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WO2013005614A1 - Copolymère à blocs conjugués et dispositif de conversion photoélectrique l'utilisant - Google Patents

Copolymère à blocs conjugués et dispositif de conversion photoélectrique l'utilisant Download PDF

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Publication number
WO2013005614A1
WO2013005614A1 PCT/JP2012/066363 JP2012066363W WO2013005614A1 WO 2013005614 A1 WO2013005614 A1 WO 2013005614A1 JP 2012066363 W JP2012066363 W JP 2012066363W WO 2013005614 A1 WO2013005614 A1 WO 2013005614A1
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conjugated
group
conjugated polymer
block copolymer
polymer block
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Japanese (ja)
Inventor
淳裕 中原
雅典 三浦
隆文 伊澤
拓也 稲垣
杉岡　尚
明士 藤田
大木　弘之
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Kuraray Co Ltd
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Kuraray Co Ltd
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Definitions

  • the present invention relates to a conjugated block copolymer that forms an organic thin film that becomes an organic photoelectric conversion layer of a photoelectric conversion element, and a photoelectric conversion element manufactured using the same.
  • Solar cells are attracting attention as a powerful energy source that is friendly to the environment.
  • inorganic materials such as silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and compound semiconductor materials such as GaAs, CIGS, and CdTe are used as photoelectric conversion elements for solar cells.
  • These photoelectric conversion elements have a relatively high photoelectric conversion efficiency, but are expensive compared to other power supply costs.
  • the cause of the high cost is the process in which the semiconductor thin film must be manufactured under high vacuum and high temperature. Therefore, organic semiconductor cells using organic semiconductors such as conjugated polymers and organic crystals and organic dyes are being studied as semiconductor materials that are expected to simplify the manufacturing process. Since these organic semiconductor materials can be formed into a film by a coating method or a printing method, they are attracting attention because the manufacturing process is simplified, mass production is possible, and inexpensive organic solar cells can be obtained.
  • An organic solar cell has a structure in which an organic photoelectric conversion layer is provided between two different electrodes.
  • the organic photoelectric conversion layer is formed from a mixture of a conjugated polymer and a fullerene derivative.
  • a typical example is a composition containing poly (3-hexylthiophene) as a conjugated polymer and [6,6] -phenyl C 61 butyric acid methyl ester (PC 61 BM) as a fullerene derivative.
  • the problem of organic solar cells is to increase the photoelectric conversion efficiency, and in particular, reports have been made on improving the photoelectric conversion efficiency by changing the morphology of the organic photoelectric conversion layer.
  • Methods for changing the morphology of the organic photoelectric conversion layer include, for example, a method of treating with heat or solvent vapor, a method of devising a solvent that dissolves a conjugated polymer or fullerene derivative, a method of adding a high-boiling compound, and a low volatilization rate of the solvent. The method of doing is mentioned.
  • Non-Patent Document 1 proposes a conjugated block copolymer in which a polar group is introduced into one block of a block copolymer to improve microphase separation performance.
  • the polarity is very high and the affinity with the fullerene derivative, which is an N-type organic semiconductor, is small, the fullerene derivative easily aggregates, and sufficient conversion efficiency cannot be obtained. This may be because the fullerene derivative is aggregated and a good morphology is not formed.
  • the resulting conjugated block copolymers also have a similar skeleton. It becomes a thing, and a co-crystal is made or it melt
  • micro-phase separation peculiar to the block copolymer is not formed, and only crystal-amorphous phase separation is observed.
  • the morphology control by microphase separation which is an advantage of using a conjugated block copolymer, cannot be achieved, and for example, an acceptor material such as a fullerene derivative can be unevenly distributed in one polymer domain of the block copolymer. Therefore, improvement in conversion efficiency cannot be expected so much.
  • the present invention has been made in order to solve the above-mentioned problems.
  • a conjugated block copolymer having good solubility in a solvent and capable of forming an organic thin film with controlled morphology by microphase separation aims at providing the photoelectric conversion element which has the photoelectric conversion efficiency which was excellent using the organic thin film to contain.
  • the conjugated block copolymer according to claim 1 which has been made to achieve the above object, contains a divalent heterocyclic group in the main chain and is substituted with a fluorine atom or a hydroxyl group.
  • a difference in solubility parameter from a conjugated polymer block having a minimum parameter is from 0.6 to 2.0.
  • the conjugated block copolymer according to claim 2 is the conjugated block copolymer according to claim 1, wherein the conjugated polymer block includes at least one thiophene ring as a part of a chemical structure. And a divalent heterocyclic group having at least one heterocyclic skeleton selected from a carbazole skeleton, a dibenzosilole skeleton, and a dibenzogermol skeleton in the main chain.
  • the conjugated block copolymer according to claim 3 is the one according to claim 1, wherein the conjugated polymer block is a cyclopentadithiophene diyl group, a dithienopyrrole diyl group, or a dithienosilole diyl group.
  • At least one divalent heterocyclic group selected from dithienogermolediyl group, benzodithiophenediyl group, naphthodithiophenediyl group, thienothiophenediyl group, thienopyrroledionediyl group and diketopyrrolopyrrolediyl group It is contained in the main chain.
  • the conjugated block copolymer according to claim 4 is the one described in any one of claims 1 to 3, wherein two types of the conjugated polymer block are the minimum in the divalent heterocyclic group.
  • a conjugated polymer block in which a side chain of an alkyl group or an alkoxy group having 8 carbon atoms is bonded to the same or different divalent heterocyclic group is an alkyl group or an alkoxy group having 6 carbon atoms at the maximum It is characterized by being a conjugated polymer block to which side chains are bonded.
  • the conjugated block copolymer according to claim 5 is the conjugated block copolymer described in claim 3, wherein the total number of carbon atoms in the side chain of one conjugated polymer block and the side chain of the other conjugated polymer block. The difference from the total number of carbon atoms is 6 or more and 16 or less.
  • a conjugated block copolymer according to a sixth aspect is the one according to any one of the first to third aspects, wherein two types of the conjugated polymer block include a fluorine atom on the divalent heterocyclic group.
  • a conjugated polymer block to which a side chain of an alkyl group or an alkoxy group which is not contained is bonded, and an alkyl group substituted with at least three fluorine atoms on the same or different divalent heterocyclic group, or It is characterized by being a conjugated polymer block to which a side chain which is an alkoxy group is bonded.
  • a composition according to claim 7 is characterized by containing the conjugated block copolymer according to any one of claims 1 to 6 and a fullerene derivative.
  • An organic thin film according to claim 8 is characterized by containing the conjugated block copolymer according to any one of claims 1 to 6.
  • the organic thin film element of Claim 9 equips a board
  • the photoelectric conversion element according to claim 10 is characterized in that the organic thin film according to claim 6 is sandwiched between at least two electrodes.
  • the conjugated block copolymer of the present invention contains at least two kinds of conjugated polymer blocks, and microphase separation can be formed by adjusting the solubility parameter thereof. With this microphase separation structure, it is possible to form an organic thin film with high photoelectric conversion efficiency with controlled morphology.
  • composition of the present invention forms an organic thin film in which the morphology is controlled by microphase separation using a conjugated block copolymer which is an organic semiconductor material and has a good affinity with an acceptor material contained together. be able to.
  • the organic thin film of the present invention can provide a photoelectric conversion element having excellent photoelectric conversion efficiency.
  • the photoelectric conversion element of the present invention has excellent photoelectric conversion performance, and can be applied to various photoelectric conversion devices using a photoelectric conversion function and an optical rectification function.
  • the conjugated block copolymer of the present invention is a block copolymer in which at least two kinds of conjugated polymer blocks, for example, conjugated polymer block A and conjugated polymer block B are copolymerized and bonded.
  • the conjugated polymer block constituting each block is a polymer composed of a conjugated divalent monomer, which contains a divalent heterocyclic group in its main chain and is substituted with a fluorine atom or a hydroxyl group.
  • the main chain refers to the longest chain of a compound composed of a divalent heterocyclic group.
  • the conjugated divalent monomer constituting the conjugated polymer block is a divalent group in which electrons of bonds in the molecule are delocalized, and is a compound composed of a divalent heterocyclic group. .
  • divalent heterocyclic group examples include dibenzosilol diyl group, dibenzogermole diyl group, dibenzofurandiyl group, carbazolediyl group, thiophenediyl group, furandyl group, pyrroldiyl group, benzothiadiazole diyl group, and thienylene.
  • Examples include vinylene diyl group and benzotriazole diyl group.
  • Examples of the thiophenediyl group include a thiophenediyl group having a monocyclic structure and a thiophenediyl group having a condensed ring structure, and a thiophenediyl group having a condensed ring structure is more preferable.
  • Examples of the thiophene diyl group having a condensed ring structure include cyclopentadithiophene diyl group, dithienopyrrole diyl group, dithienosilole diyl group, dithienogermol diyl group, benzodithiophene diyl group, naphthodithiophene diyl group, thienothiophene Examples thereof include a diyl group, a thienopyrrole dione diyl group, and a diketopyrrolopyrrole diyl group.
  • the thiophenediyl group of these condensed ring structures may be a polycyclic structure in which a monocyclic or condensed aromatic ring or heterocyclic ring is directly bonded.
  • Examples of the monocyclic or condensed aromatic ring or heterocyclic ring include thiophene, furan, benzene, naphthalene, pyrrole, and pyridine, and thiophene is preferable.
  • These aromatic rings or heterocyclic rings directly bonded to the condensed thiophenediyl group are conjugated with a divalent heterocyclic group constituting the main chain and ⁇ electrons, and are part of the main chain skeleton.
  • a condensed ⁇ -conjugated skeleton containing at least one thiophene ring as a part of the chemical structure, carbazole from the viewpoint that the morphology is easy to control and the performance as a photoelectric conversion element is high.
  • a skeleton, a dibenzosilole skeleton, or a dibenzogermol skeleton is preferable, and a condensed ⁇ -conjugated skeleton including at least one thiophene ring as a part of the chemical structure is more preferable.
  • a thiophenediyl group having a monocyclic structure is easy to synthesize, but the wavelength range of light to be absorbed is a short wavelength, and when used for a photoelectric conversion element, the photoelectric conversion efficiency may not be high.
  • connection structure of two or more kinds of conjugated polymer blocks contained in the conjugated block copolymer of the present invention is not particularly limited.
  • two kinds of conjugated polymer blocks are contained, for example, an AB type diblock copolymer, an ABBA type triblock copolymer, an ABBA type tetrablock copolymer And ABABABA type pentablock copolymer.
  • ABC type triblock copolymers, ABC type tetrablock copolymers, and the like can be mentioned.
  • the bonding mode of the conjugated block copolymer is not particularly limited as long as microphase separation of the conjugated block copolymer is formed.
  • the binding sites may be linked by ⁇ conjugation or may be bound by a non-conjugated structure.
  • the monomer unit of the conjugated polymer block is not limited to one unit having, for example, a structure in which only the monomer unit -a- is repeated, as long as it has a plurality of constant repeating structures in the conjugated polymer block.
  • a structure in which a plurality of valent heterocyclic groups are linked, for example, a monomer unit -ab- is included as one unit. That is, the completely alternating copolymer block of the monomer unit -a- and the monomer unit -b- is a homopolymer of the monomer unit -ab as long as it is a repeating unit having the same substituent. It shall be regarded as a block.
  • the total number of only carbon atoms constituting the ring structure excluding substituents in one type of monomer unit including up to the embodiment of the monomer unit -ab- Is preferably 6 to 30.
  • the alkyl group or alkoxy group which may be substituted with a fluorine atom or a hydroxyl group as a side chain is at least the monomer unit -a- or the monomer unit- It may be bonded to either of b-.
  • the cyclopentadithiophene diyl group (a) and the benzothiadiazole diyl group (b) are alternately bonded, the adjacent cyclopentadithiophene diyl group (a) and the benzothiadiazole diyl group
  • the group (b) can be regarded as a monomer unit of the present invention as one monomer unit -ab.
  • the conjugated block copolymer of the present invention includes a conjugated polymer block A having a maximum solubility parameter and a conjugated polymer block B having a minimum solubility parameter among the solubility parameters of the conjugated polymer block constituting each block.
  • the difference is 0.6 or more and 2.0 or less.
  • the difference between the maximum value and the minimum value of the solubility parameter is preferably 0.6 or more and 1.8 or less, and more preferably 0.6 or more and 1.6 or less.
  • the conjugated block copolymer can be microphase-separated by setting the difference between the maximum value and the minimum value of the solubility parameter to 0.6 or more. When it is less than 0.6, the polarities of the conjugated polymer blocks of the respective blocks are close to each other, and phase separation is difficult. It is also important that the difference between the maximum and minimum solubility parameters is 2.0 or less. When the difference between the maximum value and the minimum value of the solubility parameter is larger than 2.0, the solubility in the solvent is remarkably lowered, and it becomes difficult to obtain a thin film, or the conjugated block copolymer has a micelle structure.
  • the ideal micro phase separation structure means that two or more block components contained in the conjugated block copolymer have a co-continuous structure. It is also important that one domain of these phase separation structures contains a fullerene derivative that is more electron accepting material than the other domains. By forming such a morphology, charges can be transported to the electrode without recombination or deactivation, so that the short-circuit current density is increased and a high-performance photoelectric conversion element can be manufactured.
  • the solubility parameter of the conjugated polymer block can be controlled by its molecular structure.
  • a method for controlling the solubility parameter for example, when a diblock copolymer is considered, it is possible to adjust the solubility parameter by changing the main chain skeleton of the conjugated polymer block.
  • the main chain skeleton of the conjugated polymer is generally similar, it is preferable to adjust the solubility parameter by the side chain structure or the side chain density.
  • the solubility parameter When controlling the solubility parameter by changing the side chain structure, it can be controlled by the number of carbons in the side chain, the type of atoms bonded to the side chain carbon, and the functional group bonded to the side chain, but the conjugated polymer block In order to impart crystallinity, it is important that the side chain is an alkyl group or an alkoxy group which may be substituted with a fluorine atom or a hydroxyl group.
  • the side chain means a portion having carbon branched from a conjugated main chain.
  • different side chains refer to side chains having different structures in each copolymer block.
  • the number of carbon atoms in the side chain is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more. Further, the number of carbon atoms in the side chain is preferably 20 or less, and more preferably 16 or less.
  • the carbon number of the side chain means the carbon number per side chain bonded to the main chain.
  • the conjugated polymer block has a plurality of different types of side chains
  • at least one of them may be an alkyl group or an alkoxy group which may be substituted with a fluorine atom or a hydroxyl group.
  • the content of the side chain other than the alkyl group or alkoxy group is not particularly limited as long as the difference in solubility parameter can be adjusted. Examples of such other side chains include acyl groups and ester groups.
  • solubility parameter it is not preferable to control the solubility parameter by the type of the functional group bonded to the carbon of the alkyl group or alkoxy group which may be substituted with a fluorine atom or a hydroxyl group as a side chain.
  • a functional group such as an ether group, an epoxy group, an amino group, an amide group, or an iodine atom is not preferable in that the packing of the polymer is inhibited, the crystallinity is lowered, and the hole movement does not occur smoothly.
  • the functional group bonded to the alkyl group or alkoxy group which may be substituted with a fluorine atom or a hydroxyl group is a bulky functional group, crystallization is inhibited, and hole movement does not occur smoothly.
  • fluorine atoms are useful because they do not inhibit crystallization, but rather promote crystallization.
  • a hydroxyl group is also useful because it can be expected to be crystallized by hydrogen bonding. However, when two or more hydroxyl groups are present per side chain, crystallization may be inhibited by forming strong hydrogen bonds between them or by hydrogen bonding between side chains in one polymer. This is not preferable.
  • alkyl group substituted with a hydroxyl group examples include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 3-hydroxyisopropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 3 -Hydroxyisobutyl group, hydroxy tert-butyl group, 5-hydroxypentyl group, 4-hydroxyisopentyl group, 6-hydroxyhexyl group, 6-hydroxy-2-ethylhexyl group, 7-hydroxyheptyl group, 8-hydroxyoctyl group , 9-hydroxynonyl group, 10-hydroxydecyl group, 12-hydroxydodecyl group, 16-hydroxyhexadecyl group, 8-hydroxy-3,7-dimethyloctyl group, etc. other than ⁇ -hydroxyalkyl group and ⁇ -position An alkyl group having a hydroxy group It is.
  • the preferred alkoxy group substituted with a hydroxyl group specifically includes a hydroxymethoxy group, a 2-hydroxyethoxy group, a 3-hydroxypropoxy group, a 3-hydroxyisopropoxy group, a 4-hydroxybutoxy group, a 3-hydroxybutoxy group, 3-hydroxyisobutoxy group, hydroxy tert-butoxy group, 5-hydroxypentyloxy group, 4-hydroxyisopentyloxy group, 6-hydroxyhexyloxy group, 6-hydroxy-2-ethylhexyloxy group, 7-hydroxyheptyloxy group Group, 8-hydroxyoctyloxy group, 9-hydroxynonyloxy group, 10-hydroxyoxy group, 12-hydroxydodecyloxy group, 16-hydroxyhexadecyloxy group, 8-hydroxy-3,7-dimethyloctyloxy group, etc. , An alkoxy group having a hydroxy group in addition ⁇ - hydroxyalkoxy group and ⁇ - positions.
  • conjugated polymer blocks having different alkyl groups or alkoxy groups When adjusting the difference in solubility parameter using the number of carbons in the side chain, it is possible to adjust to the desired difference in solubility parameter by combining conjugated polymer blocks having different alkyl groups or alkoxy groups.
  • a combination of a conjugated polymer block mainly containing at least a side chain having 8 carbon atoms and a conjugated polymer block mainly containing at most a side chain having 6 carbon atoms is preferable, and has 8 or more carbon atoms.
  • a combination of a conjugated polymer block mainly containing 20 or less side chains and a conjugated polymer block mainly containing side chains having 3 to 6 carbon atoms is more preferred.
  • the solubility parameter difference there is a certain difference between the total number of carbon atoms in the side chain of one conjugated polymer block and the total number of carbon atoms in the side chain of the other conjugated polymer block.
  • the difference in the total number of carbon atoms in the side chain is preferably 6 or more and 16 or less, and more preferably 6 or more and 10 or less.
  • the conjugated polymer block constituting the conjugated block copolymer has a plurality of side chains, when comparing at least one different side chain among the side chains contained in each monomer unit, It is preferred that the combined block has a minimum of 8 carbon side chains and the other conjugated polymer block has a maximum of 6 carbon side chains.
  • conjugated polymer block having a side chain with a large number of carbon atoms it is possible to reduce the value of the solubility parameter, but when the number of carbon atoms is as large as 20 or more, it is difficult for the conjugated polymer block chains to approach each other, The movement of charges and excitons between conjugated polymer block chains is difficult to occur, and components that do not contribute to photoelectric conversion increase, resulting in a decrease in short-circuit current density.
  • These side chains do not have to be all side chains limited to the number of carbon atoms in the conjugated polymer block, and can be combined with other side chains.
  • preferred alkyl groups for adjusting the solubility parameter of the conjugated polymer block using the carbon number of the side chain include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group.
  • alkoxy groups when adjusting the solubility parameter of the conjugated polymer block using the carbon number of the side chain include methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, n-hexyl group, n-octyloxy group, n-decyloxy group, 2-ethylhexyloxy group, n-dodecyloxy group, n-hexadecyloxy group, 3,7-dimethyloctyloxy group, n-dodecyloxy group, etc. Is mentioned.
  • the difference in solubility parameter can be adjusted by combining conjugated polymer blocks having side chains in which different atoms are bonded to the side chain carbon.
  • fluorine atoms are particularly useful because they have the greatest Pauling electronegativity.
  • the number of fluorine atoms depends on the number of carbons in the side chain, but when the number of carbon atoms is 6 or more, the number of fluorine atoms contains 3 or more.
  • a side chain is preferred, a side chain containing 5 or more is more preferred, and a side chain containing 5 or more and 13 or less is more preferred.
  • the polymer block has a plurality of side chains, when comparing at least one different side chain among the side chains contained in each monomer unit, one polymer block contains 3 or more fluorine atoms It is preferable to have a side chain.
  • a conjugated block copolymer having a desired difference in solubility parameter By combining such a conjugated polymer block having a side chain and a conjugated polymer block having a side chain not containing a fluorine atom, a conjugated block copolymer having a desired difference in solubility parameter can be obtained.
  • the solubility parameter of the conjugated polymer block having a side chain containing a fluorine atom decreases as the number of fluorine atoms increases.
  • the solubility parameter can be increased.
  • the difference between the maximum value and the minimum value of the solubility parameter becomes small.
  • fluorinated alkoxy groups include trifluoromethoxy group, 2,2,2-trimethyl group.
  • the Bicerano method is used in the present invention.
  • Other methods include, for example, the Hildebrand method, Small method, Fedors method, Van Krevelen method, Hansen method, Hoy method, Ascadskii method, Okitsu method, etc. Cannot be used because it cannot be calculated or is not accurate.
  • the calculation method by the Bicerano method is described in “Prediction of Polymer Properties, 3rd Ed.” (2002), CRC Press, written by Jozef Bicerano.
  • the unit of the solubility parameter is MPa 1/2 .
  • Various computer software can be used when calculating solubility parameters using the Bicerano method.
  • Examples of the computer software include Scigress Explorer Professional 7.6.0.52 (Fujitsu) and Polymer-Design Tools (DTW Associates, Inc).
  • DTW Associates, Inc Polymer-Design Tools
  • When dealing with elements that have no data in the Bicerano method substitute elements that are the same element in the periodic table and that have a smaller cycle number. For example, when there is no silicon data, the solubility parameter calculated with the structure substituted with carbon is used.
  • the conjugated block copolymer of the present invention it is necessary to calculate a solubility parameter for the conjugated polymer block constituting each block of the conjugated block copolymer.
  • the solubility parameter of the random copolymer is calculated as shown in the following formula (A).
  • the mass ratio of each of the two or more kinds of conjugated polymer blocks contained in the conjugated block copolymer of the present invention is not particularly limited, but is preferably 95: 5 to 5:95 mass ratio, and 90:10 to 10 : 90 mass ratio, more preferably 85:15 to 15:85.
  • the content of the conjugated polymer block giving higher photoelectric conversion efficiency is larger.
  • the number average molecular weight of the conjugated block copolymer is not particularly limited, but is preferably from 600 to 1,000,000 g / mol from the viewpoint of hole mobility and mechanical properties, and more preferably from 5,000 to 500,000 g / mol. It is preferably 10,000 to 200,000 g / mol.
  • the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.
  • At least one block of the conjugated block copolymer is preferably a crystalline polymer.
  • the crystalline polymer here is a polymer in which a part of the polymer is crystallized or in a liquid crystal state. Discrimination of the crystalline polymer can be analyzed by X-ray diffraction or DSC. In the present invention, the weak polymer packing state observed only by the aromatic ring ⁇ - ⁇ stack by the X-ray diffraction method is judged as having crystallinity.
  • a divalent group other than the divalent heterocyclic group can be copolymerized in the conjugated block copolymer and in the conjugated polymer block constituting each block. it can.
  • the copolymerization rate is preferably 30% by mass or less, more preferably 20% by mass or less, based on the conjugated block copolymer. More preferably, it is 10 mass% or less.
  • the copolymerization rate is too high, the performance of the photoelectric conversion element may deteriorate.
  • Specific examples of the divalent group other than the divalent heterocyclic group include an acetylene group and an arylene group.
  • the conjugated block copolymer of the present invention may contain a conjugated polymer in addition to the exemplified conjugated polymer block.
  • the content is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass from the viewpoint of controlling the morphology and the conversion efficiency of the photoelectric conversion element obtained by controlling the morphology. % Or less is more preferable.
  • the conjugated polymer other than the conjugated block copolymer of the present invention is preferably a conjugated polymer having the same structure as one block of the conjugated block copolymer of the present invention.
  • the conjugated block copolymer may contain other non-conjugated polymer blocks as long as it contains two or more kinds of conjugated polymer blocks.
  • the content of the non-conjugated polymer block is not particularly limited as long as it does not decrease the conversion efficiency of the photoelectric conversion element, but is preferably 50% by mass or less, and preferably 30% by mass or less with respect to the total mass of the conjugated block copolymer. More preferred is 10% by mass or less.
  • Such non-conjugated polymer blocks are not involved in the solubility parameter in the present invention.
  • connection method As a first method for producing a conjugated block copolymer, at least two kinds of conjugated polymer blocks constituting each block, for example, conjugated polymer block A and conjugated polymer block B are synthesized separately, There is a method of connecting the two (hereinafter, referred to as “connection method”).
  • connection method As a second method, there is a method in which the conjugated polymer block A and the conjugated polymer block B are sequentially polymerized by pseudo-living polymerization (hereinafter sometimes referred to as “sequential polymerization method”).
  • second method there is a method of polymerizing the conjugated block B in the presence of the conjugated polymer block A (hereinafter sometimes referred to as “macroinitiator method”).
  • mecroinitiator method As the linking method, sequential polymerization method, and macroinitiator method, an optimum method can be used depending on the conjugated block copolymer to be synthesized. .
  • a and B are conjugated polymer blocks
  • X is a halogen atom
  • M p is boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3 (where R a has 1 to 4 carbon atoms)
  • R a has 1 to 4 carbon atoms
  • X is as defined above.
  • terminal substituents may be interchanged, and as shown in the following reaction formula (II), the compound BX having the conjugated polymer block B and the conjugated polymer block the compound a-M p with a can be prepared by carrying out the coupling reaction in the presence of a catalyst.
  • B and A are conjugated polymer blocks
  • X is a halogen atom
  • M p is boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3 (where R a has 1 to 4 carbon atoms)
  • R a has 1 to 4 carbon atoms
  • X is as defined above.
  • the monomers M q1 -YM q1 and M q2 -ZM q2 are reacted in the presence of a catalyst, and a conjugated polymer block A or a conjugated polymer is reacted by a so-called coupling reaction.
  • Compound AX or compound BX containing combined block B can be prepared.
  • Y and M represent a heterocyclic skeleton constituting at least a part of the monomer unit of the conjugated block copolymer of the present invention.
  • M q1 and M q2 are not the same and are each independently a halogen atom, or a boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3 (wherein R a has 1 to 4 carbon atoms)
  • A represents a copolymer of Y and Z
  • M p represents a boronic acid, a boronic acid ester, —MgX, —ZnX, —SnR a 3 . .
  • M q1 is a halogen atom
  • M q2 is boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3
  • M q1 is boronic acid, boronic acid ester, -MgX, -ZnX, -SnR a 3
  • Conjugated polymer block A or a conjugated polymer block B may be carried out a coupling reaction using a compound represented as compound M q1 -Y-M q1 Compound M q2 -Z-M q2 the formula Ar-M r It is also possible to manufacture by.
  • Ar is an aryl group
  • M r represents M p or X
  • M p is boronic acid, boronic acid ester, -MgX, -ZnX, (alkyl group R a from 1 to 4 carbon atoms) -SnR a 3
  • X represents a halogen atom.
  • the conjugated polymer block A or the conjugated polymer block B of the compound AX or the compound BX is polythiophene
  • the conjugated polymer block A or the conjugated polymer is obtained by the pseudo-living polymerization method described in the sequential polymerization method.
  • Block B can also be manufactured.
  • the sequential polymerization method is an effective method particularly when polythiophene is used as the main chain skeleton of both the conjugated polymer block A and the conjugated polymer block B.
  • the basic polymerization reaction can be produced using the method shown below.
  • the order of producing the conjugated polymer block may be the conjugated polymer block B after the conjugated polymer block A, or vice versa, and the optimum order is selected according to the intended conjugated block copolymer. it can.
  • Grignard metathesis reaction which is an exchange reaction with an organomagnesium halogen compound represented by the following chemical formula (VI)
  • W is a divalent thienylene group which may have a substituent, X is a halogen atom, and two Xs are the same or different) to obtain an organomagnesium compound.
  • a conjugated block copolymer is obtained from the obtained organomagnesium compound (VI) by a so-called coupling reaction in a solvent in the presence of a metal complex catalyst.
  • a series of reactions is shown in the schematic reaction formula (VII).
  • W of the resulting conjugated block copolymer is a copolymer composed of a divalent thienylene group which may have a substituent.
  • the macroinitiator method is a method in which the conjugated polymer block B is polymerized by allowing the terminal functionalized conjugated polymer block A to coexist in the initial stage of polymerization of the conjugated polymer block B or in the middle of polymerization.
  • the order in which the conjugated polymer block is produced may be obtained by polymerizing the conjugated polymer block B in the presence of the conjugated polymer block A, or vice versa, depending on the target conjugated block copolymer. You can choose.
  • XX which is a conjugated polymer block A and M q1 -YM q1 and M q2 -ZM q2 are reacted in the presence of a catalyst in the presence of a so-called cup.
  • the conjugated block copolymer of the present invention can be obtained after the polymerization by bonding the terminal of the conjugated polymer block A and the polymerizable monomer of the conjugated polymer block B or the polymer block B during the polymerization by a ring reaction. it can.
  • conjugated block copolymer of the present invention is obtained after the polymerization by bonding the terminal of the conjugated polymer block A and the polymerizable monomer of the conjugated polymer block B or the polymer block B during the polymerization by a coupling reaction. be able to.
  • M q1 and M q2 are not the same and are each independently a halogen atom, or a boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3 (where R a is C represents a linear alkyl group having 1 to 4 carbon atoms, X represents the same as described above, A and B represent a copolymer of Y and Z, M p represents boronic acid, boronic acid ester, -MgX, -ZnX,- Represents SnR a 3 .
  • M q1 is a halogen atom
  • M q2 is boronic acid, boronic acid ester, —MgX, —ZnX, —SnR a 3
  • M q1 is boronic acid, boronic acid ester, -MgX, -ZnX, -SnR a 3
  • transition metal complex As a catalyst for both the linking method, sequential polymerization method and macroinitiator method.
  • transition metal complexes belonging to Group 3 to Group 10 of the periodic table Group 18 long-period type periodic table, particularly Group 8 to Group 10 are listed.
  • known complexes such as Ni, Pd, Ti, Zr, V, Cr, Co, and Fe can be used. Of these, Ni complexes and Pd complexes are more preferable.
  • the ligand of the complex to be used is a monodentate phosphine coordination such as trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-t-butylphosphine, tricyclohexylphosphine, triphenylphosphine, tris (2-methylphenyl) phosphine, etc.
  • Diphenylphosphinomethane (dppm), 1,2-diphenylphosphinoethane (dppe), 1,3-diphenylphosphinopropane (dppp), 1,4-diphenylphosphinobutane (pdbb), 1,3- Bidentate phosphine compounds such as bis (dicyclohexylphosphino) propane (dcpp), 1,1′-bis (diphenylphosphino) ferrocene (dppf), 2,2-dimethyl-1,3-bis (diphenylphosphino) propane Lico; tetramethyl ester Diamine, bipyridine, it is preferable that such a nitrogen-containing ligands such as acetonitrile is contained.
  • a nitrogen-containing ligands such as acetonitrile
  • the amount of the complex used varies depending on the kind of the conjugated block copolymer produced by both the linking method, the sequential polymerization method and the macroinitiator method, but is preferably 0.001 to 0.1 mol relative to the monomer. . If the amount of the catalyst is too large, it will cause a decrease in the molecular weight of the resulting polymer, which is also disadvantageous economically. On the other hand, if the amount is too small, the reaction rate becomes slow and stable production becomes difficult.
  • Solvents that can be used for the production of the conjugated block copolymer need to be properly used depending on the type of the conjugated block copolymer to be produced, but are generally commercially available for both the linking method, sequential polymerization method and macroinitiator method. A solvent can be selected.
  • ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, t-butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, diphenyl ether , Aliphatic or alicyclic saturated hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, alkyl halide solvents such as dichloromethane and chloroform, chlorobenzene, di Aromatic aryl halide solvents such as chlorobenzene, amide solvents such as dimethylformamide, diethylformamide, N-methylpyrrolidone, water, and mixtures thereof And the following the
  • the amount of the organic solvent used is preferably in the range of 1 to 1000 times by weight based on the monomer of the conjugated block copolymer to be produced, from the viewpoint of the solubility of the resulting linked body and the stirring efficiency of the reaction solution. Is preferably 10 times by weight or more, and preferably 100 times by weight or less from the viewpoint of reaction rate.
  • the polymerization temperature varies depending on the type of conjugated block copolymer to be produced.
  • the linking method, sequential polymerization method and macroinitiator method are usually carried out in the range of ⁇ 80 ° C. to 200 ° C.
  • the pressure in the reaction system is not particularly limited, but is preferably 0.1 to 10 atmospheres.
  • the reaction is usually carried out at around 1 atm.
  • the reaction time varies depending on the polymer block A and polymer block B to be produced, but is usually 20 minutes to 100 hours.
  • Conjugated block copolymers obtained by the linking method, sequential polymerization method and macroinitiator method are, for example, reprecipitation, solvent removal under heating, solvent removal under reduced pressure, and solvent removal with steam (steam stripping).
  • the conjugated block copolymer can be separated and obtained from the reaction mixture by a normal operation for isolating the conjugated block copolymer from the solution.
  • the obtained crude product can be purified by washing or extraction using a commercially available solvent using a Soxhlet extractor.
  • tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, dimethyl ether, ethyl methyl ether, diethyl ether, dipropyl ether, butyl methyl ether, t-butyl methyl ether, dibutyl ether, cyclopentyl methyl ether, diphenyl ether, and ether solvents Aliphatic or alicyclic saturated hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, aromatic hydrocarbon solvents such as benzene, toluene, xylene, ketone solvents such as acetone, ethyl methyl ketone, diethyl ketone, Alkyl halide solvents such as dichloromethane and chloroform, aromatic aryl halide solvents such as chlorobenzene and dichlorobenzene, dimethylformamide, die
  • the conjugated block copolymer of the present invention has, as a terminal group, a halogen atom, a trialkyltin group, a boronic acid group, a boronic acid ester group or other coupling residue, or a hydrogen atom from which these atoms or groups are eliminated. It may have a terminal structure in which these terminal groups are further substituted with a terminal blocking agent composed of an aromatic halide such as benzene bromide or an aromatic boronic acid compound.
  • the conjugated block copolymer thus obtained can be used as a composition that is an organic semiconductor material that forms an organic thin film by being mixed with a fullerene derivative that is an electron-accepting material.
  • These conjugated block copolymers may be used individually by 1 type in a composition, and may be used in combination of 2 or more type.
  • composition of the present invention at least a conjugated block copolymer and a fullerene derivative are mixed in the presence of a solvent.
  • This composition is useful, for example, as a functional layer of a photoelectric conversion element.
  • the ratio of the conjugated block copolymer to the fullerene derivative in the composition is preferably 10 to 1000 parts by weight, and more preferably 50 to 500 parts by weight with respect to 100 parts by weight of the conjugated block copolymer. preferable.
  • conjugated block copolymer and fullerene derivative which are essential components in this composition, contains a third component such as a non-conjugated polymer, a surfactant, a high-boiling solvent such as 1,8-diiodooctane, etc. You may do it.
  • the content of the third component is preferably 30% by mass or less and 10% by mass or less with respect to the total weight of the conjugated block copolymer and the fullerene derivative from the viewpoint of the performance of the photoelectric conversion element. And more preferred.
  • fullerene derivative contained in the composition include C 60 , C 70 , C 84 and derivatives thereof. Specific structural examples of the fullerene derivative are shown in the following chemical formulas (A) to (N).
  • the mixing method of the conjugated block copolymer and the fullerene derivative is not particularly limited.
  • a mixing method of the conjugated block copolymer and the fullerene derivative for example, after adding to a solvent at a desired ratio, one or a plurality of methods such as heating, stirring and ultrasonic irradiation are combined and dissolved and mixed in the solvent. A method is mentioned.
  • the solvent used when mixing the conjugated block copolymer and the fullerene derivative is not particularly limited as long as it is a solvent that can be mostly dissolved.
  • Specific examples of the solvent include ethers such as tetrahydrofuran, halogen solvents such as methylene chloride and chloroform, and aromatic solvents such as benzene, toluene, orthoxylene, chlorobenzene, orthodichlorobenzene and pyridine.
  • a composition containing a conjugated block copolymer and a fullerene derivative can form an organic thin film by a known printing method or coating method.
  • Specific film forming methods include spin coating, casting, micro gravure coating, gravure coating, slot die coating, bar coating, roll coating, dip coating, spray coating, screen printing, flexographic printing.
  • Known methods such as a printing method, an offset printing method, an ink jet printing method, a nozzle coating method, and a capillary coating method can be used.
  • the obtained organic thin film is useful as an organic transistor or a photoelectric conversion element.
  • the film thickness of the organic thin film containing the conjugated block copolymer is difficult to determine in general depending on the intended use, but is usually 1 nm to 1 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm. It is ⁇ 500 nm, more preferably 20 nm to 300 nm.
  • the film thickness is too thin, light is not sufficiently absorbed, and conversely if it is too thick, it becomes difficult for carriers to reach the electrode and high conversion efficiency cannot be obtained.
  • the photoelectric conversion element of the present invention has an organic photoelectric conversion layer formed by using the conjugated block copolymer of the present invention between at least two different electrodes, that is, a positive electrode and a negative electrode.
  • the electrode of the photoelectric conversion element has optical transparency in either the positive electrode or the negative electrode.
  • the optical transparency of the electrode is not particularly limited as long as incident light reaches the organic photoelectric conversion layer and an electromotive force is generated.
  • the thickness of the electrode is not particularly limited as long as it has optical transparency and electrical conductivity, and varies depending on the electrode material, but is preferably 20 nm to 300 nm. Note that in the case where one electrode has light transparency, the light transmission property is not necessarily required as long as the other electrode has conductivity. Furthermore, the thickness of this electrode is not particularly limited.
  • the electrode material it is preferable to use a conductive material having a high work function for one electrode and a conductive material having a low work function for the other electrode.
  • An electrode using a conductive material having a large work function is a positive electrode.
  • Conductive materials with a large work function include metals such as gold, platinum, chromium and nickel, transparent metal oxides such as indium and tin, composite metal oxides (indium tin oxide (ITO), indium Zinc oxide (IZO), fluorine-doped tin oxide (FTO), etc.) are preferably used.
  • the conductive material used for the positive electrode is preferably an ohmic junction with the organic photoelectric conversion layer.
  • the conductive material used for the positive electrode is an ohmic contact with the hole transport layer.
  • An electrode using a conductive material having a small work function is a negative electrode, and as the conductive material having a small work function, alkali metal or alkaline earth metal, specifically lithium, magnesium, or calcium is used. Tin, silver, and aluminum are also preferably used. Furthermore, an electrode made of an alloy made of the above metal or a laminate of the above metal is also preferably used.
  • the conductive material used for the negative electrode is preferably one that is in ohmic contact with the organic photoelectric conversion layer. Furthermore, when the electron transport layer is used, it is preferable that the conductive material used for the negative electrode is in ohmic contact with the electron transport layer.
  • the photoelectric conversion element is usually formed on a base material.
  • This substrate may be any substrate that does not change when the electrode is formed and the organic photoelectric conversion layer is formed.
  • substrate materials include inorganic materials such as non-alkali glass and quartz glass, metal films such as aluminum, polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene, epoxy resin, fluorine resin, and the like.
  • a film or plate produced from any organic material by any method can be used. If an opaque substrate is used, the opposite electrode, i.e. the electrode far from the substrate, must be transparent or translucent.
  • the film thickness of the substrate is not particularly limited, but is usually in the range of 1 ⁇ m to 10 mm.
  • ultraviolet ozone treatment corona discharge treatment
  • plasma treatment It is preferable to clean and modify the surface by physical means such as A method of chemically modifying the surface of the solid substrate such as a silane coupling agent, a titanate coupling agent, and a self-assembled monolayer is also effective.
  • a hole transport layer may be provided between the positive electrode and the organic photoelectric conversion layer as necessary.
  • the material for forming the hole transport layer include conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H 2 Pc, CuPc, ZnPc, etc.) ), Low molecular organic compounds exhibiting p-type semiconductor properties such as porphyrin derivatives are preferably used.
  • PEDOT polyethylenedioxythiophene
  • PEDOT polyethylenedioxythiophene
  • PEDOT polyethylenedioxythiophene
  • PEDOT polyethylenedioxythiophene
  • the thickness of the hole transport layer is preferably 5 nm to 600 nm, more preferably 20 nm to 300 nm.
  • the photoelectric conversion element may be provided with an electron transport layer between the negative electrode and the organic photoelectric conversion layer as necessary.
  • n-type semiconductor materials such as phenanthrene compounds such as bathocuproine, naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and N-type inorganic oxides such as titanium oxide, zinc oxide, and gallium oxide, and alkali metal compounds such as lithium fluoride, sodium fluoride, and cesium fluoride can be used.
  • a layer made of a single n-type semiconductor material used for the bulk heterojunction layer can also be used.
  • the photoelectric conversion element may further have an inorganic layer.
  • the material contained in the inorganic layer include titanium oxide, tin oxide, zinc oxide, iron oxide, tungsten oxide, zirconium oxide, hafnium oxide, strontium oxide, indium oxide, cerium oxide, yttrium oxide, lanthanum oxide, and vanadium oxide.
  • Metal oxides such as niobium oxide, tantalum oxide, gallium oxide, nickel oxide, strontium titanate, barium titanate, potassium niobate, sodium tantalate; silver iodide, silver bromide, copper iodide, copper bromide, Metal halides such as lithium fluoride; metals such as zinc sulfide, titanium sulfide, indium sulfide, bismuth sulfide, cadmium sulfide, zirconium sulfide, tantalum sulfide, molybdenum sulfide, silver sulfide, copper sulfide, tin sulfide, tungsten sulfide, and antimony sulfide Sulfide; Cadmium selenide Metal selenides such as zirconium selenide, zinc selenide, titanium selenide, indium selenide, tungsten selenide, molybdenum selenide
  • the photoelectric conversion element of the present invention can be obtained, for example, by the following manufacturing process.
  • a composition prepared from a conjugated block copolymer and an electron-accepting material is formed on a substrate on which a positive electrode is formed on a glass by using the above-described film forming method, and then dried to form an organic material.
  • a photoelectric conversion layer is formed.
  • a photoelectric conversion element can be manufactured by forming the electrode used as a negative electrode on this organic photoelectric converting layer.
  • the photoelectric conversion element of the present invention can be applied to various photoelectric conversion devices using a photoelectric conversion function, an optical rectification function (photo-diode), and the like.
  • a photoelectric conversion function an optical rectification function
  • optical recording materials such as photovoltaic cells such as solar cells, optical sensors, optical switches, electronic devices such as phototransistors, and optical memories.
  • the conjugated polymer block A1 was synthesized according to the following reaction formula (1).
  • ethylhexyl as a substituent is abbreviated as EtHex or HexEt.
  • the reaction solution was poured into methanol (500 mL), the precipitated solid was collected by filtration, washed with water (100 mL) and methanol (100 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (200 mL) and hexane (200 mL) using a Soxhlet extractor and then extracted with chloroform (200 mL).
  • the obtained solution was poured into methanol (2 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated polymer block A1 as a black purple solid (1.04 g, 41%).
  • the obtained conjugated polymer block A1 was subjected to physicochemical analysis.
  • the molecular structure was identified by 1 H-NMR (nuclear magnetic resonance) measurement.
  • 1 H-NMR (270 MHz): ⁇ 8.10-7.95 (m, 2H), 7.80-7.61 (m, 2H), 2.35-2.12 (m, 4H), 1 .60-1.32 (m, 18H), 1.18-0.82 (m, 12H)
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • THF as a solvent was purified by distillation of dehydrated tetrahydrofuran (without stabilizer) manufactured by Wako Pure Chemical Industries, Ltd. in the presence of metallic sodium, and then on molecular sieves 5A manufactured by Wako Pure Chemical Industries, Ltd. for one day or more. Purification was carried out by contact.
  • the polymer was purified using a preparative GPC column.
  • the apparatus used was Recycling Preparative HPLC LC-908 manufactured by Japan Analytical Industry.
  • the type of the column is one in which two styrene polymer columns 2H-40 and 2.5H-40 manufactured by Nippon Analytical Industrial Co., Ltd. are connected in series. Further, chloroform was used as an elution solvent.
  • Example 1 The conjugated block copolymer 1 was synthesized according to the following reaction formula (4).
  • “-b-” indicates block copolymerization
  • “-r-” or “-ran-” indicates random copolymerization. .
  • a conjugated polymer block A1 (0.80 g), a conjugated polymer block A3 (0.80 g), toluene (20 mL), a 2M aqueous potassium carbonate solution (10 mL, 20 mmol), tetrakis (triphenylphosphine) in a 100 mL three-necked flask.
  • Palladium (0) (20.5 mg, 17.7 ⁇ mol) and aliquat 336 (0.8 mg, 1.98 ⁇ mol) were added, followed by stirring at 80 ° C. for 24 hours.
  • the reaction solution was poured into methanol (200 mL), the precipitated solid was collected by filtration, washed with water (20 mL) and methanol (20 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (100 mL) and hexane (100 mL) using a Soxhlet extractor, and then extracted with chloroform (100 mL).
  • the obtained solution was poured into methanol (1 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated block copolymer 1 as a black purple solid (0.53 g, 33%).
  • Example 2 The conjugated block copolymer 2 was synthesized according to the following reaction formula (5).
  • a conjugated polymer block A2 (0.80 g), a conjugated polymer block A3 (0.80 g), toluene (20 mL), a 2M aqueous potassium carbonate solution (10 mL, 20 mmol), tetrakis (triphenylphosphine) in a 100 mL three-necked flask.
  • Palladium (0) (20.5 mg, 17.7 ⁇ mol) and aliquat 336 (0.8 mg, 1.98 ⁇ mol) were added, followed by stirring at 80 ° C. for 24 hours.
  • the reaction solution was poured into methanol (200 mL), the precipitated solid was collected by filtration, washed with water (20 mL) and methanol (20 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (100 mL) and hexane (100 mL) using a Soxhlet extractor, and then extracted with chloroform (100 mL).
  • the obtained solution was poured into methanol (1 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated block copolymer 2 as a black purple solid (0.53 g, 33%).
  • the reaction solution was poured into methanol (500 mL), the precipitated solid was collected by filtration, washed with water (100 mL) and methanol (100 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (200 mL) and hexane (200 mL) using a Soxhlet extractor and then extracted with chloroform (200 mL).
  • the obtained solution was poured into methanol (2 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated polymer block A4 as a black purple solid (1.06, 42%).
  • a conjugated polymer block A4 (0.80 g), a conjugated polymer block A5 (0.80 g), toluene (20 mL), a 2M aqueous potassium carbonate solution (10 mL, 20 mmol), tetrakis (triphenylphosphine) in a 100 mL three-necked flask.
  • Palladium (0) (20.5 mg, 17.7 ⁇ mol) and aliquat 336 (0.8 mg, 1.98 ⁇ mol) were added, followed by stirring at 80 ° C. for 24 hours.
  • the reaction solution was poured into methanol (200 mL), the precipitated solid was collected by filtration, washed with water (20 mL) and methanol (20 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (100 mL) and hexane (100 mL) using a Soxhlet extractor, and then extracted with chloroform (100 mL).
  • the obtained solution was poured into methanol (1 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated block copolymer 3 as a black purple solid (0.58 g, 36%).
  • a polymer block A4 (0.80 g) and a polymer represented by the polymer block A6 (0.80 g), toluene (20 mL), 2M aqueous potassium carbonate solution (10 mL, 20 mmol), tetrakis (tri Phenylphosphine) palladium (0) (20.5 mg, 17.7 ⁇ mol) and aliquat 336 (0.8 mg, 1.98 ⁇ mol) were added, followed by stirring at 80 ° C. for 24 hours.
  • the reaction solution was poured into methanol (200 mL), the precipitated solid was collected by filtration, washed with water (20 mL) and methanol (20 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (100 mL) and hexane (100 mL) using a Soxhlet extractor, and then extracted with chloroform (100 mL).
  • the obtained solution was poured into methanol (1 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated block copolymer 4 as a black purple solid (0.67 g, 42%).
  • the number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (PDI) of the conjugated block copolymer 5 obtained were determined in the same manner as in Polymerization Example 1.
  • the number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (PDI) of the conjugated block copolymer 6 obtained were determined in the same manner as in Polymerization Example 1.
  • the conjugated polymer block A8 was synthesized according to the following reaction formula (14).
  • 3-heptyl as a substituent is abbreviated as 3-Hep or Hep-3.
  • methyl as a substituent is abbreviated as Me.
  • the resulting conjugated polymer A8 was purified using a preparative GPC column.
  • a preparative GPC column As a device for purification, Recycling Preparative HPLC LC-908 manufactured by Japan Analytical Industry Co., Ltd. was used.
  • the type of the column is one in which two styrene polymer columns 2H-40 and 2.5H-40 manufactured by Nippon Analytical Industries, Ltd. are connected in series.
  • the column and injector were 145 ° C., and the elution solvent was chloroform.
  • the number average molecular weight (Mn) and the weight average molecular weight (Mw) were both determined in terms of polystyrene based on measurement by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • GPC / V2000 manufactured by Waters was used as the GPC apparatus, and a Shodex AT-G806MS manufactured by Showa Denko was connected in series as the column.
  • the column and injector were 145 ° C., and o-dichlorobenzene was used as an elution solvent.
  • the resulting conjugated polymer block A8 (0.51 g, 86%) had a weight average molecular weight (Mw) of 33,100, a number average molecular weight (Mn) of 14,600, and a polydispersity of 2.27.
  • 1H NMR (270 MHz, CDCl3): ⁇ 7.60-7.30 (br, 3H), 3.30-3.00 (Br, 5H), 2.00-1.10 (br, 52H), 1 .00-0.70 (br, 12H) (Example 7)
  • the conjugated block copolymer 7 was synthesized according to the following reaction formula (15).
  • a conjugated polymer block A8 (160.0 mg, 0.12 mol) and 2,6-bis (trimethyltin) -4,8-bis ( 2-ethylhexyloxy) benzo [1,2-b: 4,5-b ′] dithiophene (113.0 mg, 0.16 mmol), 2,6-bis (trimethyltin) -4,8-dipropylbenzo [1 , 2-b: 4,5-b ′] dithiophene (40.9 mg, 0.07 mmol) and 1- (4,6-dibromothieno [3,4-b] thiophen-2-yl) -2-ethylhexane- 1-one (86.0 mg, 0.20 mmol) was added, DMF (0.3 mL), toluene (1.4 mL), tetrakis (triphenylphosphine) palladium (0) (3.4 mg).
  • the obtained conjugated block copolymer 7 was purified by the same method and conditions as in Polymerization Example 8.
  • the obtained conjugated block copolymer 7 was subjected to physicochemical analysis under the same method and conditions as in Polymerization Example 8.
  • the following physicochemical analysis results support the chemical structure shown in the above reaction formula.
  • Conjugated polymer block A8 (0.59 g, 0.75 mmol) and 2,6-bis (trimethyltin) -4,8-bis (5- (2-ethylhexyl) thiophene as a monomer constituting the polymer block B 2-yl) benzo [1,2-b: 4,5-b ′] dithiophene (0.68 g, 0.75 mmol) and 1- (4,6-dibromothieno [3,4-b] thiophen-2-yl ) Conjugated block copolymer 8 was obtained using the same method as in Example 7 except that 2-ethylhexane-1-one (0.32 g, 0.75 mmol) was used (0.48 g, 76%). ).
  • the obtained conjugated block copolymer C1 had a weight average molecular weight of 21,600 and a number average molecular weight of 17,900.
  • the content of poly (3-hexylthiophene) block was 79 mol%.
  • the obtained conjugated block copolymer C2 has a weight average molecular weight (Mw) of 23,400, a number average molecular weight (Mn) of 20,800, and a dispersity (Mw / Mn) of 1.13.
  • Example 5 A diblock copolymer having a molar ratio of 3-hexylthiophene to styrene of 1: 1 was synthesized to obtain a non-conjugated block copolymer C5 of Comparative Example 5.
  • the detailed procedure for the synthesis of the non-conjugated block copolymer C5 followed Non-Patent Document 2.
  • the obtained nonconjugated block copolymer C5 had a weight average molecular weight (Mw) of 24,000, a number average molecular weight (Mn) of 16,900, and a dispersity (Mw / Mn) of 1.42.
  • a 100 mL three-necked flask was charged with a conjugated polymer block A4 (0.80 g) and a polymer represented by a conjugated polymer block A7 (0.80 g), toluene (20 mL), 2M aqueous potassium carbonate solution (10 mL, 20 mmol), tetrakis.
  • (Triphenylphosphine) palladium (0) (20.5 mg, 17.7 ⁇ mol) and aliquat 336 (0.8 mg, 1.98 ⁇ mol) were added, followed by stirring at 80 ° C. for 24 hours.
  • the reaction solution was poured into methanol (200 mL), the precipitated solid was collected by filtration, washed with water (20 mL) and methanol (20 mL), and the resulting solid was dried under reduced pressure to obtain a crude product. It was.
  • the crude product was washed with acetone (100 mL) and hexane (100 mL) using a Soxhlet extractor, and then extracted with chloroform (100 mL).
  • the obtained solution was poured into methanol (1 L), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain a conjugated block copolymer C6 as a black purple solid (0.67 g, 42%).
  • a polymer blend D1 was prepared by mixing the conjugated polymer block A8 obtained in Polymerization Example 8 and the conjugated polymer C9 obtained in Comparative Example 9 at a weight fraction of 50:50.
  • a solution containing PC 61 BM was produced by the same method for each polymer obtained in Examples 2, 5, and 6 and Comparative Examples 1 to 5, and 8.
  • a glass substrate provided with an ITO film (resistance value 10 ⁇ / ⁇ ) with a thickness of 150 nm by sputtering was subjected to surface treatment by ozone UV treatment for 15 minutes.
  • a PEDOT: PSS aqueous solution (manufactured by HC Starck: CLEVIOS PH500) serving as a hole transport layer was formed on the substrate to a thickness of 40 nm by a spin coating method. After heating and drying at 140 ° C.
  • Examples 1, 2, 5, 6 and Comparative Examples 1-5, 8 were subjected to thermal annealing at 120 ° C. for 30 minutes. Then, lithium fluoride was vapor-deposited with a film thickness of 1 nm by a vacuum vapor deposition machine, and then aluminum was vapor-deposited with a film thickness of 100 nm. The degree of vacuum at the time of vapor deposition was 2 ⁇ 10 ⁇ 4 Pa or less. As a result, an organic thin film solar cell which is a photoelectric conversion element using a conjugated block copolymer was obtained. The shape of the organic thin film solar cell was a 5 ⁇ 5 mm regular square.
  • Table 1 (Examples 1 to 4), Table 2 (Examples 5 to 8), Table 3 (Comparative Examples 1 to 5), and Table 4 (Comparative Examples 6 to 10) constitute conjugated block copolymers.
  • the structure of the conjugated polymer block, the solubility parameter (SP value) of the conjugated polymer block, the difference in SP value, and the photoelectric conversion efficiency of the organic thin film solar cell are shown.
  • the conjugated polymer block having the maximum solubility parameter is the conjugated polymer block A
  • the conjugated polymer block having the minimum solubility parameter is the conjugated polymer. Shown as block B.
  • the difference of SP value of each blended homopolymer was shown in the table
  • the difference between the maximum value (polymer block A) and the minimum value (polymer block B) is 0.6 or more and 2.0 or less. It can be seen that the organic thin-film solar cell using the conjugated block copolymer has higher conversion efficiency than the conventional conjugated block copolymer.
  • the solubility parameter can be adjusted by changing the divalent heterocyclic group of the main chain, and a preferred conjugated block copolymer can be synthesized. By changing the length of the side chain (Example 3) or by appropriately selecting the number of fluorine atoms bonded to the side chain (Examples 4 and 6), each polymer block has a favorable solubility parameter difference.
  • conjugated block copolymer can be synthesized. It can also be seen that the solubility parameter can be appropriately adjusted by bonding a hydroxyl group to the side chain (Example 5). From Examples 5 and 7, it can be seen that the polymer block A or B may be a polymer block made of a random copolymer.
  • the difference between the maximum value (conjugated polymer block A) and the minimum value (conjugated polymer block B) among the solubility parameters of the conjugated polymer block constituting each block from Comparative Examples 1, 2, 3, and 6 is 0. It can be seen that high conversion efficiency cannot be obtained unless it is in the range of. Even if the difference in solubility parameter is within the prescribed range of the present invention, the block containing mainly Comparative Example 4 and an unconjugated polymer block having an alkyl group substituted with a functional group other than a fluorine atom and a hydroxyl group in the side chain. It turns out that the comparative example 5 which is a polymer has low conversion efficiency.
  • the conjugated block copolymer which is a ⁇ -conjugated system of the present invention can be used as a photoelectric conversion layer of a photoelectric conversion element.
  • the photoelectric conversion element which consists of the conjugated block copolymer is used widely as various photosensors including a solar cell.

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Abstract

L'invention concerne un copolymère à blocs conjugués qui présente une excellente solubilité dans les solvants et qui est apte à former un film mince organique dans lequel une morphologie est régulée par une séparation de microphases. Le copolymère à blocs conjugués comprend un groupe hétérocyclique bivalent dans une chaîne principale et au moins deux types de blocs polymères conjugués contenant une chaîne latérale qui est un groupe alkyle ou un groupe alcoxy qui peut être substitué par un atome de fluor ou un groupe hydroxyle, et la différence en paramètre de solubilité entre les blocs polymères conjugués dont le paramètre de solubilité présente une valeur maximale et un bloc polymère conjugué dont le paramètre de solubilité présente une valeur minimale étant de 0,6-2,0.
PCT/JP2012/066363 2011-07-01 2012-06-27 Copolymère à blocs conjugués et dispositif de conversion photoélectrique l'utilisant Ceased WO2013005614A1 (fr)

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