules, 2001, 34, 4324.).

A THF solution obtained from monomer 1 (504 mg, 1.0 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at room temperature for 1 hour (THF solution 1).
A THF solution obtained from 2,5-dibromo-3-hexylthiophene (326 mg, 1 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at 60 ° C. for 1 hour (THF solution 2). . THF solution 2 was added to 1, and [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.71 mg, 0.005 mmol) was further added, and the mixture was heated to reflux for 20 hours.
The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain 250 mg (49%) of polymer 1.
Analysis by GPC gave number average molecular weight: 23.8 kg / mol; average molecular weight: 33.3 kg / mol; molecular weight distribution: 1.4.
¹ H-NMR (CDCl ₃ ): δ 0.75-1.00 (3H, m), 1.00-1.80 (8H, m), 2.45-2.65 (0.3H, m), 2.65-2.90 (1.7H, m), 3.85- 4.15 (1.4H, m), 2.45-2.70 (0.7H, m), 2.70-2.85 (0.7H, m), 6.85-7.35 (1.7H, m).
From the integrated value of the NMR chart, it was estimated that n: m = 2: 3 in the polymer.

  Example 2

  In the same manner as in Example 1, polymer 2 was synthesized from monomer 3 and 2,5-dibromo-3-hexylthiophene.

Number average molecular weight: 14.2 kg / mol; average molecular weight: 28.1 kg / mol; molecular weight distribution: 1.98.
¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3H, m), 1.10-1.60 (6H, m), 1.60-1.80 (2H, m), 2.30-2.60 (0.36H, m), 2.70-2.90 (2H, m), 3.07-3.20 (0.36H, m), 6.90-7.10 (1.2H, m).

  From the integrated value of the NMR chart, it was estimated that n: m = 1: 5.5 in the polymer.

  Example 3

In the same manner as in Example 1, polymer 3 was synthesized from monomer 2 and 2,5-dibromo-3-hexylthiophene (yield 47%).
Number average molecular weight: 30.2 kg / mol; average molecular weight: 48.3 kg / mol; molecular weight distribution: 1.6.

¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3H, m), 1.10-1.80 (8H, m), 2.45-2.65 (0.3H, m), 2.70-2.90 (1.7H, m), 3.70- 4.05 (1.4H, m), 4.50-4.70 (0.7H, m), 4.70-4.90 (0.7H, m), 6.90-7.30 (1.7H, m).
From the integrated value of the NMR chart, it was estimated that n: m = 2: 3 in the polymer.

  Example 4

A THF solution obtained from monomer 2 (536 mg, 1.0 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at room temperature for 1 hour.
[1,3-Bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.71 mg, 0.005 mmol) was added to the THF solution, and the mixture was heated to reflux for 20 hours.
The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain 37 mg (10%) of polymer 4.
Analysis by GPC gave number average molecular weight: 5.4 kg / mol; average molecular weight: 6.5 kg / mol; molecular weight distribution: 1.2.
¹ H-NMR (CDCl ₃ ): δ 3.70-4.00 (2H, m), 4.50-4.65 (1H, m), 4.65-4.80 (1H, m), 7.15-7.30 (1H, m).

Synthesis example 4
Synthesis of 3,5-bis [(perfluorohexyl) ethyl] bromobenzene

To a THF suspension of zinc (2.62 g, 40 mmol; used with 1,2-dibromoethane, activated with chlorotriethylsilane) in a THF solution of 2- (perfluorohexyl) ethyl iodide (14.22 g, 30 mmol) ( 30 mL) was added dropwise at room temperature, and the mixture was stirred for 12 hours. The solution obtained here was added dropwise to a THF solution (5 mL) of 3,5-diiodobromobenzene (4.0 g, 10 mmol) and Pd (PPh3) 4 (517 mg, 0.45 mmol) at room temperature. The reaction was stirred at 45 ° C. for 15 hours and then filtered through celite. The reaction product remaining in the celite layer was extracted with acetone. The combined organic phases were concentrated under reduced pressure, and the resulting reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain the desired product (2.55 g, 30%).

3,5-bis [(perfluorohexyl) ethyl] bromobenzene
¹ H-NMR (CDCl ₃ ): δ 2.25-2.45 (m, 4H), 2.80-2.98 (m, 4H), 7.00 (s, 1H), 7.26 (bs, 2H).

Synthesis example 5
3,5-bis [(perfluorobutyl) ethyl] bromobenzene was synthesized in the same manner (yield 10%).
¹ H-NMR (CDCl ₃ ): δ 2.25-2.45 (m, 4H), 2.80-2.95 (m, 4H), 7.00 (s, 1H), 7.26 (bs, 2H).

  Example 5 Synthesis of fluorinated thiophene octamer (polymer 5)

The thiophene trimer (3 ′, 4′-dihexyl-2,2 ′: 5 ′, 2 ″ -terthiophene) was synthesized according to Chemistry A European Journal, 2000, volume 6 pages 1663.
Purification by HPLC (GPC) was performed using the following apparatus and column.
Apparatus: JASCO LC-9201S
Column: JAIGEL H series (2H-1H is used in two-linkage)
Solvent: Chloroform

1) Synthesis of 5-tributylstannyl-3 ′, 4′-dihexyl-2,2 ′: 5 ′, 2 ″ -terthiophene (Compound 1) In a nitrogen atmosphere, thiophene trimer (416 mg, 1 mmol) To a THF (3 ml) solution, 1.65M n-BuLi (0.64 ml, 1.05 mmol) was added dropwise at −78 ° C., and the mixture was stirred at this temperature for 30 minutes.Tributyltin chloride (0.33 ml, 1.2 mmol) was added to the reaction solution. The reaction solution was dropped to room temperature and stirred for 1 hour.
The reaction solution was opened in water and the reaction product was extracted with hexane. The organic phase was concentrated under reduced pressure, and the resulting product was purified by HPLC to obtain the desired product (yield 70%).
¹ H-NMR (CDCl ₃ ): δ 0.88-0.93 (m, 15H), 1.04-1.21 (m, 6H), 1.31-1.43 (m, 20H), 1.56-1.66 (m, 8H), 2.67-2.73 ( m, 4H), 7.04-7.06 (m, 1H), 7.10 (d, J = 3.2Hz, 1H), 7.12-7.13 (m, 1H), 7.25 (d, J = 3.2Hz, 1H), 7.28-7.30 (m, 1H)

2) 5- (3,5-bis [(perfluorohexyl) ethyl] phenyl-3 ', 4'-dihexyl-2,2': 5 ', 2 " -terthiophene (Compound 2) Synthesis Compound 1 (706 mg , 1 mmol), 3,5-bis [(perfluorohexyl) ethyl] bromobenzene (861 mg, 1 mmol), Pd (PPh ₃ ) ₄ (35 mg, 0,03 mmol) in toluene (3 mL) under nitrogen atmosphere The mixture was stirred for 12 hours at 120 ° C. The reaction solution was concentrated under reduced pressure and purified by column chromatography (SiO ₂ : n-hexane) to obtain Compound 2 (yield 74%).
¹ H-NMR (CDCl ₃ ): δ 0.87-0.95 (m, 6H), 1.30-1.37 (m, 8H), 1.39-1.49 (m, 4H), 1.55-1.65 (m, 4H), 2.35-2.49 ( m, 4H), 2.68-2.77 (m, 4H), 2.93-2.97 (m, 4H), 6.99 (s, 1H), 7.05 (dd, 1H), 7.10 (d, J = 3.7Hz, 1H), 7.12 -7.15 (m, 1H), 7.27 (d, J = 4.1Hz, 1H), 7.30-7.32 (m, 1H), 7.33 (s, 1H), 7.33 (s, 1H).

3) 5 "-Bromo-5- (3,5-bis [(perfluorohexyl) ethyl] phenyl-3 ', 4'-dihexyl-2,2': 5 ', 2" -terthiophene (compound 3) A chloroform solution (3 mL) of synthetic compound 2 (1.18 g, 1 mmol) and NBS (178 mg, 1 mmol) was stirred at room temperature for 1 hour, the reaction solution was opened in a saturated aqueous solution of sodium hydrogen sulfite, and the reaction product was extracted with chloroform. The solvent was distilled off under reduced pressure, and the resulting product was purified by column chromatography (SiO ₂ : n-hexane) to obtain Compound 3 (yield 99%).
¹ H-NMR (CDCl ₃ ): δ 0.90-0.93 (m, 6H), 1.32-1.34 (m, 8H), 1.40-1.48 (m, 4H), 1.52-1.62 (m, 4H), 2.35-2.49 ( m, 4H), 2.64-2.75 (m, 4H), 2.93-2.97 (m, 4H), 6.88 (d, J = 3.6Hz, 1H), 7.00 (s, 1H), 7.02 (d, J = 3.7Hz , 1H), 7.10 (d, J = 3.6Hz, 1H), 7.27 (d, J = 3.7Hz, 1H), 7.30 (s, 1H), 7.30 (s, 1H).

4) Synthesis of Polymer 5 Toluene solution (3 mL) of compound 3 (1.26 g, 1 mmol), bisstanylbithiophene (373 mg, 0.5 mmol), Pd (PPh ₃ ) ₄ (116 mg, 0,1 mmol) in a nitrogen atmosphere Stir at 120 ° C. for 12 hours. The reaction solution was concentrated under reduced pressure and then purified by column chromatography (SiO ₂ : n-hexane) followed by HPLC to obtain polymer 5 (yield 68%).
¹ H-NMR (CDCl ₃ ): δ 0.90-0.93 (m, 12H), 1.32-1.34 (m, 16H), 1.40-1.48 (m, 8H), 1.52-1.62 (m, 8H), 2.36-2.50 ( m, 8H), 2.72-2.78 (m, 8H), 2.94-2.98 (m, 8H), 7.00 (s, 2H), 7.06 (d, J = 4.1Hz, 2H), 7.11 (s, 4H), 7.12 (d, J = 3.6Hz, 2H), 7.14 (d, J = 3.7Hz, 2H), 7.29 (d, J = 3.6Hz, 2H), 7.33 (s, 2H), 7.33 (s, 2H).

Example 6 Synthesis of fluorinated thiophene octamer (polymer 6)

1) Synthesis of 5- (3,5-bis [(perfluorobutyl) ethyl] phenyl-3 ′, 4′-dihexyl-2,2 ′: 5 ′, 2 ″ -terthiophene (Compound 4) Compound 1 (740 mg , 1.05 mmol), 3,5-bis [(perfluorobutyl) ethyl] bromobenzene (649 mg, 1 mmol) and Pd (PPh ₃ ) ₄ (35 mg, 0,03 mmol) in a toluene solution (3 mL) under a nitrogen atmosphere The mixture was stirred under wave irradiation for 9 minutes at 180 ° C. The reaction solution was concentrated under reduced pressure and purified by column chromatography (SiO ₂ : n-hexane) to obtain Compound 4 (217 mg, 73% yield).

Compound 4
¹ H-NMR (CDCl ₃ ): δ0.85-0.95 (m, 6H), 1.25-1.55 (m, 12H), 1.55-1.65 (m, 4H), 2.35-2.49 (m, 4H), 2.65-2.80 (m, 4H), 2.90-3.00 (m, 4H), 6.99 (bs, 1H), 7.07 (dd, J = 5.5, 3.7 Hz, 1H), 7.11 (d, J = 3.7Hz, 1H), 7.14 ( dd, J = 3.7, 0.9 Hz, 1H), 7.27 (d, J = 3.7 Hz, 1H), 7.31 (dd, J = 5.5, 0.9 Hz, 1H), 7.33 (s, 1H), 7.33 (s, 1H ).

2) 5 "-Bromo-5- (3,5-bis [(perfluorobutyl) ethyl] phenyl-3 ', 4'-dihexyl-2,2': 5 ', 2" -terthiophene (compound 5) A mixed solution of synthetic compound 4 (217 mg, 0.73 mmol) and NBS (136 mg, 0.77 mmol) in DMF-chloroform (1: 1; 3 mL) was stirred for 1 hour at room temperature. The reaction product was extracted with chloroform, the solvent was distilled off under reduced pressure, and the resulting product was purified by column chromatography (SiO ₂ : n-hexane) to obtain Compound 5 (100 mg, yield). 98%).

Compound 5
¹ H-NMR (CDCl ₃ ): δ0.85-1.00 (m, 6H), 1.25-1.50 (m, 12H), 1.50-1.65 (m, 4H), 2.35-2.49 (m, 4H), 2.62-2.75 (m, 4H), 2.93-3.00 (m, 4H), 6.88 (d, J = 3.7Hz, 1H), 7.00 (bs, 1H), 7.02 (d, J = 3.7Hz, 1H), 7.10 (d, J = 3.7Hz, 1H), 7.27 (d, J = 3.7Hz, 1H), 7.32 (bs, 2H).

3) Synthesis of polymer 6 Compound 5 (100 mg, 0.72 mmol), bisstanylbithiophene (267 mg, 0.36 mmol), Pd (PPh ₃ ) ₄ (83 mg, 0.07 mmol) in toluene solution (3 mL) in nitrogen atmosphere The mixture was stirred at 120 ° C. for 12 hours. The reaction solution was concentrated under reduced pressure and then purified by column chromatography (SiO ₂ : n-hexane) followed by HPLC to obtain polymer 6 (68 mg, yield 68%).

Polymer 6
¹ H-NMR (CDCl ₃ ): δ 0.85-0.95 (m, 12H), 1.32-1.40 (m, 16H), 1.40-1.50 (m, 8H), 1.50-1.65 (m, 8H), 2.36-2.50 ( m, 8H), 2.70-2.80 (m, 8H), 2.90-3.00 (m, 8H), 6.99 (bs, 2H), 7.06 (d, J = 3.7 Hz, 2H), 7.11 (s, 4H), 7.12 (d, J = 3.7Hz, 2H), 7.13 (d, J = 3.7Hz, 2H), 7.28 (d, J = 3.7Hz, 2H), 7.32 (s, 2H), 7.33 (s, 2H).

Synthesis Example 6 Synthesis of raw thiophene monomer 4
2-Bromo-3-bromomethylthiophene was purchased from Aldrich.
2-Bromo-3- [perfluoro (1,1,3,3, -tetrahydro-2-oxo) heptyl] thiophene C ₄ F in a suspension of sodium hydride (235 mg, 9.7 mmol) in DMF (18 ml) ₉ CH ₂ OH (2.08 g, 8.8 mmol) was added dropwise at 0 ° C. After the addition, this suspension was stirred at room temperature for 5 minutes. To this was added dropwise a DMF solution (10 ml) of 2-bromo-3-bromomethylthiophene (2.5 g, 9.7 mmol) at 0 ° C. The reaction solution was stirred at room temperature for 15 hours, then opened in ice water and extracted with diisopropyl ether. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain the desired product (1.1 g, yield 30%).
¹ H-NMR (CDCl ₃ ): δ 3.92 (2H, t, J = 14.3 Hz), 4.61 (2H, s), 6.97 (1H, d, J = 5.9 Hz), 7.27 (1H, d, J = 5.5 Hz).

Synthesis Example 7 Synthesis of raw thiophene monomer 5
In a test tube, thiophene monomer 4 (1.0 g, 2.4 mmol), 2-bromo-4-hexyl-5-stannylthiophene (1.0 g, 2.4 mmol), Pd (PPh ₃ ) ₄ (277 mg, 0.24 mmol) and toluene (4 ml) was added and stirred in a microwave reactor at 180 ° C. for 10 minutes. The reaction solution was concentrated, passed through silica gel column chromatography (eluent n-hexane), and purified by preparative GPC to obtain the desired product (899 mg, yield 75%).
¹ H-NMR (CDCl ₃ ): δ 0.88 (3H, t, J = 6.4 Hz), 1.28-1.37 (6H, m), 1.58-1.66 (2H, m), 2.59 (2H, t, J = 7.3 Hz ), 3.94 (2H, t, J = 14 Hz), 4.72 (2H, s), 6.92 (1H, d, J = 1.4 Hz), 6.98 (1H, d, J = 1.4 Hz), 7.08 (1H, d , J = 5.0 Hz), 7.21 (1H, d, J = 5.5 Hz).

Synthesis Example 8 Synthesis of raw thiophene monomer 6
N-bromosuccinimide (628 mg, 3.5 mmol) was added to a DMF solution (17 ml) of thiophene monomer 5 (899 mg, 1.8 mmol). The reaction solution was stirred at room temperature for 5 hours, then quenched with an aqueous hydrogen sulfite solution, and extracted with n-hexane. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain the desired product (746 mg, yield 64%).
¹ H-NMR (CDCl ₃ ): δ 0.88 (3H, t, J = 4.6 Hz), 1.29-1.35 (6H, m), 1.54-1.58 (2H, m), 2.54 (2H, t, J = 7.8 Hz ), 3.95 (2H, t, J = 14 Hz), 4.58 (2H, s), 6.80 (1H, s), 7.04 (1H, s).

Synthesis Example 9. Synthesis of raw material thiophene monomer 7
2-Bromo-3- [perfluoro (1,1,3,3, -tetrahydro-2,5,8-trioxo) nonyl] thiophene DMF (15 mL) suspension of sodium hydride (192 mg, 11.7 mmol) A DMF solution (10 mL) of CF ₃ OCF ₂ CF ₂ OCF ₂ CH ₂ OH (2.21 g, 7.8 mmol) was added dropwise at 0 ° C. After the addition, this suspension was stirred at room temperature for 30 minutes. A DMF solution (8 mL) of 2-dibromo-3-bromomethylthiophene (2.23 g, 8.7 mmol) was added dropwise thereto at 0 ° C. The reaction solution was stirred at room temperature for 15 hours, then opened in ice water and extracted with diisopropyl ether. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) (Rf value: 0.15) to obtain the desired product (1.26 g, yield 36%).
¹ H-NMR (CDCl ₃ ): δ 3.82 (2H, t, J = 9.6 Hz), 4.62 (2H, s), 6.97 (1H, d, J = 5.5 Hz), 7.27 (1H, d, J = 5.5 Hz).

Synthesis Example 10. Synthesis of raw material thiophene monomer 8
In a test tube, thiophene monomer 7 (1.5 g, 2.0 mmol), 2-bromo-4-hexyl-5-stannylthiophene (1.5 g, 2.0 mmol), Pd (PPh ₃ ) ₄ (207 mg, 0.18 mmol) and toluene (4 ml) was added and stirred in a microwave reactor at 180 ° C. for 10 minutes. The reaction solution was concentrated, separated by column chromatography (SiO ₂ , n-hexane), and further purified by preparative GPC to obtain the desired product (583 mg, yield 54%).
¹ H-NMR (CDCl ₃ ): δ 0.88 (3H, t, J = 6.9 Hz), 1.30-1.37 (6H, m), 1.58-1.66 (2H, m), 2.59 (2H, t, J = 7.8 Hz ), 3.84 (2H, t, J = 10 Hz), 4.73 (2H, s), 6.92 (1H, d, J = 1.4 Hz), 6.97 (1H, d, J = 1.4 Hz), 7.08 (1H, d , J = 5.5 Hz), 7.21 (1H, d, J = 5.0 Hz).

Synthesis Example 11. Synthesis of raw material thiophene monomer 9
NBS (382 mg) was added to a DMF solution (6 mL) of thiophene monomer 8 (583 mg, 1.1 mmol). The reaction solution was stirred at room temperature for 5 hours, then quenched with an aqueous hydrogen sulfite solution, and extracted with n-hexane. The obtained organic phase was washed with saturated brine, dehydrated with magnesium sulfate, and concentrated under reduced pressure. The remaining reaction product was purified by column chromatography (SiO ₂ , n-hexane) to obtain the desired product (610 mg, yield 81%).
¹ H-NMR (CDCl ₃ ): δ 0.88 (3H, t, J = 6.8 Hz), 1.30-1.38 (6H, m), 1.54-1.59 (2H, m), 2.54 (2H, t, J = 7.8 Hz ), 3.84 (2H, t, J = 10 Hz), 4.60 (2H, s), 6.79 (1H, s), 7.03 (1H, s).

Example 7 Synthesis of Polymer 7
A THF solution obtained from thiophene monomer 1 (536 mg, 1.0 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at room temperature for 1 hour. [1,3-Bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.71 mg, 0.005 mmol) was added to the THF solution, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain polymer 7 (37 mg, 10%). Analysis by GPC gave a number average molecular weight of 5.3 kg / mol, a weight average molecular weight of 6.2 kg / mol, and a molecular weight distribution of 1.2.
¹ H-NMR (CDCl ₃ ): δ 3.85-4.15 (1H, m), 4.50-4.65 (1H, m), 4.65-4.80 (1H, m), 7.10-7.30 (1H, m).

Example 8 Synthesis of Polymer 8
A THF solution obtained from thiophene monomer 6 (536 mg, 1.0 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at room temperature for 1 hour. [1,3-Bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.71 mg, 0.005 mmol) was added to the THF solution, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain 37 mg (10%) of polymer 4. Analysis by GPC gave a number average molecular weight of 7.8 kg / mol, an average molecular weight of 13 kg / mol, and a molecular weight distribution of 1.7.
¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3H, m), 1.10-1.75 (8H, m), 2.70-2.85 (2H, m), 4.04 (2H, t, J = 13.7Hz), 4.70 -4.85 (2H, m), 7.05 (1H, bs), 7.15 (1H, bs).

Example 9 Synthesis of Polymer 9
A THF solution obtained from thiophene monomer 6 (162 mg, 0.241 mmol) and n-hexylmagnesium bromide (2M THF solution, 121 μL, 0.241 mmol) was stirred at room temperature for 1 hour (THF solution 1). A THF solution obtained from 2,5-dibromo-3-hexylthiophene (786 mg, 2.41 mmol) and n-hexylmagnesium bromide (2M THF solution, 1.21 mL, 2.41 mmol) was stirred at 60 ° C. for 1 hour (THF Solution 2). THF solution 2 was added to 1, and [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride complex (7.18 mg, 0.013 mmol) was further added, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain a polymer in a yield of 254 mg (yield 27%). Analysis by GPC gave number average molecular weight: 46.2 kg / mol; average molecular weight: 88.5 kg / mol; molecular weight distribution: 1.9.

Polymer 9
¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3.1H, m), 1.10-1.80 (8.4H, m), 2.70 -2.90 (2.1H, m), 3.94 (0.09H, t, J = 10.1 Hz), 4.79 (0.09H, bs), 6.97 (1H, bs), 7.03 (0.05H, bs), 7.13 (0.05H, bs).
From the integrated value of the NMR chart, it was estimated that x: y = 1: 21 in the polymer.

Example 10 Synthesis of Polymer 10
A THF solution obtained from thiophene monomer 9 (536 mg, 1.0 mmol) and n-hexylmagnesium bromide (2M THF solution, 525 μL, 1.05 mmol) was stirred at room temperature for 1 hour. [1,3-Bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.71 mg, 0.005 mmol) was added to the THF solution, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain polymer 4 (37 mg, 10%). Analysis by GPC gave a number average molecular weight of 5.4 kg / mol, an average molecular weight of 6.5 kg / mol, and a molecular weight distribution of 1.2.

Example 11 Synthesis of Polymer 11
A THF solution obtained from thiophene monomer 9 (169 mg, 0.241 mmol) and n-hexylmagnesium bromide (2M THF solution, 126 μL, 0.253 mmol) was stirred at room temperature for 1 hour (THF solution 1). A THF solution obtained from 2,5-dibromo-3-hexylthiophene (786 mg, 2.41 mmol) and n-hexylmagnesium bromide (2M THF solution, 1.21 mL, 2.41 mmol) was stirred at 60 ° C. for 1 hour (THF Solution 2). THF solution 2 was added to 1, and [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride complex (7.18 mg, 0.013 mmol) was further added, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain a polymer (280 mg, 47%). From GPC analysis, number average molecular weight: 54.6 kg / mol; average molecular weight: 87.8 kg / mol

Polymer 11
¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3.1H, m), 1.10-1.80 (8.3H, m), 2.70 -2.90 (2.1H, m), 3.94 (0.08H, t, J = 10.1 Hz), 4.79 (0.08H, bs), 6.97 (1H, bs), 7.03 (0.04H, bs), 7.13 (0.04H, bs).
From the integrated value of the NMR chart, it was estimated that x: y = 1: 24 in the polymer.

Example 12 Synthesis of Polymer 12
A THF solution obtained from thiophene monomer 9 (108 mg, 0.154 mmol) and n-hexylmagnesium bromide (2M THF solution, 77 μL, 0.154 mmol) was stirred at room temperature for 1 hour (THF solution 1). A THF solution obtained from 2,5-dibromo-3-hexylthiophene (251 mg, 0.769 mmol) and n-hexylmagnesium bromide (2M THF solution, 0.769 mL, 0.769 mmol) was stirred at 60 ° C. for 1 hour (THF Solution 2). THF solution 2 was added to 1, and [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride complex (2.5 mg, 0.005 mmol) was further added, and the mixture was heated to reflux for 20 hours. The reaction solution was opened in methanol, and the resulting solid was collected by filtration. This was subjected to a Soxhlet extractor, and fractions extracted with chloroform were collected except for the fraction eluted with methanol and n-hexane. The solvent was distilled off under reduced pressure to obtain a polymer in a yield of 65 mg (yield 20%). Analysis by GPC gave number average molecular weight: 22.5 kg / mol; average molecular weight: 45.0 kg / mol; molecular weight distribution: 2.0.

Polymer 12
¹ H-NMR (CDCl ₃ ): δ 0.80-1.00 (3.3H, m), 1.10-1.80 (8.8H, m), 2.70 -2.90 (2.2H, m), 3.94 (0.2H, t, J = 10.1 Hz), 4.79 (0.2H, bs), 6.97 (1H, bs), 7.03 (0.1H, bs), 7.13 (0.1H, bs).
From the integrated value of the NMR chart, it was estimated that x: y = 1: 10 in the polymer.

Example 13 Synthesis of Fullerene 3
PCBM (100 mg, 0.11 mmol), concentrated hydrochloric acid (6 mL), acetic acid (15 mL), and toluene (15 mL)
The mixture was heated at 100 ° C. with stirring for 30 hours. The reaction solution was transferred to a separatory funnel, the reaction solution was washed with water, and the remaining organic phase was concentrated under reduced pressure. The obtained reaction product was washed with methanol, ether, and toluene. The remaining crystals were transferred to an eggplant flask, 15 mL of carbon disulfide and 1.5 mL of thionyl chloride were added under a nitrogen atmosphere, and the mixture was stirred for 3 days while heating to reflux to obtain a carboxylic acid chloride.
The reaction solution was concentrated under reduced pressure, and the remaining reaction product was added to CF ₃ OCF ₂ CF ₂ OCF ₂ CH ₂ OH (282 mg, 1 mmol), triethylamine (2 mL), 4-dimethylaminopyridine (25 mg, 0.2 mmol) and bromobenzene (10 mL) were added at 0 ° C., and the mixture was stirred at room temperature for 2 days. The reaction solution was concentrated under reduced pressure and the resulting reaction was purified by column chromatography (SiO _2, n-hexane: toluene = 5: 1 to 2: 1) to give the fullerene 3 (55 mg, yield: 43%).
¹ H-NMR (CDCl ₃ ) δ: 2.16-2.26 (2H, m), 2.62 (2H, t, J = 7.3Hz), 2.87-2.95 (2H, m), 4.48 (2H, t, J = 9.6Hz ), 7.50-7.62 (3H, m), 7.88-7.95 (2H, m).
¹⁹ F-NMR (CDCl ₃ ) -54.96 (3F, t, J = 8.6Hz), -76.91--77.05 (2F, m), -88.32--88.44 (2F, m), -90.57 (2F, q, J = 8.6Hz).

  Example 14 Functional evaluation

Evaluation of electron conductivity Field effect transistor preparation A silicon substrate was ultrasonically cleaned with toluene, acetone, deionized water, and isopropyl alcohol for 15 minutes each. Thereafter, the substrate is cleaned with ozone for 30 minutes, covered with a trichlorethylene solution of octadecyltrimethoxysilane for 10 seconds, and rotated at 3000 rpm using an ABLE / ASS-301 type spin coat film forming apparatus. After allowing to stand for 10 hours in an ammonium atmosphere, the substrate was ultrasonically washed with toluene and acetone for 15 minutes each.
As shown in FIG. 2, gold was vacuum deposited as an electrode. Further, a 1 wt% chlorobenzene solution of the polymer was dropped thereon, and a spin coat film was prepared at 500 rpm using an ABLE / ASS-301 type spin coat film forming apparatus. The obtained device was applied with a source-drain voltage of 80 V under vacuum, and the gate voltage was changed in the range of −20 V to 80 V, and the FET performance was measured.

<Result>

  Example 15 Performance Test Example

Fluorine-containing fullerene derivatives (fullerene 1, fullerene 2, fullerene 3) using the fluorine-containing thiophene polymer (polymer 1, polymer 3, polymer 5, polymer 9, polymer 11, polymer 12) obtained in the above examples as a p-type semiconductor material Was used as an n-type semiconductor material to produce solar cells by the following method, and the functions of the respective organic semiconductor materials obtained here were evaluated.
PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate)) as the charge transport layer material, ITO (indium tin oxide) (anode), aluminum (cathode) as the electrode ) Were used.

(1) Production of test solar cell A test solar cell was produced according to the following procedure.
1) Substrate pretreatment A mask was attached to an ITO glass substrate, and a portion of ITO was etched by immersing in concentrated hydrochloric acid for 15 minutes. After the etching, the ITO glass substrate was taken out from hydrochloric acid, thoroughly washed with water, and then dried in an air atmosphere. Subsequently, the etched ITO glass substrate was washed with ultrasonic waves in the order of toluene, acetone, water, and IPA (isopropyl alcohol) for 15 minutes each.
Next, the ITO glass substrate was put in a UV ozone cleaner apparatus of Filgen / UV253 and treated in the order of oxygen gas for 6 minutes, ozone gas for 30 minutes to 60 minutes, and nitrogen gas for 2 minutes.
2) Production of PEDOT: PSS thin film PEDOT: PSS thin film is formed on the ITO glass substrate which has been pretreated above using a PEDOT: PSS mixed solution using an ABLE / ASS-301 type spin coat film forming apparatus. did. The spin coating conditions were 500 rpm (5 seconds) and 3000 rpm (3 minutes).
3) Annealing The ITO glass substrate on which the PEDOT: PSS thin film was formed in 2) above was annealed for 10 minutes at 135 ° C. in a hot atmosphere on an air atmosphere. After annealing, it was cooled to room temperature.
4) Preparation of organic semiconductor film (organic power generation layer) Using an ABLE / ASS-301 type spin coat method film forming apparatus (manual spinner), a solution containing a thiophene polymer dissolved in chlorobenzene and a fullerene derivative in advance is formed into a PEDOT: PSS thin film. An organic semiconductor thin film (organic power generation layer) having a thickness of about 120 to 150 nm was obtained by spin coating at 2000 rpm for 2 minutes. As the solvent in the above solution, chloroform, toluene, chlorobenzene, or a mixed solvent thereof was used depending on the type of fullerene derivative.
5) Vacuum deposition of metal electrode Using a small high vacuum deposition apparatus of ULVAC / VPC-260F, the ITO glass substrate on which the laminated film prepared above was formed was placed on the mask in the high vacuum deposition apparatus, and 100 nm of aluminum was deposited. Vapor deposited.

(2) Current measurement by simulated sunlight irradiation A source meter (keithley, model number 2400), current-voltage measurement software, and simulated sunlight irradiation device (Minaga Electric Works, XES-301S) were used. The test solar cell produced by the method described above was irradiated with AM1.5 pseudo-sunlight, the generated current and voltage were measured, and the energy conversion efficiency was calculated by the following equation.
The measurement results of short-circuit current, open-circuit voltage, fill factor (FF) and conversion efficiency are shown in Table 2 below. The conversion efficiency is a value obtained by the following equation.
Conversion efficiency η (%) = FF (Voc · Jsc / Pin) x 100
FF: fill factor, Voc: open circuit voltage, Jsc: short circuit current, Pin: incident light intensity (density)

P3HT: Poly (3-hexylthiophene)

From this result, it can be seen that the conversion efficiency is higher when the regioselectivity of the bond between the fluoroalkyl group-containing thiophene and alkylthiophene is higher.
In the comparison with fullerene 3, it can be seen that the conversion efficiency is higher when the thiophene polymer contains a fluoroalkyl group.

The semiconductor thin film of the present invention is suitably used for a field effect capacitor (eg, organic thin film transistor (TFT)), a photoelectric conversion element (eg, organic thin film solar cell) and the like.
In particular, it is effective as a power generation layer for organic thin-film solar cells.

DESCRIPTION OF SYMBOLS 1 Electrode 2 Electrode 3 Organic power generation layer 100 Organic thin film solar cell

Claims (14)

Formula (1):
[Where:
Ring A represents a 3- or 5-membered ring optionally having a nitrogen atom in addition to a carbon atom as a ring-constituting atom,
R ^a represents an organic group substituted with one or more substituents (at least one of the substituents is a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group);
R ^b is the same or different at each occurrence and represents a hydrocarbon group;
na represents 1 or 2,
Ring B represents fullerene. ]
And a fullerene derivative represented by formula (2a):
[Where:
R ^5a represents a perfluoroalkyl group or a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and L ^5a represents a linker having 1 to 5 atoms in the main chain. ]
And having the repeating unit represented by formula (2b):
[Where:
R ^{5a ′} represents hydrogen or an alkyl group, and R ^5b represents an alkyl group. ]
Or a polythiophene derivative A which may further have a repeating unit represented by formula (3):
[Where:
R ^6a , R ^6b , R ^6c , and R ^6d each independently represent a perfluoroalkyl group,
L ^6a , L ^6b , L ^6c and L ^6d each independently represent a bond or an alkylene chain;
R ^7a and R ^7b are the same or different and are the same or different at each occurrence,
Hydrogen and an alkyl group are represented, and n3 represents a repeating number. ]
A p-type semiconductor compound which is a polythiophene derivative B represented by:
An organic power generation layer formed of the n-type semiconductor compound and the p-type semiconductor compound. The fullerene derivative is
Formula (1a):
[Where:
R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group,
R ^3a represents an alkyl group,
R ^4a represents hydrogen or an alkyl group,
n1 represents an integer of 0 to 2,
Ring B represents fullerene. ]
The organic power generation layer according to claim 1, which is a compound represented by the formula: The fullerene derivative is
Formula (1a ′):
[Where:
R ^1a represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
R ^2a is the same or different at each occurrence and represents a perfluoroalkyl group, a perfluoroalkoxy group, a perfluoropolyether group, or an alkyl group,
R ^3a represents an alkyl group,
R ^4a represents hydrogen or an alkyl group,
n1 represents the integer of 0-2. ]
The organic power generation layer according to claim 2, which is an n-type semiconductor compound that is a fullerene derivative represented by the formula: The organic power generation layer according to claim 2 or 3, wherein R ^1a is a perfluoroalkyl group. In formula (1a) or formula (1a ′),
The part represented by
[The symbols in the formula are as defined above. ]
The organic power generation layer according to any one of claims 2 to 4. ^R4a is an alkyl group, The organic power generation layer of any one of Claims 2-5. The organic power generation layer according to any one of claims 2 to 5, wherein R ^4a is hydrogen. The fullerene derivative is
Formula (1b):
[Where:
R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
L ^b represents a linker having 1 to 5 atoms in the main chain;
R ^2b represents an optionally substituted aromatic group,
nb represents an integer of 1 to 20,
Ring B represents fullerene. ]
The organic power generation layer according to claim 1, which is a compound represented by the formula: The fullerene derivative is
Formula (1b ′):
[Where:
R ^1b represents a perfluoroalkyl group, a perfluoroalkoxy group, or a perfluoropolyether group,
L ^b represents a linker;
R ^2b represents an optionally substituted aromatic group,
nb represents an integer of 1 to 20. ]
The organic power generation layer according to claim 8, which is a compound represented by: The organic power generation layer according to claim 8 or 9, wherein R ^1b is a perfluoropolyether group. The p-type semiconductor compound is polythiophene derivative A;
R ^5a is a C 4-12 perfluoroalkyl group or a C 4-18 perfluoropolyether group, and L ^5a is — (CH ₂ ) _n2 —, or —CH ₂ —O— (CH The organic power generation layer according to any one of claims 1 to 10, wherein ₂ ) _n2- (wherein n2 is an integer of 1 to 3). The p-type semiconductor compound is a polythiophene derivative B;
R ^6a , R ^6b , R ^6c , and R ^6d are the same or different and are a C 4-12 perfluoroalkyl group or a C 4-18 perfluoropolyether group,
L ^6a , L ^6b , L ^6c , and L ^6d are the same or different and each is an alkylene chain having 1 to 5 carbon atoms,
R ^7a and R ^7b are the same or different and are the same or different at each occurrence,
The organic power generation layer according to any one of claims 1 to 11, wherein the organic power generation layer is hydrogen or a carbon number of 4 to 12, and n3 is an integer of 6 to 20. The organic thin-film solar cell containing the organic electric power generation layer of any one of Claims 1-12. formula:
[Where:
R ^5a represents a perfluoropolyether group,
R ^{5a ′} represents hydrogen or an alkyl group, and n2 represents an integer of 1 to 3. ]
A compound represented by