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WO2013018853A1 - Composition à base de polymères conjugués et élément de conversion photoélectrique l'utilisant - Google Patents

Composition à base de polymères conjugués et élément de conversion photoélectrique l'utilisant Download PDF

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WO2013018853A1
WO2013018853A1 PCT/JP2012/069664 JP2012069664W WO2013018853A1 WO 2013018853 A1 WO2013018853 A1 WO 2013018853A1 JP 2012069664 W JP2012069664 W JP 2012069664W WO 2013018853 A1 WO2013018853 A1 WO 2013018853A1
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conjugated polymer
group
conjugated
polymer composition
photoelectric conversion
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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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Definitions

  • the present invention relates to a conjugated polymer composition for forming an organic thin film and a photoelectric conversion element using the organic thin film.
  • Solar cells are attracting attention as a powerful energy source that is friendly to the environment.
  • inorganic materials such as single crystal silicon, polycrystalline silicon, amorphous silicon, and compound semiconductors are used as photoelectric conversion elements for solar cells.
  • These photoelectric conversion elements have a relatively high photoelectric conversion efficiency, but are expensive.
  • the main factor of this high cost is that the photoelectric conversion element is expensive due to the process of manufacturing the semiconductor thin film under high vacuum and high temperature. Therefore, organic solar 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 made of an organic thin film is provided between two different electrodes.
  • the organic photoelectric conversion layer is formed from a mixture of a bulk heterojunction structure 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 (PCBM) as a fullerene derivative.
  • the problem of the organic solar cell is to increase the photoelectric conversion efficiency.
  • the photoelectric conversion efficiency can be improved by changing the morphology of the organic photoelectric conversion layer.
  • a method of treating with heat or solvent vapor a method of devising a solvent for dissolving a conjugated polymer or fullerene derivative, a method of adding a high boiling point compound, a method of reducing the volatilization rate of the solvent, and the like can be mentioned.
  • Non-Patent Document 1 In the organic semiconductor composition of a low molecular compound and a high molecular compound disclosed in Patent Document 1, it is difficult to mix a low molecular compound and a conjugated polymer that is a high molecular compound, macrophase separation, The stability of the compound is low because the compound bleeds out.
  • one of the conjugated polymers is not a condensed ⁇ -conjugated skeleton but has a HOMO level mismatch, so that charge transfer does not occur smoothly, and as a result, high conversion efficiency is not obtained.
  • the present invention has been made to solve the above-described problems, and can form an ideal phase separation structure for a photoelectric conversion element, can form a good organic thin film with high solubility in a solvent.
  • An object of the present invention is to provide a possible conjugated polymer composition and a photoelectric conversion element having an excellent photoelectric conversion efficiency using an organic thin film containing the composition.
  • the conjugated polymer composition according to claim 1, which has been made to achieve the above object, includes a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in a main chain, and a fluorine atom.
  • the difference between the conjugated polymer having the maximum value and the conjugated polymer having the minimum value in the solubility parameter of each conjugated polymer is 0.6 or more and 2.0 or less.
  • the conjugated polymer composition according to claim 2 is the conjugated polymer composition according to claim 1, wherein the heterocyclic group is composed of a condensed ⁇ -conjugated skeleton containing at least one thiophene ring as part of a chemical structure. It is characterized by that.
  • the conjugated polymer composition according to claim 3 is the composition according to claim 2, wherein the conjugated polymer comprises a cyclopentadithiophene diyl group, a dithienopyrrole diyl group, a dithienosilole diyl group, a dithieno. It consists of a monomer unit containing at least one divalent heterocyclic group selected from a germoldiyl group, a benzodithiophenediyl group, a naphthodithiophenediyl group, a thienothiophenediyl group, and a thienopyrroledione group. And
  • a conjugated polymer composition according to a fourth aspect is the one according to any one of the first to third aspects, wherein two types of the conjugated polymers have at least 12 carbon atoms in the divalent heterocyclic group.
  • a side chain that is an alkyl group or an alkoxy group, and a side chain that is an alkyl group or an alkoxy group having a maximum of 8 carbon atoms are bonded to the same or different divalent heterocyclic group.
  • a conjugated polymer is the one according to any one of the first to third aspects, wherein two types of the conjugated polymers have at least 12 carbon atoms in the divalent heterocyclic group.
  • a side chain that is an alkyl group or an alkoxy group, and a side chain that is an alkyl group or an alkoxy group having a maximum of 8 carbon atoms are bonded to the same or different divalent heterocyclic group.
  • a conjugated polymer is the one according to any one of the first to third aspects, wherein two types of the
  • the conjugated polymer composition described in claim 5 is the conjugated polymer composition described in any one of claims 1 to 4, wherein two types of the conjugated polymers are obtained by replacing the divalent heterocyclic group with a fluorine-unsubstituted group.
  • the conjugated polymer composition according to claim 6 is the conjugated polymer composition according to any one of claims 1 to 5, wherein at least one of the conjugated polymers is a divalent complex having a condensed ⁇ -conjugated skeleton. It is a random copolymer comprising at least two types of monomer units having a cyclic group.
  • the conjugated polymer composition described in claim 7 is the one described in any one of claims 1 to 6, wherein the conjugated polymer having the maximum solubility parameter and the minimum included in the conjugated polymer composition.
  • An organic semiconductor composition according to claim 8 is characterized by containing the conjugated polymer composition according to any one of claims 1 to 7 and a fullerene derivative.
  • An organic thin film according to claim 9 is characterized by containing the conjugated polymer composition according to any one of claims 1 to 7.
  • the organic thin film element of Claim 10 equips a board
  • the photoelectric conversion element according to claim 11 is characterized in that the organic thin film according to claim 9 is sandwiched between at least two electrodes.
  • the conjugated polymer composition of the present invention contains at least two kinds of conjugated polymers, and a phase separation structure can be formed by adjusting their solubility parameters. With this phase separation structure, it is possible to form an organic thin film with high photoelectric conversion efficiency with controlled morphology.
  • the conjugated polymer composition can form a phase-separated structure, and can control a morphology, whereby a photoelectric conversion element with improved photoelectric conversion efficiency can be obtained.
  • the organic semiconductor composition of the present invention contains a fullerene derivative which is an electron-accepting material together with a conjugated polymer composition having high solubility in a solvent, and can form an ideal phase separation structure.
  • the morphology of the organic thin film of the present invention is controlled, and when used in a photoelectric conversion element, it is possible to produce a high-performance photoelectric conversion element by imparting excellent photoelectric conversion efficiency.
  • the photoelectric conversion element of the present invention includes an organic thin film containing a conjugated polymer composition that controls morphology and improves photoelectric conversion efficiency as an organic photoelectric conversion layer, has excellent photoelectric conversion performance, It can be applied to various photoelectric conversion devices using the optical rectification function.
  • the conjugated polymer composition of the present invention contains a mixture of at least two kinds of conjugated polymers, for example, conjugated polymer A and conjugated polymer B.
  • conjugated polymers is composed of a conjugated divalent monomer and includes a divalent heterocyclic group in its main chain.
  • a conjugated divalent monomer is a divalent group in which electrons in a bond in the molecule are delocalized.
  • the main chain refers to the longest chain in a compound composed of a divalent heterocyclic group.
  • At least two of these conjugated polymers contain a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in the main chain, and are side chains that are alkyl groups or alkoxy groups that may be substituted with fluorine atoms or hydroxyl groups. It is the structure which has. That is, the conjugated polymer composition of the present invention contains the conjugated polymer containing a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in the main chain as an essential component.
  • divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton examples include a dibenzosilolediyl group, a dibenzogermoldiyl group, a dibenzofurandiyl group, a carbazolediyl group, a benzothiadiazolediyl group, a benzotriazole group, Examples include pentadithiophene diyl group, dithienopyrrole diyl group, dithienosilole diyl group, dithienogermole diyl group, benzodithiophene diyl group, naphthodithiophene diyl group, thienothiophene diyl group, and thienopyrrole dione group. .
  • a condensed ⁇ -conjugated skeleton containing at least one thiophene ring as a part of the chemical structure is preferable from the viewpoint that the morphology is easily controlled and the performance as a photoelectric conversion element is high.
  • cyclopentadithiophene diyl group, dithienopyrrole diyl group, dithienosilole diyl group, dithienogermol diyl group, benzodithiophene diyl group, naphthodithiophene diyl group, thienothiophene diyl group, thienopyrrole A dione group is preferred.
  • any of the conjugated polymers contained in the conjugated polymer composition of the present invention is composed of a divalent monomer composed of a heterocyclic group having a monocyclic structure
  • photoelectric conversion Since efficiency is not high, it is not preferable.
  • the divalent heterocyclic group is an unsubstituted or substituted thiophenediyl group having a monocyclic structure
  • synthesis is easy, but the wavelength range of light to be absorbed is a short wavelength, and it was used for a photoelectric conversion element. In this case, the photoelectric conversion efficiency is not high, which is not preferable.
  • the conjugated polymer contained in the conjugated polymer composition has a charge transport that the main chain skeleton is a divalent heterocyclic group composed of the same condensed ⁇ -conjugated skeleton. From the viewpoint of
  • the conjugated polymer has a structure in which a plurality of divalent heterocyclic groups are linked (for example, monomer unit -ab-) as one unit. And is regarded as a conjugated divalent monomer unit composed of a condensed ⁇ -conjugated skeleton in the present invention. That is, the completely alternating copolymer 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. Shall be deemed.
  • a ring structure excluding substituents in one type of monomer unit including the embodiment of the monomer unit -ab- is constituted.
  • the total number of carbon atoms alone is preferably 6-30.
  • the alkyl group or alkoxy group which may be substituted with a fluorine atom or hydroxyl group as a side chain is at least the monomer unit -a- or the monomer unit. It suffices to bind to either of -b-.
  • -ab can be regarded as a conjugated divalent monomer composed of a condensed ⁇ -conjugated skeleton constituting a conjugated polymer.
  • the copolymerization rate is preferably 50% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass with respect to the conjugated polymer. % Or less is more preferable.
  • 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 number average molecular weight of the conjugated polymer which is an essential component contained in the conjugated polymer composition, is the number average molecular weight in terms of polystyrene from the viewpoint of easy phase separation of the conjugated polymer composition, hole mobility and mechanical properties. It is preferably 10,000 g / mol or more, specifically 10,000 to 500,000 g / mol, more preferably 15,000 to 250,000 g / mol, and most preferably 20,000 to 150,000 g / mol.
  • a method for measuring the number average molecular weight known methods can be used, but measurement by size exclusion chromatography is preferred because it is simple and has a wide range of applicable polymers.
  • a standard polymer having a narrow molecular weight distribution and a known molecular weight can be used, but in the present invention, standard polystyrene is used and a polystyrene-equivalent number average molecular weight is adopted.
  • a known method can be used. That is, various coupling polymerizations can be used. Examples of the coupling reaction include Suzuki coupling, Kumada coupling, leek coupling, Stille coupling, Sonogashira coupling and the like.
  • the respective mass ratios of the conjugated polymer having the maximum solubility parameter and the conjugated polymer having the minimum solubility parameter are not particularly limited.
  • the mass ratio is preferably 95: 5 to 5:95, more preferably 90:10 to 10:90, and still more preferably 85:15 to 15:85.
  • the content of the conjugated polymer giving higher photoelectric conversion efficiency is larger.
  • the conjugated polymer composition preferably contains at least one crystalline conjugated polymer from the viewpoint of hole mobility.
  • the crystalline conjugated polymer referred to here is a polymer in which a part of the polymer is crystallized or in a liquid crystal state.
  • the crystalline polymer can be discriminated by X-ray diffraction or differential scanning calorimetry (DSC). In the present invention, it is determined that the weak polymer packing state, which is observed only by the aromatic ring ⁇ - ⁇ stack by the X-ray diffraction method, is also crystalline.
  • the conjugated polymer composition may contain a conjugated polymer having a structure other than the conjugated polymer which is an essential component.
  • the content is preferably 50% by mass or less, more preferably 30% by mass or less, from the viewpoint of controlling the morphology and the conversion efficiency of the photoelectric conversion element obtained by controlling the morphology, More preferably, it is at most mass%.
  • the conjugated polymer having a structure other than the conjugated polymer which is an essential component is preferably a conjugated polymer having a structure close to the structure of either the conjugated polymer A or the conjugated polymer B which is an essential component of the conjugated polymer composition.
  • the conjugated polymer composition may contain other non-conjugated polymers as long as it contains two or more kinds of conjugated polymers as essential components.
  • the content of the non-conjugated polymer is not particularly limited as long as it does not lower the conversion efficiency of the photoelectric conversion element, but is preferably 50% by mass or less, and 30% by mass or less with respect to the total mass of the conjugated polymer composition. Is more preferable, and is most preferably 10% by mass or less.
  • Such non-conjugated polymers are not involved in the solubility parameter in the present invention.
  • the difference between the conjugated polymer A having the maximum solubility parameter and the conjugated polymer B having the minimum solubility parameter is 0.6. It is the feature that it is 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, more preferably 0.6 or more and 1.6 or less, and 0.7 or more and 1.6 or less. Is most preferable.
  • the conjugated polymer composition can be phase-separated.
  • the difference between the maximum and minimum solubility parameters is 2.0 or less. If the difference between the maximum value and the minimum value of the solubility parameter is greater than 2.0, the solubility of the conjugated polymer in the solvent will be significantly reduced, making it difficult to obtain a thin film, In some cases, the phase separation size becomes too large, and high conversion efficiency may not be obtained when a photoelectric conversion element is used.
  • the ideal phase separation structure means that the components which are two or more kinds of conjugated polymers contained in the conjugated polymer composition have a co-continuous structure. It is also important that one conjugated polymer domain of these phase separation structures contains more fullerene derivatives, which are electron accepting materials than the other domains. By forming such a morphology, charge can be carried 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 method for controlling the solubility parameter can be controlled by the molecular structure of the conjugated polymer.
  • the solubility parameter can be adjusted by changing the main chain skeleton of each conjugated polymer. It is also possible to adjust the solubility parameter by changing the side chain structure and the side chain density.
  • the solubility parameter is controlled 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.
  • 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 refers to a part having carbon branched from a conjugated main chain.
  • the number of carbon atoms in the side chain is preferably 1 or more, more preferably 2 or more, and even more 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 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.
  • a bulky functional group that is bonded to an alkyl group or alkoxy group that may be substituted with a fluorine atom or a hydroxyl group is not preferable in that 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 is inhibited by forming strong hydrogen bonds between them or by hydrogen bonding between side chains in one polymer. Since there are cases, it is not preferable.
  • Preferred examples of the alkyl group substituted with a hydroxyl group include a 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.
  • Preferred alkoxy groups substituted with a hydroxyl group include, for example, hydroxymethoxy group, 2-hydroxyethoxy group, 3-hydroxypropoxy group, 3-hydroxyisopropoxy group, 4-hydroxybutoxy group, 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 ⁇ - hydroxyalkyl groups and ⁇ - positions.
  • conjugated polymers having different numbers of alkyl groups or alkoxy groups A combination of a conjugated polymer mainly containing side chains having 8 or less carbon atoms and a conjugated polymer mainly containing side chains having 12 to 20 carbon atoms is preferred, and has 3 to 8 carbon atoms. A combination of a conjugated polymer mainly containing the following side chains and a conjugated polymer mainly containing 12 to 20 side chains is more preferred. In the case of a conjugated polymer having a side chain with a small number of carbon atoms, it is possible to increase the value of the solubility parameter.
  • the solubility of the conjugated polymer in a solvent is reduced, which is a preferable organic thin film. Cannot be obtained.
  • the solubility parameter it is possible to reduce the value of the solubility parameter.
  • the number of carbon atoms is as large as 20 or more, it is difficult for the conjugated polymer chains to approach each other. This makes it difficult for the charges and excitons to move, and increases the number of components that do not contribute to photoelectric conversion, thereby reducing the short-circuit current density.
  • side chains do not need to be side chains in which all the side chains in the conjugated polymer are limited to these carbon numbers, and can be combined with other side chains.
  • the monomer unit of the conjugated polymer has a plurality of side chains
  • one conjugated polymer has a carbon number.
  • Preferred alkyl groups for adjusting the solubility parameter of the conjugated polymer by the number of carbons in the side chain include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group Tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, isohexyl group, 2-ethylhexyl group, n-heptyl group, n-octyl group, n-nonyl group, Examples include n-decyl group, n-hexadecyl group, 3,7-dimethyloctyl group, n-dodecyl group and the like.
  • Preferred alkoxy groups for adjusting the solubility parameter of the conjugated polymer by the number of carbons in the side chain include, for example, methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group, n-butoxy group, n-hexyl group, Examples thereof include an n-octyloxy group, an n-decyloxy group, a 2-ethylhexyloxy group, an n-dodecyloxy group, an n-hexadecyloxy group, a 3,7-dimethyloctyloxy group, and an n-dodecyloxy group.
  • 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 monomer unit of the conjugated polymer has a plurality of side chains, when comparing at least one side chain different from each other among the side chains contained in each monomer unit, one conjugated polymer contains 3 fluorine atoms. It is preferable to have at least one side chain.
  • a conjugated polymer composition having a desired difference in solubility parameter can be obtained by combining such a conjugated polymer having a side chain and a conjugated polymer having a side chain not containing a fluorine atom.
  • the solubility parameter of the conjugated polymer 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.
  • preferred fluorinated alkyl groups include, for example, trifluoromethyl group, 2,2,2-trifluoroethyl group 2,2,2,1,1-pentafluoroethyl group, 4,4,4-trifluorobutyl group, 6,6,6-trifluorohexyl group, 5,5,6,6,6-pentafluoro Hexyl group, 7,7,7-trifluoroheptyl group, 4,4,5,5,6,6,7,7,7-nonafluoroheptyl group, 8,8,8-trifluorooctyl group, 7, ⁇ -trifluoromethylalkyl group and perfluoroalkyl group such as 7,8,8,8-pentafluorooctyl group, 5,5,6,6,7,7,8,8,8-nonafluorooctyl
  • preferred fluorinated alkoxy groups include, for example, trifluoromethoxy group, 2,2,2-trifluoroethoxy group 2,2,2,1,1-pentafluoroethoxy group, 4,4,4-trifluorobutoxy group, 6,6,6-trifluorohexyloxy group, 5,5,6,6,6-penta Fluorohexyloxy group, 7,7,7-trifluoroheptyloxy group, 4,4,5,5,6,6,7,7,7-nonafluoroheptyloxy group, 8,8,8-trifluorooctyl ⁇ -trifluoro such as oxy group, 7,7,8,8,8-pentafluorooctyloxy group, 5,5,6,6,7,7,8,8,8-nonafluorooctyloxy group Chiruarukok
  • the conjugated polymer which is an essential component constituting the conjugated polymer composition of the present invention may be a homopolymer comprising one type of monomer unit or a random copolymer having two or more types of monomer units. It may be a graft copolymer or a block copolymer.
  • the solubility parameter can also be controlled by using at least one of the conjugated polymers constituting the conjugated polymer composition as a homopolymer and the other as a copolymer.
  • at least one of the conjugated polymers is a random copolymer composed of at least two types of monomer units having a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton.
  • the Bicerano method is used.
  • Other methods include, for example, Hildebrand method, Small method, Fedors method, Van Krevelen method, Hansen method, Hoy method, Ascadskii method, Okitsu method, etc., but in these methods the solubility parameter of the polymer having a heterocyclic ring 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.
  • the conjugated polymer composition of the present invention needs to calculate a solubility parameter for each conjugated polymer contained.
  • the solubility parameter of the random copolymer is calculated as in the following formula (A).
  • [Solubility parameter of random copolymer] ⁇ ( ⁇ i ⁇ ⁇ i) (A)
  • ⁇ i Solubility parameter of a polymer consisting only of i units that are components of a random copolymer
  • a conjugated polymer composition containing each conjugated polymer with adjusted solubility parameters is useful as an organic semiconductor material, and can form an organic thin film with controlled morphology.
  • a fullerene derivative is preferably used as the electron-accepting material. Therefore, it becomes an organic semiconductor composition which forms an organic thin film by mixing at least the conjugated polymer composition of the present invention and a fullerene derivative.
  • the organic semiconductor composition of the present invention is a mixture of at least a conjugated polymer composition and a fullerene derivative in the presence of a solvent. This organic semiconductor composition is useful as a functional layer of a photoelectric conversion element.
  • fullerene derivative which is an electron-accepting material examples include C 60 , C 70 , C 84 and derivatives thereof. Specific structural examples of fullerene derivatives are shown in the following chemical formulas (a) to (nu).
  • the ratio of the conjugated polymer composition to the fullerene derivative is preferably 10 to 1000 parts by weight, and preferably 50 to 500 parts by weight with respect to 100 parts by weight of the conjugated polymer composition. More preferably.
  • the content of the third component is preferably 30% by mass or less, and preferably 10% by mass or less, based on the total weight of the conjugated polymer composition and the fullerene derivative, from the viewpoint of the performance of the photoelectric conversion element. preferable.
  • the method for mixing the conjugated polymer composition and the fullerene derivative is not particularly limited, but after adding to the solvent at a desired ratio, one or more methods such as heating, stirring, and ultrasonic irradiation are combined. And a method of dissolving and mixing in a solvent.
  • the solvent used when mixing the conjugated polymer composition and the fullerene derivative is not particularly limited as long as it is a solvent that can be mostly dissolved.
  • Specific examples 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.
  • the organic semiconductor composition containing the conjugated polymer composition of the present invention and the conjugated polymer composition and fullerene derivative can form an organic thin film by a known printing method or coating method.
  • a film formation method spin coating method, casting method, micro gravure coating method, gravure coating method, slot die coating method, bar coating method, roll coating method, dip coating method, spray coating method, screen printing method, A flexographic printing method, an offset printing method, an ink jet printing method, a nozzle coating method, a capillary coating method, and the like can be used.
  • An organic thin film containing a conjugated polymer composition is useful as an organic transistor, a photoelectric conversion element, or an organic thin film element.
  • the organic thin film element is, for example, one in which an organic thin film containing a conjugated polymer composition is attached to the substrate surface.
  • the film thickness of the organic thin film containing this conjugated polymer composition 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 photoelectric conversion element of the present invention is an organic thin film containing the conjugated polymer composition of the present invention between at least two different electrodes, that is, a positive electrode 2 and a negative electrode 4 on a substrate 5.
  • a certain organic photoelectric conversion layer 3 is provided.
  • the photoelectric conversion element 1 may be one in which the positions of the positive electrode 2 and the negative electrode 4 are reversed depending on the type of the electrode.
  • the electrode of the photoelectric conversion element 1 has optical transparency in either the positive electrode 2 or the negative electrode 4.
  • the light transmittance of the electrode is not particularly limited as long as incident light reaches the organic photoelectric conversion layer 3 and an electromotive force is generated.
  • the thickness of the electrode may be in a range having light transmittance and 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 the positive electrode 2.
  • 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 2 is preferably one that is in ohmic contact with the organic photoelectric conversion layer 3. Furthermore, when a hole transport layer described later is used, it is preferable that the conductive material used for the positive electrode 2 is in ohmic contact with the hole transport layer.
  • An electrode using a conductive material having a small work function is the negative electrode 4, 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. Further, it is possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride into the interface between the negative electrode 4 and the electron transport layer.
  • the conductive material used for the negative electrode 4 is preferably one that is in ohmic contact with the organic photoelectric conversion layer 3. Furthermore, when the electron transport layer is used, it is preferable that the conductive material used for the negative electrode 4 is in ohmic contact with the electron transport layer.
  • the substrate 5 may be any substrate that does not change when the electrode is formed and the organic photoelectric conversion layer 3 is formed.
  • inorganic materials such as alkali-free glass and quartz glass, metal films such as aluminum, and any organic material such as polyester, polycarbonate, polyolefin, polyamide, polyimide, polyphenylene sulfide, polyparaxylene, epoxy resin and fluorine resin Films and plates produced by the 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 5 is not particularly limited, but is usually in the range of 1 ⁇ m to 10 mm.
  • the surface is cleaned and modified by physical means such as ultraviolet ozone treatment, corona discharge treatment, and plasma treatment. It is preferable to apply.
  • 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.
  • the photoelectric conversion element 1 may be provided with a hole transport layer between the positive electrode 2 and the organic photoelectric conversion layer 3 as necessary.
  • conductive polymers such as polythiophene polymers, poly-p-phenylene vinylene polymers, polyfluorene polymers, phthalocyanine derivatives (H2Pc, 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 polystyrene sulfonate
  • 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 1 may be provided with an electron transport layer between the negative electrode 4 and the organic photoelectric conversion layer 3 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 1 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 Sulfides; cadmium selenide, selenium Metal selenides such as zirconium selenide, zinc selenide, titanium selenide, indium selenide, tungsten selenide, moly
  • the photoelectric conversion element 1 of the present invention has a photoelectric conversion function and an optical rectification function (photo It can be applied to various photoelectric conversion devices using diodes). For example, it is useful for photovoltaic cells (such as solar cells), electronic devices (such as optical sensors, optical switches, phototransistors), optical recording materials (such as optical memories), and the like.
  • photovoltaic cells such as solar cells
  • electronic devices such as optical sensors, optical switches, phototransistors
  • optical recording materials such as optical memories
  • the conjugated polymer A1 was synthesized according to the following reaction formula (1).
  • ethylhexyl as a substituent is abbreviated as EtHex or HexEt.
  • EtHex ethylhexyl
  • HexEt HexEt
  • 2,6-dibromo-4,4′-bis (2-ethylhexyl) -cyclopenta [2,1-b: 3,4-b ′] dithiophene (1.50 g, 2.68 mmol).
  • 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 A1 as a black purple solid (1.04 g, 41%).
  • the obtained conjugated polymer 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
  • phenylboronic acid pinacol ester (273 mg, 1.34 mmol) was added, and the mixture was stirred at 80 ° C. for 18 hours.
  • 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 A2 as a black purple solid (1.03 g, 38%).
  • the conjugated polymer A3 was synthesized according to the following reaction formula (3).
  • 2,6-dibromo-4,4′-bis (2-ethylhexyl) -cyclopenta [2,1-b: 3,4-b ′] dithiophene (1.50 g, 2.68 mmol).
  • 4,7-bis (3,3,4,4-tetramethyl-2,5,1-dioxaborolan-1-yl) benzo [c] [1,2,5] thiadiazole (1.04 g, 2.
  • 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 A3 as a black purple solid (1.06, 42%).
  • the conjugated polymer A7 was synthesized according to the following reaction formula.
  • a well-dried eggplant flask A that had been purged with argon was treated with 25 mL of dehydrated and peroxide-removed THF, 1.865 g (5 mmol) of 2-bromo-5-iodo-3-hexylthiophene, and i-propyl.
  • 2.5 mL of a 2.0 M solution of magnesium chloride was added and stirred at 0 ° C. for 30 minutes to synthesize an organomagnesium compound solution represented by the chemical formula (a1) in the above reaction formula.
  • 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. As the apparatus, Recycling Preparative HPLC LC-908 manufactured by Japan Analytical Industry was used. The column type used was a series of two styrene polymer columns 2H-40 and 2.5H-40 manufactured by Nihon Analytical Industries. Further, chloroform was used as an elution solvent.
  • the conjugated polymer A10 was synthesized according to the following reaction formula.
  • 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 A10 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) of the resulting conjugated polymer A10 (0.51 g, 86%) are both in terms of polystyrene based on measurement by gel permeation chromatography (GPC). Obtained by value.
  • GPC / V2000 manufactured by Waters was used as the GPC apparatus, and two columns of Shodex AT-G806MS manufactured by Showa Denko were connected in series as the column. The column and injector were 145 ° C., and o-dichlorobenzene was used as an elution solvent.
  • conjugated polymer A12 As a monomer constituting the conjugated polymer A12, 2,6-bis (trimethyltin) -4,8-dipropylbenzo [1,2-b: 4,5-b ′] dithiophene (0.45 g, 0.75 mmol) ) And 1- (4,6-dibromothieno [3,4-b] thiophen-2-yl) -2-ethylhexane-1-one (0.32 g, 0.75 mmol) A similar method was used to obtain conjugated polymer A12 (0.31 g, 77%).
  • Example 4 For each conjugated polymer composition obtained in Example 4 and Comparative Examples 9 and 10, 5.0 mg of the conjugated polymer composition and 7.5 mg of PC 71 BM (E110 manufactured by Frontier Carbon Co.) as an electron-accepting material were used. A solution containing the conjugated polymer composition and PC 71 BM was prepared in the same manner except that it was used.
  • PC 71 BM E110 manufactured by Frontier Carbon Co.
  • 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 Co., Ltd .: CLEVIOS PH500) serving as a hole transport layer was formed on the substrate to a thickness of 40 nm by spin coating. After heating and drying at 140 ° C.
  • Tables 1 to 3 show the conjugated polymer composition and conjugated polymer used as a thin film forming material for the organic photoelectric conversion layer, the structure of the conjugated polymer constituting the conjugated polymer composition, its solubility parameter (SP value), and the conjugated polymer. The difference of the solubility parameter of A and B and the photoelectric conversion efficiency of the organic thin film solar cell were shown.
  • conjugated polymers constituting the conjugated polymer composition contain a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in the main chain, and the number average molecular weight of each conjugated polymer is at least 10,000 g /
  • the conjugated polymer composition of the present invention in which the difference between the maximum value (conjugated polymer A) and the minimum value (conjugated polymer B) among the solubility parameters of each conjugated polymer is 0.6 or more and 2.0 or less is used. It can be seen that the organic thin film solar cells (Examples 1 to 4) had high conversion efficiency.
  • Comparative Examples 1, 4 to 6, 9, and 10 have high conversion efficiency because they contain only one type of conjugated polymer containing a divalent heterocyclic group consisting of a condensed ⁇ -conjugated skeleton in the main chain. Absent.
  • Comparative Example 2 contains two types of conjugated polymers containing a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in the main chain, the solubility parameter of the conjugated polymer constituting the composition is the maximum value (conjugated) Since the difference between the polymer A) and the minimum value (conjugated polymer B) is not in the range of 0.6 or more and 2.0 or less, it can be seen that high conversion efficiency is not obtained.
  • Comparative Examples 3 and 7 do not contain a conjugated polymer containing a divalent heterocyclic group composed of a condensed ⁇ -conjugated skeleton in the main chain, the conversion efficiency is inferior.
  • the number average molecular weight of the conjugated polymer contained is less than 10,000 g / mol, and the conversion efficiency is inferior because the constituent requirements of the present invention are not satisfied.
  • the conjugated polymer composition of the present invention can be used as a photoelectric conversion layer of a photoelectric conversion element.
  • the photoelectric conversion element using the organic thin film containing the conjugated polymer composition is used widely as various optical sensors including a solar cell.
  • 1 is a photoelectric conversion element
  • 2 is a positive electrode
  • 3 is an organic photoelectric conversion layer
  • 4 is a negative electrode
  • 5 is a substrate.

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Abstract

La présente invention concerne une composition à base de polymères conjugués permettant la formation d'une structure à phases séparées se révélant idéale en vue d'une utilisation dans un élément de conversion photoélectrique et permettant également l'obtention d'une couche organique mince avantageuse, car hautement soluble dans les solvants. Cette composition à base de polymères conjugués comporte une chaîne principale comprenant un groupe hétérocyclique divalent à chaîne principale n-conjuguée à un noyau fusionné, comporte une chaîne latérale constituée d'un groupe alcoxy ou d'un groupe alkyle éventuellement substitué par un atome de fluor ou un groupe hydroxyle, et contient au moins deux types de polymères conjugués présentant une masse moléculaire moyenne en nombre en termes de polystyrène au moins égale à 10 000 g/mol, la différence entre le polymère conjugué présentant le paramètre de solubilité le plus élevé et le polymère conjugué présentant le paramètre de solubilité le plus faible variant de 0,6 à 2,0.
PCT/JP2012/069664 2011-08-04 2012-08-02 Composition à base de polymères conjugués et élément de conversion photoélectrique l'utilisant Ceased WO2013018853A1 (fr)

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JP2014189721A (ja) * 2013-03-28 2014-10-06 Sumitomo Chemical Co Ltd 高分子化合物
JP2014205737A (ja) * 2013-04-11 2014-10-30 住友化学株式会社 化合物及びそれを用いた電子素子
CN109749061A (zh) * 2018-12-24 2019-05-14 国家纳米科学中心 联受体型聚合物光伏材料及其制备和应用

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