WO2010041687A1 - Élément de conversion photoélectrique organique, cellule solaire, et réseau de capteurs optiques - Google Patents

Élément de conversion photoélectrique organique, cellule solaire, et réseau de capteurs optiques Download PDF

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WO2010041687A1
WO2010041687A1 PCT/JP2009/067493 JP2009067493W WO2010041687A1 WO 2010041687 A1 WO2010041687 A1 WO 2010041687A1 JP 2009067493 W JP2009067493 W JP 2009067493W WO 2010041687 A1 WO2010041687 A1 WO 2010041687A1
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photoelectric conversion
group
organic photoelectric
general formula
atom
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Japanese (ja)
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大久保　康
野島　隆彦
伊東　宏明
晃矢子 和地
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コニカミノルタホールディングス株式会社
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Priority to JP2010532941A priority Critical patent/JP5655568B2/ja
Publication of WO2010041687A1 publication Critical patent/WO2010041687A1/fr

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Definitions

  • the present invention relates to an organic photoelectric conversion element, a solar cell, and an optical sensor array, and more particularly to a bulk heterojunction type organic photoelectric conversion element, a solar cell using the organic photoelectric conversion element, and an optical sensor array.
  • these bulk heterojunction solar cells are formed by a coating process except for the anode and cathode, it is expected that they can be manufactured at high speed and at low cost, and may solve the above-mentioned problem of power generation cost. . Furthermore, unlike the above Si-based solar cells, compound semiconductor-based solar cells, dye-sensitized solar cells, etc., there is no process at a temperature higher than 160 ° C., so it is expected that it can be formed on a cheap and lightweight plastic substrate. Is done.
  • the power generation cost must be calculated including the power generation efficiency and the durability of the element.
  • Non-Patent Document 1 a long wave that efficiently absorbs the solar spectrum is used. By using organic polymer, conversion efficiency exceeding 5% has been achieved.
  • a p-type semiconductor material with high mobility can be obtained by a method of increasing the ⁇ stack area of the compound by using a condensed polycyclic compound. (See Patent Document 1, Non-Patent Documents 4, 5, etc.).
  • these condensed polycyclic compounds are phen-type condensed rings (series that are not linearly condensed, such as phenanthrene) due to the condensed ring form, and have an absorption wavelength of only around 400 nm, and are for solar cells. Absorption of a wide range of wavelengths required as a material cannot be performed, and even if these are used as they are, an organic thin film solar cell with high conversion efficiency cannot be obtained. It was necessary.
  • the object of the present invention is to achieve a high conversion efficiency, a high durability, a coating process that enables inexpensive manufacturing, and an organic material that does not require heat treatment at a high temperature so that it can be formed on an inexpensive plastic substrate.
  • the object is to provide a thin-film solar cell material.
  • An organic photoelectric conversion element comprising a compound having a bulk heterojunction layer between a transparent electrode and a counter electrode and having a partial structure represented by the following general formula (1).
  • R 1 and R 10 are independently a substituted or unsubstituted nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom, a silicon atom, germanium atom, and represents an atom selected from a selenium atom
  • R 1 ⁇ R 10 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, a halogenated alkyl group, an alkynyl group, an aryl group, a heteroaryl group, a cycloalkyl group, a silyl group, an ether group, or a thioether.
  • the bulk heterojunction layer contains a low-molecular compound having a partial structure represented by the general formula (1) as a p-type semiconductor material and a fullerene derivative as an n-type semiconductor material.
  • the organic photoelectric conversion element as described in 2.
  • R 2 and R 6 in the low molecular compound having a partial structure represented by the general formula (1) is substituted with a substituted or unsubstituted heterocyclic group, The organic photoelectric conversion element of any one of these.
  • R 2 and R 6 in the low molecular compound having the partial structure represented by the general formula (1) is a heterocyclic group represented by any one of the following general formulas (2) to (4). 6.
  • X 3 to X 5 each independently represents an atom selected from a substituted or unsubstituted nitrogen atom, oxygen atom, carbon atom, sulfur atom, silicon atom, germanium atom, and selenium atom;
  • R 11 to R 16 each independently represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, amino group, Represents a group selected from the group of ring structures bonded to each other.
  • the low molecular compound having a partial structure represented by the general formula (1) is a compound represented by the following general formula (5), and the compound is contained in a bulk heterojunction layer. 7.
  • the organic photoelectric conversion device according to any one of 1 to 6.
  • X 1 and X 2 represent an atom having the same meaning as X 1 and X 2 in the general formula (1)
  • R 1 , R 3 to R 5 , and R 7 to R 10 represent the general formula (1).
  • Q and r are integers of 0 to 8, q + r is an integer of 1 or more, and n is an integer of 1 or more.
  • 8 The organic as described in 6 or 7 above, wherein at least one of the atoms represented by X 3 to X 5 in the heterocyclic groups represented by the general formulas (2) to (4) is a sulfur atom Photoelectric conversion element.
  • a heterocyclic group the heterocyclic group represented by A 1 in the compound represented by the general formula (5) is represented by the general formula (2), and wherein the heterocyclic group represented by A 2 9.
  • any one of A 1 and A 3 is a heterocyclic group represented by the general formulas (2) to (4), and 10.
  • That at least one of the atoms represented by X 1 and X 2 in the compound having the partial structure represented by the general formula (1) or the compound represented by the general formula (5) is a sulfur atom. 12.
  • the bulk heterojunction layer containing a compound having a partial structure represented by the general formula (1) and a fullerene derivative is formed by a solution process, Organic photoelectric conversion element.
  • a solar cell comprising the organic photoelectric conversion device as described in any one of 1 to 13 above.
  • An optical sensor array comprising the organic photoelectric conversion elements according to any one of 1 to 13 arranged in an array.
  • an organic thin film solar that can achieve high conversion efficiency, has high durability, can be applied to a coating process that enables low-cost manufacturing, and is heat-insoluble at high temperatures so that it can be formed on an inexpensive plastic substrate Battery material could be provided.
  • the inventors of the present invention have made extensive studies on the above problems and found that these phene condensed polycyclic compounds have a structure having a specific substituent in the phene condensed polycyclic compound having high mobility. It can absorb even long wavelengths, can improve the utilization rate of sunlight and achieve high conversion efficiency, and can provide organic photoelectric conversion elements with excellent durability due to its rigid and stable structure. I found.
  • FIG. 1 is a cross-sectional view showing a solar cell comprising a bulk heterojunction organic photoelectric conversion element.
  • a bulk heterojunction type organic photoelectric conversion element 10 has a transparent electrode 12, a bulk heterojunction layer photoelectric conversion unit 14, and a counter electrode 13 sequentially stacked on one surface of a substrate 11.
  • the substrate 11 is a member that holds the transparent electrode 12, the photoelectric conversion unit 14, and the counter electrode 13 that are sequentially stacked. In the present embodiment, since light that is photoelectrically converted enters from the substrate 11 side, the substrate 11 can transmit the light that is photoelectrically converted, that is, with respect to the wavelength of the light to be photoelectrically converted. It is a transparent member.
  • the substrate 11 for example, a glass substrate or a resin substrate is used.
  • the substrate 11 is not essential.
  • the bulk heterojunction type organic photoelectric conversion element 10 may be configured by forming the transparent electrode 12 and the counter electrode 13 on both surfaces of the photoelectric conversion unit 14.
  • the transparent electrode 12 is an electrode that can transmit light that is photoelectrically converted in the photoelectric conversion unit 14, and is preferably an electrode that transmits light of 300 to 800 nm.
  • transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 , ZnO, metal thin films such as gold, silver, platinum, or nanoparticle / nanowire layers, and conductive polymers are used. be able to.
  • the counter electrode 13 may be made of metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon, or the material of the transparent electrode 12, but is not limited thereto.
  • the photoelectric conversion unit 14 is sandwiched between the transparent electrode 12 and the counter electrode 13, but the pair of comb-like electrodes are arranged on one side of the photoelectric conversion unit 14.
  • the back contact type organic photoelectric conversion element 10 may be configured such that the back contact type organic photoelectric conversion element 10 is disposed.
  • the photoelectric conversion unit 14 is a layer that converts light energy into electric energy, and includes a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed.
  • the p-type semiconductor material functions relatively as an electron donor (donor)
  • the n-type semiconductor material functions relatively as an electron acceptor (acceptor).
  • the electron donor and the electron acceptor are “an electron donor in which, when light is absorbed, electrons move from the electron donor to the electron acceptor to form a hole-electron pair (charge separation state)”.
  • an electron acceptor which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.
  • the compound of the present invention is used, but a known compound such as a tetrabenzoporphyrin derivative may be used in combination.
  • a fullerene derivative is used, for example.
  • any method such as a vapor deposition method and a coating method (including a casting method and a spin coating method) may be used.
  • a coating method that excels in resistance is preferable.
  • the bulk heterojunction layer of the photoelectric conversion part 14 is annealed at a predetermined temperature during the manufacturing process to be partially crystallized in order to improve the photoelectric conversion rate.
  • the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • FIG. 1 light incident from the transparent electrode 12 through the substrate 11 is absorbed by the electron acceptor or electron donor in the bulk heterojunction layer of the photoelectric conversion unit 14, and electrons move from the electron donor to the electron acceptor.
  • a hole-electron pair charge separation state
  • the generated electric charge is caused by an internal electric field, for example, when the work functions of the transparent electrode 12 and the counter electrode 13 are different, the electrons pass between the electron acceptors due to the potential difference between the transparent electrode 12 and the counter electrode 13, and the holes are , Passed between the electron donors and carried to different electrodes, and photocurrent is detected.
  • the transport direction of electrons and holes can be controlled.
  • the photoelectric conversion unit 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, but the mixing ratio of the electron acceptor and the electron donor is changed. You may comprise by the changed multiple layer.
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a vapor deposition method and a coating method (including a casting method and a spin coating method).
  • the coating method is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • After coating it is preferable to perform heating in order to cause removal of residual solvent, moisture and gas, and improvement of mobility and absorption longwave due to crystallization of the semiconductor material.
  • the bulk heterojunction type organic photoelectric conversion element 10 includes the transparent electrode 12, the bulk heterojunction layer photoelectric conversion unit 14 and the counter electrode 13 which are sequentially stacked on the substrate 11, but is not limited thereto.
  • there are other layers such as a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, or a smoothing layer between the transparent electrode 12 or the counter electrode 13 and the photoelectric conversion unit 14 and bulk hetero
  • the junction type organic photoelectric conversion element 10 may be configured.
  • a hole transport layer 17 is placed between the bulk heterojunction layer and the anode (usually the transparent electrode 12 side), and a cathode (usually the counter electrode 13 side). Since it is possible to more efficiently take out the charges generated in the bulk heterojunction layer by forming the electron transport layer 18, it is preferable to have these layers.
  • FIG. 3 is a cross-sectional view showing a solar cell composed of an organic photoelectric conversion element including a tandem bulk heterojunction layer.
  • the transparent electrode 12 and the first photoelectric conversion unit 14 ′ are sequentially stacked on the substrate 11, the charge recombination layer 15 is stacked, the second photoelectric conversion unit 16, and then the counter electrode.
  • stacking 13 a tandem configuration can be obtained.
  • the second photoelectric conversion unit 16 may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion unit 14 'or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. is there.
  • the material of the charge recombination layer 15 is preferably a layer using a compound having both transparency and conductivity, such as transparent metal oxides such as ITO, AZO, FTO, and titanium oxide, Ag, Al, and Au.
  • a very thin metal layer such as PEDOT: PSS or a conductive polymer material such as polyaniline is preferable.
  • the “partial structure” in the low molecular weight compound having the partial structure represented by the general formula (1) or the partial structure represented by the general formula (1) is R in the general formula (1).
  • a part of 1 to R 10 is substituted with a bond to indicate that the compound is further bonded to another chemical structure.
  • X 1 and X 2 each independently represent an atom selected from a substituted or unsubstituted nitrogen atom, oxygen atom, carbon atom, sulfur atom, silicon atom, germanium atom, and selenium atom. Is preferably a nitrogen atom, an oxygen atom or a sulfur atom, more preferably a sulfur atom. This is because sulfur atoms tend to be crystallized or have high mobility due to the interaction between sulfur atoms.
  • R 1 to R 10 are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, halogenated alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether And a group selected from a group, a thioether group, an amino group, a ring structure bonded to each other, and an aromatic ring structure bonded to each other. More preferred are a substituted or unsubstituted alkyl group, a halogenated alkyl group, an aryl group, and a heteroaryl group.
  • R 2 and R 6 are substituted with a substituent selected from a substituted or unsubstituted aryl group or heteroaryl group. This is because substitution at this position with a ⁇ -electron-based substituent increases the ⁇ -conjugated length and improves the short absorption wavelength, which is a disadvantage of the phen-based compound.
  • X 3 to X 5 each independently represents an atom selected from a nitrogen atom, an oxygen atom, a carbon atom, a sulfur atom, a silicon atom, a germanium atom, and a selenium atom, Preferably they are a nitrogen atom, an oxygen atom, and a sulfur atom, More preferably, it is a sulfur atom.
  • R 11 to R 16 are each independently a hydrogen atom, halogen atom, substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, cycloalkyl group, silyl group, ether group, thioether group, A group selected from an amino group, a group having a ring structure bonded to each other, and a group selected from an aromatic ring structure bonded to each other.
  • a substituted or unsubstituted alkyl group and a halogenated alkyl group are preferable, and an unsubstituted alkyl group and a halogenated alkyl group are more preferable.
  • the compound having a partial structure represented by the general formula (1) is preferably a low molecular compound.
  • the low molecular weight compound means a single molecule having no distribution in the molecular weight of the compound.
  • the polymer compound means an aggregate of compounds having a certain molecular weight distribution by reacting a predetermined monomer.
  • a compound having a molecular weight of 3000 or less is preferably classified as a low molecular compound. More preferably, it is 2000 or less, More preferably, it is 1500 or less.
  • the compound has a molecular weight of 300 or more practically as a compound capable of forming a stable thin film without volatilization.
  • the molecular weight can be measured by mass spectrum or gel permeation chromatography (GPC).
  • the low molecular compound having a partial structure represented by the general formula (1) is a compound represented by the general formula (5).
  • the 5-membered heteroaryl group is more advantageous in terms of longer wave length, but on the other hand, there is a chemically active site in the aromatic ring (for example, the 2,5-position of thiophene).
  • the carrier may deteriorate when it deactivates without reaching the electrode.
  • the stability of the compound can be greatly improved by replacing the terminal of the 5-membered heteroaryl group with a phenyl group which is the most stable aromatic ring. The durability of can be improved.
  • X 1 and X 2 represents X 1 and X 2 synonymous atoms in the general formula (1)
  • R 1 ⁇ R 1 ⁇ R 10 R 10 is the formula in (1)
  • the preferred atoms and groups are the same as the above-described atoms X 1 and X 2 and the groups R 1 to R 10 .
  • p is an integer having the same meaning as p in the general formula (1).
  • n represents an integer of 1 or more.
  • a 1 and A 2 each independently represent a heterocyclic group represented by the general formulas (2) to (4), and preferably A1 represents an electron withdrawing represented by the general formulas (3) and (4).
  • R11 to R15 is preferably substituted with an alkyl group.
  • Substitution with an alkyl group improves the solubility of the compound and makes it easier to form a bulk heterojunction layer by a solution process.
  • crystallinity of the compound is increased by using a so-called fastener effect in which alkyl chains try to pack each other, and higher photoelectric conversion efficiency can be obtained.
  • alkyl group examples include methyl, ethyl, propyl, isopropyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, octyl, dodecyl, tridecyl, tetradecyl, pentadecyl, etc.
  • a C6 to C20 linear alkyl group n-hexyl group, n-octyl group, n-dodecyl group, etc.
  • low molecular weight compound having the partial structure represented by the general formula (1) of the present invention are shown below, but the present invention is not limited to these. These compounds can be synthesized with reference to Non-Patent Documents 4 and 5 described above.
  • the organic photoelectric conversion element of the present invention is preferably applied to a bulk heterojunction layer in which an n-type semiconductor material and a p-type semiconductor material are mixed, and the low molecular compound of the present invention may be used as the p-type semiconductor material.
  • the material is not particularly limited.
  • aromatic carboxylic acid anhydrides such as carboxylic acid anhydrides and perylene tetracarboxylic acid diimides
  • polymer compounds containing the imidized product thereof as a skeleton are examples of aromatic carboxylic acid anhydrides such as carboxylic acid anhydrides and perylene tetracarboxylic acid diimides
  • Fullerene derivatives include fullerene C60, fullerene C70, fullerene C76, fullerene C78, fullerene C84, fullerene C240, fullerene C540, mixed fullerene, fullerene nanotubes, multi-walled nanotubes, single-walled nanotubes, nanohorns (conical), and the like.
  • PCBM [6,6] -phenyl C61-butyric acid methyl ester
  • PCBnB [6,6] -phenyl C61-butyric acid-n-butyl ester
  • PCBiB [6,6] -phenyl C61-buty Rick acid-isobutyl ester
  • PCBH [6,6] -phenyl C61-butyric acid-n-hexyl ester
  • Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a dry process such as a vapor deposition method and a solution process such as a coating method (including a cast method and a spin coating method). be able to.
  • the solution process is preferable in order to increase the area of the interface where charges and electrons are separated from each other as described above and to produce a device having high photoelectric conversion efficiency.
  • the solution process is also excellent in production rate.
  • annealing is performed at a predetermined temperature during the manufacturing process, a part of the particles is microscopically aggregated or crystallized, and the bulk heterojunction layer can have an appropriate phase separation structure. As a result, the carrier mobility of the bulk heterojunction layer is improved and high efficiency can be obtained.
  • the photoelectric conversion part (bulk heterojunction layer) 14 may be composed of a single layer in which the electron acceptor and the electron donor are uniformly mixed, or a plurality of the mixture ratios of the electron acceptor and the electron donor being changed. It may consist of layers.
  • the hole mobility and electron mobility of the organic photoelectric conversion element are p-type material and n-type. Since it also correlates with the mixing ratio of the materials, it is more preferably 2: 1 to 1: 5, and further preferably 5: 4 to 1: 2.
  • the electron transport layer As the electron transport layer, octaazaporphyrin and p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.) can be used.
  • the HOMO level of the p-type semiconductor material used for the photoelectric conversion layer is used.
  • the electron transport layer having the HOMO level deeper than the level is given a hole blocking function having a rectifying effect so that holes generated in the photoelectric conversion layer do not flow to the cathode side. More preferably, a material deeper than the HOMO level of the n-type semiconductor is used as the electron transport layer.
  • Such an electron transport layer is also called a hole blocking layer, and it is preferable to use an electron transport layer having such a function.
  • examples of such materials include phenanthrene compounds such as bathocuproine, n-type semiconductor materials such as naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylenetetracarboxylic acid diimide, and titanium oxide.
  • N-type inorganic oxides such as 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 photoelectric conversion layer can also be used.
  • the means for forming these layers may be either a vacuum vapor deposition method or a solution coating method, but is preferably a solution coating method.
  • the organic photoelectric conversion element of the present invention has a hole transport layer between the photoelectric conversion layer and the anode, and it is possible to take out charges generated in the photoelectric conversion layer more efficiently. It is preferable.
  • the material constituting these layers include, as the hole transport layer, PEDOT such as Stark Vuitec, trade name BaytronP, polyaniline and its doped material, cyan described in International Publication No. 06/019270, etc. Compounds, etc. can be used.
  • the hole transport layer having a LUMO level shallower than the LUMO level of the n-type semiconductor material used for the photoelectric conversion layer has a rectifying effect that prevents electrons generated in the photoelectric conversion layer from flowing to the anode side. It has an electronic block function.
  • Such a hole transport layer is also called an electron block layer, and it is preferable to use a hole transport layer having such a function.
  • triarylamine compounds described in JP-A-5-271166 metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.
  • a layer made of a single p-type semiconductor material used for the photoelectric conversion layer can also be used.
  • the means for forming these layers may be either a vacuum deposition method or a solution coating method, but is preferably a solution coating method. Forming a coating film in the lower layer before forming the photoelectric conversion layer is preferable because it has the effect of leveling the coating surface and reduces the influence of leakage and the like.
  • the intermediate layer include a hole block layer, an electron block layer, a hole injection layer, an electron injection layer, an exciton block layer, a UV absorption layer, a light reflection layer, and a wavelength conversion layer.
  • the organic photoelectric conversion element of the present invention has at least an anode and a cathode. Moreover, when taking a tandem configuration, the tandem configuration can be achieved by using an intermediate electrode.
  • an electrode through which holes mainly flow is called an anode, and an electrode through which electrons mainly flow is called a cathode.
  • a translucent electrode is referred to as a transparent electrode and a non-translucent electrode is referred to as a counter electrode because of the function of whether or not it has translucency.
  • the anode is a translucent transparent electrode
  • the cathode is a non-translucent counter electrode.
  • the anode of the present invention is preferably an electrode that transmits light of 380 to 800 nm.
  • the material for example, transparent conductive metal oxides such as indium tin oxide (ITO), SnO 2 and ZnO, metal thin films such as gold, silver and platinum, metal nanowires and carbon nanotubes can be used.
  • Conductive polymers can also be used. Further, a plurality of these conductive compounds can be combined to form an anode.
  • the cathode may be a single layer of a conductive material, but in addition to a conductive material, a resin that holds these may be used in combination.
  • a conductive material for the cathode a material having a work function (4 eV or less) metal, alloy, electrically conductive compound, and a mixture thereof as an electrode material is used.
  • electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al 2 O 3 ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like.
  • a mixture of these metals and a second metal which is a stable metal having a larger work function value than this for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al 2 O 3 ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the film thickness is usually selected in the range of 10 nm to 5 ⁇ m, preferably 50 to 200 nm.
  • the light coming to the cathode side is reflected and reflected to the first electrode side, and this light can be reused and absorbed again by the photoelectric conversion layer. Improved and preferable.
  • the cathode may be a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon nanoparticles, nanowires, nanostructures, or a nanowire dispersion. If so, a transparent and highly conductive cathode can be formed by a coating method, which is preferable.
  • a metal for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.
  • the cathode side is made light transmissive, for example, a conductive material suitable for the cathode such as aluminum and aluminum alloy, silver and silver compound is made thin with a film thickness of about 1 to 20 nm, and then the anode By providing a film of the conductive light-transmitting material mentioned in the description, a light-transmitting cathode can be obtained.
  • a conductive material suitable for the cathode such as aluminum and aluminum alloy
  • silver and silver compound is made thin with a film thickness of about 1 to 20 nm
  • the intermediate electrode material required in the case of the tandem structure as shown in FIG. 3 is preferably a layer using a compound having both transparency and conductivity.
  • Transparent metal oxides such as ITO, AZO, FTO, titanium oxide, very thin metal layers such as Ag, Al, Au, or layers containing nanoparticles / nanowires, conductive polymer materials such as PEDOT: PSS, polyaniline, etc. ) Can be used.
  • the substrate is preferably a member that can transmit the light that is photoelectrically converted, that is, a member that is transparent to the wavelength of the light to be photoelectrically converted.
  • a transparent resin film from the viewpoint of light weight and flexibility.
  • the material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.
  • polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) modified polyester, polyethylene (PE) resin film, polypropylene (PP) resin film, polystyrene resin film, polyolefin resins such as cyclic olefin resin Film, vinyl resin film such as polyvinyl chloride, polyvinylidene chloride, polyether ether ketone (PEEK) resin film, polysulfone (PSF) resin film, polyether sulfone (PES) resin film, polycarbonate (PC) resin film, A polyamide resin film, a polyimide resin film, an acrylic resin film, a triacetyl cellulose (TAC) resin film, and the like can be given. If the resin film transmittance of 80% or more at 0 ⁇ 800 nm), can be preferably applied to a transparent resin film according to the present invention.
  • biaxially stretched polyethylene terephthalate film preferably a biaxially stretched polyethylene terephthalate film, a biaxially stretched polyethylene naphthalate film, a polyethersulfone film, or a polycarbonate film. More preferred are a stretched polyethylene terephthalate film and a biaxially stretched polyethylene naphthalate film.
  • the transparent substrate used in the present invention can be subjected to a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a surface treatment or an easy adhesion layer in order to ensure the wettability and adhesion of the coating solution.
  • a conventionally well-known technique can be used about a surface treatment or an easily bonding layer.
  • the surface treatment includes surface activation treatment such as corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • Examples of the easy adhesion layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, and epoxy copolymer.
  • a barrier coat layer may be formed in advance on the transparent substrate, or a hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred. Good.
  • the organic photoelectric conversion element of the present invention may have various optical functional layers for the purpose of more efficient reception of sunlight.
  • a light condensing layer such as an antireflection film or a microlens array, or a light diffusion layer that can scatter light reflected by the cathode and enter the power generation layer again may be provided. .
  • the antireflection layer can be provided as the antireflection layer.
  • the refractive index of the easy adhesion layer adjacent to the film is 1.57. It is more preferable to set it to ⁇ 1.63 because the transmittance can be improved by reducing the interface reflection between the film substrate and the easy adhesion layer.
  • the method for adjusting the refractive index can be carried out by appropriately adjusting the ratio of the oxide sol having a relatively high refractive index such as tin oxide sol or cerium oxide sol and the binder resin.
  • the easy adhesion layer may be a single layer, but may be composed of two or more layers in order to improve adhesion.
  • the condensing layer for example, it is processed so as to provide a structure on the microlens array on the sunlight receiving side of the support substrate, or the amount of light received from a specific direction is increased by combining with a so-called condensing sheet. Conversely, the incident angle dependency of sunlight can be reduced.
  • quadrangular pyramids having a side of 30 ⁇ m and an apex angle of 90 degrees are arranged two-dimensionally on the light extraction side of the substrate.
  • One side is preferably 10 to 100 ⁇ m. If it is smaller than this, the effect of diffraction is generated and colored.
  • the light scattering layer examples include various antiglare layers, layers in which nanoparticles or nanowires such as metals or various inorganic oxides are dispersed in a colorless and transparent polymer, and the like.
  • the method and process for patterning the electrode, the power generation layer, the hole transport layer, the electron transport layer, and the like according to the present invention are not particularly limited, and known methods can be appropriately applied.
  • the electrode can be patterned by a known method such as mask vapor deposition during vacuum deposition or etching or lift-off.
  • the pattern may be formed by transferring a pattern formed on another substrate.
  • a method of sealing a cap made of aluminum or glass by bonding with an adhesive, a plastic film on which a gas barrier layer such as aluminum, silicon oxide, or aluminum oxide is formed and an organic photoelectric conversion element are pasted with an adhesive.
  • Method, spin coating of organic polymer material with high gas barrier property (polyvinyl alcohol, etc.), inorganic thin film with high gas barrier property (silicon oxide, aluminum oxide, etc.) or organic film (parylene etc.) are deposited under vacuum. Examples thereof include a method and a method of laminating these in a composite manner.
  • optical sensor array Next, an optical sensor array to which the bulk heterojunction type organic photoelectric conversion element 10 described above is applied will be described in detail.
  • the optical sensor array is produced by arranging the photoelectric conversion elements in a fine pixel form by utilizing the fact that the bulk heterojunction type organic photoelectric conversion elements generate a current upon receiving light, and projected onto the optical sensor array.
  • FIG. 4 is a diagram showing the configuration of the optical sensor array. 4A is a top view, and FIG. 4B is a cross-sectional view taken along the line AA ′ in FIG. 4A.
  • the optical sensor array 20 is paired with a transparent electrode 22 as a lower electrode, a photoelectric conversion unit 24 that converts light energy into electric energy, and a transparent electrode 22 on a substrate 21 as a holding member.
  • the counter electrode 23 is sequentially laminated.
  • the photoelectric conversion unit 24 includes two layers, a photoelectric conversion layer 24b having a bulk heterojunction layer in which a p-type semiconductor material and an n-type semiconductor material are uniformly mixed, and a buffer layer 24a. In the example shown in FIG. 4, six bulk heterojunction type organic photoelectric conversion elements are formed.
  • the substrate 21, the transparent electrode 22, the photoelectric conversion layer 24 b, and the counter electrode 23 have the same configuration and role as the transparent electrode 12, the photoelectric conversion unit 14, and the counter electrode 13 in the bulk heterojunction photoelectric conversion element 10 described above. It is.
  • the low-molecular compound 12 of the present invention is used as the p-type semiconductor material of the photoelectric conversion layer 24b, and bis-PCBM is used as the n-type semiconductor material, for example.
  • the hole transport layer 24a is made of PEDOT (poly-3,4-ethylenedioxythiophene) -PSS (polystyrene sulfonic acid) conductive polymer (trade name Baytron P4083 manufactured by Starck Vitec).
  • PEDOT poly-3,4-ethylenedioxythiophene
  • PSS polystyrene sulfonic acid
  • Such an optical sensor array 20 was manufactured as follows.
  • An ITO film was formed on the glass substrate by sputtering and processed into a predetermined pattern shape by photolithography.
  • the thickness of the glass substrate was 0.7 mm
  • the thickness of the ITO film was 200 nm
  • the measurement area (light receiving area) of the ITO film after photolithography was 1 mm ⁇ 1 mm.
  • the thickness of the PEDOT-PSS film after drying was 30 nm.
  • a metal mask having a predetermined pattern opening was used, and a lithium fluoride layer having a thickness of 5 nm and an aluminum layer serving as an upper electrode having a thickness of 100 nm were formed on the bulk heterojunction layer by a vapor deposition method.
  • the optical sensor array 20 was produced as described above.
  • the manufactured photosensor array 20 having 2 rows ⁇ 3 columns of pixels is irradiated with light so that only two pixels in the center column are exposed to light, and the 6 pixels are sequentially placed between ⁇ 0.
  • the current value was read by applying a voltage of 5 V, the current was observed only in the pixels that were exposed to light, and no current flowed in the pixels that were not exposed to light. Therefore, it was confirmed that the optical sensor array 20 operates as an optical sensor.
  • Example 1 Preparation of Comparative Organic Photoelectric Conversion Element 1> An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate with a thickness of 110 nm (sheet resistance 13 ⁇ / ⁇ ) is patterned to a width of 2 mm using a normal photolithography technique and hydrochloric acid etching, and transparent An electrode was formed.
  • ITO indium tin oxide
  • the patterned transparent electrode was cleaned in the order of ultrasonic cleaning with a surfactant and ultrapure water, followed by ultrasonic cleaning with ultrapure water, dried by nitrogen blowing, and finally subjected to ultraviolet ozone cleaning.
  • Baytron P4083 manufactured by Starck Vitec, which is a conductive polymer, was spin-coated with a film thickness of 30 nm, and then heat-dried at 140 ° C. for 10 minutes in the air.
  • the substrate was brought into the glove box and worked in a nitrogen atmosphere.
  • the substrate was heat-treated at 140 ° C. for 3 minutes in a nitrogen atmosphere.
  • a liquid was prepared by dissolving 1.0% by mass of P3HT (Plexcore OS2100 manufactured by Plextronics) as a p-type semiconductor material and 1.0% by mass of bis-PCBM (manufactured by Solenne) as an n-type semiconductor material in chlorobenzene. While being filtered through a 0.45 ⁇ m filter, spin coating was performed at 500 rpm for 60 seconds, then at 2200 rpm for 1 second, and heated at room temperature for 30 minutes.
  • P3HT Pexcore OS2100 manufactured by Plextronics
  • bis-PCBM manufactured by Solenne
  • the substrate on which the series of organic layers was formed was placed in a vacuum deposition apparatus.
  • the element was set so that the shadow mask with a width of 2 mm was orthogonal to the transparent electrode, and the inside of the vacuum deposition apparatus was depressurized to 10 ⁇ 3 Pa or less, and then 5 nm of lithium fluoride and 80 nm of Al were evaporated.
  • the heating for 30 minutes was performed at 120 degreeC, and the comparative organic photoelectric conversion element 1 was obtained.
  • the vapor deposition rate was 2 nm / second for all, and the size was 2 mm square.
  • the obtained organic photoelectric conversion element 1 was sealed with an aluminum cap and a UV curable resin (manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1) in a nitrogen atmosphere, and then taken out into the atmosphere to be a solar simulator.
  • a UV curable resin manufactured by Nagase ChemteX Corporation, UV RESIN XNR5570-B1
  • voltage-current characteristics were measured, and initial conversion efficiency was measured.
  • the initial conversion efficiency at this time was 100
  • the conversion efficiency after 100 hours of irradiation with 100 mW / cm 2 irradiation intensity with the resistance connected between the anode and the cathode was evaluated, and the relative reduction efficiency was calculated. .
  • the obtained organic photoelectric conversion element 2 was sealed with an aluminum can and a UV curable resin in a nitrogen atmosphere, and then taken out into the atmosphere.
  • the solar simulator (AM1.5G) was irradiated with light of 100 mW / cm 2 . Irradiated with intensity, voltage-current characteristics were measured, and initial conversion efficiency was measured. Furthermore, the initial conversion efficiency at this time was set to 100, and the conversion efficiency after 100 hours of irradiation with an irradiation intensity of 100 mW / cm 2 with the resistance connected between the anode and the cathode was evaluated.
  • the organic photoelectric conversion element of the present invention has high efficiency and durability.

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Abstract

La présente invention concerne un élément de conversion photoélectrique organique présentant une haute efficacité de conversion et une durabilité élevée. Cet élément de conversion photoélectrique organique comporte entre une électrode transparente et une paire d'électrodes une couche d'hétérojonctions en vrac. L'élément organique de conversion photoélectrique organique contient un composé chimique présentant une structure partielle représentée par la formule générale (1).
PCT/JP2009/067493 2008-10-09 2009-10-07 Élément de conversion photoélectrique organique, cellule solaire, et réseau de capteurs optiques WO2010041687A1 (fr)

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JP2011060881A (ja) * 2009-09-08 2011-03-24 Toray Ind Inc 光起電力素子用材料および光起電力素子
WO2012035934A1 (fr) * 2010-09-13 2012-03-22 新日鐵化学株式会社 Élément électroluminescent organique
WO2012050003A1 (fr) * 2010-10-13 2012-04-19 新日鐵化学株式会社 Élément électroluminescent organique
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US9555038B2 (en) 2013-01-16 2017-01-31 Merck Sharp & Dohme Corp. Heterocycle-substituted tetracyclic compounds and methods of use thereof for the treatment of viral diseases
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