WO2013099926A1 - Élément de conversion photoélectrique et procédé de fabrication de celui-ci - Google Patents

Élément de conversion photoélectrique et procédé de fabrication de celui-ci Download PDF

Info

Publication number
WO2013099926A1
WO2013099926A1 PCT/JP2012/083613 JP2012083613W WO2013099926A1 WO 2013099926 A1 WO2013099926 A1 WO 2013099926A1 JP 2012083613 W JP2012083613 W JP 2012083613W WO 2013099926 A1 WO2013099926 A1 WO 2013099926A1
Authority
WO
WIPO (PCT)
Prior art keywords
photoelectric conversion
conversion element
substrate
image
solvent
Prior art date
Application number
PCT/JP2012/083613
Other languages
English (en)
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
Original Assignee
株式会社クラレ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社クラレ filed Critical 株式会社クラレ
Publication of WO2013099926A1 publication Critical patent/WO2013099926A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/191—Deposition of organic active material characterised by provisions for the orientation or alignment of the layer to be deposited
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • H10K85/215—Fullerenes, e.g. C60 comprising substituents, e.g. PCBM
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a photoelectric conversion element useful as a solar cell or various optical sensors.
  • 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 a photoelectric conversion layer is provided between two different electrodes.
  • the 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 the conjugated polymer and [6,6] -phenyl C 61 butyric acid methyl ester (PCBM) as the fullerene derivative.
  • the problem of the organic solar cell 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 photoelectric conversion layer.
  • a method of treating with heat or solvent vapor for example, a method of treating with heat or solvent vapor (Patent Document 1), a method of devising a solvent for dissolving a conjugated polymer or a fullerene derivative (Patent Document 2), a high boiling point compound And a method of reducing the volatilization rate of the solvent.
  • Non-Patent Documents 1 to 3 These methods can be achieved only in a small area at the laboratory level, are difficult to increase in area, and are uneconomical methods. Since usable compounds are limited to low molecules, high conversion efficiency can be expected. It was difficult to apply to molecules, and the conversion efficiency of photoelectric conversion elements was limited.
  • the morphology in the film thickness direction is not controlled, the performance improvement of the photoelectric conversion element is limited, and when using nanoimprint or compound-derived crystal growth, Although the morphology is relatively controlled, it is uneconomical, applicable compounds are limited, and conversion efficiency performance is limited. Therefore, there has been a demand for a photoelectric conversion element that can achieve high conversion efficiency by forming a photoelectric conversion layer whose morphology is controlled in the cross-sectional direction of the film, that is, in the film thickness direction by an inexpensive method.
  • the present invention has been made in order to solve the above-described problems, and includes a photoelectric conversion layer whose morphology in the film thickness direction is controlled by an inexpensive method, and exhibits high photoelectric conversion efficiency and excellent photoelectric conversion performance. It is an object of the present invention to provide a photoelectric conversion element and a manufacturing method thereof.
  • the photoelectric conversion device which has been made to achieve the above object, includes a structural unit including at least one condensed ⁇ -conjugated skeleton including a thiophene ring as part of a chemical structure.
  • a photoelectric conversion layer containing a p-type polymer semiconductor and an n-type organic semiconductor containing a polymer is sandwiched between a positive electrode and a negative electrode on a substrate, and a morphology image of a cross section of the photoelectric conversion layer is obtained.
  • the relationship is characterized by 0.1 ⁇ Y / X ⁇ 0.7.
  • the photoelectric conversion device according to claim 2 is the one according to claim 1, wherein the n-type organic semiconductor has a fullerene derivative.
  • the photoelectric conversion device according to claim 3 is the photoelectric conversion device according to claim 1, wherein the p-type polymer semiconductor includes at least one condensed ⁇ -conjugated skeleton including a thiophene ring as part of a chemical structure. It is a block copolymer having a structural unit.
  • the photoelectric conversion device according to claim 4 is the photoelectric conversion device according to claim 2, wherein the p-type polymer semiconductor has at least one condensed ⁇ -conjugated skeleton including a thiophene ring as a part of a chemical structure. It is a block polymer having a constitutional unit containing it.
  • the method for producing a photoelectric conversion device wherein the solvent is added to a coating film obtained by applying a solution containing an n-type organic semiconductor, a p-type polymer semiconductor, and a solvent on the electrode layer on the substrate.
  • the coating film is exposed to solvent vapor, dried and solidified to form a photoelectric conversion layer.
  • the method for producing a photoelectric conversion device according to claim 6 is the method according to claim 5, wherein the vapor of the solvent does not dissolve the p-type polymer semiconductor.
  • the method for producing a photoelectric conversion device is the method according to claim 5, wherein the solvent exposed as the vapor of the solvent is acetone, methyl ethyl ketone, methyl butyl ketone, methanol, ethanol, isopropanol, Ethyl acetate, hexane, cyclohexane, methylene chloride, chloroform, carbon tetrachloride, 1-chloronaphthalene, 1,2-dibromoethane, benzene, toluene, orthoxylene, anisole, methyl benzoate, pyridine, dimethylformamide, acetonitrile, morpholine, tetrahydrofuran And at least one selected from the group consisting of 1,4-dioxane.
  • the photoelectric conversion element of the present invention has a photoelectric conversion layer whose morphology is controlled in the film thickness direction, that is, the direction perpendicular to the substrate, and can exhibit excellent photoelectric conversion efficiency. Moreover, this photoelectric conversion element has excellent photoelectric conversion performance, and can be applied to various photoelectric conversion devices using a photoelectric conversion function and an optical rectification function.
  • a photoelectric conversion layer whose morphology is controlled by an inexpensive method can be formed, and a photoelectric conversion element having excellent photoelectric conversion efficiency can be formed on a small scale such as a laboratory level. It is economical and can be provided on an industrial scale such as the plant level.
  • FIG. 5 is a diagram showing a line profile in a direction corresponding to a substrate vertical direction in the two-dimensional Fourier transformed image of FIG. 4.
  • FIG. 5 is a diagram illustrating a line profile in a direction corresponding to the horizontal direction of the substrate in the two-dimensional Fourier transform image of FIG. 4.
  • 8 is an image obtained by two-dimensional Fourier transform of the scanning transmission electron micrograph of FIG. It is a figure which shows the line profile of the direction corresponding to a board
  • 12 is an image obtained by two-dimensional Fourier transform of the scanning transmission electron micrograph of FIG.
  • 1 is a photoelectric conversion element (before the upper electrode is formed)
  • 2 is a crystal part of a p-type polymer semiconductor
  • 3 is an amorphous part of a p-type polymer semiconductor
  • 4 is an n-type organic semiconductor
  • 5 is a photoelectric conversion layer
  • 6 is An electrode layer
  • 6a is a PEDOT / PSS film
  • 6b is an ITO electrode film
  • 6c is an aluminum electrode
  • 7 is a substrate.
  • a photoelectric conversion layer containing an n-type organic semiconductor and a p-type polymer semiconductor is sandwiched between at least two different electrode layers, that is, a positive electrode and a negative electrode, on a substrate.
  • the half width when fitting the line profile corresponding to the substrate vertical direction with a Gaussian function is “X”, and the substrate horizontal direction
  • the relationship between X and Y is expressed by 0.1 ⁇ Y / X ⁇ 0.7, where “Y” is the half width when the line profile corresponding to is fitted with a Gaussian function.
  • the acquisition of the morphology image of the cross section of the photoelectric conversion layer can be performed by observing a thin film slice in the cross-sectional direction with a transmission electron microscope (TEM) or a scanning transmission electron microscope (STEM), A well-known method such as a method of observing with a high-resolution SEM) or a scanning probe microscope (SPM) can be used.
  • the morphology obtained here is an image of phase separation between an n-type organic semiconductor and a p-type polymer semiconductor.
  • a thin film slice for TEM or STEM depends on the domain size of the n-type organic semiconductor and the p-type polymer semiconductor, but is usually preferably 10 nm to 100 nm, more preferably 20 nm to 70 nm, and most preferably 20 nm to 50 nm. If the film thickness is too thin, only the portion that has deteriorated during the preparation of the thin film slice will be observed, and the true morphology cannot be observed. If it is too thick, contrast cannot be obtained and phase separation cannot be seen. In addition, it is preferable to cool the sample as much as possible during TEM or STEM observation because the sample is less damaged. The temperature during cooling is preferably ⁇ 100 ° C. or lower.
  • a method for producing a thin film slice when observing a morphological image of a photoelectric conversion layer cross section with a TEM or STEM a method of cutting the cross section using a focused ion beam (FIB) or an ion milling method may be mentioned.
  • FIB focused ion beam
  • the acceleration voltage is small because the sample is less damaged.
  • the temperature during cooling is preferably ⁇ 100 ° C. or lower.
  • Elemental mapping by TEM-EELS is useful when acquiring a morphological image of the cross section of the photoelectric conversion layer with TEM.
  • An image with higher contrast can be obtained by mapping with an element that is uniquely contained in an n-type organic semiconductor or a p-type polymer semiconductor, or by acquiring a plasmon loss image.
  • an image with higher contrast may be obtained by observing at a low acceleration voltage.
  • the resolution of the image is preferably 0.2 pixels / nm or more.
  • it is 0.4 pixel / nm or more, More preferably, it is 1 pixel / nm or more.
  • the analysis of the morphology image of the cross section of the photoelectric conversion layer focuses only on the photoelectric conversion layer, the electrodes present on both sides of the photoelectric conversion layer, the electron transport layer provided between the negative electrode and the photoelectric conversion layer as necessary, Inorganic layers are not included in the analysis. That is, image analysis is performed by trimming only the photoelectric conversion layer. The contrast, brightness, and gamma value of the image can be adjusted as appropriate so that the obtained image has sufficient contrast. In addition, a clearer contrast can be obtained by binarizing the n-type organic semiconductor domain and the p-type polymer semiconductor domain.
  • the volume fraction prepared for the n-type organic semiconductor and the p-type polymer semiconductor and the binarized area ratio are made the same, and at that time, each domain is binarized in units of pixels. It is necessary to be careful not to make it. In the case of an image having sufficient contrast, the interface between the photoelectric conversion layer and the electrode or other layer (electron transport layer or inorganic layer) can be visually discriminated.
  • the obtained morphology image of the cross section of the photoelectric conversion layer is converted into a grayscale or two-tone image, and then subjected to two-dimensional Fourier transform using image analysis software.
  • the output of the image is set so that the low frequency component is centered and the high frequency component is outside with the frequency zero as the origin.
  • the image analysis software is preferably Image Pro Plus (Media Cybernetics).
  • a Fourier transform image of the morphology image is obtained as a real part image of F (x, y), an imaginary part image, or a power spectrum indicating the intensity of F (x, y). Any image may be used for the analysis.
  • the morphology image is expressed by a Gaussian function such as the following formula (1).
  • a and b are positive real numbers.
  • it morphology represented by Gaussian function takes a long oval shape in a narrow r v direction r h direction about the origin, that is, oriented shaped substrate vertically Means.
  • 2 obtained from the function after the Fourier transform of f (r v , r h ) is expressed by the following equation (2). From equation (2), it can be seen that when the morphology expressed by a Gaussian function is oriented in the direction perpendicular to the substrate, its power spectrum
  • the half width Y can be obtained narrower. That is, it can be seen that Y / X is smaller than 1 when the morphology is oriented in the direction perpendicular to the substrate. On the other hand, it can be seen that Y / X is greater than 1 when the morphology is oriented in the horizontal direction of the substrate.
  • the morphology image of the cross section of the photoelectric conversion layer has a more complicated shape than the mathematical model as described above.
  • any morphology can be expressed approximately accurately with a linear combination of Gaussian functions, and the Fourier transform function F (X, y) is obtained as the sum of contributions of the respective Gaussian functions. Accordingly, in the actual morphology image, Y / X represents the degree of orientation of the entire morphology in the substrate vertical direction or substrate horizontal direction.
  • Each one-dimensional profile obtained in this way is fitted with a Gaussian function to calculate the half width.
  • fitting with a Gaussian function is performed to calculate the half width.
  • the half-value width obtained from the one-dimensional profile corresponding to the substrate vertical direction in the morphology image before Fourier transform processing is “X”, and the substrate horizontal direction in the morphology image before Fourier transform processing.
  • Y / X which is a parameter in the present invention, is calculated by setting the half width obtained from the one-dimensional profile to be “Y”.
  • Y / X obtained from the above analysis can be considered as a number representing the anisotropy of the phase separation size in the substrate vertical direction and substrate horizontal direction of the photoelectric conversion layer.
  • the phase separation domain of the n-type organic semiconductor or the p-type polymer semiconductor is vertical as Y / X is smaller than 1, that is, the value of the half width Y obtained from the one-dimensional profile corresponding to the horizontal direction of the substrate is smaller. It shows that it is oriented.
  • Y / X is larger than 1, it indicates that the phase separation domain of the n-type organic semiconductor or p-type polymer semiconductor is aligned horizontally with the substrate.
  • the phase separation domains are oriented vertically because it is easy to transport charges to the electrode and there is little deactivation during the process.
  • the range of Y / X is 0.1 or more and 0.7 or less, a more preferable range is 0.1 or more and 0.6 or less, and a further preferable range is 0.3 or more and 0.6 or less. It is as follows. When it is larger than 0.7, the orientation of the phase separation domain of the n-type organic semiconductor or p-type polymer semiconductor is insufficient, and it is difficult to expect high conversion efficiency of the photoelectric conversion element. Further, when smaller than 0.1, it means that the size of the phase separation domain in the horizontal direction of the substrate is small. Therefore, the p-type and n-type semiconductors required for the n-type organic semiconductor or p-type polymer semiconductor to transport charges to the electrodes are used. The continuous phase separation domain is not formed, which is not preferable from the viewpoint of conversion efficiency.
  • the photoelectric conversion element 1 has a configuration in which an electrode layer 6 is provided on a substrate 7 and a photoelectric conversion layer 5 is further provided thereon.
  • a relatively large number of n-type organic semiconductors 4 are present in the amorphous part 3 of the p-type polymer semiconductor, and the n-type organic semiconductors 4 are oriented in a direction perpendicular to the substrate (thickness direction).
  • a separation structure (morphology) is formed.
  • FIG. 1 is an example of the photoelectric conversion element of the present invention, and even if the photoelectric conversion element has a configuration different from that of FIG. To be included in the scope.
  • the photoelectric conversion layer having such a specific morphology is formed from an organic semiconductor composition that is a solution containing an n-type organic semiconductor, a p-type polymer semiconductor, and a solvent for mixing them.
  • the n-type organic semiconductor suitably used for the photoelectric conversion element has a HOMO energy of the n-type organic semiconductor lower than that of the p-type polymer semiconductor, and a LUMO energy of the n-type organic semiconductor of the p-type polymer semiconductor. Lower than LUMO energy.
  • the n-type organic semiconductor may be a low molecular compound or a high molecular compound.
  • Low molecular weight compounds include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and metal complexes of derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof, fullerenes and derivatives thereof such as C 60, 2,9-dimethyl And phenanthrene derivatives such as -4,7-diphenyl-1,10-phenanthroline.
  • polymer compound examples include polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine in the side chain or main chain, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and Examples thereof include polythienylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, carbon nanotubes and derivatives thereof. Of these, fullerenes and derivatives thereof are particularly preferred.
  • fullerenes and derivatives thereof examples include C 60 , C 70 , C 84 and derivatives thereof. Specific structural examples of fullerenes and derivatives thereof are shown in the following chemical formulas (i) to (x).
  • the p-type polymer semiconductor contained in the photoelectric conversion layer is a polymer composed of a conjugated divalent monomer and includes a divalent heterocyclic group in its main chain.
  • the main chain refers to the longest chain of a compound composed of a divalent heterocyclic group.
  • the conjugated divalent monomer composing the p-type polymer semiconductor is a divalent group in which electrons in a bond in the molecule are delocalized, and is a compound composed of a divalent heterocyclic group. is there.
  • the p-type polymer semiconductor includes at least one condensed ⁇ -conjugated skeleton including at least one thiophene ring as a part of the chemical structure from the viewpoint that the morphology is easy to control and the performance as a photoelectric conversion element is high. It is preferable to contain a polymer having units. Examples of such a condensed ⁇ -conjugated skeleton include a cyclopentadithiophene diyl group, a dithienopyrrole diyl group, a dithienosilole diyl group, a dithienogermol diyl group, a benzodithiophene diyl group, and a naphthodithiophene diyl group.
  • divalent heterocyclic groups such as thienothiophenediyl group, thienopyrazinediyl group, and thienopyrroledionediyl group.
  • the p-type polymer semiconductor of the present invention is a copolymer having two or more kinds of divalent heterocyclic groups as a structural unit, even if the polymer has only one of these divalent heterocyclic groups as a structural unit. May be.
  • a polymer having a benzodithiophenediyl group-thienothiophenediyl group as one constituent unit may be used.
  • the p-type polymer semiconductor may have a divalent heterocyclic group other than a condensed ⁇ -conjugated skeleton containing at least one thiophene ring as part of the chemical structure as a structural unit.
  • divalent heterocyclic groups include a dibenzosilol diyl group, a dibenzogermole diyl group, a dibenzofurandiyl group, a carbazolediyl group, a thiophenediyl group, a furandyl group, a pyrroldiyl group, and a benzothiadiazole diyl group.
  • thienylene vinylene diyl group include a dibenzosilol diyl group, a dibenzogermole diyl group, a dibenzofurandiyl group, a carbazolediyl group, a thiophenediyl group, a furandyl group, a pyrroldiyl group, and a benzo
  • the p-type polymer semiconductor may have a substituent in the main chain skeleton for the purpose of controlling its solubility and polarity.
  • substituents include an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an alkylcarbonyl group, and a halogen atom. From the viewpoint of improving solubility, the substituent preferably has 3 to 20 carbon atoms.
  • the number average molecular weight of the p-type polymer semiconductor is not particularly limited, but is preferably from 600 to 1,000,000 g / mol, more preferably from 5,000 to 500,000 g / mol, from the viewpoint of hole mobility and mechanical properties. More preferably, ⁇ 200,000 g / mol is more preferred, and 20,000 to 200,000 g / mol is most preferred.
  • the number average molecular weight means a molecular weight in terms of polystyrene by gel permeation chromatography.
  • the crystalline p-type polymer semiconductor is a p-type polymer semiconductor in which a part of the p-type polymer semiconductor is crystallized or in a liquid crystal state.
  • the crystalline p-type polymer semiconductor it can be analyzed by an X-ray diffraction method or differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the p-type polymer semiconductor may be a polymer having any structure of a random copolymer, a block copolymer, a star polymer, and a graft copolymer.
  • a random copolymer and a block copolymer are more preferable from the viewpoint of morphology control, and a block copolymer is more preferable from the viewpoint of controlling crystallinity.
  • the connection structure of a block copolymer is not specifically limited. When 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.
  • the p-type polymer semiconductor is a block copolymer
  • at least one of the polymer blocks constituting the block copolymer has a condensed ⁇ -conjugated skeleton containing a thiophene ring as part of the chemical structure. It is sufficient if it is a polymer block composed of a structural unit containing at least one.
  • connection method As a first method for producing a 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 connection (hereinafter sometimes referred to as “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”). As a third 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”). As the linking method, sequential polymerization, and macroinitiator method, an optimum method can be used depending on the p-type polymer semiconductor to be synthesized.
  • the mixing ratio of the p-type polymer semiconductor and the n-type organic semiconductor 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 p-type polymer semiconductor. More preferred.
  • a p-type polymer semiconductor may be used in combination of two or more of the above polymers. Further, it may contain a third component other than the p-type polymer semiconductor and the n-type organic semiconductor. The content of the third component is preferably 30% by mass or less and preferably 10% by mass or less with respect to the total weight of the p-type polymer semiconductor and the fullerene derivative from the viewpoint of the performance of the photoelectric conversion element. Further preferred.
  • Examples of the third component include halogenated alkyls such as 1,8-dichlorooctane, 1,8-dibromooctane and 1,8-diiodooctane, naphthalene, 1-chloronaphthalene, 1-bromonaphthalene and 1-iodonaphthalene.
  • non-conjugated polymers such as polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyethylene glycol, polydimethylsiloxane, and polyvinylidene fluoride.
  • the mixing method of the p-type polymer semiconductor and the n-type organic semiconductor is not particularly limited.
  • a method for mixing the p-type polymer semiconductor and the n-type organic semiconductor for example, after adding to the solvent at a desired ratio, one or more methods such as heating, stirring, and ultrasonic irradiation are combined in the solvent. The method of mixing is mentioned.
  • the solvent used when mixing the p-type polymer semiconductor and the n-type organic semiconductor is particularly a solvent that can dissolve most of the p-type polymer semiconductor and the n-type organic semiconductor. It is not limited.
  • the soluble solvent preferably has a solubility at 20 ° C. of 1 mg / mL or more, and more preferably 3 mg / mL or more for each of the p-type polymer semiconductor and the n-type organic semiconductor.
  • the soluble solvent include ethers such as diethyl ether, tetrahydrofuran, diisopropyl ether, dioxane, dimethoxyethane, and dibutyl ether; halogen solvents such as methylene chloride and chloroform; benzene, toluene, orthoxylene, metaxylene, and chlorobenzene.
  • Aromatic solvents such as bromobenzene, iodobenzene, orthodichlorobenzene and pyridine.
  • solvents may be used singly or in combination of two or more, but ortho-dichlorobenzene, chlorobenzene, bromobenzene, iodobenzene having high solubility of both p-type polymer semiconductor and n-type organic semiconductor. , Chloroform, ortho-xylene, and mixtures thereof. Particularly preferred are orthodichlorobenzene, chlorobenzene, chloroform and mixtures thereof.
  • the organic semiconductor composition which is a solution prepared by mixing these p-type polymer semiconductor and n-type organic semiconductor, and a solvent (dissolvable solvent) for mixing them, is an electrode that becomes a positive electrode or a negative electrode on a glass substrate. Is applied to the formed electrode layer, and in the state containing the solvent in the coating film, the coating film is exposed to the vapor of the solvent to form a photoelectric conversion layer having a specific morphology, on the photoelectric conversion layer A photoelectric conversion element can be manufactured by forming the upper surface electrode used as a negative electrode or a positive electrode in this.
  • the formed photoelectric conversion layer is a film that is dried and solidified by removing the solvent from the coating film.
  • the electrode previously formed on the substrate side may be a positive electrode or a negative electrode.
  • a peculiar morphology in the present invention that is, a morphology in which the phase separation domain of an n-type organic semiconductor or p-type polymer semiconductor is oriented perpendicular to the substrate
  • an n-type organic semiconductor and a p-type polymer semiconductor are used.
  • the coating film may be exposed to vapor of a solvent different from the organic semiconductor composition in a state where the coating film contains the solvent derived from the organic semiconductor composition.
  • a solvent that does not dissolve the p-type polymer semiconductor is particularly preferably used.
  • the coating film contains a soluble solvent.
  • the p-type polymer semiconductor is deposited from the exposed surface to form the crystal part 2 of the p-type polymer semiconductor.
  • the solvent contained in the coating film evaporates, but this solvent passes through the amorphous part 3 of the p-type polymer semiconductor, which is a gap between the crystal parts 2 of the p-type polymer semiconductor, and evaporates into the atmosphere. .
  • the morphology of the photoelectric conversion layer 5 as seen from the cross section has a p-type polymer semiconductor having an inclined structure, and a large number of crystal parts 2 exist on the surface. Furthermore, the p-type polymer semiconductor is ideal as the photoelectric conversion layer 5 because the crystal growth direction is the film thickness direction, and the width is limited to several tens of nanometers due to the path through which the originally contained solvent volatilizes. A typical comb structure is formed. As a result, the n-type organic semiconductor 4 also has an inclined structure and forms a comb structure. Since this structure is a comb structure, it has anisotropy in the film thickness direction and the film surface direction.
  • the electrode layer 6 has at least an electrode, and may further contain a hole transport layer, an electron transport layer, or an inorganic layer.
  • the content of the solvent derived from the solution contained in the coating film is preferably 20% by mass or more and 30% by mass with respect to 100% by mass of the total amount of the solution containing the n-type organic semiconductor, the p-type polymer semiconductor and the solvent. % To 90% by mass is more preferable, and 35% to 75% by mass is more preferable. If the content of the solvent derived from the solution contained in the coating film is small, the p-type polymer semiconductor will crystallize before being exposed to the solvent vapor, and the morphology cannot be controlled. However, crystallization may not proceed.
  • the solvent to be exposed as the solvent vapor is preferably a solvent in which the p-type polymer semiconductor to be used is not dissolved, and is preferably a solvent in which the n-type organic semiconductor is dissolved.
  • solvents include ketones such as acetone, methyl ethyl ketone, and methyl butyl ketone, alcohols such as methanol, ethanol, and isopropanol, esters such as ethyl acetate, hydrocarbons such as hexane and cyclohexane, methylene chloride, chloroform, Halogen solvents such as carbon tetrachloride, 1-chloronaphthalene and 1,2-dibromoethane, aromatic solvents such as benzene, toluene, orthoxylene, anisole, methylbenzoate and pyridine, nitrogen-containing solvents such as dimethylformamide, acetonitrile and morpholine , Ethers such as tetrahydro
  • acetone, cyclohexane, methylene chloride, 1-chloronaphthalene, 1,2-dibromoethane, anisole, methylbenzoate, pyridine, dimethylformamide, morpholine, tetrahydrofuran, and 1,4-dioxane are particularly preferable.
  • One of these solvents may be used alone, or two or more thereof may be mixed and vaporized for exposure.
  • the solvent vapor exposure is performed by applying a coating solution obtained by applying a composition solution containing an n-type organic semiconductor, a p-type polymer semiconductor having a condensed ⁇ -conjugated skeleton, and a dissolvable solvent, and a solvent to be exposed.
  • a coating solution obtained by applying a composition solution containing an n-type organic semiconductor, a p-type polymer semiconductor having a condensed ⁇ -conjugated skeleton, and a dissolvable solvent, and a solvent to be exposed.
  • the time of exposure to the solvent vapor is not particularly limited, but if it is too long, the aggregation of the n-type organic semiconductor is excessively promoted and the photoelectric conversion efficiency is lowered, and therefore the range of 3 seconds to 1 hour is preferable. A range of 5 minutes to 40 minutes is more preferable.
  • the temperature exposed to the solvent vapor is ⁇ 20 ° C. to 200 ° C., more preferably 0 ° C. to 100 ° C. If the temperature is too high, the photoelectric conversion layer is oxidized and / or decomposed, and sufficient photoelectric conversion characteristics cannot be obtained.
  • the solvent vapor exposure may be performed in an air atmosphere or an inert gas atmosphere, or may be performed under reduced pressure or under pressure.
  • An organic semiconductor composition containing a p-type polymer semiconductor and an n-type organic semiconductor can be applied onto an electrode layer on a substrate by a known printing method or coating method to form a photoelectric conversion layer.
  • Specific coating methods include spin coating, casting, micro gravure coating, gravure coating, slot die coating, bar coating, roll coating, dip coating, spray coating, screen printing, and flexo.
  • 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 film thickness of the photoelectric conversion layer of the photoelectric conversion element of the present invention is difficult to determine unconditionally 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. If the film thickness is too thin, the light is not sufficiently absorbed. Conversely, if the film thickness is too thick, it becomes difficult for the carriers to reach the electrode, and high conversion efficiency cannot be obtained.
  • an electrode layer is usually formed on a substrate, and a photoelectric conversion layer is further formed thereon.
  • This substrate may be any substrate that does not change when an electrode is formed and a photoelectric conversion layer is formed.
  • the material for the substrate include inorganic materials such as alkali-free 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 made of an 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.
  • the electrode of the photoelectric conversion element has optical transparency in either the positive electrode or the negative electrode.
  • the light transmittance of the electrode is not particularly limited as long as incident light reaches the photoelectric conversion layer and 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 photoelectric conversion layer.
  • a hole transport layer described later it is preferable that 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. Further, it is possible to improve the extraction current by introducing a metal fluoride such as lithium fluoride or cesium fluoride at the interface between the negative electrode and the electron transport layer described later.
  • the conductive material used for the negative electrode is preferably an ohmic junction with the photoelectric conversion layer.
  • the conductive material used for the negative electrode is in ohmic contact with the electron transport layer.
  • the electrode layer means an electrode or an electrode provided with a hole transport layer, an electron transport layer, or an inorganic layer described below.
  • ultraviolet ozone treatment corona discharge
  • the surface is preferably cleaned or modified by physical means such as treatment or plasma treatment.
  • 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 of this invention may provide a positive hole transport layer between a positive electrode and a photoelectric converting layer as needed.
  • 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
  • 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 may be provided with an electron transport layer between the negative electrode and the photoelectric conversion layer as necessary.
  • n-type organic semiconductor materials such as phenanthrene compounds such as bathocuproine, naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide
  • 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.
  • unit used for the photoelectric converting 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
  • Polymer block A1 was synthesized according to the following reaction formula.
  • n represents the number of repeating units.
  • purification was performed using a preparative GPC column.
  • a device for purification Recycling Preparative HPLC LC-908 manufactured by Nippon Analytical Industrial 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 Industrial Co., Ltd. are connected in series. Further, chloroform was used as an elution solvent.
  • the polymerization solvent for the polymer block A1 was obtained by subjecting dehydrated tetrahydrofuran (without stabilizer) manufactured by Wako Pure Chemical Industries, Ltd. to a molecular sieve 5A manufactured by Wako Pure Chemical Industries, after distillation purification in the presence of metallic sodium. Purification was carried out by contact for more than one day.
  • the obtained polymer block A1 was subjected to physicochemical analysis.
  • the molecular structure was identified by 1 H-NMR (nuclear magnetic resonance) measurement.
  • the number average molecular weight and the weight average molecular weight were both determined in terms of polystyrene based on measurement by gel permeation chromatography (GPC).
  • HLC-8020 product number manufactured by Tosoh Corporation was used as the GPC apparatus, and TSKgel Multipore HZ manufactured by Tosoh Corporation was connected in series as the column.
  • PDI dispersity
  • Polymerization example 2 The block copolymer 1 was synthesized according to the following reaction formula.
  • n and m each represent the number of repeating units.
  • the ethylhexyl group is abbreviated as EtHex.
  • polymer block A1 (0.70 g), 2,6-dibromo-4,4′-bis (2-ethylhexyl) -cyclopenta [2,1-b: 3,4-b '] Dithiophene (0.51 g, 0.90 mmol), 4,7-bis (3,3,4,4-tetramethyl-2,5,1-dioxaborolan-1-yl) benzo [c] [1,2 , 5] thiadiazole (0.35 g, 0.90 mmol), toluene (17 mL), aqueous potassium carbonate solution (17 mL, 3.6 mmol), tetrakis (triphenylphosphine) palladium (0) (20.9 mg, 18.0 ⁇ mol), Aliquat 336 (0.8 mg, 1.98 ⁇ mol) was added, followed by stirring at 80 ° C.
  • 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 block copolymer 1 as a black purple solid (1.11 g, 70%).
  • Polymer block A2 was synthesized according to the following reaction formula.
  • 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 physicochemical analysis result of the obtained polymer block A2 supports the chemical structure shown in the reaction formula.
  • the block copolymer 2 was synthesized according to the following reaction formula.
  • n and m each represent the number of repeating units.
  • the ethylhexyl group is abbreviated as EtHex.
  • the polymer block A2 (160.0 mg, 0.12 mol) was added to a 5 mL flask 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, 2 98Myumol) were added and
  • the reaction solution was poured into methanol (300 mL), the precipitated solid was collected by filtration, and the obtained solid was dried under reduced pressure to obtain a crude product.
  • 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 concentrated, poured into methanol (300 mL), and the precipitated solid was collected by filtration and dried under reduced pressure to obtain block copolymer 3 as a black purple solid (0.48 g, 76%).
  • Example 1 9.68 mg of [6,6] -phenyl C 71 -butyric acid methyl ester (abbreviation: PC 71 BM; ADS71BFA manufactured by American Dice Source) as an n-type organic semiconductor, and block copolymer 1 as a p-type polymer semiconductor 4.15 mg was weighed into a sealed container and 0.432 mL of orthodichlorobenzene was added under a nitrogen atmosphere. The solution was stirred and dissolved at 80 ° C. for 6 hours, and then filtered through a PTFE filter having a pore size of 1.0 ⁇ m to obtain an organic semiconductor composition.
  • PC 71 BM ADS71BFA manufactured by American Dice Source
  • ITO film (resistance value 10 ⁇ / ⁇ ) with a thickness of 150 nm is formed on a glass substrate by sputtering, surface treatment is performed by ozone UV treatment for 15 minutes, and a PEDOT: PSS aqueous solution (hole transport layer) is formed thereon.
  • HC Starck; CLEVIOS PH500 was deposited to a thickness of 40 nm by spin coating. It was heated and dried at 140 ° C. for 20 minutes with a hot plate to obtain an electrode layer.
  • the solution of the prepared organic semiconductor composition was applied onto the formed electrode layer by spin coating. Spin was stopped 10 seconds after the start of spin coating, and a coating film of an organic semiconductor composition containing a solvent was obtained. Next, 200 ⁇ L of anisole was placed in the bottom of a glass container with a lid of 300 mL capacity, and a glass base having a height of about 4 cm was placed in the glass container with a lid and the lid was capped. A coating film of the organic semiconductor composition containing the solvent was placed on a table in the glass container, immediately covered, and exposed to anisole vapor at room temperature of 25 ° C. for 30 minutes. After 30 minutes, the coating film of the organic semiconductor composition was taken out of the container, dried at room temperature, and further dried under reduced pressure at room temperature.
  • the mass of the coating film after the solvent was removed by drying under reduced pressure was reduced by 70% by mass with respect to that before exposure to anisole vapor.
  • the film thickness of the photoelectric conversion layer obtained using a stylus type surface shape measuring instrument manufactured by ULVAC, Inc .; Dektak
  • the film thickness was about 110 nm.
  • the photoelectric conversion element by the block copolymer 1 was obtained.
  • the shape of the photoelectric conversion element was a regular square of 5 ⁇ 5 mm.
  • the morphology of the cross section of the photoelectric conversion layer was observed and analyzed by the following method. Using an ion milling method (manufactured by JEOL Ltd .; IB-09060 CIS) while cooling a thin film section in a cross-sectional direction of a photoelectric conversion element having a photoelectric conversion layer to ⁇ 100 ° C. or less with liquid nitrogen, argon ions, 1.5 It was produced at an acceleration voltage of ⁇ 4.5 kV.
  • the prepared thin film section had a thickness of 20 to 30 nm.
  • a cross-sectional morphology image was obtained from the prepared thin film slice.
  • the acquisition of the morphology image by the STEM method was performed at an accelerating voltage of 200 kV while being cooled to ⁇ 100 ° C. or lower with liquid nitrogen.
  • the obtained image had a resolution of 2 pixels / nm or higher, and after conversion to grayscale, the contrast and brightness were adjusted so that the morphology contrast was easy to understand.
  • a morphology image of a cross section of the photoelectric conversion element obtained by the STEM method is shown in FIG.
  • FIG. 3 shows a morphology image of the cross section of the photoelectric conversion layer obtained by trimming only the photoelectric conversion layer from FIG. In this observation, the dark part is a p-type polymer semiconductor rich phase with a low electron density, and the bright part is an n-type organic semiconductor rich phase.
  • the image obtained by trimming only the photoelectric conversion layer portion had a width of 0.3 ⁇ m in the horizontal direction on the substrate.
  • This image was subjected to a two-dimensional Fourier transform using Image Pro Plus (Media Cybernetics). This image is shown in FIG.
  • the obtained two-dimensional Fourier transform image has the center as the origin, the horizontal direction of the obtained image is the x-axis (corresponding to the substrate vertical direction in the morphology image before the two-dimensional Fourier transform processing), and the vertical direction is the y-axis (two-dimensional Fourier).
  • Example 2 1.95 mg of [6,6] -phenyl C 71 -butyric acid methyl ester (abbreviation: PC 71 BM; E110 manufactured by Frontier Carbon Co.) as an n-type organic semiconductor and block copolymer 2 as a p-type polymer semiconductor 1.05 mg was weighed into a sealed container, and the same method as in Example 1 was used except that 0.150 mL of chlorobenzene mixed with 2.5 vol% of 1,8-diiodooctane was added under a nitrogen atmosphere. Thus, a photoelectric conversion element was prepared. Similarly to Example 1, the photoelectric conversion efficiency of the obtained photoelectric conversion element was measured, and the measurement result is shown in Table 1 below.
  • FIG. 7 shows an image obtained by converting the cross-sectional image of the photoelectric conversion layer obtained by trimming from the cross-sectional image of the photoelectric conversion element obtained by the STEM method into two gradations.
  • FIG. 8 shows an image obtained by Fourier transforming the photoelectric conversion layer of FIG. The line profile in the x-axis direction of the Fourier transform image in FIG. 8 is shown in FIG. 9, and the line profile in the y-axis direction is shown in FIG.
  • Example 3 1.95 mg of [6,6] -phenyl C 71 -butyric acid methyl ester (E110 manufactured by Frontier Carbon Co.) as an n-type organic semiconductor, and 1.05 mg of block copolymer 3 as a p-type polymer semiconductor, A photoelectric conversion element was prepared using the same method as in Example 1 except that 0.150 mL of chlorobenzene mixed with 2.5 vol% of 1,8-diiodooctane was added under a nitrogen atmosphere. did.
  • Example 1 the photoelectric conversion efficiency of the obtained photoelectric conversion element was measured, and the measurement results are shown in Table 1 below. Further, in the same manner as in Example 1, a thin film slice of the obtained photoelectric conversion element was prepared, and the morphology of the cross section was observed and analyzed to calculate Y / X. Similarly, the results are shown in Table 1 below. Further, FIG. 11 shows an image obtained by converting the cross-sectional image of the photoelectric conversion layer obtained by trimming from the cross-sectional image of the photoelectric conversion element obtained by the STEM method into two gradations. Further, FIG. 12 shows an image obtained by Fourier transforming the photoelectric conversion layer of FIG. The line profile in the x-axis direction of the Fourier transform image in FIG. 12 is shown in FIG. 13 and the line profile in the y-axis direction is shown in FIG.
  • Example 1 The solution of the organic semiconductor composition prepared in Example 1 was applied by spin coating for 180 seconds and dried under reduced pressure without being exposed to anisole vapor to form a photoelectric conversion layer, as in Example 1. Thus, a photoelectric conversion element was produced.
  • FIG. 15 shows a cross-sectional image of the photoelectric conversion layer obtained by trimming from a cross-sectional image of the photoelectric conversion element obtained by the STEM method.
  • FIG. 16 shows an image obtained by Fourier transforming the photoelectric conversion layer of FIG. The line profile in the x-axis direction of the Fourier transform image in FIG. 16 is shown in FIG. 17 and the line profile in the y-axis direction is shown in FIG.
  • Example 2 In the same manner as in Example 1, an electrode layer was formed on a substrate, and an n-type organic semiconductor layer having a thickness of about 25 nm was formed thereon from a chlorobenzene solution of PC 71 BM (manufactured by Frontier Carbon Corporation; E110) by spin coating. did. Separately, a p-type organic semiconductor layer having a thickness of about 60 nm is formed on a silicon substrate by spin coating from a chlorobenzene solution of polymer block A1 in polymerization example 1, and then this polymer block A1 film is formed on distilled water.
  • PC 71 BM manufactured by Frontier Carbon Corporation
  • Example 1 the photoelectric conversion efficiency of the obtained photoelectric conversion element was measured. The measurement results are shown in Table 1. Further, in the same manner as in Example 1, a thin film slice of the obtained photoelectric conversion element was prepared, and the morphology of the cross section was observed and analyzed to calculate Y / X. The results are also shown in Table 1.
  • FIG. 19 shows a cross-sectional image of the photoelectric conversion layer obtained by trimming from a cross-sectional image of the photoelectric conversion element obtained by the STEM method. Further, FIG. 20 shows an image obtained by Fourier transforming the photoelectric conversion layer of FIG. The line profile in the x-axis direction of the Fourier transform image of FIG. 20 is shown in FIG. 21, and the line profile in the y-axis direction is shown in FIG.
  • Y / X is within the specified range of the present invention, and the morphology of the n-type organic semiconductor and the p-type polymer semiconductor in the photoelectric conversion layer is oriented in the substrate vertical direction (film thickness direction). Examples 1, 2 and 3 showed excellent conversion efficiency. On the other hand, Comparative Examples 1 and 2 in which Y / X exceeds 0.7 resulted in insufficient orientation of the phase separation domains and poor conversion efficiency.
  • 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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mathematical Physics (AREA)
  • Theoretical Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un élément de conversion photoélectrique comprenant une couche de conversion photoélectrique dans laquelle la morphologie dans la direction de l'épaisseur du film est contrôlée par une technique peu coûteuse, avec laquelle une haute efficacité de conversion photoélectrique est démontrée et avec laquelle une performance de conversion photoélectrique est supérieure. Un élément de conversion photoélectrique (1) a une couche de conversion photoélectrique (5), incluant des semi-conducteurs organiques de type n (4) et des parties de cristaux semi-conducteurs de polymère de type p (2) et des parties non cristallines (3), qui est prise en sandwich entre des couches d'électrode positive et d'électrode négative (6), le tout sur un substrat (7). La relation entre une largeur de demi-valeur (X) dans laquelle un profil de ligne correspondant à une direction qui est perpendiculaire au substrat (7) est ajustée à une fonction gaussienne d'une image dans laquelle une image de morphologie d'une section transversale de la couche de conversion photoélectrique (5) a subi une transformation de Fourier, et une largeur de demi-valeur (Y) dans laquelle un profil de ligne correspondant à une direction qui est horizontale par rapport au substrat (7) est ajustée à la fonction gaussienne, est telle que 0,1 ≤ Y/X ≤0,7.
PCT/JP2012/083613 2011-12-28 2012-12-26 Élément de conversion photoélectrique et procédé de fabrication de celui-ci WO2013099926A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011287494 2011-12-28
JP2011-287494 2011-12-28
JP2012-136175 2012-06-15
JP2012136175 2012-06-15

Publications (1)

Publication Number Publication Date
WO2013099926A1 true WO2013099926A1 (fr) 2013-07-04

Family

ID=48697410

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/083613 WO2013099926A1 (fr) 2011-12-28 2012-12-26 Élément de conversion photoélectrique et procédé de fabrication de celui-ci

Country Status (2)

Country Link
JP (1) JPWO2013099926A1 (fr)
WO (1) WO2013099926A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015115458A (ja) * 2013-12-11 2015-06-22 三菱電機株式会社 太陽電池およびその製造方法
JPWO2017006520A1 (ja) * 2015-07-08 2017-08-10 パナソニックＩｐマネジメント株式会社 撮像装置
WO2024075812A1 (fr) * 2022-10-05 2024-04-11 三菱ケミカル株式会社 Composition d'encre semi-conductrice organique ainsi que procédé de fabrication de celle-ci, film de conversion photoélectrique organique, et élément de conversion photoélectrique organique

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007011739A2 (fr) * 2005-07-14 2007-01-25 Konarka Technologies, Inc. Polymeres a faible bande interdite et a mobilite de charge elevee
WO2008088595A2 (fr) * 2006-10-11 2008-07-24 Konarka Technologies, Inc. Cellule photovoltaïque avec un polymère contenant des siloles
WO2008093831A1 (fr) * 2007-02-01 2008-08-07 Sumitomo Chemical Company, Limited Bloc copolymère, composition utilisant ledit bloc copolymère, composition liquide, film mince électroluminescent et dispositif électroluminescent polymère

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007011739A2 (fr) * 2005-07-14 2007-01-25 Konarka Technologies, Inc. Polymeres a faible bande interdite et a mobilite de charge elevee
WO2008088595A2 (fr) * 2006-10-11 2008-07-24 Konarka Technologies, Inc. Cellule photovoltaïque avec un polymère contenant des siloles
WO2008093831A1 (fr) * 2007-02-01 2008-08-07 Sumitomo Chemical Company, Limited Bloc copolymère, composition utilisant ledit bloc copolymère, composition liquide, film mince électroluminescent et dispositif électroluminescent polymère

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
JONG HWAN PARK ET AL.: "Effect of Annealing Solvent Solubility on the Performance of Poly (3-hexylthiophene)/Methanofullerene Solar Cells", JOURNAL OF PHYSICAL CHEMISTRY C, vol. 113, no. 40, 8 October 2009 (2009-10-08), pages 17579 - 17584, XP055073542 *
YUN ZHAO ET AL.: "Solvent-vapor treatment induced performance enhancement of poly(3- hexylthiophene):methanofullerene bulk- heterojunction photovoltaic cells", APPLIED PHYSICS LETTERS, vol. 90, 23 January 2007 (2007-01-23), pages 043504-1 - 043504-4, XP012095751 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015115458A (ja) * 2013-12-11 2015-06-22 三菱電機株式会社 太陽電池およびその製造方法
JPWO2017006520A1 (ja) * 2015-07-08 2017-08-10 パナソニックＩｐマネジメント株式会社 撮像装置
WO2024075812A1 (fr) * 2022-10-05 2024-04-11 三菱ケミカル株式会社 Composition d'encre semi-conductrice organique ainsi que procédé de fabrication de celle-ci, film de conversion photoélectrique organique, et élément de conversion photoélectrique organique

Also Published As

Publication number Publication date
JPWO2013099926A1 (ja) 2015-05-07

Similar Documents

Publication Publication Date Title
KR101361312B1 (ko) 광기전력 소자용 전자 공여성 유기 재료, 광기전력 소자용 재료 및 광기전력 소자
JP5359173B2 (ja) 光起電力素子用電子供与性有機材料、光起電力素子用材料および光起電力素子
JP4981672B2 (ja) 光電池におけるヘテロ原子位置規則性ポリ（３−置換チオフェン）
Cho et al. n-Doping of thermally polymerizable fullerenes as an electron transporting layer for inverted polymer solar cells
JP6592429B2 (ja) 有機電子デバイスの電子注入層における使用のための改善された電子移動組成物
JP6610096B2 (ja) 共役系化合物、これを用いた電子供与性有機材料、光起電力素子用材料および光起電力素子
JP2010041022A (ja) 光電変換素子
Sasajima et al. Flexible inverted polymer solar cells containing an amorphous titanium oxide electron collection electrode
WO2013065621A1 (fr) Élément de conversion photoélectrique et son procédé de fabrication
Liang et al. Chemically treating poly (3-hexylthiophene) defects to improve bulk heterojunction photovoltaics
JP5736456B2 (ja) 共役ブロック共重合体及びそれを用いた光電変換素子
WO2013099926A1 (fr) Élément de conversion photoélectrique et procédé de fabrication de celui-ci
Im et al. Improved photovoltaic performance by enhanced crystallinity of poly (3-hexyl) thiophene
JP2013219190A (ja) 有機光電変換素子
JP5844368B2 (ja) 共役ポリマー組成物及びそれを用いた光電変換素子
JP2015026716A (ja) 光電変換素子の製造方法
JP2008091886A (ja) 光起電力素子用材料および光起電力素子
JP6032284B2 (ja) 有機光電変換素子の製造方法
WO2013176180A1 (fr) Élément de puissance photovoltaïque et procédé de fabrication d'un élément de puissance photovoltaïque
JP2020200447A (ja) 共役系化合物、これを用いた電子供与性有機材料、光起電力素子用材料および光起電力素子
Zhang Influence of Microstructure on Thermo-and Photo-stability in Organic Bulk-heterojunction Solar Cell
Ho Synthesis and Characterization of Poly (3-alkylthiophene)-containing Block Copolymers
JP2014051583A (ja) 共役ブロック共重合体及びそれを用いた光電変換素子
Ren Studies of Organic Semiconductor Nanostructures and Their Photovoltaic Applications
Boudouris Polythiophene-containing block copolymers for organic photovoltaic applications.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12863816

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2013551729

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12863816

Country of ref document: EP

Kind code of ref document: A1