JP2010161270A - Organic photoelectric conversion element and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic photoelectric conversion element (bulk heterojunction-type organic solar cell), having a charge transport layer which has superior block capability, in a low-temperature film forming process, with respect to the recombination of electronsdes generated by light absorption and holes (charge carriers) and having improved energy conversion rate, and to provide a method for manufacturing the element. <P>SOLUTION: The organic photoelectric conversion element 10 is formed, by laminating at least a photoelectric conversion layer 14 and a hole transport layer or electron transport layer between a first electrode 12 and a second electrode 15, and has the hole transport layer or electron transport layer made of a thermal conversion material, and the thermal conversion material is converted into a composition of the hole transport layer or electron transport layer by heat. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic photoelectric conversion element having improved energy conversion efficiency and a method for producing the same.

  Bulk heterojunction organic solar cells (organic photoelectric conversion elements) are characterized by efficient charge separation before quenching excitons formed by light absorption, but the generated free carriers are organic donor materials or organic acceptor materials. However, since the free carriers of both polarities are recombined on the electrode, the energy conversion efficiency is liable to decrease.

  On the other hand, a technique that suppresses carrier recombination on the electrode by providing an exciton blocking layer between the power generation layer and the electrode has been introduced (see, for example, Patent Document 1), and important knowledge for higher efficiency is introduced. It can be said. As a similar technique, a technique has been introduced in which a layer made of nickel oxide is formed between a power generation layer and an electrode using a pulse laser film forming method to obtain high carrier separation (for example, Non-Patent Document 1). However, in these manufacturing methods, it is necessary to form a highly uniform layer under vacuum, and high productivity of the organic solar cell is spoiled.

  Further, as a method of forming such a layer having a blocking ability (charge transport layer) by a coating method, a method of forming a conjugated polymer layer having a band gap of 1.8 eV or more between the photoelectric conversion layer and the electrode (for example, Patent Documents) 2), a method of forming a heat conversion type benzoporphyrin layer (for example, Patent Document 3), a method of applying a metal alkoxide solution and hydrolyzing it in the atmosphere to form a metal oxide layer (for example, Patent Document) 4 or Patent Document 5).

  However, such a coating type charge transport layer still has low carrier separation ability, and recombination of free carriers on the electrode has not been sufficiently suppressed. When the metal oxide described above is used for the charge transport layer, a firing process of at least 300 ° C. or more is required in order to impart high blocking ability, and an element using an organic substance or an element using a flexible resin substrate Therefore, a method for forming a charge transport layer having an excellent blocking ability in a low temperature film forming process has been desired.

US Pat. No. 7,026,041 International Publication No. 04/017422 Pamphlet JP 2008-135622 A International Publication No. 07/011741 Pamphlet JP 2007-273939 A

Michael D. Irwin et al. , PNAS, vol. 105, no. 8,2783-2787

  The present invention has been made in view of the above problems and circumstances, and its solution is to provide excellent blocking ability in a low-temperature film-forming process against recombination of electrons and holes (charge carriers) generated by light absorption. It is to provide an organic photoelectric conversion element (bulk heterojunction type organic solar cell) having a charge transport layer having improved energy conversion efficiency and a method for producing the same.

  The above-mentioned problem according to the present invention is solved by the following means.

  1. An organic photoelectric conversion element in which at least a photoelectric conversion layer and a hole transport layer or an electron transport layer are laminated between a first electrode and a second electrode, wherein the hole transport layer or the electron transport layer is An organic photoelectric conversion element comprising a heat conversion material, wherein the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat.

  2. At least a part of the hole transport layer or the electron transport layer includes (i) an area containing a heat conversion material or a heat conversion material, and (ii) adjacent to or close to the area containing the heat conversion material or the heat conversion material. When an electromagnetic wave absorbing substance or an area containing an electromagnetic wave absorbing substance is disposed and the electromagnetic wave is irradiated, the heat conversion material is corrected by heat generated by the electromagnetic wave absorbing substance. 2. The organic photoelectric conversion element as described in 1 above, which has been converted into a composition of a hole transport layer or an electron transport layer.

  3. At least a part of the hole transport layer or the electron transport layer is provided with a heat conversion material and an area containing a substance having an electromagnetic wave absorbing ability, and when the electromagnetic wave is irradiated, the substance having the electromagnetic wave absorbing ability is generated. 2. The organic photoelectric conversion element as described in 1 above, wherein the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat to be generated.

  4). 4. The organic photoelectric conversion element as described in 2 or 3 above, wherein the substance having electromagnetic wave absorbing ability is a conductive metal oxide.

  5. 5. The organic photoelectric conversion element according to any one of 1 to 4, wherein the heat conversion material is an inorganic semiconductor precursor containing at least three or more kinds of metal elements and is converted into an inorganic semiconductor. .

  6). 6. The organic photoelectric conversion element as described in 5 above, wherein the inorganic semiconductor contains at least one element of In, Zn, and Sn.

  7). The organic photoelectric conversion element according to any one of 4 to 6, wherein the inorganic semiconductor contains Ga or Al.

  8). 8. The organic photoelectric conversion element according to any one of 5 to 7, wherein the inorganic semiconductor is a metal oxide semiconductor.

  9. 5. The organic photoelectric conversion element according to any one of 1 to 4, wherein the heat conversion material is an organic semiconductor precursor and is converted into an organic semiconductor.

  10. It is a manufacturing method of the organic photoelectric conversion element which manufactures the organic photoelectric conversion element as described in any one of said 1 to 9, Comprising: At least one part of a positive hole transport layer or an electron carrying layer, (i) Thermal conversion An area containing a material or a heat conversion material, and (ii) an area containing an electromagnetic wave absorbing substance or a substance having an electromagnetic wave absorbing ability adjacent to or in close proximity to the heat conversion material or the area containing the heat conversion material are arranged. An organic photoelectric conversion element characterized by converting the heat conversion material into a composition of a hole transport layer or an electron transport layer by heat generated by the substance having the ability to absorb electromagnetic waves by irradiating electromagnetic waves Production method.

  11. It is a manufacturing method of the organic photoelectric conversion element which manufactures the organic photoelectric conversion element as described in any one of said 1 to 9, Comprising: At least one part of a positive hole transport layer or an electron carrying layer WHEREIN: A heat conversion material and electromagnetic waves An area including a substance having an absorptive ability is arranged, irradiated with electromagnetic waves, and the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat generated by the substance having the ability to absorb electromagnetic waves. The manufacturing method of the organic photoelectric conversion element characterized by the above-mentioned.

  12 A layer containing the heat conversion material is formed by coating and forming a layer containing a heat conversion material on an electrode layer having electromagnetic wave absorption ability formed on one surface of the substrate, and irradiating the electromagnetic wave. 11. The method for producing an organic photoelectric conversion element as described in 10 above, wherein the compound is converted into a hole transport layer or an electron transport layer.

  13. A layer containing the heat conversion material is formed by applying a layer containing a heat conversion material on the electrode layer formed on one surface of the substrate having electromagnetic wave absorption ability and irradiating the electromagnetic wave, thereby generating heat from the substrate. 11. The method for producing an organic photoelectric conversion element as described in 10 above, wherein the compound is converted into a hole transport layer or an electron transport layer.

  14 On the electrode layer formed on one surface of the substrate, a layer containing a heat conversion material and a substance having an electromagnetic wave absorbing ability is applied and formed by irradiating the electromagnetic wave, thereby generating heat from the substance having the electromagnetic wave absorbing ability, 12. The method for producing an organic photoelectric conversion element as described in 11 above, wherein the layer containing the heat conversion material is converted into a hole transport layer or an electron transport layer.

  15. 15. The method for producing an organic photoelectric conversion element according to any one of 10 to 14, wherein the electromagnetic wave is a microwave.

  An organic material comprising a charge transport layer having an excellent blocking ability in a low-temperature film-forming process against recombination of electrons and holes (charge carriers) generated by light absorption by the above means of the present invention, and improving energy conversion efficiency A photoelectric conversion element (bulk heterojunction type organic solar cell) and a manufacturing method thereof can be provided.

The schematic sectional drawing which shows the basic structure of the organic photoelectric conversion element of this invention. The conceptual diagram of the process by which a heat conversion material is converted into the composition of an electric charge transport layer.

  The organic photoelectric conversion element of the present invention includes at least a photoelectric conversion layer and a hole transport layer or an electron transport layer (hereinafter referred to as “hole transport layer” and “electron transport layer” between the first electrode and the second electrode. Is generally referred to as a “charge transport layer”), and the hole transport layer or the electron transport layer is made of a heat conversion material, and the heat conversion material is heated by heat. The composition is converted into a composition of a hole transport layer or an electron transport layer. This feature is a technical feature common to the inventions according to claims 1 to 15.

  In an embodiment of the present invention, from the viewpoint of the effect of the invention, at least a part of the charge transport layer includes (i) an area containing a heat conversion material or a heat conversion material, and (ii) the heat conversion material or the heat conversion. A substance having electromagnetic wave absorbing ability or an area containing an electromagnetic wave absorbing substance is arranged adjacent to or close to the area containing the material, and when the electromagnetic wave is irradiated, the substance having the electromagnetic wave absorbing ability is generated. The heat conversion material is preferably converted into a charge transport layer composition by heat. Further, at least a part of the charge transport layer is provided with a heat conversion material and an area containing a substance having electromagnetic wave absorption ability, and when irradiated with electromagnetic waves, the heat generated by the substance having electromagnetic wave absorption ability is generated. It is also preferable that the heat conversion material is converted into a charge transport layer composition.

  In this invention, it is preferable that the said heat conversion material is an inorganic semiconductor precursor containing at least 3 or more types of metal elements, and is the aspect converted into the inorganic semiconductor. The inorganic semiconductor preferably contains at least one of In, Zn, and Sn. Further, the inorganic semiconductor preferably contains either Ga or Al.

  The inorganic semiconductor is preferably a metal oxide semiconductor.

  In this invention, it is also preferable that the said heat conversion material is an organic-semiconductor precursor, and is the aspect converted into the organic semiconductor.

  On the other hand, it is preferable that the substance having electromagnetic wave absorbing ability is a conductive metal oxide.

  The organic photoelectric conversion device manufacturing method for manufacturing the organic photoelectric conversion device of the present invention includes (i) a heat conversion material or an area containing the heat conversion material in at least a part of the charge transport layer, and (ii) the heat conversion. A substance having an electromagnetic wave absorbing ability or an area containing an electromagnetic wave absorbing substance adjacent to or in the vicinity of an area containing a material or a heat conversion material is disposed and irradiated with an electromagnetic wave. It is preferable that the heat conversion material is converted into the charge transport layer composition by the generated heat. In addition, an area including a heat conversion material and a substance having electromagnetic wave absorbing ability is disposed in at least a part of the charge transport layer, and the heat conversion is performed by heat generated by the substance having the electromagnetic wave absorbing ability by irradiation with electromagnetic waves. It is also preferred that the material be converted into a charge transport layer composition.

  In the present invention, a layer containing a heat conversion material is applied and formed on an electrode layer having electromagnetic wave absorption ability formed on one surface of a substrate, and the heat is generated by the heat generated from the electrode by irradiating the electromagnetic wave. It is preferable that the production method has a mode in which a layer containing a conversion material is converted into a charge transport layer. In addition, a layer containing a heat conversion material is applied and formed on an electrode layer formed on one surface of a substrate having electromagnetic wave absorbing ability, and the heat conversion material is applied by heat generated from the substrate by irradiating the electromagnetic wave. It is also preferable that the production method has a mode in which the layer to be contained is converted into a charge transport layer. Further, a heat conversion material and a layer containing a substance capable of absorbing electromagnetic waves are applied and formed on the electrode layer formed on one side of the substrate, and heat generated from the substance having the ability to absorb electromagnetic waves is irradiated by electromagnetic waves. Thus, it is preferable that the layer containing the heat conversion material is converted into a charge transport layer.

  In the present invention, the electromagnetic wave is preferably a microwave.

  Hereinafter, the present invention, its components, and the best mode and mode for carrying out the present invention will be described in detail.

(Basic structure of the organic photoelectric conversion device of the present invention)
The organic photoelectric conversion element of the present invention is an organic photoelectric conversion element formed by laminating at least a photoelectric conversion layer and a charge transport layer between a first electrode and a second electrode. A schematic sectional view of an example of the basic structure is shown in FIG. In FIG. 1, an organic photoelectric conversion element 10 is formed on one surface of a substrate 11 by mixing a first electrode 12, a first charge transport layer 13, and a bulk heterojunction structure (including a p-type semiconductor layer and an n-type semiconductor layer). 1 has a structure in which a photoelectric conversion layer 14 (hereinafter also referred to as a “bulk heterojunction layer”), a second charge transport layer 15, and a second electrode 16 are sequentially stacked as shown in FIG. .

  In order for external light to enter the photoelectric conversion layer 14, the substrate 11 and the first electrode 12 or the second electrode are preferably substantially transparent to the wavelength range of light that contributes to power generation. More preferably, the substrate 11 and the first electrode are transparent, and the second electrode is incident from the first electrode side and reflects light transmitted through the photoelectric conversion layer 14. A configuration in which the substrate 11 and the first electrode and the second electrode are both transparent can also be preferably used in the present invention.

  When the first electrode is a positive electrode, the first charge transport layer 13 described above is preferably a hole transport layer because of the configuration in which holes are mainly extracted from free charges composed of holes and electrons. . Similarly, in the case where the second electrode is a cathode, the second charge transport layer 15 is preferably an electron transport layer because of a configuration in which electrons are mainly extracted.

  In the present invention, the charges transported in the first charge transport layer and the second charge transport layer may be either electrons or holes, and more preferably selected in pairs. Moreover, the organic photoelectric conversion element of this invention should just have a layer of at least one of a 1st charge transport layer and a 2nd charge transport layer, and as FIG. 1 shows, the photoelectric converting layer 14 is shown. It is more preferable to have each of the first charge transport layer and the second charge transport layer in such a form that is sandwiched from above and below.

(Heat conversion material and substance with electromagnetic wave absorption ability)
The charge transport layer according to the present invention includes, at least in part, (i) an area including a heat conversion material or a heat conversion material, and (ii) adjacent to or close to the area including the heat conversion material or the heat conversion material. When the electromagnetic wave absorbing substance or the area containing the electromagnetic wave absorbing substance is disposed and the electromagnetic wave is irradiated, the heat conversion material is charged by the heat generated by the electromagnetic wave absorbing substance. It is preferable that it is the aspect converted into the composition of a transport layer. Further, at least a part of the charge transport layer is provided with a heat conversion material and an area containing a substance having electromagnetic wave absorption ability, and when irradiated with electromagnetic waves, the heat generated by the substance having electromagnetic wave absorption ability is generated. It is also preferable that the heat conversion material is converted into the charge transport layer composition.

<Heat conversion material>
The heat conversion material according to the present invention is an inorganic semiconductor precursor containing at least three or more kinds of metal elements, and is preferably a material that is converted into an inorganic semiconductor.

  The inorganic semiconductor is preferably a semiconductor containing at least one of In, Zn, and Sn. Furthermore, the inorganic semiconductor may be a semiconductor containing either Ga or Al.

  In the present invention, the inorganic semiconductor is particularly preferably a metal oxide semiconductor. Moreover, it is also preferable to use the material which is an organic semiconductor precursor and is converted into an organic semiconductor as the heat conversion material.

  Hereinafter, the heat conversion material will be described in more detail.

  In the present invention, a metal oxide semiconductor precursor or an organic semiconductor precursor material can also be used as the semiconductor precursor that is a heat conversion material.

(Metal oxide semiconductor)
Examples of the metal oxide semiconductor precursor include a metal element-containing compound, and examples of the metal element-containing compound include metal salts, metal halide compounds, and organic metal compounds containing a metal element.

  Metals of metal salts, halogen metal compounds, and organometallic compounds include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl, Pb, Bi, Ce, Pr Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and the like.

  Among these metal elements, it is preferable to include any metal ion of In (indium), Zn (zinc), or Sn (tin), and they may be used in combination.

  Further, it is preferable that other metal elements include Ga (gallium) and Al (aluminum).

  As the metal salt, nitrate, acetate and the like can be suitably used, and as the halogen metal compound, chloride, iodide, bromide and the like can be suitably used.

  Examples of the organometallic compound include those represented by the following general formula (OMI).

General formula (OMI) R ¹ _x MR ² _y R ³ _z
In the formula, M is a metal, R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group). X + y + z = m, x = 0 to m, or x = 0 to m−1, and y = 0 to m, z = 0. ~ M, each of which is 0 or a positive integer. Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Further, a hydrogen atom in the alkyl group may be substituted with a fluorine atom. Examples of the group selected from a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group) of R ³ include, for example, 2,4 -Pentanedione (also called acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione , 1,1,1-trifluoro-2,4-pentanedione, and the β-ketocarboxylic acid ester complex group includes, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethylacetate Examples thereof include ethyl acetate, methyl trifluoroacetoacetate and the like, and examples of β-ketocarboxylic acid include Examples thereof include acetoacetic acid and trimethylacetoacetic acid, and examples of ketooxy include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, and methacryloyloxy group. These groups preferably have 18 or less carbon atoms. Further, it may be linear or branched, or a hydrogen atom may be a fluorine atom. Among organometallic compounds, those having at least one oxygen in the molecule are preferable. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group (ketooxy group) of R ³ Most preferred are metal compounds having at least one group selected from (complex groups). Among the metal salts, nitrate is preferable. Nitrate is easily available as a high-purity product and has high solubility in water, which is preferable as a medium for use. Examples of nitrates include indium nitrate, tin nitrate, zinc nitrate, and gallium nitrate.

  Of the above metal oxide semiconductor precursors, metal nitrates, metal halides, and alkoxides are preferable. Specific examples include indium nitrate, zinc nitrate, gallium nitrate, tin nitrate, aluminum nitrate, indium chloride, zinc chloride, tin chloride (divalent), tin chloride (tetravalent), gallium chloride, aluminum chloride, tri-i-. Examples include propoxyindium, diethoxyzinc, bis (dipivaloylmethanato) zinc, tetraethoxytin, tetra-i-propoxytin, tri-i-propoxygallium, and tri-i-propoxyaluminum.

(Metal oxide semiconductor precursor thin film deposition method)
In order to form a thin film containing a metal as a precursor of these metal oxide semiconductors, a known film formation method, vacuum deposition method, molecular beam epitaxial growth method, ion cluster beam method, low energy ion beam method, ion A plating method, a CVD method, a sputtering method, an atmospheric pressure plasma method, and the like can be used. In the present invention, a solution in which a metal salt, a halide, an organometallic compound, or the like is dissolved in an appropriate solvent is used on the substrate. The continuous coating is preferable because it can greatly improve the productivity. Also from this point, it is more preferable from the viewpoint of solubility to use a chloride, nitrate, acetate, metal alkoxide or the like as the metal compound.

  The solvent is not particularly limited as long as it dissolves the metal compound to be used in addition to water, but water, alcohols such as ethanol, propanol, and ethylene glycol, ethers such as tetrahydrofuran and dioxane, acetic acid, and the like. Esters such as methyl and ethyl acetate, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, glycol ethers such as diethylene glycol monomethyl ether, acetonitrile, and aromatic hydrocarbon solvents such as xylene and toluene, o-dichlorobenzene , Aromatic solvents such as nitrobenzene and m-cresol, aliphatic hydrocarbon solvents such as hexane, cyclohexane and tridecane, α-terpineol, and halogenated alkyl solvents such as chloroform and 1,2-dichloroethane N- methylpyrrolidone, can be preferably used carbon disulfide and the like.

  When a metal halide and / or metal alkoxide is used, a solvent having a relatively high polarity is preferable. Among them, water having a boiling point of 100 ° C. or less, alcohols such as ethanol and propanol, acetonitrile, or a mixture thereof is dried. Since the temperature can be lowered, it is possible to coat the resin substrate, which is more preferable.

  Addition of metal alkoxide and various ligands such as alkanolamines, α-hydroxy ketones, β-diketones and other chelating ligands in the solvent stabilizes the metal alkoxide and the solubility of the carboxylate. It is preferable to add it in a range that does not cause adverse effects.

  Examples of methods for forming a thin film by applying a liquid containing a semiconductor precursor material onto a substrate include spin coating, spray coating, blade coating, dip coating, casting, bar coating, and die coating. Examples of the coating method include a method by coating in a broad sense such as a printing method such as a relief printing plate, an intaglio plate, a planographic printing method, a screen printing method, and an ink jet printing method, and a method of patterning by this. Alternatively, the coating film may be patterned by photolithography, laser ablation, or the like. Among these, the ink jet method, spray coating method, etc. which can apply | coat a thin film are preferable.

  In the case of film formation, a thin film of a metal oxide precursor is formed by volatilizing the solvent at about 150 ° C. after coating. In addition, when dropping the solution, it is preferable to heat the substrate itself to about 150 ° C. because two processes of coating and drying can be performed simultaneously.

(Composition ratio of metal)
As a preferred metal composition ratio, when In is 1, Zn _y Sn _1-y (where y is a positive number from 0 to ₁ ) is 0.2 to 5, preferably 0.5 to 2. . Furthermore, when In is set to 1, the composition ratio of Ga is 0.2 to 5, preferably 0.5 to 2.

  Moreover, the film thickness of the thin film containing the metal used as a precursor is 1-200 nm, More preferably, it is 5-100 nm.

(Amorphous oxide)
As the metal oxide semiconductor to be formed, any state of single crystal, polycrystal, and amorphous can be used, but an amorphous thin film is preferably used.

(Organic semiconductor materials)
Examples of the organic semiconductor precursor material include bicyclo compounds (bicycloporphyrin compounds) having a cyclic structure as described in JP-A-2003-304014. A film formed of these compounds undergoes a deethylation reaction by heating, whereby a film such as tetrabenzoporphyrin having high planarity can be obtained, and a highly efficient organic semiconductor layer is formed. By using these bicycloporphyrin compounds or metal complexes thereof as a semiconductor precursor, an organic semiconductor layer having high planarity can be formed by heat generated by electromagnetic wave absorption of the ITO electrode.

  Specific examples of these bicycloporphyrin compounds are described in the above-mentioned organic Japanese Patent Application Laid-Open No. 2003-304014, paragraphs (0022) to (0025), and these compounds and metal complexes such as copper are used. be able to. Specific examples are given below.

  These bicyclo compounds can also be dissolved and applied in a solvent as required. Particularly useful are those in which the molecules converted by the deethyleneation reaction are hardly soluble in the solvent. Coating methods include casting methods, spin coating methods, spray coating methods, blade coating methods, dip coating methods, bar coating methods, die coating methods, and printing methods such as relief printing, intaglio printing, lithographic printing, screen printing, and inkjet printing. A method by coating in a broad sense such as a method can be used. Moreover, the method of patterning by this is mentioned. Alternatively, the coating film may be patterned by photolithography, laser ablation, or the like.

<Areas containing substances that absorb electromagnetic waves>
The substance having electromagnetic wave absorbing ability according to the present invention absorbs the irradiated electromagnetic wave and changes heat, so that the substance itself generates heat and becomes a heat source. preferable.

  A metal oxide is preferable as the material having electromagnetic wave absorbing ability. As the metal oxide, titanium, copper, nickel, zinc, tin, and indium oxides are preferable.

  In the case where a metal oxide is oxidized by irradiation with electromagnetic waves in the presence of oxygen, a metal salt, halide, or organometallic compound containing a metal atom can also be used.

  Metals of metal salts, metal oxides, organometallic compounds, halogen metal compounds, metal hydrides include Li, Be, B, Na, Mg, Al, Si, K, Ca, Sc, Ti, V, Cr, Mn Fe, Co, Ni, Cu, Zn, Ga, Ge, Rb, Sr, Y, Zr, Nb, Mo, Cd, In, Ir, Sn, Sb, Cs, Ba, La, Hf, Ta, W, Tl , Pb, Bi, Ce, Pr, Nd, Pm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and the like.

  As metal salts, nitrates, acetates and the like can be suitably used, and as halides, chlorides, iodides, bromides and the like can be suitably used.

  Examples of the organometallic compound include those represented by the following general formula (I).

Formula (I) R ¹ _x MR ² _y R ³ _z
In the formula, M is a metal, R ¹ is an alkyl group, R ² is an alkoxy group, R ³ is a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group, and a ketooxy group (ketooxy complex group). X + y + z = m, x = 0 to m, or x = 0 to m−1, and y = 0 to m, z = 0. ~ M, each of which is 0 or a positive integer.

Examples of the alkyl group for R ¹ include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the alkoxy group for R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and a 3,3,3-trifluoropropoxy group. Moreover, what substituted the hydrogen atom of the alkyl group by the fluorine atom may be used.

Examples of the group selected from the β-diketone complex group, the β-ketocarboxylic acid ester complex group, the β-ketocarboxylic acid complex group, and the ketooxy group (ketooxy complex group) of R ³ include, for example, 2,4 -Pentanedione (also called acetylacetone or acetoacetone), 1,1,1,5,5,5-hexamethyl-2,4-pentanedione, 2,2,6,6-tetramethyl-3,5-heptanedione , 1,1,1-trifluoro-2,4-pentanedione, and the β-ketocarboxylic acid ester complex group includes, for example, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid propyl ester, trimethylacetate Examples thereof include ethyl acetate, methyl trifluoroacetoacetate and the like, and examples of β-ketocarboxylic acid include Examples thereof include acetoacetic acid and trimethylacetoacetic acid, and examples of ketooxy include acetooxy group (or acetoxy group), propionyloxy group, butyryloxy group, acryloyloxy group, and methacryloyloxy group. These groups preferably have 18 or less carbon atoms.

Further, a straight chain or branched chain, or a hydrogen atom converted to a fluorine atom may be used. Among organometallic compounds, those having at least one oxygen in the molecule are preferable. As such, an organometallic compound containing at least one alkoxy group of R ² , a β-diketone complex group, a β-ketocarboxylic acid ester complex group, a β-ketocarboxylic acid complex group and a ketooxy group of R ³ ( Most preferred is a metal compound having at least one group selected from a ketooxy complex group.

  Among metal salts, nitrate is preferable. Nitrate is easily available as a high-purity product and has high solubility in water, which is preferable as a medium for use. Examples of nitrates include indium nitrate, tin nitrate, zinc nitrate, and gallium nitrate.

  Of these, preferred are metal nitrates, halides and alkoxides. Specific examples include indium nitrate, zinc nitrate, gallium nitrate, tin nitrate, aluminum nitrate, indium chloride, zinc chloride, tin chloride (divalent), tin chloride (tetravalent), gallium chloride, aluminum chloride, tri-i-. Examples include propoxyindium, diethoxyzinc, bis (dipivaloylmethanato) zinc, tetraethoxytin, tetra-i-propoxytin, tri-i-propoxygallium, and tri-i-propoxyaluminum.

  As a substance having electromagnetic wave absorbing ability that can be preferably used in the present invention, a metal can be suitably used. For example, platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, Palladium, tellurium, rhenium, iridium, aluminum, ruthenium, germanium, molybdenum, tungsten, tin oxide / antimony, indium tin oxide (ITO), fluorine-doped zinc oxide, zinc, carbon, graphite, glassy carbon, silver paste and carbon paste , Lithium, beryllium, sodium, magnesium, potassium, calcium, scandium, titanium, manganese, zirconium, gallium, niobium, sodium, sodium-potassium alloy, magnesium, lithium, aluminum, magnesium Copper mixture, a magnesium / silver mixture, a magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide mixture, can be used lithium / aluminum mixtures.

  The substance having electromagnetic wave absorbing ability according to the present invention is also preferably added as particles for use as a heat source.

  The substance having the ability to absorb electromagnetic waves (particles that absorb electromagnetic waves) made of the particles may exist in the form of being embedded in an area adjacent to the heat conversion material, but is mixed with the layer in which the heat conversion material exists. May exist.

  More specifically, after forming a heat conversion material layer containing particles that absorb electromagnetic waves, the heat conversion material layer is irradiated with electromagnetic waves, and the particles that absorb the electromagnetic waves contained in the heat conversion material layer are heated. Thus, a form in which the heat conversion material is converted into the composition of the charge transport layer can also be preferably used.

  Particles that absorb electromagnetic waves, which is a preferred form of the present invention, are materials that generate heat efficiently due to large dielectric loss or resistance loss because the particles themselves generate heat by becoming a heat source by absorbing irradiated electromagnetic waves and changing heat. Is preferred.

  Furthermore, although it is not necessary to reduce the particle size of the particles that absorb electromagnetic waves, it is preferable to use fine particles having an average particle size of 1 to 500 nm. More preferably, it is 1-100 nm, More preferably, it is 5-50 nm. Moreover, in an organic photoelectric conversion element, it is good also as a structure which has light scattering ability as a particle size of a Mie scattering area | region.

(Process in which the heat conversion material is converted into the composition of the charge transport layer)
In the present invention, at least a part of the charge transport layer includes (i) a heat conversion material or an area containing the heat conversion material, and (ii) an electromagnetic wave absorption adjacent to or close to the heat conversion material or the area containing the heat conversion material. And a region containing a substance having an electromagnetic wave absorption ability, and radiating an electromagnetic wave, and the heat conversion material is converted into a composition of the charge transport layer by heat generated by the substance having the electromagnetic wave absorption ability It is the manufacturing method of the organic photoelectric conversion element characterized by converting into.

  The process in which the heat conversion material according to the present invention is converted into the composition of the charge transport layer will be described with reference to FIGS.

  FIG. 2 (A) is a preferred embodiment of the present invention, in which a layer containing a heat conversion material is applied and formed on an electrode layer having electromagnetic wave absorbing ability formed on one surface of a substrate (not shown) and irradiated with electromagnetic waves. FIG. 6 is a diagram illustrating a mode in which a layer containing the heat conversion material is converted into a hole transport layer or an electron transport layer (first charge transport layer) by heat generated from the electrode.

  FIG. 2 (B) is a preferred embodiment of the present invention. On the electrode layer formed on one surface of the substrate having electromagnetic wave absorbing ability, a layer containing a heat conversion material is applied and irradiated with electromagnetic waves. It is the figure which illustrated the form which converts the layer containing the said heat conversion material into the positive hole transport layer or the electron carrying layer (1st charge transport layer) with the heat which generate | occur | produces from the said board | substrate. In the present invention, a substance that absorbs electromagnetic waves may be selected for the substrate itself, or a substrate in which the above-described substances having electromagnetic wave absorbing ability are mixed or composited or a substance having electromagnetic wave absorbing ability is formed on the surface as a thin film. In addition, it can be preferably used in the present invention as a substrate having a laminated structure of two or more layers. It is preferable in the present invention that the substrate referred to here is not necessarily required to have conductivity, unlike the above-described electrode having electromagnetic wave absorbing ability.

  FIG. 2C shows a preferred embodiment of the present invention, in which a layer containing a heat conversion material and a substance having electromagnetic wave absorbing ability is applied and formed on an electrode layer formed on one surface of a substrate (not shown). It is the figure which illustrated the form which converts the layer containing the said heat conversion material into a positive hole transport layer or an electron transport layer with the heat which generate | occur | produces from the said substance which has the electromagnetic wave absorption ability by irradiating.

  In the process of converting the heat conversion material shown in FIGS. 2A to 2C into the composition of the charge transport layer, the layer containing the heat conversion material adjacent to or close to the substance having electromagnetic wave absorbing ability. It is possible to heat-convert by irradiating electromagnetic waves immediately without forming the upper layer, but after forming the layer containing the heat conversion material, the photoelectric conversion layer and other functional layers are stacked. Thereafter, a method of irradiating electromagnetic waves to thermally convert the heat conversion material into a charge transport layer composition can also be preferably used.

(Method of forming an area containing a substance having electromagnetic wave absorption ability)
There is no particular limitation on a method for forming an area containing a substance having an electromagnetic wave absorbing ability in relation to the above-described FIG. 2A or 2B, and a vacuum deposition method, a sputtering method, a spray pyrolysis method, a plasma CVD method is used. Any method such as a coating method or a printing method may be used. From the viewpoint of productivity, preferably, by using a dispersion or solution obtained by dispersing or dissolving the substance having electromagnetic wave absorbing ability in an appropriate solvent, by continuous coating on a functional layer such as a substrate or a photoelectric conversion layer. A method of forming a film (also referred to as “wet process”) is preferable.

(Preparation of dispersion of heat conversion material and substance with electromagnetic wave absorption ability)
In relation to FIG. 2C described above, when a layer containing a heat conversion material and a substance having electromagnetic wave absorbing ability is applied (wet process), the substance having the electromagnetic wave absorbing ability is appropriately dispersed. It is preferable to use a colloidal dispersion in which the heat conversion material is dispersed or dissolved in a dispersion medium.

(Electromagnetic radiation)
The electromagnetic wave according to the present invention refers to ionizing radiation (X-rays or gamma rays), ultraviolet rays, visible rays (light visible to the human eye), infrared rays, radio waves (microwaves, etc.). In the present invention, 0.3 GHz It is preferable to use a microwave having a frequency of ˜50 GHz.

  In the following, components other than those described above will be described in detail.

(substrate)
The substrate is a member that holds the first electrode, the first charge transport layer, the photoelectric conversion layer, the second charge transport layer, and the second electrode that are sequentially stacked. In the present embodiment, the substrate is transparent to the wavelength of light to be photoelectrically converted so that light that is photoelectrically converted from at least the first electrode or the second electrode, or both electrodes can be transmitted. It is desirable.

  As a substrate (hereinafter also referred to as “transparent substrate”), for example, a glass substrate, a resin substrate, and the like are preferable examples. However, it is more preferable to use a transparent resin film from the viewpoint of lightness and flexibility. There is no restriction | limiting in particular in the transparent resin film which can be preferably used as a transparent substrate by this invention, The material, a shape, a structure, thickness, etc. can be suitably selected from well-known things.

  For example, 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 ~780nm), can be preferably applied to a transparent resin film according to the present invention.

  Among them, from the viewpoint of transparency, heat resistance, ease of handling, strength and cost, it is 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 conventionally well-known technique can be used about a surface treatment or an easily bonding layer. For example, 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.

  When the transparent resin film is a biaxially stretched polyethylene terephthalate film, by making the refractive index of the easy adhesion layer adjacent to the film 1.57-1.63, the interface reflection between the film substrate and the easy adhesion layer can be achieved. Since it can reduce and can improve the transmittance | permeability, it is more preferable. 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. Moreover, the barrier coat layer may be formed in advance on the transparent substrate, or the hard coat layer may be formed in advance on the opposite side to which the transparent conductive layer is transferred.

(First electrode)
The cathode and anode of the first electrode (also referred to as “first electrode”) are not particularly limited, and can be selected depending on the element configuration. An electrode that can transmit light that is photoelectrically converted in the photoelectric conversion layer is preferable, and an electrode that transmits light of 300 to 800 nm is more preferable.

  The first electrode in the present invention is a substance that absorbs electromagnetic waves and generates heat, and also has the characteristics of having conductivity as an electrode and electrical bonding with an adjacent functional layer. This is also a form that can be preferably used in the present invention.

Specific examples of the material include transparent conductive metal oxides such as indium tin oxide (ITO), SnO ₂ , fluorine-doped SnO ₂ (FTO), ZnO, and aluminum-doped ZnO (AZO), gold, silver, platinum, and the like. Metal thin films, metal nanowires, carbon nanotubes, and conductive polymers can be used.

(Second electrode)
The second electrode of the counter electrode (also referred to as “first electrode”) is a metal (for example, gold, silver, copper, platinum, rhodium, ruthenium, aluminum, magnesium, indium, etc.), carbon, or the first electrode Although material etc. can be used, it is not restricted to this.

(Photoelectric conversion layer)
The photoelectric conversion layer 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 relatively functions as an electron donor (donor), and the n-type semiconductor material relatively functions as an electron acceptor (acceptor). Here, the electron donor and the electron acceptor are “an electron donor that moves from the electron donor to the electron acceptor when absorbing light and forms a hole-electron pair (charge separation state) and It is an “electron acceptor”, which does not simply donate or accept electrons like an electrode, but donates or accepts electrons by a photoreaction.

  Examples of the p-type semiconductor material used in the present invention include various condensed polycyclic aromatic compounds and conjugated compounds.

  As the condensed polycyclic aromatic compound, for example, anthracene, tetracene, pentacene, hexacene, heptacene, chrysene, picene, fluorene, pyrene, peropyrene, perylene, terylene, quaterylene, coronene, ovalene, sarkham anthracene, bisanthene, zestrene, heptazelene, Examples thereof include compounds such as pyranthrene, violanthene, isoviolanthene, cacobiphenyl, anthradithiophene, and derivatives and precursors thereof.

  Examples of the conjugated compound include polythiophene and its oligomer, polypyrrole and its oligomer, polyaniline, polyphenylene and its oligomer, polyphenylene vinylene and its oligomer, polythienylene vinylene and its oligomer, polyacetylene, polydiacetylene, tetrathiafulvalene compound, quinone Compounds, cyano compounds such as tetracyanoquinodimethane, fullerenes and derivatives or mixtures thereof.

  In particular, among polythiophene and oligomers thereof, thiophene hexamer α-seccithiophene α, ω-dihexyl-α-sexualthiophene, α, ω-dihexyl-α-kinkethiophene, α, ω-bis (3- An oligomer such as butoxypropyl) -α-sexithiophene can be preferably used.

  Other examples of the polymer p-type semiconductor include polyacetylene, polyparaphenylene, polypyrrole, polyparaphenylene sulfide, polythiophene, polyphenylene vinylene, polycarbazole, polyisothianaphthene, polyheptadiyne, polyquinoline, polyaniline, and the like. Substituted-unsubstituted alternating copolymer polythiophenes such as JP-A-2006-36755, JP-A-2007-51289, JP-A-2005-76030, J. Org. Amer. Chem. Soc. , 2007, p4112, J.A. Amer. Chem. Soc. , 2007, p7246, etc., polymers having a condensed thiophene structure, WO08 / 664 pamphlet, Adv. Mater. , 2007, p4160, Macromolecules, 2007, Vol. Examples thereof include thiophene copolymers such as 40 and p1981.

  Further, porphyrin, copper phthalocyanine, tetrathiafulvalene (TTF) -tetracyanoquinodimethane (TCNQ) complex, bisethylenetetrathiafulvalene (BEDTTTTF) -perchloric acid complex, BEDTTTTF-iodine complex, TCNQ-iodine complex, etc. Organic molecular complexes, fullerenes such as C60, C70, C76, C78, C84, carbon nanotubes such as SWNT, dyes such as merocyanine dyes and hemicyanine dyes, σ-conjugated polymers such as polysilane, polygermane, and the like Organic-inorganic hybrid materials described in 2000-260999 can also be used.

  As the n-type semiconductor material, for example, a fullerene derivative compound or the like is used in order to realize relatively high photoelectric conversion efficiency.

  Specific examples include fullerene, octaazaporphyrin, p-type semiconductor perfluoro compounds (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalenetetracarboxylic acid anhydride, naphthalenetetracarboxylic acid diimide, perylenetetracarboxylic acid anhydride, perylene. Examples thereof include an aromatic carboxylic acid anhydride such as tetracarboxylic acid diimide and a polymer compound containing an imidized product thereof as a skeleton.

  Among these, fullerene-containing polymer compounds are preferable. Fullerene-containing polymer compounds 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), etc. Examples thereof include a polymer compound having a skeleton. As the fullerene-containing polymer compound, a polymer compound (derivative) having fullerene C60 as a skeleton is preferable.

  Examples of a method for forming a bulk heterojunction layer in which an electron acceptor and an electron donor are mixed include a coating method (including a casting method and a spin coating method). The photoelectric conversion layer is annealed at a predetermined temperature during the manufacturing process in order to improve the photoelectric conversion rate, and is partially crystallized microscopically.

(Charge transport layer)
Specific examples of the charge transport layer include a hole transport layer and an electron transport layer. In the present invention, of the charge transport layer, at least one of the hole transport layer and the electron transport layer is made of a heat conversion material as described above, and is converted into the hole transport layer or the electron transport layer by heat. It is preferable that it consists of the material made.

<Hole transport layer>
As a material constituting these layers, for example, as a hole transport layer (electron block layer), PEDOT such as Product name BaytronP manufactured by Stark Vitec, polyaniline and its doped material, Japanese Patent Laid-Open No. 5-271166, etc. The triarylamine compounds described in 1), the cyanide compounds described in WO 06/19270 pamphlet, and the like, and metal oxides such as molybdenum oxide, nickel oxide, and tungsten oxide can be used.

  Moreover, in this invention, the layer which consists of a p-type semiconductor material single-piece | unit used for the bulk heterojunction layer (photoelectric converting layer) can also be used.

<Electron transport layer>
In addition, as the electron transport layer (hole blocking layer), octaazaporphyrin, p-type semiconductor perfluoro (perfluoropentacene, perfluorophthalocyanine, etc.), naphthalene tetracarboxylic anhydride, naphthalene tetracarboxylic diimide, perylene N-type semiconductor materials such as tetracarboxylic acid anhydride and perylenetetracarboxylic acid diimide, and n-type inorganic oxides such as titanium oxide, zinc oxide and gallium oxide, and alkali metals such as lithium fluoride, sodium fluoride and cesium fluoride A compound or the like can be used.

  Moreover, the layer which consists of a n-type semiconductor material single-piece | unit used for the bulk heterojunction layer (photoelectric converting layer) can also be used.

(Tandem configuration)
For the purpose of improving the sunlight utilization rate (photoelectric conversion efficiency), a tandem configuration in which organic photoelectric conversion elements are stacked may be employed. In the case of a tandem type configuration, a transparent electrode and a first photoelectric conversion layer are sequentially stacked on a substrate, a charge recombination layer is stacked, a second photoelectric conversion layer, and then a counter electrode are stacked to form a tandem It can be configured as a mold. The second photoelectric conversion layer may be a layer that absorbs the same spectrum as the absorption spectrum of the first photoelectric conversion layer, or may be a layer that absorbs a different spectrum, but is preferably a layer that absorbs a different spectrum. The material of the charge recombination layer 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, Au, etc. A very thin metal layer, a conductive polymer material such as PEDOT: PSS, polyaniline, and the like are preferable.

(Sealing)
Moreover, it is preferable to seal by the well-known method so that the produced organic photoelectric conversion element may not deteriorate with oxygen, moisture, etc. in the environment. For example, 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. , A method of spin-coating organic polymer materials (polyvinyl alcohol, etc.) with high gas barrier properties, a method of directly depositing inorganic thin films (silicon oxide, aluminum oxide, etc.) with high gas barrier properties, and laminating these in a composite manner And the like.

  Furthermore, in the present invention, from the viewpoint of improving energy conversion efficiency and device life, the entire device may be sealed with two substrates with a barrier, and preferably a structure in which a moisture getter or the like is enclosed. Is more preferable.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

[Production of Organic Photoelectric Conversion Element SC-101]
A 150-nm thick indium tin oxide (ITO) transparent conductive film deposited on a PEN film substrate with a barrier layer (sheet resistance 13Ω / □) is patterned to a width of 1 cm using ordinary photolithography and hydrochloric acid etching. Thus, a flexible transparent electrode was formed. 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 with nitrogen, and finally with ultraviolet ozone cleaning.

  Next, a solution in which Ti-isopropoxide was dissolved in dehydrated ethanol to a concentration of 0.05 mol / l was prepared, applied to a film thickness of 20 nm, and allowed to stand at room temperature to dry. Subsequently, the extraction electrode portion was wiped and patterned, transported to a nitrogen chamber in which the amount of water vapor was controlled, and allowed to stand to form an electron transport layer.

  Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) (Mn = 52000, polymer p-type semiconductor material) and PCBM (frontier carbon: 6,6-phenyl-C61-butyric acid) were added to chlorobenzene. Methyl ester) (Mw = 911, low molecular weight n-type semiconductor material) prepared in a 1: 1 mixture so as to be 3.0% by mass, applied to a film thickness of 100 nm while filtering through a filter. And dried at room temperature in a nitrogen atmosphere to form a bulk heterojunction photoelectric conversion layer (BHJ layer). Subsequently, Baytron P 4083 (made by Starck Vitec), which is a conductive polymer, was applied to a film thickness of 50 nm, and then dried at 120 ° C. for 10 minutes in the atmosphere, and positively coated on the photoelectric conversion layer. A hole transport layer was formed.

Next, a silver nanowire layer was formed by applying silver nanowires prepared as a dispersion so as to have a basis weight of 80 mg / m ² and drying. Furthermore, after apply | coating Baytron PH510 (made by Stark Vitec) which is a conductive polymer on silver nanowire, the electrode layer was formed by making it dry at room temperature.

  Silver nanowires are described in Adv. Mater. , 2002, 14, 833 to 837, after producing silver nanowires having an average diameter of 75 nm and an average length of 35 μm, and filtering and washing the silver nanowires using an ultrafiltration membrane Then, it was re-dispersed in ethanol to prepare a silver nanowire dispersion (silver nanowire content: 5% by mass).

  The obtained element was moved to a nitrogen atmosphere glove box and subjected to heat treatment at 140 ° C. for 30 minutes on a hot plate. Furthermore, it sealed using the PEN film with a barrier, and UV curable resin, and obtained the organic photoelectric conversion element SC-101 whose light-receiving part is a 10 * 100 mm size.

[Production of Organic Photoelectric Conversion Element SC-102]
In the production of SC-101, after the electron transport layer was formed, a 2.45 GHz microwave was irradiated for 15 minutes at a power of 500 W through a Ni foam. At this time, the microwave was intermittently irradiated and the surface temperature of the electron transport layer was about 250 ° C., but no deformation or bending of the substrate was observed.

  SC-102 was obtained in the same manner as in the preparation of SC-101 except for the formation of the electron transport layer.

[Production of Organic Photoelectric Conversion Element SC-103]
In the preparation of SC-102, 10 mass% of nitrate of each metal was dissolved in water / ethanol = 9/1 (mass ratio) solvent so that the electron transport layer had an In: Zn metal ratio of 1: 1. SC-103 was obtained in the same manner as SC-102 except that a solution was prepared, applied to a dry film thickness of 20 nm, and dried at 120 ° C. to form a film. At this time, the electron transport layer formed a metal oxide layer containing In and Zn.

[Production of Organic Photoelectric Conversion Element SC-104]
In the preparation of SC-102, the nitrate of each metal is 10 in water / ethanol = 9/1 (mass ratio) solvent so that the electron transport layer has an In: Ga: Zn metal ratio of 1: 1: 1. SC-104 was obtained in the same manner as SC-102 except that a solution in which the mass% was dissolved was prepared, coated and dried to form a film. At this time, a metal oxide layer containing In, Ga, and Zn was formed as the electron transport layer.

[Production of Organic Photoelectric Conversion Element SC-105]
In the preparation of SC-102, the nitrate of each metal was used in a solvent of water / ethanol = 9/1 (mass ratio) 10 so that the electron transport layer had an In: Al: Zn metal ratio of 1: 1: 1. SC-105 was obtained in the same manner as SC-102 except that a solution in which mass% was dissolved was prepared, coated and dried to form a film. At this time, a metal oxide layer containing In, Al, and Zn was formed as the electron transport layer.

[Production of Organic Photoelectric Conversion Element SC-106]
A 150-nm thick indium tin oxide (ITO) transparent conductive film deposited on a PEN film substrate with a barrier layer (sheet resistance 13Ω / □) is patterned to a width of 1 cm using ordinary photolithography and hydrochloric acid etching. Thus, a flexible transparent electrode was formed. 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 with nitrogen, and finally with ultraviolet ozone cleaning.

  Next, a solution in which the precursor of Exemplary Compound 1 ([Chemical Formula 1]) was dissolved in 1% by mass in toluene was applied, and a hole transport layer was formed to a dry film thickness of 40 nm. After forming the hole transport layer, a 2.45 GHz microwave was irradiated for 15 minutes at a power of 500 W through a Ni foam. At this time, the microwave was intermittently irradiated, and the surface temperature of the hole transport layer was about 250 ° C., but no deformation or bending of the substrate was observed.

  Next, P3HT (manufactured by Prectronics: regioregular poly-3-hexylthiophene) (Mn = 52000, polymer p-type semiconductor material) and PCBM (frontier carbon: 6,6-phenyl-C61-butyric acid) were added to chlorobenzene. Methyl ester) (Mw = 911, low molecular weight n-type semiconductor material) prepared in a 1: 1 mixture so as to be 3.0% by mass, applied to a film thickness of 100 nm while filtering through a filter. And dried at room temperature in a nitrogen atmosphere to form a bulk heterojunction photoelectric conversion layer (BHJ layer).

  Next, a solution in which Ti-isopropoxide was dissolved in dehydrated ethanol to a concentration of 0.05 mol / l was prepared, applied to a film thickness of 20 nm, and allowed to stand at room temperature to dry. Subsequently, the extraction electrode portion was wiped and patterned, transported to a nitrogen chamber in which the amount of water vapor was controlled, and allowed to stand to form an electron transport layer.

Next, a silver nanowire layer was formed by applying silver nanowires prepared as a dispersion so as to have a basis weight of 80 mg / m ² and drying. Furthermore, after apply | coating Baytron PH510 (made by Stark Vitec) which is a conductive polymer on silver nanowire, the electrode layer was formed by making it dry at room temperature.

  Silver nanowires are described in Adv. Mater. , 2002, 14, 833 to 837, after producing silver nanowires having an average diameter of 75 nm and an average length of 35 μm, and filtering and washing the silver nanowires using an ultrafiltration membrane Then, it was re-dispersed in ethanol to prepare a silver nanowire dispersion (silver nanowire content: 5% by mass).

  The obtained element was moved to a nitrogen atmosphere glove box and subjected to heat treatment at 140 ° C. for 30 minutes on a hot plate. Furthermore, it sealed using the PEN film with a barrier, and UV curable resin, and obtained the organic photoelectric conversion element SC-106 whose light-receiving part is a 10 * 100 mm size.

[Production of Organic Photoelectric Conversion Element SC-107]
In the production of SC-104, SnO ₂ sol was coated on the PEN substrate as a substance having electromagnetic wave absorption ability, and further, silver nanowires prepared as a dispersion were applied so as to have a basis weight of 40 mg / m ² and dried. By doing so, a silver nanowire layer was formed. Furthermore, after apply | coating Baytron PH510 (made by Starck Vitec) which is a conductive polymer on silver nanowire, the electrode layer was formed by making it dry at room temperature (sheet resistance 15 ohms / square).

  Silver nanowires are described in Adv. Mater. , 2002, 14, 833 to 837, after producing silver nanowires having an average diameter of 75 nm and an average length of 35 μm, and filtering and washing the silver nanowires using an ultrafiltration membrane Then, it was re-dispersed in ethanol to prepare a silver nanowire dispersion (silver nanowire content: 5% by mass).

  SC-107 was obtained in the same manner as SC-104 except that an electron transport layer was formed on the electrode layer prepared above.

[Production of Organic Photoelectric Conversion Element SC-108]
In the production of SC-104, the nitrate of each metal was 10 in water / ethanol = 9/1 (mass ratio) solvent so that the electron transport layer had an In: Ga: Zn metal ratio of 1: 1: 1. A solution in which mass% was dissolved was prepared, and further, 5 mass% of ITO fine particles (Ciano Kasei NanoTech) as a substance having electromagnetic wave absorbing ability were mixed and uniformly dispersed to prepare a semiconductor precursor solution.

  SC-108 was obtained in the same manner as SC-104 except that the dispersion solution was applied and dried to form a film. At this time, a metal oxide layer containing In, Ga, and Zn was formed as the electron transport layer.

<Energy conversion characteristics evaluation>
About the organic photoelectric conversion element produced by the above method, an AM1.5G filter using a solar simulator, light with an intensity of 100 mW / cm ² is irradiated, the mask is overlaid on the light receiving portion, the IV characteristic is evaluated, and the characteristic value The energy conversion efficiency η (%) is obtained from the short-circuit current density Jsc (mA / cm ² ), the open-circuit voltage Voc (V), and the fill factor ff using Equation 1, and the energy conversion efficiency of SC-101 is 100. The relative values are shown in Table 1.

(Formula 1): Jsc (mA / cm ² ) × Voc (V) × ff = η (%)
<Element life evaluation>
The device prepared above was allowed to stand under high-temperature and high-humidity conditions of 60 ° C. and 90% RH for 500 hours. The energy conversion efficiency of this device was determined in the same manner as described above, the retention rate was determined according to Equation 2, and Table 1 It was shown to.

(Formula 2) Retention rate (%) = conversion efficiency after leaving at high temperature and high humidity / conversion efficiency before leaving x100
The various evaluation results are summarized in Table 1.

  As is apparent from Table 1, it was shown that by implementing the present invention, an organic photoelectric conversion element having improved energy conversion efficiency and durability under high temperature and high humidity conditions and a method for producing the same can be provided.

  Specifically, after applying Ti isopropoxide with SC-101, the element having a titanium oxide layer formed by accelerating the reaction with moisture in the air following natural drying, SC-102 and later As an example, the device is irradiated with microwaves, the microwave absorption areas / substances shown in the table generate heat by absorbing the microwaves, and the charge transport layer precursor material receives the heat to form the hole transport layer or By the structure which converts into the composition of an electron carrying layer, it became the result which showed high energy conversion efficiency and thermal-humidity durability.

  Furthermore, in SC-103 to SC-105, when a metal oxide layer composed of three or more metal elements such as In, Ga (Al), and Zn is used as an electron transport layer, higher energy conversion efficiency and durability can be obtained. You can see that This is presumably because a thin film having excellent electron transport properties can be formed at a lower temperature by using three or more elements.

  SC-106 is an example in which a material composed of an organic material is used and heat-converted in the same manner to form a composition of a hole transport layer, and it was shown that the same effect was obtained even in an organic material thin film. .

  In SC-107 to 108, a microwave absorption area / substance is newly provided, and heat conversion is caused by heat generated from the area, and in particular, the microwave absorption substance is mixed in a layer including the heat conversion material. It became clear that it showed high energy conversion efficiency.

DESCRIPTION OF SYMBOLS 10 Organic photoelectric conversion element 11 Board | substrate 12 1st electrode 13 1st charge transport layer 14 Photoelectric conversion layer 15 2nd charge transport layer 16 2nd electrode

Claims (15)

  An organic photoelectric conversion element in which at least a photoelectric conversion layer and a hole transport layer or an electron transport layer are laminated between a first electrode and a second electrode, wherein the hole transport layer or the electron transport layer is An organic photoelectric conversion element comprising a heat conversion material, wherein the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat.   At least a part of the hole transport layer or the electron transport layer includes (i) an area containing a heat conversion material or a heat conversion material, and (ii) adjacent to or close to the area containing the heat conversion material or the heat conversion material. When an electromagnetic wave absorbing substance or an area containing an electromagnetic wave absorbing substance is disposed and the electromagnetic wave is irradiated, the heat conversion material is corrected by heat generated by the electromagnetic wave absorbing substance. 2. The organic photoelectric conversion element according to claim 1, wherein the organic photoelectric conversion element is converted into a composition of a hole transport layer or an electron transport layer.   At least a part of the hole transport layer or the electron transport layer is provided with a heat conversion material and an area containing a substance having an electromagnetic wave absorbing ability, and when the electromagnetic wave is irradiated, the substance having the electromagnetic wave absorbing ability is generated. The organic photoelectric conversion element according to claim 1, wherein the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat to be generated.   The organic photoelectric conversion element according to claim 2 or 3, wherein the substance having electromagnetic wave absorbing ability is a conductive metal oxide.   The organic photoelectric device according to any one of claims 1 to 4, wherein the heat conversion material is an inorganic semiconductor precursor containing at least three or more kinds of metal elements, and has been converted into an inorganic semiconductor. Conversion element.   The organic photoelectric conversion element according to claim 5, wherein the inorganic semiconductor includes at least one of In, Zn, and Sn.   The organic photoelectric conversion element according to any one of claims 4 to 6, wherein the inorganic semiconductor contains Ga or Al.   The organic photoelectric conversion element according to any one of claims 5 to 7, wherein the inorganic semiconductor is a metal oxide semiconductor.   The organic photoelectric conversion element according to any one of claims 1 to 4, wherein the heat conversion material is an organic semiconductor precursor and is converted into an organic semiconductor.   It is a manufacturing method of the organic photoelectric conversion element which manufactures the organic photoelectric conversion element as described in any one of Claims 1-9, Comprising: At least one part of a positive hole transport layer or an electron transport layer, (i) A heat conversion material or an area containing a heat conversion material; and (ii) an area containing an electromagnetic wave absorbing substance or a substance having an electromagnetic wave absorbing ability adjacent to or close to the heat conversion material or the area containing the heat conversion material. An organic photoelectric conversion characterized in that the heat conversion material is converted into a composition of a hole transport layer or an electron transport layer by heat generated by a substance having an electromagnetic wave absorption ability, disposed and irradiated with an electromagnetic wave Device manufacturing method.   It is a manufacturing method of the organic photoelectric conversion element which manufactures the organic photoelectric conversion element as described in any one of Claims 1-9, Comprising: At least one part of a positive hole transport layer or an electron transport layer is a heat conversion material. And an area containing a substance having an electromagnetic wave absorption ability, irradiating an electromagnetic wave, and heat generated from the substance having the electromagnetic wave absorption ability, the heat conversion material is made into a composition of a hole transport layer or an electron transport layer. A method for producing an organic photoelectric conversion element, characterized by performing conversion.   A layer containing the heat conversion material is formed by coating and forming a layer containing a heat conversion material on an electrode layer having electromagnetic wave absorption ability formed on one surface of the substrate, and irradiating the electromagnetic wave. The method for producing an organic photoelectric conversion element according to claim 10, wherein the compound is converted into a hole transport layer or an electron transport layer.   A layer containing the heat conversion material is formed by applying a layer containing a heat conversion material on the electrode layer formed on one surface of the substrate having electromagnetic wave absorption ability and irradiating the electromagnetic wave, thereby generating heat from the substrate. The method for producing an organic photoelectric conversion element according to claim 10, wherein the compound is converted into a hole transport layer or an electron transport layer.   On the electrode layer formed on one surface of the substrate, a layer containing a heat conversion material and a substance having an electromagnetic wave absorbing ability is applied and formed by irradiating the electromagnetic wave, thereby generating heat from the substance having the electromagnetic wave absorbing ability, The method for producing an organic photoelectric conversion element according to claim 11, wherein the layer containing the heat conversion material is converted into a hole transport layer or an electron transport layer.   The method for producing an organic photoelectric conversion element according to any one of claims 10 to 14, wherein the electromagnetic wave is a microwave.

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