WO2013035305A1 - Organic solar cell - Google Patents
Organic solar cell Download PDFInfo
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- WO2013035305A1 WO2013035305A1 PCT/JP2012/005595 JP2012005595W WO2013035305A1 WO 2013035305 A1 WO2013035305 A1 WO 2013035305A1 JP 2012005595 W JP2012005595 W JP 2012005595W WO 2013035305 A1 WO2013035305 A1 WO 2013035305A1
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- WO
- WIPO (PCT)
- Prior art keywords
- layer
- type semiconductor
- group
- organic solar
- solar cell
- Prior art date
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- 239000010410 layer Substances 0.000 claims abstract description 286
- 239000004065 semiconductor Substances 0.000 claims abstract description 75
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/40—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising a p-i-n structure, e.g. having a perovskite absorber between p-type and n-type charge transport layers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
- H10K85/211—Fullerenes, e.g. C60
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
- H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- Non-Patent Document 1 uses an n-type organic material having a high carrier transport capability as the photoelectric conversion layer.
- Non-Patent Document 2 describes the use of a bulk heterojunction structure.
- Patent Document 1 describes an image pickup element in which a charge barrier layer is inserted, and describes a photoelectric conversion element and an image pickup element that can reduce dark current by suppressing the outflow of carriers. Yes.
- Patent Document 1 is an invention related to an image sensor, and there is no mention of an organic thin film solar cell. Moreover, although it aims at reducing a dark current, this is a concept different from the conversion efficiency improvement of an organic thin-film solar cell. Furthermore, the total thickness of the electron barrier layer is 20 nm or more, and when there are a plurality of electron barrier layers, the thickness of the electron barrier layer adjacent to the photoelectric conversion layer is 10 nm or more. Therefore, the range is different from the effective film thickness region for the charge barrier layer of the present invention.
- organic solar cells have been improved as described above, there is a problem that energy conversion efficiency is lower than that of currently used silicon (single crystal silicon, polycrystalline silicon, amorphous silicon) devices. It hasn't arrived.
- the objective of this invention is providing the organic solar cell which has a highly efficient photoelectric conversion characteristic.
- the present inventors provided a layer that efficiently transports holes and electrons to the anode and the cathode, respectively, preventing the movement of holes and preventing the movement of electrons.
- the present inventors have found that the conversion efficiency is improved by using the element configuration, and the present invention has been completed. Specifically, as a result of analysis, the following may be related as factors of the effect of hole blocking.
- An organic solar battery including a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, wherein the active layer is one of the following (A) and (B).
- A a p-type semiconductor layer, an i-layer that is a mixed layer of a p-type semiconductor material and an n-type semiconductor material, a hole barrier layer having a thickness that prevents hole movement and does not hinder electron movement, and an n-type semiconductor Active layer (B), p-type semiconductor layer, n-type semiconductor layer (I), layered in order of layers, hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement, n-type semiconductor 1.
- the ionization potential of the compound contained in the hole barrier layer is 0.01 eV to 1... From the ionization potential of the n-type semiconductor material contained in the i layer or the ionization potential of the compound contained in the n-type semiconductor layer (I).
- the electron mobility of the compound contained in the hole blocking layer is larger than the electron mobility of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). 4.
- the organic solar cell according to any one of items 1 to 3. 5.
- the thickness of the hole blocking layer in (A) is 0.1 to 19 nm. 7).
- the hole is transported to the cathode side (recombination deactivation factor) is blocked and suppressed.
- An organic solar cell having photoelectric conversion characteristics can be provided.
- the organic solar cell (organic thin film solar cell) of the present invention includes a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, and the active layer is any one of (A) and (B) below. It is.
- the cell structure of the organic solar battery of the present invention is not particularly limited as long as it has the above-described configuration, and specifically includes a structure having the following configuration on a substrate.
- a buffer layer between an electrode and an organic layer may be provided as needed.
- a structure having the following configuration can be given. (11) 1st electrode / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode (12) 1st electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / Second electrode (13) first electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode
- a well-known electroconductive material can be used.
- a metal such as tin-doped indium oxide (ITO) or gold (Au)
- an electrode (cathode) connected to the n layer silver (Ag)
- Metals such as aluminum (Al), indium (In), calcium (Ca), platinum (Pt) lithium (Li)
- binary metal systems such as Mg: Ag, Mg: In, and Al: Li are used.
- a work function smaller than that of the anode is used.
- an electrode exemplified material connected to the p layer can be used.
- the material used for the p-layer is not particularly limited, but a compound having a function as a hole acceptor is preferable.
- a compound having a function as a hole acceptor is preferable.
- organic compounds N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD), 4, Amine compounds typified by 4 ′, 4 ′′ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA), phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl phthalocyanine (TiOPc) ), Phthalocyanines such as octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetrapheny
- R 0 is hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted carbon atoms having 2 to 30 carbon atoms.
- the substituted or unsubstituted alkyl having 1 to 20 carbon atoms of R 0 preferably has 1 to 8 carbon atoms in the alkyl moiety, and the alkyl moiety may be linear, branched or cyclic, for example Methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, trifluoromethyl group, trichloromethyl group, benzyl group, ⁇ , ⁇ -dimethylbenzy
- Examples of the substituent of the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an aryl group such as a phenyl group, and the aryl group includes a methyl group, an ethyl group, a propyl group and the like. And may be further substituted with an alkyl group having 1 to 5 carbon atoms.
- substituent for the aryl group examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, a methoxy group, and an ethoxy group.
- a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
- an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, a methoxy group, and an ethoxy group.
- an alkoxy group having 1 to 5 carbon atoms such as a propoxy group, an aryl group such as a cyano group and a phenyl group, an aryl group such as a phenyl group, a heterocyclic ring such as carbazole, an arylamino group such as a diphenylamino group, and the like.
- Examples of the substituted or unsubstituted aryl having 6 to 30 ring carbon atoms of Rg 3 and Rg 4 include divalent residues corresponding to the above substituted or unsubstituted aryl having 6 to 30 ring carbon atoms of R 0. Can be mentioned.
- the substituted or unsubstituted alkenyl having 2 to 30 carbon atoms of R 0 preferably has 2 to 8 carbon atoms in the alkenyl moiety and may be linear, branched or cyclic, such as a vinyl group, Propenyl, butenyl, oleyl, eicosapentaenyl, docosahexaenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl Etc.
- an alkenyl group having 2 to 20 carbon atoms is preferable, and a vinyl group, a styryl group, and a 2,2-diphenylvinyl group are more preferable from the viewpoint of availability of raw materials.
- substituent for the alkenyl group examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group such as a phenyl group, a carbon group of 1 to 5 such as a methyl group, an ethyl group and a propyl group.
- halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom
- an aryl group such as a phenyl group
- a carbon group of 1 to 5 such as a methyl group, an ethyl group and a propyl group.
- alkyl group examples include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group such as a phenyl group, a carbon group of 1 to 5
- Examples of the substituent of the 5-membered or 6-membered heterocyclic ring having at least one nitrogen atom of Rg 1 and Rg 2 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a phenyl group, and the like. An aryl group is mentioned.
- adjacent ones may combine to form a ring, but when the substituent of Rg 1 or Rg 2 that is pyrrole forms a ring and becomes isoindole Absent.
- R 0 may be bonded to Rg 1 or Rg 2 , the substituent of Rg 1 may be bonded to Rg 3, and the substituent of Rg 2 may be bonded to Rg 4 .
- the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (deuterium), and tritium (tritium).
- the compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (B).
- R 1 to R 12 are each hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted ring forming carbon atoms having 6 to 6 carbon atoms; 30 aryl, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted arylamino having 6 to 30 carbon atoms, halogen, or substituted or unsubstituted heterocyclic ring having 5 to 40 carbon atoms
- Adjacent groups of R 1 to R 12 may be bonded to each other to form a ring. However, the case where R 1 and R 2 and R 11 and R 12 are bonded to form isoindole is not included.
- At least one of R 1 , R 2 , R 11 and R 12 is preferably aryl having 6 to 30 ring carbon atoms, and more preferably a phenyl group.
- at least one of R 4 , R 5 , R 8 and R 9 is preferably an arylamino group having 6 to 40 ring carbon atoms, and more preferably a diphenylamino group.
- R 3 and R 4 , or R 4 and R 5 may be linked to form a ring condensed with the benzene ring to which they are bonded (for example, a benzene ring).
- R 8 and R 9 , or R 9 And R 10 may be linked to form a ring (benzene ring) that is condensed with a benzene ring to which these are bonded.
- the compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (C).
- R 0 is the same as the above formula (A)
- R 13 to R 16 are each hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, Substituted or unsubstituted arylamino having 6 to 30 ring carbon atoms, halogen, or substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and adjacent groups among R 13 to R 16 are bonded to each other.
- n-type Semiconductor Layer The material used for the n-layer is not particularly limited, but a compound having a function as an electron acceptor is preferable.
- organic compounds include fullerenes such as C 60 and C 70 and derivatives thereof, carbon nanotubes, perylene derivatives, polycyclic quinones, quinacridones, and CN-poly (phenylene -Vinylene), MEH-CN-PPV, -CN group or CF 3 group-containing polymers, their -CF 3 substituted polymers, poly (fluorene) derivatives, and the like.
- a material having high electron mobility is preferable.
- a material having a small electron affinity is preferable.
- a high open-circuit voltage can be realized by combining materials having a low electron affinity as the n layer.
- the i layer is a layer in which the p-type semiconductor material and the n-type semiconductor material are mixed.
- the i-type p-type semiconductor material and the p-layer material may be the same or different, and the i-type n-type semiconductor material and the n-layer material may be the same or different.
- the ratio of the p-type semiconductor material and the n-type semiconductor material in the i layer is, for example, 10: 1 to 1:10 (volume ratio).
- the n-type semiconductor material used for the i layer is preferably C70 or a derivative thereof.
- the hole blocking layer (hole blocking layer (a)) of the active layer (A) preferably contains a compound having a larger Ip (ionization potential) than the n-type semiconductor material used for the i layer. , The holes generated in the i layer are prevented from moving to the cathode side.
- Ip forms a thin film of a target compound on an ITO glass substrate by vacuum deposition, and uses a thin film on the ITO glass substrate with a photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd .: AC-3) in the atmosphere. Can be measured. Specifically, it can be measured by irradiating the material with light and measuring the amount of electrons generated by charge separation at that time. The emitted photoelectrons are plotted by the 1/2 power with respect to the energy of the irradiation light, and the threshold value of the photoelectron emission energy is Ip.
- the compound of the hole blocking layer (a) preferably has a higher electron mobility than the n-type semiconductor material contained in the i layer.
- the electron mobility of the compound of the hole blocking layer (a) is preferably 1 ⁇ 10 ⁇ 5 cm 2 / Vs or more, more preferably 1 ⁇ 10 ⁇ 4 cm 2 / Vs or more.
- C60 As the compound of the hole blocking layer (b), C60 or a derivative thereof is preferable.
- the thickness of the hole barrier layer (b) is a thickness that prevents the movement of holes and does not prevent the movement of electrons.
- the term “thickness that prevents the movement of holes and does not hinder the movement of electrons” herein refers to a thin film that prevents the movement of holes generated at the interface between the p layer and the n layer (I) to the cathode side. This is a thickness that is not too thick, and is not too thick so as not to prevent electrons generated at the interface between the p layer and the n layer (I) from moving to the cathode side.
- Buffer layer In general, organic thin film solar cells often have a thin total film thickness, and therefore, the upper electrode and the lower electrode are short-circuited, and the yield of cell fabrication often decreases. In such a case, it is preferable to prevent this by laminating a buffer layer.
- each layer other than the hole barrier layer and the n layer (I) is not particularly limited, but is set to an appropriate film thickness. Since it is generally known that the exciton diffusion length of an organic thin film is short, if the film thickness is too thick, the exciton is deactivated before reaching the heterointerface, resulting in low photoelectric conversion efficiency. If the film thickness is too thin, pinholes and the like are generated, so that sufficient diode characteristics cannot be obtained, resulting in a decrease in conversion efficiency.
- the normal film thickness is suitably in the range of 1 nm to 10 ⁇ m, but more preferably in the range of 5 nm to 0.2 ⁇ m.
- an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film.
- Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
- the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
- C 70 is deposited at 1 ⁇ / s by resistance heating deposition to form an n layer (n layer (I)) 30 having a thickness of 10 nm, and C 60 is deposited at 1 ⁇ ⁇ ⁇ by resistance heating deposition.
- a hole blocking layer 40 having a thickness of 3 nm is formed, and C 70 is further formed thereon by resistance heating vapor deposition at 1 ⁇ / s to form an n layer (n layer (II )) 50 was formed.
- bathocuproine (BCP) was formed into a 10 nm buffer layer 60 by resistance heating vapor deposition at 1 ⁇ / s.
- metal Al was continuously deposited as a counter electrode 70 with a film thickness of 80 nm to produce the organic thin film solar cell 1.
- the element area was 1.0 cm 2 .
- Example 7 An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 10 nm. The results are shown in Table 2.
- Comparative Example 4 An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the hole blocking layer was not provided. The results are shown in Table 2.
- Comparative Example 5 An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 20 nm. The results are shown in Table 2. In Comparative Example 5, since the hole barrier layer was too thick, the movement of electrons to the cathode was hindered and the conversion efficiency was lowered.
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Abstract
This organic solar cell includes, in this order, a first electrode, an active layer, including a plurality of organic layers, and a second electrode, said active layer being (A) or (B) stated as follows: (A) an active layer formed by laminating, in this order, a p-type semiconductor layer, an i layer that is a mixed layer composed of a p-type semiconductor material and an n-type semiconductor material, a hole barrier layer having a thickness which inhibits hole transfer but does not block electron transfer, and an n-type semiconductor layer; and (B) an active layer formed by laminating, in this order, a p-type semiconductor layer, an n-type semiconductor layer (I), a hole barrier layer having a thickness that inhibits hole transfer but does not block electron transfer, and an n-type semiconductor layer (II).
Description
本発明は、有機太陽電池に関する。
The present invention relates to an organic solar cell.
有機薄膜太陽電池は、光信号を電気信号に変換するフォトダイオードや撮像素子、光エネルギーを電気エネルギーに変換する太陽電池に代表されるように、光入力に対して電気出力を示す装置である。
Organic thin-film solar cells are devices that exhibit electrical output with respect to light input, such as photodiodes and imaging devices that convert optical signals into electrical signals, and solar cells that convert optical energy into electrical energy.
太陽電池は、化石燃料の枯渇問題や地球温暖化問題を背景に、クリーンエネルギー源として近年大変注目され、研究開発が盛んに行なわれている。
従来、実用化されたのは、単結晶Si、多結晶Si及びアモルファスSi等に代表されるシリコン系太陽電池であるが、高価であることや、原料Siの不足問題等が表面化するにつれて、次世代太陽電池への要求が高まりつつある。
このような背景の中で、有機太陽電池は、安価で毒性が低く、原材料不足の懸念もないことから、シリコン系太陽電池に次ぐ次世代の太陽電池として大変注目を集めている。 In recent years, solar cells have attracted a great deal of attention as a clean energy source against the background of fossil fuel depletion problems and global warming problems, and research and development have been actively conducted.
Conventionally, silicon solar cells represented by single crystal Si, polycrystal Si, amorphous Si, and the like have been put into practical use. The demand for next generation solar cells is increasing.
Against this background, organic solar cells are attracting much attention as next-generation solar cells next to silicon-based solar cells because they are inexpensive, have low toxicity, and do not have a fear of shortage of raw materials.
従来、実用化されたのは、単結晶Si、多結晶Si及びアモルファスSi等に代表されるシリコン系太陽電池であるが、高価であることや、原料Siの不足問題等が表面化するにつれて、次世代太陽電池への要求が高まりつつある。
このような背景の中で、有機太陽電池は、安価で毒性が低く、原材料不足の懸念もないことから、シリコン系太陽電池に次ぐ次世代の太陽電池として大変注目を集めている。 In recent years, solar cells have attracted a great deal of attention as a clean energy source against the background of fossil fuel depletion problems and global warming problems, and research and development have been actively conducted.
Conventionally, silicon solar cells represented by single crystal Si, polycrystal Si, amorphous Si, and the like have been put into practical use. The demand for next generation solar cells is increasing.
Against this background, organic solar cells are attracting much attention as next-generation solar cells next to silicon-based solar cells because they are inexpensive, have low toxicity, and do not have a fear of shortage of raw materials.
有機薄膜太陽電池は、メロシアニン色素等を用いた単層膜で研究が進められてきたが、p層/n層の多層膜にすることで変換効率が向上することが見出され、それ以降多層膜が主流になっている。その後、p層とn層の間にi層(p材料とn材料の混合層)を挿入することにより、変換効率が向上することが見出された。
Organic thin-film solar cells have been studied with single-layer films using merocyanine dyes, etc., but it has been found that conversion efficiency can be improved by using p-layer / n-layer multilayer films. The film has become mainstream. Subsequently, it was found that the conversion efficiency is improved by inserting an i layer (a mixed layer of p material and n material) between the p layer and the n layer.
一方、高分子化合物を用いた有機薄膜太陽電池では、p材料(p層に用いられる材料)として導電性高分子を用い、n(n層に用いられる材料)材料としてC60誘導体を用いてそれらを混合し、熱処理することによりp層とn層のミクロ層分離を誘起してヘテロ界面を増やし、変換効率を向上させるという、所謂バルクヘテロ構造の研究が主に行なわれてきた。
On the other hand, in an organic thin film solar cell using a polymer compound, a conductive polymer is used as a p material (a material used for a p layer), and a C 60 derivative is used as an n (a material used for an n layer). The so-called bulk heterostructure has been mainly studied by inducing micro-layer separation of the p-layer and n-layer by mixing and heat-treating to increase the heterointerface and improve the conversion efficiency.
このように、有機薄膜太陽電池ではセル構成及びモルフォロジーの最適化により変換効率が向上されてきた。しかしながら、シリコン等に代表される無機太陽電池に比べると光電変換効率が低いため、実用に供することは困難であり、光電変換効率の高効率化が最大の課題となっている。
Thus, in the organic thin film solar cell, conversion efficiency has been improved by optimizing the cell configuration and morphology. However, since the photoelectric conversion efficiency is lower than that of an inorganic solar cell typified by silicon or the like, it is difficult to put it into practical use, and increasing the photoelectric conversion efficiency is the biggest issue.
高い光電変換効率を得るために、非特許文献1では光電変換層としてキャリア輸送能の高いn型有機材料を用いている。また、非特許文献2にはバルクへテロ接合構造を用いることが記載されている。
In order to obtain high photoelectric conversion efficiency, Non-Patent Document 1 uses an n-type organic material having a high carrier transport capability as the photoelectric conversion layer. Non-Patent Document 2 describes the use of a bulk heterojunction structure.
他には、例えば特許文献1において、電荷障壁層を挿入した撮像素子が記載され、キャリアの湧き出しを抑制することで、暗電流を低下させることができる光電変換素子及び撮像素子が記載されている。
In addition, for example, Patent Document 1 describes an image pickup element in which a charge barrier layer is inserted, and describes a photoelectric conversion element and an image pickup element that can reduce dark current by suppressing the outflow of carriers. Yes.
特許文献1は撮像素子に関する発明であり、有機薄膜太陽電池に関する言及はない。また、暗電流を低下することを目的としているが、これは、有機薄膜太陽電池の変換効率向上とは異なる概念である。
さらに、電子障壁層の総厚は20nm以上であり、電子障壁層が複数層の場合は、電子障壁層のうち光電変換層に隣接する層の厚さが10nm以上であることを特徴としている。従って、本発明の電荷障壁層に効果的な膜厚領域とは範囲が異なる。 Patent Document 1 is an invention related to an image sensor, and there is no mention of an organic thin film solar cell. Moreover, although it aims at reducing a dark current, this is a concept different from the conversion efficiency improvement of an organic thin-film solar cell.
Furthermore, the total thickness of the electron barrier layer is 20 nm or more, and when there are a plurality of electron barrier layers, the thickness of the electron barrier layer adjacent to the photoelectric conversion layer is 10 nm or more. Therefore, the range is different from the effective film thickness region for the charge barrier layer of the present invention.
さらに、電子障壁層の総厚は20nm以上であり、電子障壁層が複数層の場合は、電子障壁層のうち光電変換層に隣接する層の厚さが10nm以上であることを特徴としている。従って、本発明の電荷障壁層に効果的な膜厚領域とは範囲が異なる。 Patent Document 1 is an invention related to an image sensor, and there is no mention of an organic thin film solar cell. Moreover, although it aims at reducing a dark current, this is a concept different from the conversion efficiency improvement of an organic thin-film solar cell.
Furthermore, the total thickness of the electron barrier layer is 20 nm or more, and when there are a plurality of electron barrier layers, the thickness of the electron barrier layer adjacent to the photoelectric conversion layer is 10 nm or more. Therefore, the range is different from the effective film thickness region for the charge barrier layer of the present invention.
有機太陽電池は上記のように改良されてきたが、現在利用されているシリコン系(単結晶シリコン、多結晶シリコン、アモルファスシリコン)のデバイスに比べ、エネルギー変換効率が低いという問題点があり、実用化には至っていない。
本発明の目的は、高効率の光電変換特性を有する有機太陽電池を提供することである。 Although organic solar cells have been improved as described above, there is a problem that energy conversion efficiency is lower than that of currently used silicon (single crystal silicon, polycrystalline silicon, amorphous silicon) devices. It hasn't arrived.
The objective of this invention is providing the organic solar cell which has a highly efficient photoelectric conversion characteristic.
本発明の目的は、高効率の光電変換特性を有する有機太陽電池を提供することである。 Although organic solar cells have been improved as described above, there is a problem that energy conversion efficiency is lower than that of currently used silicon (single crystal silicon, polycrystalline silicon, amorphous silicon) devices. It hasn't arrived.
The objective of this invention is providing the organic solar cell which has a highly efficient photoelectric conversion characteristic.
本発明者らは、電荷ブロックの効果について鋭意検討した結果、正孔の移動を阻止し、電子の移動を妨げず、正孔と電子をそれぞれ陽極と陰極に効率的に輸送する層を設けた素子構成とすることで、変換効率の向上がもたらされることを発見し、本発明を完成させた。
具体的には、分析の結果、正孔ブロックの効果の要因として下記が関係していることが考えられる。 As a result of intensive studies on the effect of the charge blocking, the present inventors provided a layer that efficiently transports holes and electrons to the anode and the cathode, respectively, preventing the movement of holes and preventing the movement of electrons. The present inventors have found that the conversion efficiency is improved by using the element configuration, and the present invention has been completed.
Specifically, as a result of analysis, the following may be related as factors of the effect of hole blocking.
具体的には、分析の結果、正孔ブロックの効果の要因として下記が関係していることが考えられる。 As a result of intensive studies on the effect of the charge blocking, the present inventors provided a layer that efficiently transports holes and electrons to the anode and the cathode, respectively, preventing the movement of holes and preventing the movement of electrons. The present inventors have found that the conversion efficiency is improved by using the element configuration, and the present invention has been completed.
Specifically, as a result of analysis, the following may be related as factors of the effect of hole blocking.
(i)有機薄膜光電変換層の半導体材料のIp(イオン化ポテンシャル)と、正孔障壁層のIpとの関係
(ii)正孔障壁層の厚さ
(iii)有機薄膜光電変換層の半導体材料と正孔障壁層の電子輸送性(電子移動度)との関係 (I) Relationship between Ip (ionization potential) of semiconductor material of organic thin film photoelectric conversion layer and Ip of hole barrier layer (ii) Thickness of hole barrier layer (iii) Semiconductor material of organic thin film photoelectric conversion layer Relationship with electron transport property (electron mobility) of hole barrier layer
(ii)正孔障壁層の厚さ
(iii)有機薄膜光電変換層の半導体材料と正孔障壁層の電子輸送性(電子移動度)との関係 (I) Relationship between Ip (ionization potential) of semiconductor material of organic thin film photoelectric conversion layer and Ip of hole barrier layer (ii) Thickness of hole barrier layer (iii) Semiconductor material of organic thin film photoelectric conversion layer Relationship with electron transport property (electron mobility) of hole barrier layer
本発明によれば、以下の有機太陽電池が提供される。
1.第1電極、複数の有機層を含む活性層、第2電極をこの順に含む有機太陽電池であって、前記活性層が下記(A)及び(B)のいずれか一方である有機太陽電池。
(A)p型半導体層、p型半導体材料とn型半導体材料の混合層であるi層、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層の順に積層されてなる活性層
(B)p型半導体層、n型半導体層(I)、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(II)の順に積層されてなる活性層
2.前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより大きい1に記載の有機太陽電池。
3.前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより0.01eV~1.0eV大きい1又は2に記載の有機太陽電池。
4.前記正孔障壁層に含まれる化合物の電子移動度が、前記i層に含まれるn型半導体材料の電子移動度又は前記n型半導体層(I)に含まれる化合物の電子移動度よりも大きい1~3のいずれかに記載の有機太陽電池。
5.前記正孔障壁層に含まれる化合物の電子移動度が1×10-5cm2/Vs以上である1~4のいずれかに記載の有機太陽電池。
6.前記(A)における正孔障壁層の厚さが0.1~19nmである1~5のいずれかに記載の有機太陽電池。
7.前記(B)における正孔障壁層の厚さが0.1~9nmである1~5のいずれかに記載の有機太陽電池。
8.前記(B)におけるn型半導体層(I)の厚さが0.1~40nmである1~5、7のいずれかに記載の有機太陽電池。
9.前記正孔障壁層に含まれる化合物がフラーレン又はフラーレン誘導体である1~8のいずれかに記載の有機太陽電池。
10.前記正孔障壁層に含まれる化合物がC60又はその誘導体である9に記載の有機太陽電池。
11.前記i層に含まれるn型半導体材料又はn型半導体層(I)に含まれる化合物がC70又はその誘導体である1~10のいずれかに記載の有機太陽電池。 According to the present invention, the following organic solar cell is provided.
1. An organic solar battery including a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, wherein the active layer is one of the following (A) and (B).
(A) a p-type semiconductor layer, an i-layer that is a mixed layer of a p-type semiconductor material and an n-type semiconductor material, a hole barrier layer having a thickness that prevents hole movement and does not hinder electron movement, and an n-type semiconductor Active layer (B), p-type semiconductor layer, n-type semiconductor layer (I), layered in order of layers, hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement, n-type semiconductor 1. Active layer formed by laminating layers (II) in this order. 2. The organic material according to 1, wherein the ionization potential of the compound contained in the hole barrier layer is greater than the ionization potential of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). Solar cell.
3. The ionization potential of the compound contained in the hole barrier layer is 0.01 eV to 1... From the ionization potential of the n-type semiconductor material contained in the i layer or the ionization potential of the compound contained in the n-type semiconductor layer (I). The organic solar cell according to 1 or 2, which is 0 eV larger.
4). The electron mobility of the compound contained in the hole blocking layer is larger than the electron mobility of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). 4. The organic solar cell according to any one of items 1 to 3.
5. 5. The organic solar battery according to any one of 1 to 4, wherein the compound contained in the hole blocking layer has an electron mobility of 1 × 10 −5 cm 2 / Vs or more.
6). 6. The organic solar battery according to any one of 1 to 5, wherein the thickness of the hole blocking layer in (A) is 0.1 to 19 nm.
7). 6. The organic solar battery according to any one of 1 to 5, wherein the thickness of the hole blocking layer in (B) is 0.1 to 9 nm.
8). 8. The organic solar battery according to any one of 1 to 5 and 7, wherein the thickness of the n-type semiconductor layer (I) in (B) is 0.1 to 40 nm.
9. 9. The organic solar battery according to any one of 1 to 8, wherein the compound contained in the hole blocking layer is a fullerene or a fullerene derivative.
10. 10. The organic solar cell according to 9, wherein the compound contained in the hole blocking layer is C60 or a derivative thereof.
11. 11. The organic solar cell according to any one of 1 to 10, wherein the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I) is C70 or a derivative thereof.
1.第1電極、複数の有機層を含む活性層、第2電極をこの順に含む有機太陽電池であって、前記活性層が下記(A)及び(B)のいずれか一方である有機太陽電池。
(A)p型半導体層、p型半導体材料とn型半導体材料の混合層であるi層、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層の順に積層されてなる活性層
(B)p型半導体層、n型半導体層(I)、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(II)の順に積層されてなる活性層
2.前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより大きい1に記載の有機太陽電池。
3.前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより0.01eV~1.0eV大きい1又は2に記載の有機太陽電池。
4.前記正孔障壁層に含まれる化合物の電子移動度が、前記i層に含まれるn型半導体材料の電子移動度又は前記n型半導体層(I)に含まれる化合物の電子移動度よりも大きい1~3のいずれかに記載の有機太陽電池。
5.前記正孔障壁層に含まれる化合物の電子移動度が1×10-5cm2/Vs以上である1~4のいずれかに記載の有機太陽電池。
6.前記(A)における正孔障壁層の厚さが0.1~19nmである1~5のいずれかに記載の有機太陽電池。
7.前記(B)における正孔障壁層の厚さが0.1~9nmである1~5のいずれかに記載の有機太陽電池。
8.前記(B)におけるn型半導体層(I)の厚さが0.1~40nmである1~5、7のいずれかに記載の有機太陽電池。
9.前記正孔障壁層に含まれる化合物がフラーレン又はフラーレン誘導体である1~8のいずれかに記載の有機太陽電池。
10.前記正孔障壁層に含まれる化合物がC60又はその誘導体である9に記載の有機太陽電池。
11.前記i層に含まれるn型半導体材料又はn型半導体層(I)に含まれる化合物がC70又はその誘導体である1~10のいずれかに記載の有機太陽電池。 According to the present invention, the following organic solar cell is provided.
1. An organic solar battery including a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, wherein the active layer is one of the following (A) and (B).
(A) a p-type semiconductor layer, an i-layer that is a mixed layer of a p-type semiconductor material and an n-type semiconductor material, a hole barrier layer having a thickness that prevents hole movement and does not hinder electron movement, and an n-type semiconductor Active layer (B), p-type semiconductor layer, n-type semiconductor layer (I), layered in order of layers, hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement, n-type semiconductor 1. Active layer formed by laminating layers (II) in this order. 2. The organic material according to 1, wherein the ionization potential of the compound contained in the hole barrier layer is greater than the ionization potential of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). Solar cell.
3. The ionization potential of the compound contained in the hole barrier layer is 0.01 eV to 1... From the ionization potential of the n-type semiconductor material contained in the i layer or the ionization potential of the compound contained in the n-type semiconductor layer (I). The organic solar cell according to 1 or 2, which is 0 eV larger.
4). The electron mobility of the compound contained in the hole blocking layer is larger than the electron mobility of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). 4. The organic solar cell according to any one of items 1 to 3.
5. 5. The organic solar battery according to any one of 1 to 4, wherein the compound contained in the hole blocking layer has an electron mobility of 1 × 10 −5 cm 2 / Vs or more.
6). 6. The organic solar battery according to any one of 1 to 5, wherein the thickness of the hole blocking layer in (A) is 0.1 to 19 nm.
7). 6. The organic solar battery according to any one of 1 to 5, wherein the thickness of the hole blocking layer in (B) is 0.1 to 9 nm.
8). 8. The organic solar battery according to any one of 1 to 5 and 7, wherein the thickness of the n-type semiconductor layer (I) in (B) is 0.1 to 40 nm.
9. 9. The organic solar battery according to any one of 1 to 8, wherein the compound contained in the hole blocking layer is a fullerene or a fullerene derivative.
10. 10. The organic solar cell according to 9, wherein the compound contained in the hole blocking layer is C60 or a derivative thereof.
11. 11. The organic solar cell according to any one of 1 to 10, wherein the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I) is C70 or a derivative thereof.
本発明によれば、光照射時に有機薄膜光電変換層で発生した電荷のうち、正孔が陰極側へ輸送されること(再結合失活要因)をブロックし、抑制することで、高効率の光電変換特性を有する有機太陽電池が提供できる。
According to the present invention, among the charges generated in the organic thin film photoelectric conversion layer at the time of light irradiation, the hole is transported to the cathode side (recombination deactivation factor) is blocked and suppressed. An organic solar cell having photoelectric conversion characteristics can be provided.
本発明の有機太陽電池(有機薄膜太陽電池)は、第1電極、複数の有機層を含む活性層、第2電極をこの順に含み、活性層が下記(A)及び(B)のいずれか一方である。
(A)p型半導体層(p層)、p型半導体材料とn型半導体材料の混合層であるi層、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(n層)の順に積層されてなる活性層
(B)p型半導体層、n型半導体層(I)、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(II)の順に積層されてなる活性層 The organic solar cell (organic thin film solar cell) of the present invention includes a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, and the active layer is any one of (A) and (B) below. It is.
(A) p-type semiconductor layer (p-layer), i-layer that is a mixed layer of p-type semiconductor material and n-type semiconductor material, a hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement , Active layer (B) stacked in order of n-type semiconductor layer (n layer), p-type semiconductor layer, n-type semiconductor layer (I), with a thickness that prevents the movement of holes and prevents the movement of electrons An active layer formed by laminating a hole barrier layer and an n-type semiconductor layer (II) in this order
(A)p型半導体層(p層)、p型半導体材料とn型半導体材料の混合層であるi層、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(n層)の順に積層されてなる活性層
(B)p型半導体層、n型半導体層(I)、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(II)の順に積層されてなる活性層 The organic solar cell (organic thin film solar cell) of the present invention includes a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, and the active layer is any one of (A) and (B) below. It is.
(A) p-type semiconductor layer (p-layer), i-layer that is a mixed layer of p-type semiconductor material and n-type semiconductor material, a hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement , Active layer (B) stacked in order of n-type semiconductor layer (n layer), p-type semiconductor layer, n-type semiconductor layer (I), with a thickness that prevents the movement of holes and prevents the movement of electrons An active layer formed by laminating a hole barrier layer and an n-type semiconductor layer (II) in this order
本発明の有機太陽電池のセル構造は、上記の構成であれば特に限定されるものではないが、具体的には、基板上に下記の構成を有する構造が挙げられる。
(1)第1電極/p層/i層/正孔障壁層/n層/第2電極
(2)第1電極/p層/n層(I)/正孔障壁層/n層(II)/第2電極 The cell structure of the organic solar battery of the present invention is not particularly limited as long as it has the above-described configuration, and specifically includes a structure having the following configuration on a substrate.
(1) 1st electrode / p layer / i layer / hole barrier layer / n layer / second electrode (2) 1st electrode / p layer / n layer (I) / hole barrier layer / n layer (II) / Second electrode
(1)第1電極/p層/i層/正孔障壁層/n層/第2電極
(2)第1電極/p層/n層(I)/正孔障壁層/n層(II)/第2電極 The cell structure of the organic solar battery of the present invention is not particularly limited as long as it has the above-described configuration, and specifically includes a structure having the following configuration on a substrate.
(1) 1st electrode / p layer / i layer / hole barrier layer / n layer / second electrode (2) 1st electrode / p layer / n layer (I) / hole barrier layer / n layer (II) / Second electrode
また、必要に応じて電極と有機層の間にバッファー層を設けてもよい。例えば、上記構成(1)にバッファー層を設けた場合、下記構成を有する構造が挙げられる。
(11)第1電極/p層/i層/正孔障壁層/n層/バッファー層/第2電極
(12)第1電極/バッファー層/p層/i層/正孔障壁層/n層/第2電極
(13)第1電極/バッファー層/p層/i層/正孔障壁層/n層/バッファー層/第2電極 Moreover, you may provide a buffer layer between an electrode and an organic layer as needed. For example, when a buffer layer is provided in the configuration (1), a structure having the following configuration can be given.
(11) 1st electrode / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode (12) 1st electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / Second electrode (13) first electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode
(11)第1電極/p層/i層/正孔障壁層/n層/バッファー層/第2電極
(12)第1電極/バッファー層/p層/i層/正孔障壁層/n層/第2電極
(13)第1電極/バッファー層/p層/i層/正孔障壁層/n層/バッファー層/第2電極 Moreover, you may provide a buffer layer between an electrode and an organic layer as needed. For example, when a buffer layer is provided in the configuration (1), a structure having the following configuration can be given.
(11) 1st electrode / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode (12) 1st electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / Second electrode (13) first electrode / buffer layer / p layer / i layer / hole blocking layer / n layer / buffer layer / second electrode
また、上記構成(2)にバッファー層を設けた場合、下記構成を有する構造が挙げられる。
(21)第1電極/p層/n層(I)/正孔障壁層/n層(II)/バッファー層/第2電極
(22)第1電極/バッファー層/p層/n層(I)/正孔障壁層/n層(II)/第2電極
(23)第1電極/バッファー層/p層/n層(I)/正孔障壁層/n層(II)/バッファー層/第2電極 Moreover, when the buffer layer is provided in the above configuration (2), a structure having the following configuration can be given.
(21) First electrode / p layer / n layer (I) / hole barrier layer / n layer (II) / buffer layer / second electrode (22) first electrode / buffer layer / p layer / n layer (I ) / Hole barrier layer / n layer (II) / second electrode (23) first electrode / buffer layer / p layer / n layer (I) / hole barrier layer / n layer (II) / buffer layer / second 2 electrodes
(21)第1電極/p層/n層(I)/正孔障壁層/n層(II)/バッファー層/第2電極
(22)第1電極/バッファー層/p層/n層(I)/正孔障壁層/n層(II)/第2電極
(23)第1電極/バッファー層/p層/n層(I)/正孔障壁層/n層(II)/バッファー層/第2電極 Moreover, when the buffer layer is provided in the above configuration (2), a structure having the following configuration can be given.
(21) First electrode / p layer / n layer (I) / hole barrier layer / n layer (II) / buffer layer / second electrode (22) first electrode / buffer layer / p layer / n layer (I ) / Hole barrier layer / n layer (II) / second electrode (23) first electrode / buffer layer / p layer / n layer (I) / hole barrier layer / n layer (II) / buffer layer / second 2 electrodes
上記有機太陽電池における各構成部材は、有機太陽電池で使用される公知の部材や材料を使用することができる。以下、各構成部材について簡単に説明する。
As each constituent member in the organic solar cell, known members and materials used in the organic solar cell can be used. Hereinafter, each component will be briefly described.
1.第1電極、第2電極
第1電極、第2電極の材料は特に制限はなく、公知の導電性材料を使用できる。例えば、p層と接続する電極(陽極)としては、錫ドープ酸化インジウム(ITO)や金(Au)等の金属が使用でき、n層と接続する電極(陰極)としては、銀(Ag)、アルミニウム(Al)、インジウム(In)、カルシウム(Ca)、白金(Pt)リチウム(Li)等の金属や、Mg:Ag、Mg:InやAl:Li等の二成分金属系が用いられ、上記陽極に比べ仕事関数は小さいものが用いられる。またn層を構成する材料の電子準位次第では、上記p層と接続する電極例示材料が使用できる。 1. 1st electrode, 2nd electrode There is no restriction | limiting in particular in the material of a 1st electrode and a 2nd electrode, A well-known electroconductive material can be used. For example, as an electrode (anode) connected to the p layer, a metal such as tin-doped indium oxide (ITO) or gold (Au) can be used, and as an electrode (cathode) connected to the n layer, silver (Ag), Metals such as aluminum (Al), indium (In), calcium (Ca), platinum (Pt) lithium (Li), and binary metal systems such as Mg: Ag, Mg: In, and Al: Li are used. A work function smaller than that of the anode is used. Depending on the electron level of the material constituting the n layer, an electrode exemplified material connected to the p layer can be used.
第1電極、第2電極の材料は特に制限はなく、公知の導電性材料を使用できる。例えば、p層と接続する電極(陽極)としては、錫ドープ酸化インジウム(ITO)や金(Au)等の金属が使用でき、n層と接続する電極(陰極)としては、銀(Ag)、アルミニウム(Al)、インジウム(In)、カルシウム(Ca)、白金(Pt)リチウム(Li)等の金属や、Mg:Ag、Mg:InやAl:Li等の二成分金属系が用いられ、上記陽極に比べ仕事関数は小さいものが用いられる。またn層を構成する材料の電子準位次第では、上記p層と接続する電極例示材料が使用できる。 1. 1st electrode, 2nd electrode There is no restriction | limiting in particular in the material of a 1st electrode and a 2nd electrode, A well-known electroconductive material can be used. For example, as an electrode (anode) connected to the p layer, a metal such as tin-doped indium oxide (ITO) or gold (Au) can be used, and as an electrode (cathode) connected to the n layer, silver (Ag), Metals such as aluminum (Al), indium (In), calcium (Ca), platinum (Pt) lithium (Li), and binary metal systems such as Mg: Ag, Mg: In, and Al: Li are used. A work function smaller than that of the anode is used. Depending on the electron level of the material constituting the n layer, an electrode exemplified material connected to the p layer can be used.
尚、高効率の光電変換特性を得るためには、太陽電池の少なくとも一方の面は太陽光スペクトルにおいて十分透明にすることが望ましい。透明電極は、公知の導電性材料を使用して、蒸着やスパッタリング等の方法で所定の透光性が確保するように形成する。受光面の電極の光透過率は10%以上とすることが望ましい。一対の電極構成の好ましい構成では、電極部の一方が仕事関数の大きな金属を含み、他方は仕事関数の小さな金属を含む。
In order to obtain highly efficient photoelectric conversion characteristics, it is desirable that at least one surface of the solar cell be sufficiently transparent in the sunlight spectrum. The transparent electrode is formed using a known conductive material so as to ensure predetermined translucency by a method such as vapor deposition or sputtering. The light transmittance of the electrode on the light receiving surface is preferably 10% or more. In a preferred configuration of the pair of electrode configurations, one of the electrode portions includes a metal having a high work function, and the other includes a metal having a low work function.
2.p型半導体層
p層に用いる材料は特に限定されないが、正孔受容体としての機能を有する化合物が好ましい。例えば有機化合物であれば、N、N’-ビス(3-トリル)-N、N’-ジフェニルベンジジン(mTPD)、N、N’-ジナフチル-N、N’-ジフェニルベンジジン(NPD)、4、4’、4’’-トリス(フェニル-3-トリルアミノ)トリフェニルアミン(MTDATA)等に代表されるアミン化合物、フタロシアニン(Pc)、銅フタロシアニン(CuPc)、亜鉛フタロシアニン(ZnPc)、チタニルフタロシアニン(TiOPc)等のフタロシアニン類、オクタエチルポルフィリン(OEP)、白金オクタエチルポルフィリン(PtOEP)、亜鉛テトラフェニルポルフィリン(ZnTPP)等に代表されるポルフィリン類、高分子化合物であれば、ポリヘキシルチオフェン(P3HT)、メトキシエチルヘキシロキシフェニレンビニレン(MEHPPV)等の主鎖型共役高分子類、ポリビニルカルバゾール等に代表される側鎖型高分子類等が挙げられる。 2. p-type Semiconductor Layer The material used for the p-layer is not particularly limited, but a compound having a function as a hole acceptor is preferable. For example, for organic compounds, N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD), 4, Amine compounds typified by 4 ′, 4 ″ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA), phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl phthalocyanine (TiOPc) ), Phthalocyanines such as octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP) and the like, and polymer compounds such as polyhexylthiophene (P3HT), Methoxyethylhexyloxyphenylene vinyl Examples thereof include main chain conjugated polymers such as REN (MEHPPV), and side chain polymers represented by polyvinyl carbazole.
p層に用いる材料は特に限定されないが、正孔受容体としての機能を有する化合物が好ましい。例えば有機化合物であれば、N、N’-ビス(3-トリル)-N、N’-ジフェニルベンジジン(mTPD)、N、N’-ジナフチル-N、N’-ジフェニルベンジジン(NPD)、4、4’、4’’-トリス(フェニル-3-トリルアミノ)トリフェニルアミン(MTDATA)等に代表されるアミン化合物、フタロシアニン(Pc)、銅フタロシアニン(CuPc)、亜鉛フタロシアニン(ZnPc)、チタニルフタロシアニン(TiOPc)等のフタロシアニン類、オクタエチルポルフィリン(OEP)、白金オクタエチルポルフィリン(PtOEP)、亜鉛テトラフェニルポルフィリン(ZnTPP)等に代表されるポルフィリン類、高分子化合物であれば、ポリヘキシルチオフェン(P3HT)、メトキシエチルヘキシロキシフェニレンビニレン(MEHPPV)等の主鎖型共役高分子類、ポリビニルカルバゾール等に代表される側鎖型高分子類等が挙げられる。 2. p-type Semiconductor Layer The material used for the p-layer is not particularly limited, but a compound having a function as a hole acceptor is preferable. For example, for organic compounds, N, N′-bis (3-tolyl) -N, N′-diphenylbenzidine (mTPD), N, N′-dinaphthyl-N, N′-diphenylbenzidine (NPD), 4, Amine compounds typified by 4 ′, 4 ″ -tris (phenyl-3-tolylamino) triphenylamine (MTDATA), phthalocyanine (Pc), copper phthalocyanine (CuPc), zinc phthalocyanine (ZnPc), titanyl phthalocyanine (TiOPc) ), Phthalocyanines such as octaethylporphyrin (OEP), platinum octaethylporphyrin (PtOEP), zinc tetraphenylporphyrin (ZnTPP) and the like, and polymer compounds such as polyhexylthiophene (P3HT), Methoxyethylhexyloxyphenylene vinyl Examples thereof include main chain conjugated polymers such as REN (MEHPPV), and side chain polymers represented by polyvinyl carbazole.
また、p層に用いる材料として、下記式(A)で表される化合物も好ましい。
(式(A)中、R0は水素、置換もしくは無置換の炭素数1~20のアルキル,置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、
Rg1及びRg2は、それぞれ置換もしくは無置換の窒素原子を少なくとも1つ有する五員複素環、又は置換もしくは無置換の窒素原子を少なくとも1つ有する六員複素環であり、
Rg3及びRg4は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の環形成原子数5~40の複素環であり、Mは配位金属である。
R0及びRg1~Rg4の置換基のうち、隣接する基は互いに結合して環を形成してもよい。ただし、Rg1及びRg2の隣接する置換基が結合してイソインドールを形成する場合はない。) Further, as a material used for the p layer, a compound represented by the following formula (A) is also preferable.
(In the formula (A), R 0 is hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted carbon atoms having 2 to 30 carbon atoms. Alkenyl, halogen, or a substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms,
Rg 1 and Rg 2 are each a 5-membered heterocyclic ring having at least one substituted or unsubstituted nitrogen atom, or a 6-membered heterocyclic ring having at least one substituted or unsubstituted nitrogen atom;
Rg 3 and Rg 4 are each a substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and M is a coordination metal.
Of the substituents R 0 and Rg 1 to Rg 4 , adjacent groups may be bonded to each other to form a ring. However, the adjacent substituents of Rg 1 and Rg 2 are not bonded to form isoindole. )
Rg1及びRg2は、それぞれ置換もしくは無置換の窒素原子を少なくとも1つ有する五員複素環、又は置換もしくは無置換の窒素原子を少なくとも1つ有する六員複素環であり、
Rg3及びRg4は、それぞれ置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の環形成原子数5~40の複素環であり、Mは配位金属である。
R0及びRg1~Rg4の置換基のうち、隣接する基は互いに結合して環を形成してもよい。ただし、Rg1及びRg2の隣接する置換基が結合してイソインドールを形成する場合はない。) Further, as a material used for the p layer, a compound represented by the following formula (A) is also preferable.
Rg 1 and Rg 2 are each a 5-membered heterocyclic ring having at least one substituted or unsubstituted nitrogen atom, or a 6-membered heterocyclic ring having at least one substituted or unsubstituted nitrogen atom;
Rg 3 and Rg 4 are each a substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and M is a coordination metal.
Of the substituents R 0 and Rg 1 to Rg 4 , adjacent groups may be bonded to each other to form a ring. However, the adjacent substituents of Rg 1 and Rg 2 are not bonded to form isoindole. )
式(A)の2つのN-M結合のうち、いずれか一方が配位結合であり、この場合、本発明の化合物は配位化合物(錯体又はキレート錯体)である。
Mは、配位金属であり、好ましくはホウ素原子、ケイ素原子、アルミニウム原子、マグネシウム原子、鉄原子、銅原子又は亜鉛原子であり、ホウ素原子がより好ましい。 One of the two NM bonds of the formula (A) is a coordination bond, and in this case, the compound of the present invention is a coordination compound (complex or chelate complex).
M is a coordination metal, preferably a boron atom, a silicon atom, an aluminum atom, a magnesium atom, an iron atom, a copper atom or a zinc atom, and more preferably a boron atom.
Mは、配位金属であり、好ましくはホウ素原子、ケイ素原子、アルミニウム原子、マグネシウム原子、鉄原子、銅原子又は亜鉛原子であり、ホウ素原子がより好ましい。 One of the two NM bonds of the formula (A) is a coordination bond, and in this case, the compound of the present invention is a coordination compound (complex or chelate complex).
M is a coordination metal, preferably a boron atom, a silicon atom, an aluminum atom, a magnesium atom, an iron atom, a copper atom or a zinc atom, and more preferably a boron atom.
以下、R0、Rg1~Rg4の各基について説明する。
R0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。 Hereinafter, each group of R 0 and Rg 1 to Rg 4 will be described.
Examples of the halogen atom for R 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R0のハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。 Hereinafter, each group of R 0 and Rg 1 to Rg 4 will be described.
Examples of the halogen atom for R 0 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
R0の置換又は無置換の炭素数1~20のアルキルは、好ましくはアルキル部分の炭素数が1~8であり、アルキル部分は直鎖、分岐鎖又は環状のいずれであってもよく、例えばメチル基、エチル基、1-プロピル基、2-プロピル基、1-ブチル基、2-ブチル基、sec-ブチル基、tert-ブチル基、ペンチル基、ヘキシル基、オクチル基、デシル基、ドデシル基、2-エチルヘキシル基、3、7-ジメチルオクチル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基、1-アダマンチル基、2-アダマンチル基、ノルボルニル基、トリフルオロメチル基、トリクロロメチル基、ベンジル基、α、α-ジメチルベンジル基、2-フェニルエチル基、1-フェニルエチル基等が挙げられる。これらのうち、原料の入手しやすさ等の観点から、炭素数1~20のアルキル基が好ましく、メチル基、エチル基、1-プロピル基、2-プロピル基、tert-ブチル基、シクロヘキシル基が更に好ましい。
The substituted or unsubstituted alkyl having 1 to 20 carbon atoms of R 0 preferably has 1 to 8 carbon atoms in the alkyl moiety, and the alkyl moiety may be linear, branched or cyclic, for example Methyl group, ethyl group, 1-propyl group, 2-propyl group, 1-butyl group, 2-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, decyl group, dodecyl group 2-ethylhexyl group, 3,7-dimethyloctyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, 2-adamantyl group, norbornyl group, trifluoromethyl group, trichloromethyl group, benzyl group, α , Α-dimethylbenzyl group, 2-phenylethyl group, 1-phenylethyl group and the like. Of these, an alkyl group having 1 to 20 carbon atoms is preferable from the viewpoint of availability of raw materials, and a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a tert-butyl group, and a cyclohexyl group are preferable. Further preferred.
上記アルキル基の置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、フェニル基等のアリール基が挙げられ、当該アリール基はメチル基、エチル基、プロピル基等の炭素数1~5のアルキル基でさらに置換されていてもよい。
Examples of the substituent of the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and an aryl group such as a phenyl group, and the aryl group includes a methyl group, an ethyl group, a propyl group and the like. And may be further substituted with an alkyl group having 1 to 5 carbon atoms.
R0の置換又は無置換の環形成炭素数6~30のアリールは、好ましくはアリール部分の環形成炭素数が6~20であり、例えば、フェニル基、2-トリル基、4-トリル基、4-トリフルオロメチルフェニル基、4-メトキシフェニル基、4-シアノフェニル基、2-ビフェニリル基、3-ビフェニリル基、4-ビフェニリル基、ターフェニリル基、3、5-ジフェニルフェニル基、3、4-ジフェニルフェニル基、ペンタフェニルフェニル基、4-(2、2-ジフェニルビニル)フェニル基、4-(1、2、2-トリフェニルビニル)フェニル基、フルオレニル基、1-ナフチル基、2-ナフチル基、2-(1、4-ジフェニル)ナフチル基、9-アントリル基、2-アントリル基、2-(1、4-ジフェニル)アントリル基)、2-(9、10-ジフェニル)アントリル基、9-フェナントリル基、1-ピレニル基、クリセニル基、ナフタセニル基、コロニル基等が挙げられる。これらのうち、原料の入手しやすさ等の観点から、環形成炭素数6~30のアリール基が好ましく、フェニル基、4-ビフェニリル基、1-ナフチル基、2-ナフチル基、2-アントリル基、9-フェナントリル基等が更に好ましい。
The substituted or unsubstituted aryl having 6 to 30 ring carbon atoms of R 0 preferably has 6 to 20 ring carbon atoms in the aryl moiety. For example, a phenyl group, a 2-tolyl group, a 4-tolyl group, 4-trifluoromethylphenyl group, 4-methoxyphenyl group, 4-cyanophenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, terphenylyl group, 3,5-diphenylphenyl group, 3,4- Diphenylphenyl group, pentaphenylphenyl group, 4- (2,2-diphenylvinyl) phenyl group, 4- (1,2,2-triphenylvinyl) phenyl group, fluorenyl group, 1-naphthyl group, 2-naphthyl group 2- (1,4-diphenyl) naphthyl group, 9-anthryl group, 2-anthryl group, 2- (1,4-diphenyl) anthryl group), 2- ( 9,10-diphenyl) anthryl group, 9-phenanthryl group, 1-pyrenyl group, chrycenyl group, naphthacenyl group, coronyl group and the like. Of these, aryl groups having 6 to 30 ring carbon atoms are preferable from the viewpoint of availability of raw materials, etc., and include phenyl, 4-biphenylyl, 1-naphthyl, 2-naphthyl, and 2-anthryl groups. , 9-phenanthryl group and the like are more preferable.
上記アリール基の置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、メチル基、エチル基、プロピル基等の炭素数1~5のアルキル基、メトキシ基、エトキシ基、プロポキシ基等の炭素数1~5のアルコキシ基、シアノ基、フェニル基等のアリール基、フェニル基等のアリール基、カルバゾール等の複素環、ジフェニルアミノ基等のアリールアミノ基等が挙げられる。
Examples of the substituent for the aryl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group, a methoxy group, and an ethoxy group. Group, an alkoxy group having 1 to 5 carbon atoms such as a propoxy group, an aryl group such as a cyano group and a phenyl group, an aryl group such as a phenyl group, a heterocyclic ring such as carbazole, an arylamino group such as a diphenylamino group, and the like. .
Rg3及びRg4の置換又は無置換の環形成炭素数6~30のアリールとしては、上記R0の置換又は無置換の環形成炭素数6~30のアリールに対応する2価の残基が挙げられる。
Examples of the substituted or unsubstituted aryl having 6 to 30 ring carbon atoms of Rg 3 and Rg 4 include divalent residues corresponding to the above substituted or unsubstituted aryl having 6 to 30 ring carbon atoms of R 0. Can be mentioned.
R0の置換又は無置換の炭素数2~30のアルケニルは、好ましくはアルケニル部分の炭素数が2~8であり、直鎖、分岐鎖又は環状のいずれであってもよく、例えばビニル基、プロペニル基、ブテニル基、オレイル基、エイコサペンタエニル基、ドコサヘキサエニル基、スチリル基、2、2-ジフェニルビニル基、1、2、2-トリフェニルビニル基、2-フェニル-2-プロペニル基等が挙げられる。これらのうち、原料の入手しやすさ等の観点から、炭素数2~20のアルケニル基が好ましく、ビニル基、スチリル基、2、2-ジフェニルビニル基が更に好ましい。
The substituted or unsubstituted alkenyl having 2 to 30 carbon atoms of R 0 preferably has 2 to 8 carbon atoms in the alkenyl moiety and may be linear, branched or cyclic, such as a vinyl group, Propenyl, butenyl, oleyl, eicosapentaenyl, docosahexaenyl, styryl, 2,2-diphenylvinyl, 1,2,2-triphenylvinyl, 2-phenyl-2-propenyl Etc. Of these, an alkenyl group having 2 to 20 carbon atoms is preferable, and a vinyl group, a styryl group, and a 2,2-diphenylvinyl group are more preferable from the viewpoint of availability of raw materials.
上記のアルケニル基の置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、フェニル基等のアリール基、メチル基、エチル基、プロピル基等の炭素数1~5のアルキル基が挙げられる。
Examples of the substituent for the alkenyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an aryl group such as a phenyl group, a carbon group of 1 to 5 such as a methyl group, an ethyl group and a propyl group. Of the alkyl group.
R0、Rg3及びRg4の置換又は無置換の環形成原子数5~40の複素環は、好ましくは複素環の環形成原子数5~15であり、例えば、フラン、チオフェン、ピロール、イミダゾール、ベンズイミダゾール、ピラゾール、ベンズピラゾール、トリアゾール、オキサジアゾール、ピリジン、ピラジン、トリアジン、キノリン、ベンゾフラン、ジベンゾフラン、ベンゾチオフェン、ジベンゾチオフェン及びカルバゾールに対応する1価又は2価の残基が挙げられる。これらのうち、原料の入手しやすさ等の観点から、フラン、チオフェン、ピリジン、カルバゾール等が好ましい。
The substituted or unsubstituted heterocycle having 5 to 40 ring atoms of R 0 , Rg 3 and Rg 4 is preferably a heterocycle having 5 to 15 ring atoms. For example, furan, thiophene, pyrrole, imidazole And monovalent or divalent residues corresponding to benzimidazole, pyrazole, benzpyrazole, triazole, oxadiazole, pyridine, pyrazine, triazine, quinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene and carbazole. Of these, furan, thiophene, pyridine, carbazole and the like are preferable from the viewpoint of availability of raw materials.
上記複素環の置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子やメチル基、エチル基、プロピル基等の炭素数1~5のアルキル基が挙げられる。
Examples of the substituent of the heterocyclic ring include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, and alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group and propyl group.
Rg1及びRg2の窒素原子を少なくとも1つ有する五員複素環又は六員複素環としては、ピロール、イミダゾール、ピリジン等が挙げられ、好ましくはピロールである。
Examples of the 5-membered or 6-membered heterocyclic ring having at least one nitrogen atom of Rg 1 and Rg 2 include pyrrole, imidazole, pyridine and the like, and pyrrole is preferable.
Rg1及びRg2の窒素原子を少なくとも1つ有する五員複素環又は六員複素環の置換基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子、フェニル基等のアリール基が挙げられる。
Rg1及びRg2の置換基のうち、隣接するものは結合して環を形成してもよいが、ピロールであるRg1又はRg2の置換基が環を形成してイソインドールとなる場合はない。 Examples of the substituent of the 5-membered or 6-membered heterocyclic ring having at least one nitrogen atom of Rg 1 and Rg 2 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a phenyl group, and the like. An aryl group is mentioned.
Among the substituents of Rg 1 and Rg 2 , adjacent ones may combine to form a ring, but when the substituent of Rg 1 or Rg 2 that is pyrrole forms a ring and becomes isoindole Absent.
Rg1及びRg2の置換基のうち、隣接するものは結合して環を形成してもよいが、ピロールであるRg1又はRg2の置換基が環を形成してイソインドールとなる場合はない。 Examples of the substituent of the 5-membered or 6-membered heterocyclic ring having at least one nitrogen atom of Rg 1 and Rg 2 include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a phenyl group, and the like. An aryl group is mentioned.
Among the substituents of Rg 1 and Rg 2 , adjacent ones may combine to form a ring, but when the substituent of Rg 1 or Rg 2 that is pyrrole forms a ring and becomes isoindole Absent.
また、R0はRg1又はRg2に結合してもよく、Rg1の置換基はRg3と結合してもよく、Rg2の置換基はRg4と結合してもよい。
R 0 may be bonded to Rg 1 or Rg 2 , the substituent of Rg 1 may be bonded to Rg 3, and the substituent of Rg 2 may be bonded to Rg 4 .
尚、本発明において、水素原子とは、中性子数が異なる同位体、即ち、軽水素(protium)、重水素(deuterium)、三重水素(tritium)を包含する。
In the present invention, the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (deuterium), and tritium (tritium).
式(A)で表される化合物は、好ましくは下記式(B)で表されるピロメテンホウ素キレート化合物である。
(式中、R0は上記式(A)と同じであり、R1~R12はそれぞれ水素、置換もしくは無置換の炭素数1~20のアルキル、置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、置換もしくは無置換の環形成炭素数6~30のアリールアミノ、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、
R1~R12のうち隣接する基は互いに結合して環を形成してもよい。但し、R1とR2及びR11とR12がそれぞれ結合して、イソインドールを形成する場合を含まない。) The compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (B).
(Wherein R 0 is the same as the above formula (A), R 1 to R 12 are each hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted ring forming carbon atoms having 6 to 6 carbon atoms; 30 aryl, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted arylamino having 6 to 30 carbon atoms, halogen, or substituted or unsubstituted heterocyclic ring having 5 to 40 carbon atoms And
Adjacent groups of R 1 to R 12 may be bonded to each other to form a ring. However, the case where R 1 and R 2 and R 11 and R 12 are bonded to form isoindole is not included. )
R1~R12のうち隣接する基は互いに結合して環を形成してもよい。但し、R1とR2及びR11とR12がそれぞれ結合して、イソインドールを形成する場合を含まない。) The compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (B).
Adjacent groups of R 1 to R 12 may be bonded to each other to form a ring. However, the case where R 1 and R 2 and R 11 and R 12 are bonded to form isoindole is not included. )
式(B)において、アルキル、アリール、アルケニル、アリールアミノ、ハロゲン及び複素環は、上記と同じである。尚、R1~R16は式(A)のRg1~Rg4の置換基に対応する。
In the formula (B), alkyl, aryl, alkenyl, arylamino, halogen and heterocycle are the same as above. R 1 to R 16 correspond to the substituents Rg 1 to Rg 4 in the formula (A).
式(B)において、R1、R2、R11及びR12のうち少なくとも1つが環形成炭素数6~30のアリールであると好ましく、フェニル基であるとより好ましい。また、R4、R5、R8及びR9のうち少なくとも1つが環形成炭素数6~40のアリールアミノ基であると好ましく、ジフェニルアミノ基であるとより好ましい。
また、R3及びR4、又はR4及びR5が連結して、これらが結合するベンゼン環に縮合する環(例えばベンゼン環)を形成してもよく、R8及びR9、又はR9及びR10が連結して、これらが結合するベンゼン環に縮合する環(ベンゼン環)を形成してもよい。 In the formula (B), at least one of R 1 , R 2 , R 11 and R 12 is preferably aryl having 6 to 30 ring carbon atoms, and more preferably a phenyl group. Further, at least one of R 4 , R 5 , R 8 and R 9 is preferably an arylamino group having 6 to 40 ring carbon atoms, and more preferably a diphenylamino group.
In addition, R 3 and R 4 , or R 4 and R 5 may be linked to form a ring condensed with the benzene ring to which they are bonded (for example, a benzene ring). R 8 and R 9 , or R 9 And R 10 may be linked to form a ring (benzene ring) that is condensed with a benzene ring to which these are bonded.
また、R3及びR4、又はR4及びR5が連結して、これらが結合するベンゼン環に縮合する環(例えばベンゼン環)を形成してもよく、R8及びR9、又はR9及びR10が連結して、これらが結合するベンゼン環に縮合する環(ベンゼン環)を形成してもよい。 In the formula (B), at least one of R 1 , R 2 , R 11 and R 12 is preferably aryl having 6 to 30 ring carbon atoms, and more preferably a phenyl group. Further, at least one of R 4 , R 5 , R 8 and R 9 is preferably an arylamino group having 6 to 40 ring carbon atoms, and more preferably a diphenylamino group.
In addition, R 3 and R 4 , or R 4 and R 5 may be linked to form a ring condensed with the benzene ring to which they are bonded (for example, a benzene ring). R 8 and R 9 , or R 9 And R 10 may be linked to form a ring (benzene ring) that is condensed with a benzene ring to which these are bonded.
式(A)で表される化合物は、好ましくは下記式(C)で表されるピロメテンホウ素キレート化合物である。
(式中、R0は上記式(A)と同じであり、
R13~R16はそれぞれ水素、置換もしくは無置換の炭素数1~20のアルキル、置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、置換もしくは無置換の環形成炭素数6~30のアリールアミノ、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、R13~R16のうち隣接する基は互いに結合して環を形成してもよい。但し、R13とR14及びR15とR16がそれぞれ結合して、イソインドールを形成する場合を含まない。
X1~X6はそれぞれO、S又はC-Rである。Rは水素、置換もしくは無置換の炭素数1~20のアルキル、置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、置換もしくは無置換の環形成炭素数6~30のアリールアミノ、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、隣接するRは互いに結合して環を形成してもよい。点線で示した五員環において、各炭素原子は隣接する炭素原子と二重結合を形成してもよい。) The compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (C).
(In the formula, R 0 is the same as the above formula (A),
R 13 to R 16 are each hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, Substituted or unsubstituted arylamino having 6 to 30 ring carbon atoms, halogen, or substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and adjacent groups among R 13 to R 16 are bonded to each other. To form a ring. However, the case where R 13 and R 14 and R 15 and R 16 are bonded to form isoindole is not included.
X 1 to X 6 are each O, S or C—R. R is hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted It is arylamino having 6 to 30 ring carbon atoms, halogen or a substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and adjacent Rs may be bonded to each other to form a ring. In the five-membered ring indicated by the dotted line, each carbon atom may form a double bond with an adjacent carbon atom. )
R13~R16はそれぞれ水素、置換もしくは無置換の炭素数1~20のアルキル、置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、置換もしくは無置換の環形成炭素数6~30のアリールアミノ、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、R13~R16のうち隣接する基は互いに結合して環を形成してもよい。但し、R13とR14及びR15とR16がそれぞれ結合して、イソインドールを形成する場合を含まない。
X1~X6はそれぞれO、S又はC-Rである。Rは水素、置換もしくは無置換の炭素数1~20のアルキル、置換もしくは無置換の環形成炭素数6~30のアリール、置換もしくは無置換の炭素数2~30のアルケニル、置換もしくは無置換の環形成炭素数6~30のアリールアミノ、ハロゲン又は置換もしくは無置換の環形成原子数5~40の複素環であり、隣接するRは互いに結合して環を形成してもよい。点線で示した五員環において、各炭素原子は隣接する炭素原子と二重結合を形成してもよい。) The compound represented by the formula (A) is preferably a pyromethene boron chelate compound represented by the following formula (C).
R 13 to R 16 are each hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, Substituted or unsubstituted arylamino having 6 to 30 ring carbon atoms, halogen, or substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and adjacent groups among R 13 to R 16 are bonded to each other. To form a ring. However, the case where R 13 and R 14 and R 15 and R 16 are bonded to form isoindole is not included.
X 1 to X 6 are each O, S or C—R. R is hydrogen, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 30 ring carbon atoms, substituted or unsubstituted alkenyl having 2 to 30 carbon atoms, substituted or unsubstituted It is arylamino having 6 to 30 ring carbon atoms, halogen or a substituted or unsubstituted heterocyclic ring having 5 to 40 ring atoms, and adjacent Rs may be bonded to each other to form a ring. In the five-membered ring indicated by the dotted line, each carbon atom may form a double bond with an adjacent carbon atom. )
式(C)は、例えば下記式(C-1)~(C-3)で表わすことができる。
(式中、R、R0、R13~R16は上記式(C)と同じであり、XはそれぞれO又はSである。)
Formula (C) can be represented by, for example, the following formulas (C-1) to (C-3).
(In the formula, R, R 0 , R 13 to R 16 are the same as in the above formula (C), and X is O or S, respectively.)
式(C)において、R13~R16のうち少なくとも1つが環形成炭素数6~30のアリールであると好ましく、フェニル基であるとより好ましい。
式(C-1)又は(C-3)において、隣接するRが連結して、これらが結合する5員環に縮合する環(例えばベンゼン環)を形成してもよい。 In the formula (C), at least one of R 13 to R 16 is preferably aryl having 6 to 30 ring carbon atoms, and more preferably a phenyl group.
In the formula (C-1) or (C-3), adjacent Rs may be linked to form a ring (for example, a benzene ring) that is fused to the 5-membered ring to which they are bonded.
式(C-1)又は(C-3)において、隣接するRが連結して、これらが結合する5員環に縮合する環(例えばベンゼン環)を形成してもよい。 In the formula (C), at least one of R 13 to R 16 is preferably aryl having 6 to 30 ring carbon atoms, and more preferably a phenyl group.
In the formula (C-1) or (C-3), adjacent Rs may be linked to form a ring (for example, a benzene ring) that is fused to the 5-membered ring to which they are bonded.
3.n型半導体層
n層に用いる材料は特に限定されないが、電子受容体としての機能を有する化合物が好ましい。
例えば、有機化合物であれば、C60、C70等のフラーレン、及びその誘導体、カーボンナノチューブ、ペリレン誘導体、多環キノン、キナクリドン等が挙げられ、高分子の有機化合物であればCN-ポリ(フェニレン-ビニレン)、MEH-CN-PPV、-CN基又はCF3基含有ポリマー、それらの-CF3置換ポリマー、ポリ(フルオレン)誘導体等を挙げることができる。
また、電子の移動度が高い材料が好ましい。さらに、電子親和力が小さい材料が好ましい。電子親和力の小さい材料をn層として組み合わせることで高い開放端電圧を実現することができる。 3. n-type Semiconductor Layer The material used for the n-layer is not particularly limited, but a compound having a function as an electron acceptor is preferable.
Examples of organic compounds include fullerenes such as C 60 and C 70 and derivatives thereof, carbon nanotubes, perylene derivatives, polycyclic quinones, quinacridones, and CN-poly (phenylene -Vinylene), MEH-CN-PPV, -CN group or CF 3 group-containing polymers, their -CF 3 substituted polymers, poly (fluorene) derivatives, and the like.
A material having high electron mobility is preferable. Furthermore, a material having a small electron affinity is preferable. A high open-circuit voltage can be realized by combining materials having a low electron affinity as the n layer.
n層に用いる材料は特に限定されないが、電子受容体としての機能を有する化合物が好ましい。
例えば、有機化合物であれば、C60、C70等のフラーレン、及びその誘導体、カーボンナノチューブ、ペリレン誘導体、多環キノン、キナクリドン等が挙げられ、高分子の有機化合物であればCN-ポリ(フェニレン-ビニレン)、MEH-CN-PPV、-CN基又はCF3基含有ポリマー、それらの-CF3置換ポリマー、ポリ(フルオレン)誘導体等を挙げることができる。
また、電子の移動度が高い材料が好ましい。さらに、電子親和力が小さい材料が好ましい。電子親和力の小さい材料をn層として組み合わせることで高い開放端電圧を実現することができる。 3. n-type Semiconductor Layer The material used for the n-layer is not particularly limited, but a compound having a function as an electron acceptor is preferable.
Examples of organic compounds include fullerenes such as C 60 and C 70 and derivatives thereof, carbon nanotubes, perylene derivatives, polycyclic quinones, quinacridones, and CN-poly (phenylene -Vinylene), MEH-CN-PPV, -CN group or CF 3 group-containing polymers, their -CF 3 substituted polymers, poly (fluorene) derivatives, and the like.
A material having high electron mobility is preferable. Furthermore, a material having a small electron affinity is preferable. A high open-circuit voltage can be realized by combining materials having a low electron affinity as the n layer.
無機化合物であれば、n型特性の無機半導体化合物を挙げることができる。具体的には、n-Si、GaAs、CdS、PbS、CdSe、InP、Nb2O5、WO3、Fe2O3等のドーピング半導体及び化合物半導体、二酸化チタン(TiO2)、一酸化チタン(TiO)、三酸化二チタン(Ti2O3)等の酸化チタン、酸化亜鉛(ZnO)、酸化スズ(SnO2)等の導電性酸化物が挙げられ、これらのうちの1種又は2種以上を組み合わせて用いてもよい。好ましくは酸化チタンであり、特に好ましくは二酸化チタンを用いる。
Examples of inorganic compounds include n-type inorganic semiconductor compounds. Specifically, doping semiconductors and compound semiconductors such as n-Si, GaAs, CdS, PbS, CdSe, InP, Nb 2 O 5 , WO 3 , Fe 2 O 3 , titanium dioxide (TiO 2 ), titanium monoxide ( TiO), titanium oxides such as dititanium trioxide (Ti 2 O 3 ), and conductive oxides such as zinc oxide (ZnO) and tin oxide (SnO 2 ), and one or more of these May be used in combination. Titanium oxide is preferred, and titanium dioxide is particularly preferred.
上記活性層(B)に用いるn層(I)とn層(II)の化合物は同一でも異なっていてもよい。
The compounds of the n layer (I) and the n layer (II) used for the active layer (B) may be the same or different.
4.i層
i層は、上記p型半導体材料とn型半導体材料を混合した層である。i層のp型半導体材料とp層の材料は同一でも異なっていてもよく、i層のn型半導体材料とn層の材料は同一でも異なっていてもよい。i層におけるp型半導体材料とn型半導体材料の割合は、例えば10:1~1:10(体積比)である。
i層に用いるn型半導体材料としてはC70又はその誘導体が好ましい。 4). i layer The i layer is a layer in which the p-type semiconductor material and the n-type semiconductor material are mixed. The i-type p-type semiconductor material and the p-layer material may be the same or different, and the i-type n-type semiconductor material and the n-layer material may be the same or different. The ratio of the p-type semiconductor material and the n-type semiconductor material in the i layer is, for example, 10: 1 to 1:10 (volume ratio).
The n-type semiconductor material used for the i layer is preferably C70 or a derivative thereof.
i層は、上記p型半導体材料とn型半導体材料を混合した層である。i層のp型半導体材料とp層の材料は同一でも異なっていてもよく、i層のn型半導体材料とn層の材料は同一でも異なっていてもよい。i層におけるp型半導体材料とn型半導体材料の割合は、例えば10:1~1:10(体積比)である。
i層に用いるn型半導体材料としてはC70又はその誘導体が好ましい。 4). i layer The i layer is a layer in which the p-type semiconductor material and the n-type semiconductor material are mixed. The i-type p-type semiconductor material and the p-layer material may be the same or different, and the i-type n-type semiconductor material and the n-layer material may be the same or different. The ratio of the p-type semiconductor material and the n-type semiconductor material in the i layer is, for example, 10: 1 to 1:10 (volume ratio).
The n-type semiconductor material used for the i layer is preferably C70 or a derivative thereof.
5.正孔障壁層
活性層(A)の正孔障壁層(正孔障壁層(a))は、好ましくは上記i層に用いられるn型半導体材料よりIp(イオン化ポテンシャル)が大きい化合物を含むことにより、i層で生じた正孔が陰極側へ移動することを阻止する。 5. Hole blocking layer The hole blocking layer (hole blocking layer (a)) of the active layer (A) preferably contains a compound having a larger Ip (ionization potential) than the n-type semiconductor material used for the i layer. , The holes generated in the i layer are prevented from moving to the cathode side.
活性層(A)の正孔障壁層(正孔障壁層(a))は、好ましくは上記i層に用いられるn型半導体材料よりIp(イオン化ポテンシャル)が大きい化合物を含むことにより、i層で生じた正孔が陰極側へ移動することを阻止する。 5. Hole blocking layer The hole blocking layer (hole blocking layer (a)) of the active layer (A) preferably contains a compound having a larger Ip (ionization potential) than the n-type semiconductor material used for the i layer. , The holes generated in the i layer are prevented from moving to the cathode side.
正孔障壁層(a)に用いる化合物としては、上記n型半導体材料と同じものが挙げられ、i層のn型半導体材料よりもIpが大きい化合物が好ましい。
正孔障壁層(a)に用いる化合物は、i層のn型半導体材料よりもIpが0.01eV~1.0eV大きいと好ましい。また、i層のn型半導体材料よりも0.05eV~0.5eV大きいとより好ましく、0.05eV~0.2eV大きいとさらに好ましく、0.1eV大きいとさらに好ましい。 Examples of the compound used for the hole blocking layer (a) include the same compounds as the n-type semiconductor material described above, and compounds having a larger Ip than the n-type semiconductor material of the i layer are preferable.
The compound used for the hole blocking layer (a) preferably has an Ip of 0.01 eV to 1.0 eV larger than the n-type semiconductor material of the i layer. Further, it is more preferably 0.05 eV to 0.5 eV larger than the n-type semiconductor material of the i layer, more preferably 0.05 eV to 0.2 eV, and further preferably 0.1 eV.
正孔障壁層(a)に用いる化合物は、i層のn型半導体材料よりもIpが0.01eV~1.0eV大きいと好ましい。また、i層のn型半導体材料よりも0.05eV~0.5eV大きいとより好ましく、0.05eV~0.2eV大きいとさらに好ましく、0.1eV大きいとさらに好ましい。 Examples of the compound used for the hole blocking layer (a) include the same compounds as the n-type semiconductor material described above, and compounds having a larger Ip than the n-type semiconductor material of the i layer are preferable.
The compound used for the hole blocking layer (a) preferably has an Ip of 0.01 eV to 1.0 eV larger than the n-type semiconductor material of the i layer. Further, it is more preferably 0.05 eV to 0.5 eV larger than the n-type semiconductor material of the i layer, more preferably 0.05 eV to 0.2 eV, and further preferably 0.1 eV.
Ipは、ITOガラス基板上に真空蒸着で目的化合物の薄膜を成膜し、ITOガラス基板上の薄膜を用いて大気下で光電子分光装置(理研計器(株)社製:AC-3)を用いて測定することができる。
具体的には、材料に光を照射し、その際に電荷分離によって生じる電子量を測定することにより測定することができる。照射光のエネルギーに対し、放出された光電子を1/2乗でプロットし、光電子放出エネルギーのしきい値をIpとする。 Ip forms a thin film of a target compound on an ITO glass substrate by vacuum deposition, and uses a thin film on the ITO glass substrate with a photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd .: AC-3) in the atmosphere. Can be measured.
Specifically, it can be measured by irradiating the material with light and measuring the amount of electrons generated by charge separation at that time. The emitted photoelectrons are plotted by the 1/2 power with respect to the energy of the irradiation light, and the threshold value of the photoelectron emission energy is Ip.
具体的には、材料に光を照射し、その際に電荷分離によって生じる電子量を測定することにより測定することができる。照射光のエネルギーに対し、放出された光電子を1/2乗でプロットし、光電子放出エネルギーのしきい値をIpとする。 Ip forms a thin film of a target compound on an ITO glass substrate by vacuum deposition, and uses a thin film on the ITO glass substrate with a photoelectron spectrometer (manufactured by Riken Keiki Co., Ltd .: AC-3) in the atmosphere. Can be measured.
Specifically, it can be measured by irradiating the material with light and measuring the amount of electrons generated by charge separation at that time. The emitted photoelectrons are plotted by the 1/2 power with respect to the energy of the irradiation light, and the threshold value of the photoelectron emission energy is Ip.
また、正孔障壁層(a)の化合物は、i層に含まれるn型半導体材料よりも電子移動度が大きいと好ましい。正孔障壁層(a)の化合物の電子移動度は、好ましくは1×10-5cm2/Vs以上、より好ましくは1×10-4cm2/Vs以上である。
The compound of the hole blocking layer (a) preferably has a higher electron mobility than the n-type semiconductor material contained in the i layer. The electron mobility of the compound of the hole blocking layer (a) is preferably 1 × 10 −5 cm 2 / Vs or more, more preferably 1 × 10 −4 cm 2 / Vs or more.
電子移動度は、電界効果トランジスタ(FET)法によって測定する。作製した有機薄膜トランジスタのゲート電極にゲート電圧を印加し、ソース-ドレイン間にソースドレイン電圧を印加して電流を流し、閾値電圧(Vth)及び電界効果移動度μを評価する。各電圧の印加及びソース-ドレイン電極間電流の測定は、例えば半導体特性評価システム(ケースレーインスツルメンツ(株)製 4200SCS)を用いて行うことができる。
Electron mobility is measured by the field effect transistor (FET) method. A gate voltage is applied to the gate electrode of the produced organic thin film transistor, a source / drain voltage is applied between the source and the drain to pass a current, and a threshold voltage (Vth) and a field effect mobility μ are evaluated. The application of each voltage and the measurement of the current between the source and drain electrodes can be performed using, for example, a semiconductor characteristic evaluation system (4200SCS manufactured by Keithley Instruments Co., Ltd.).
電界効果移動度μは、下記式(A)を用いて算出できる。
ID=(W/2L)・C・μ・(VG-VT)2 (A)
(式中、IDはソース-ドレイン間電流、Wはチャンネル幅、Lはチャンネル長、Cはゲート絶縁体層の単位面積あたりの電気容量、VTはゲート閾値電圧、VGはゲート電圧である。)
移動度は、線形領域や飽和領域の特性から求めることができる。例えば、トランスファ特性の結果から、√Id―Vgのグラフを作製し、この傾きから電界効果移度を導く方法が挙げられる。本明細書では特にこだわらない限り、この手法で評価している。 The field effect mobility μ can be calculated using the following formula (A).
I D = (W / 2L) · C · μ · (V G −V T ) 2 (A)
(Where ID is the source-drain current, W is the channel width, L is the channel length, C is the capacitance per unit area of the gate insulator layer, V T is the gate threshold voltage, and V G is the gate voltage. is there.)
The mobility can be obtained from the characteristics of the linear region and the saturation region. For example, a method of creating a graph of √Id−Vg from the result of the transfer characteristics and deriving the field effect transfer from this slope can be mentioned. In this specification, evaluation is made by this method unless otherwise noted.
ID=(W/2L)・C・μ・(VG-VT)2 (A)
(式中、IDはソース-ドレイン間電流、Wはチャンネル幅、Lはチャンネル長、Cはゲート絶縁体層の単位面積あたりの電気容量、VTはゲート閾値電圧、VGはゲート電圧である。)
移動度は、線形領域や飽和領域の特性から求めることができる。例えば、トランスファ特性の結果から、√Id―Vgのグラフを作製し、この傾きから電界効果移度を導く方法が挙げられる。本明細書では特にこだわらない限り、この手法で評価している。 The field effect mobility μ can be calculated using the following formula (A).
I D = (W / 2L) · C · μ · (V G −V T ) 2 (A)
(Where ID is the source-drain current, W is the channel width, L is the channel length, C is the capacitance per unit area of the gate insulator layer, V T is the gate threshold voltage, and V G is the gate voltage. is there.)
The mobility can be obtained from the characteristics of the linear region and the saturation region. For example, a method of creating a graph of √Id−Vg from the result of the transfer characteristics and deriving the field effect transfer from this slope can be mentioned. In this specification, evaluation is made by this method unless otherwise noted.
正孔障壁層(a)の化合物としては、C60又はその誘導体が好ましい。
As the compound of the hole blocking layer (a), C60 or a derivative thereof is preferable.
また、正孔障壁層(a)の厚さは、正孔の移動を阻止し、電子の移動を妨げない厚さである。ここでいう「正孔の移動を阻止し、電子の移動を妨げない厚さ」とは、i層で生じた正孔の陰極側への移動を妨げるために薄すぎない厚さであり、かつi層で生じた電子が陰極側へ移動するのを妨げないために厚すぎない厚さをいう。このようにすることで、再結合失活要因をブロックし、抑制することで、高効率の光電変換特性と有する有機太陽電池が作製できる。「正孔の移動を阻止し、電子の移動を妨げない厚さ」は材料に依存するが、0.1~19nmであると好ましく、0.1~15nmであるとより好ましく、0.1~10nmであるとより好ましい。
0.1nm未満であると正孔障壁としての機能が十分機能しないおそれがあり、19nm超であると電子の移動を妨げるおそれがある。 The thickness of the hole blocking layer (a) is a thickness that prevents the movement of holes and does not prevent the movement of electrons. The term “thickness that prevents the movement of holes and does not hinder the movement of electrons” here is a thickness that is not too thin to prevent the movement of holes generated in the i layer to the cathode side, and The thickness is not too thick in order not to prevent the electrons generated in the i layer from moving to the cathode side. By doing in this way, the organic solar cell which has a highly efficient photoelectric conversion characteristic can be produced by blocking and suppressing a recombination deactivation factor. “Thickness that prevents the movement of holes and does not prevent the movement of electrons” depends on the material, but is preferably 0.1 to 19 nm, more preferably 0.1 to 15 nm, More preferably, it is 10 nm.
If it is less than 0.1 nm, the function as a hole barrier may not function sufficiently, and if it exceeds 19 nm, movement of electrons may be hindered.
0.1nm未満であると正孔障壁としての機能が十分機能しないおそれがあり、19nm超であると電子の移動を妨げるおそれがある。 The thickness of the hole blocking layer (a) is a thickness that prevents the movement of holes and does not prevent the movement of electrons. The term “thickness that prevents the movement of holes and does not hinder the movement of electrons” here is a thickness that is not too thin to prevent the movement of holes generated in the i layer to the cathode side, and The thickness is not too thick in order not to prevent the electrons generated in the i layer from moving to the cathode side. By doing in this way, the organic solar cell which has a highly efficient photoelectric conversion characteristic can be produced by blocking and suppressing a recombination deactivation factor. “Thickness that prevents the movement of holes and does not prevent the movement of electrons” depends on the material, but is preferably 0.1 to 19 nm, more preferably 0.1 to 15 nm, More preferably, it is 10 nm.
If it is less than 0.1 nm, the function as a hole barrier may not function sufficiently, and if it exceeds 19 nm, movement of electrons may be hindered.
活性層(B)の正孔障壁層(正孔障壁層(b))は、好ましくはn層(I)のn型半導体材料よりIpが大きい化合物を含むことにより、p層とn層の界面で生じた正孔が陰極側へ移動することを阻止する。
The hole barrier layer (hole barrier layer (b)) of the active layer (B) preferably contains a compound having a larger Ip than the n-type semiconductor material of the n layer (I), so that the interface between the p layer and the n layer This prevents the holes generated in step 1 from moving to the cathode side.
正孔障壁層(b)に用いる化合物としては、上記n型半導体材料と同じものが挙げられ、n層(I)のn型半導体材料よりもIpが大きい化合物が好ましい。正孔障壁層(b)に用いる化合物は、n層(I)のn型半導体材料よりもIpが0.01eV~1.0eV大きいと好ましい。また、n層(I)のn型半導体材料よりも0.05eV~0.5eV大きいとより好ましく、0.05eV~0.2eV大きいとさらに好ましく、0.1eV大きいとさらに好ましい。
Examples of the compound used for the hole blocking layer (b) include the same compounds as the n-type semiconductor material, and a compound having a larger Ip than the n-type semiconductor material of the n layer (I) is preferable. The compound used for the hole blocking layer (b) preferably has an Ip of 0.01 eV to 1.0 eV higher than the n-type semiconductor material of the n layer (I). Further, it is more preferably 0.05 eV to 0.5 eV larger than the n-type semiconductor material of the n layer (I), more preferably 0.05 eV to 0.2 eV, and further preferably 0.1 eV.
また、正孔障壁層(b)の化合物は、n層(I)のn型半導体材料より電子移動度が大きいと好ましい。正孔障壁層(b)の化合物の電子移動度は、好ましくは1×10-5cm2/Vs以上であり、より好ましくは1×10-4cm2/Vs以上である。電子移動度の測定方法は上記と同じである。
The compound of the hole blocking layer (b) preferably has a higher electron mobility than the n-type semiconductor material of the n layer (I). The electron mobility of the compound of the hole blocking layer (b) is preferably 1 × 10 −5 cm 2 / Vs or more, more preferably 1 × 10 −4 cm 2 / Vs or more. The method for measuring electron mobility is the same as described above.
正孔障壁層(b)の化合物としては、C60又はその誘導体が好ましい。
As the compound of the hole blocking layer (b), C60 or a derivative thereof is preferable.
また、正孔障壁層(b)の厚さは、正孔の移動を阻止し、電子の移動を妨げない厚さである。ここでいう「正孔の移動を阻止し、電子の移動を妨げない厚さ」とは、p層とn層(I)の界面で生じた正孔の陰極側への移動を妨げるために薄すぎない厚さであり、かつp層とn層(I)の界面で生じた電子が陰極側へ移動するのを妨げないために厚すぎない厚さをいう。このようにすることで、再結合失活要因をブロックし、抑制することで、高効率の光電変換特性と有する有機太陽電池が作製できる。「正孔の移動を阻止し、電子の移動を妨げない厚さ」は材料に依存するが、0.1~9nmであると好ましく、0.1~5nmであるとより好ましく、0.1~3nmであるとより好ましい。
0.1nm未満であると正孔障壁としての機能が十分機能しないおそれがあり、9nm超であると電子の移動を妨げるおそれがある。 The thickness of the hole barrier layer (b) is a thickness that prevents the movement of holes and does not prevent the movement of electrons. The term “thickness that prevents the movement of holes and does not hinder the movement of electrons” herein refers to a thin film that prevents the movement of holes generated at the interface between the p layer and the n layer (I) to the cathode side. This is a thickness that is not too thick, and is not too thick so as not to prevent electrons generated at the interface between the p layer and the n layer (I) from moving to the cathode side. By doing in this way, the organic solar cell which has a highly efficient photoelectric conversion characteristic can be produced by blocking and suppressing a recombination deactivation factor. “Thickness that prevents the movement of holes and does not prevent the movement of electrons” depends on the material, but is preferably 0.1 to 9 nm, more preferably 0.1 to 5 nm, and more preferably 0.1 to 5 nm. More preferably, it is 3 nm.
If the thickness is less than 0.1 nm, the function as a hole barrier may not function sufficiently, and if it exceeds 9 nm, the movement of electrons may be hindered.
0.1nm未満であると正孔障壁としての機能が十分機能しないおそれがあり、9nm超であると電子の移動を妨げるおそれがある。 The thickness of the hole barrier layer (b) is a thickness that prevents the movement of holes and does not prevent the movement of electrons. The term “thickness that prevents the movement of holes and does not hinder the movement of electrons” herein refers to a thin film that prevents the movement of holes generated at the interface between the p layer and the n layer (I) to the cathode side. This is a thickness that is not too thick, and is not too thick so as not to prevent electrons generated at the interface between the p layer and the n layer (I) from moving to the cathode side. By doing in this way, the organic solar cell which has a highly efficient photoelectric conversion characteristic can be produced by blocking and suppressing a recombination deactivation factor. “Thickness that prevents the movement of holes and does not prevent the movement of electrons” depends on the material, but is preferably 0.1 to 9 nm, more preferably 0.1 to 5 nm, and more preferably 0.1 to 5 nm. More preferably, it is 3 nm.
If the thickness is less than 0.1 nm, the function as a hole barrier may not function sufficiently, and if it exceeds 9 nm, the movement of electrons may be hindered.
また、正孔障壁層(b)は、p層とn層(I)の界面近くに設けられていると好ましく、p層とn層(I)の界面との距離、即ちn層(I)の厚さが、例えば0.1~40nmであり、好ましくは1.0~40nmである。更に好ましくは1.0~30nmである。
p層とn層(I)の界面と正孔障壁層(b)の距離が近いほど、より正孔をブロックし電子の輸送を促進することが考えられる。 The hole blocking layer (b) is preferably provided near the interface between the p layer and the n layer (I), and the distance between the interface between the p layer and the n layer (I), that is, the n layer (I). Is, for example, 0.1 to 40 nm, preferably 1.0 to 40 nm. More preferably, it is 1.0 to 30 nm.
It is conceivable that the closer the distance between the interface between the p layer and the n layer (I) and the hole blocking layer (b), the more the holes are blocked and the electron transport is promoted.
p層とn層(I)の界面と正孔障壁層(b)の距離が近いほど、より正孔をブロックし電子の輸送を促進することが考えられる。 The hole blocking layer (b) is preferably provided near the interface between the p layer and the n layer (I), and the distance between the interface between the p layer and the n layer (I), that is, the n layer (I). Is, for example, 0.1 to 40 nm, preferably 1.0 to 40 nm. More preferably, it is 1.0 to 30 nm.
It is conceivable that the closer the distance between the interface between the p layer and the n layer (I) and the hole blocking layer (b), the more the holes are blocked and the electron transport is promoted.
6.バッファー層
一般に、有機薄膜太陽電池は総膜厚が薄いことが多く、そのため上部電極と下部電極が短絡し、セル作製の歩留まりが低下することが多い。このような場合には、バッファー層を積層することによってこれを防止することが好ましい。 6). Buffer layer In general, organic thin film solar cells often have a thin total film thickness, and therefore, the upper electrode and the lower electrode are short-circuited, and the yield of cell fabrication often decreases. In such a case, it is preferable to prevent this by laminating a buffer layer.
一般に、有機薄膜太陽電池は総膜厚が薄いことが多く、そのため上部電極と下部電極が短絡し、セル作製の歩留まりが低下することが多い。このような場合には、バッファー層を積層することによってこれを防止することが好ましい。 6). Buffer layer In general, organic thin film solar cells often have a thin total film thickness, and therefore, the upper electrode and the lower electrode are short-circuited, and the yield of cell fabrication often decreases. In such a case, it is preferable to prevent this by laminating a buffer layer.
バッファー層に好ましい化合物としては、膜厚を厚くしても短絡電流が低下しないようにキャリア移動度が充分に高い化合物が好ましい。例えば、低分子化合物であれば下記に示すNTCDAに代表される芳香族環状酸無水物等が挙げられ、高分子化合物であればポリ(3、4-エチレンジオキシ)チオフェン:ポリスチレンスルホネート(PEDOT:PSS)、ポリアニリン:カンファースルホン酸(PANI:CSA)等に代表される公知の導電性高分子等が挙げられる。
As a preferable compound for the buffer layer, a compound having sufficiently high carrier mobility is preferable so that the short-circuit current does not decrease even when the film thickness is increased. For example, an aromatic cyclic acid anhydride represented by NTCDA shown below is exemplified for a low molecular compound, and poly (3,4-ethylenedioxy) thiophene: polystyrene sulfonate (PEDOT: PSS), polyaniline: camphorsulfonic acid (PANI: CSA), and other known conductive polymers.
また、バッファー層には、励起子が電極まで拡散して失活してしまうのを防止する役割を持たせることも可能である。このように励起子阻止層としてバッファー層を挿入することは、高効率化のために有効である。励起子阻止層は陽極側、陰極側のいずれにも挿入することができ、両方同時に挿入することも可能である。
Also, the buffer layer can have a role of preventing the excitons from diffusing to the electrodes and being deactivated. Inserting a buffer layer as an exciton blocking layer in this way is effective for increasing efficiency. The exciton blocking layer can be inserted on either the anode side or the cathode side, or both can be inserted simultaneously.
この場合、励起子阻止層として好ましい材料としては、例えば有機EL用途で公知な正孔障壁層用材料又は電子障壁層用材料等が挙げられる。正孔障壁層として好ましい材料は、イオン化ポテンシャルが充分に大きい化合物であり、電子障壁層として好ましい材料は、電子親和力が充分に小さい化合物である。具体的には有機EL用途で公知な材料であるバソクプロイン(BCP)、バソフェナントロリン(BPhen)等が陰極側の正孔障壁層材料として挙げられる。
In this case, as a preferable material for the exciton blocking layer, for example, a well-known material for a hole barrier layer or a material for an electron barrier layer in organic EL applications can be used. A preferable material for the hole blocking layer is a compound having a sufficiently large ionization potential, and a preferable material for the electron blocking layer is a compound having a sufficiently small electron affinity. Specifically, bathocuproin (BCP), bathophenanthroline (BPhen), and the like, which are well-known materials for organic EL applications, can be used as the cathode-side hole barrier layer material.
さらに、バッファー層には、上記n層材料として例示した無機半導体化合物を用いてもよい。また、p型無機半導体化合物としてはCdTe、p-Si、SiC、GaAs、WO3等を用いることができる。
Furthermore, you may use the inorganic semiconductor compound illustrated as said n layer material for a buffer layer. Further, as the p-type inorganic semiconductor compound, CdTe, p-Si, SiC, GaAs, WO 3 or the like can be used.
7.基板
基板は、機械的、熱的強度を有し、透明性を有するものが好ましい。例えば、ガラス基板及び透明性樹脂フィルムがある。透明性樹脂フィルムとしては、ポリエチレン、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、ポリプロピレン、ポリスチレン、ポリメチルメタアクリレート、ポリ塩化ビニル、ポリビニルアルコール、ポリビニルブチラール、ナイロン、ポリエーテルエーテルケトン、ポリサルホン、ポリエーテルサルフォン、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、ポリビニルフルオライド、テトラフルオロエチレン-エチレン共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、ポリエステル、ポリカーボネート、ポリウレタン、ポリイミド、ポリエーテルイミド、ポリイミド、ポリプロピレン等が挙げられる。 7). Substrate The substrate preferably has mechanical and thermal strength and transparency. For example, there are a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.
基板は、機械的、熱的強度を有し、透明性を有するものが好ましい。例えば、ガラス基板及び透明性樹脂フィルムがある。透明性樹脂フィルムとしては、ポリエチレン、エチレン-酢酸ビニル共重合体、エチレン-ビニルアルコール共重合体、ポリプロピレン、ポリスチレン、ポリメチルメタアクリレート、ポリ塩化ビニル、ポリビニルアルコール、ポリビニルブチラール、ナイロン、ポリエーテルエーテルケトン、ポリサルホン、ポリエーテルサルフォン、テトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体、ポリビニルフルオライド、テトラフルオロエチレン-エチレン共重合体、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体、ポリクロロトリフルオロエチレン、ポリビニリデンフルオライド、ポリエステル、ポリカーボネート、ポリウレタン、ポリイミド、ポリエーテルイミド、ポリイミド、ポリプロピレン等が挙げられる。 7). Substrate The substrate preferably has mechanical and thermal strength and transparency. For example, there are a glass substrate and a transparent resin film. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, polypropylene, etc. It is.
本発明の有機太陽電池の各層の形成は、真空蒸着、スパッタリング、プラズマ、イオンプレーティング等の乾式成膜法やスピンコーティング、ディップコート、キャスティング、ロールコート、フローコーティング、インクジェット等の湿式成膜法を適用することができる。
The formation of each layer of the organic solar cell of the present invention is performed by a dry film formation method such as vacuum deposition, sputtering, plasma, ion plating, or a wet film formation method such as spin coating, dip coating, casting, roll coating, flow coating, and ink jet. Can be applied.
正孔障壁層、n層(I)以外の各層の膜厚は特に限定されないが、適切な膜厚に設定する。一般に有機薄膜の励起子拡散長は短いことが知られているため、膜厚が厚すぎると励起子がヘテロ界面に到達する前に失活してしまうため光電変換効率が低くなる。膜厚が薄すぎるとピンホール等が発生してしまうため、充分なダイオード特性が得られないため、変換効率が低下する。通常の膜厚は1nmから10μmの範囲が適しているが、5nmから0.2μmの範囲がさらに好ましい。
The film thickness of each layer other than the hole barrier layer and the n layer (I) is not particularly limited, but is set to an appropriate film thickness. Since it is generally known that the exciton diffusion length of an organic thin film is short, if the film thickness is too thick, the exciton is deactivated before reaching the heterointerface, resulting in low photoelectric conversion efficiency. If the film thickness is too thin, pinholes and the like are generated, so that sufficient diode characteristics cannot be obtained, resulting in a decrease in conversion efficiency. The normal film thickness is suitably in the range of 1 nm to 10 μm, but more preferably in the range of 5 nm to 0.2 μm.
乾式成膜法の場合、公知の抵抗加熱法が好ましく、混合層の形成には、例えば、複数の蒸発源からの同時蒸着による成膜方法が好ましい。さらに好ましくは、成膜時に基板温度を制御する。
In the case of a dry film forming method, a known resistance heating method is preferable, and for forming a mixed layer, for example, a film forming method by simultaneous vapor deposition from a plurality of evaporation sources is preferable. More preferably, the substrate temperature is controlled during film formation.
湿式成膜法の場合、各層を形成する材料を、適切な溶媒に溶解又は分散させて発光性有機溶液を調製し、薄膜を形成するが、任意の溶媒を使用できる。例えば、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素、テトラクロロエタン、トリクロロエタン、クロロベンゼン、ジクロロベンゼン、クロロトルエン等のハロゲン系炭化水素系溶媒や、ジブチルエーテル、テトラヒドロフラン、ジオキサン、アニソール等のエーテル系溶媒、メタノールやエタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノール、メチルセロソルブ、エチルセロソルブ、エチレングリコール等のアルコール系溶媒、ベンゼン、トルエン、キシレン、エチルベンゼン、ヘキサン、オクタン、デカン、テトラリン等の炭化水素系溶媒、酢酸エチル、酢酸ブチル、酢酸アミル等のエステル系溶媒等が挙げられる。
中でも、炭化水素系溶媒又はエーテル系溶媒が好ましい。また、これらの溶媒は単独で使用しても複数混合して用いてもよい。尚、使用可能な溶媒は、これらに限定されるものではない。 In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a light-emitting organic solution to form a thin film, and any solvent can be used. For example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, methanol, Alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, tetralin, Examples include ester solvents such as ethyl acetate, butyl acetate, and amyl acetate.
Of these, hydrocarbon solvents or ether solvents are preferred. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.
中でも、炭化水素系溶媒又はエーテル系溶媒が好ましい。また、これらの溶媒は単独で使用しても複数混合して用いてもよい。尚、使用可能な溶媒は、これらに限定されるものではない。 In the case of a wet film forming method, a material for forming each layer is dissolved or dispersed in an appropriate solvent to prepare a light-emitting organic solution to form a thin film, and any solvent can be used. For example, halogenated hydrocarbon solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ether solvents such as dibutyl ether, tetrahydrofuran, dioxane, anisole, methanol, Alcohol solvents such as ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, hexane, octane, decane, tetralin, Examples include ester solvents such as ethyl acetate, butyl acetate, and amyl acetate.
Of these, hydrocarbon solvents or ether solvents are preferred. These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.
本発明においては、有機太陽電池のいずれの有機薄膜層においても、成膜性向上、膜のピンホール防止等のため適切な樹脂や添加剤を使用してもよい。使用の可能な樹脂としては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリウレタン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース等の絶縁性樹脂及びそれらの共重合体、ポリ-N-ビニルカルバゾール、ポリシラン等の光導電性樹脂、ポリチオフェン、ポリピロール等の導電性樹脂を挙げられる。
また、添加剤としては、酸化防止剤、紫外線吸収剤、可塑剤等が挙げられる。 In the present invention, in any organic thin film layer of the organic solar battery, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film. Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
また、添加剤としては、酸化防止剤、紫外線吸収剤、可塑剤等が挙げられる。 In the present invention, in any organic thin film layer of the organic solar battery, an appropriate resin or additive may be used for improving the film formability and preventing pinholes in the film. Usable resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose and other insulating resins and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.
Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.
実施例1
図1に示す有機太陽電池1を作製した。具体的には、25mm×75mm×0.7mm厚のITO透明電極10付きガラス基板をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間実施した。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず下部電極である透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして、化合物Aを抵抗加熱蒸着により1Å/sで成膜し、膜厚40nmのp層20とした。 Example 1
The organic solar cell 1 shown in FIG. 1 was produced. Specifically, the glass substrate with the ITO transparent electrode 10 having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line as the lower electrode is formed. Was formed by resistance heating vapor deposition at 1 Å / s to form a p-layer 20 having a thickness of 40 nm.
図1に示す有機太陽電池1を作製した。具体的には、25mm×75mm×0.7mm厚のITO透明電極10付きガラス基板をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間実施した。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず下部電極である透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして、化合物Aを抵抗加熱蒸着により1Å/sで成膜し、膜厚40nmのp層20とした。 Example 1
The organic solar cell 1 shown in FIG. 1 was produced. Specifically, the glass substrate with the ITO transparent electrode 10 having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line as the lower electrode is formed. Was formed by resistance heating vapor deposition at 1 Å / s to form a p-
続けてその上に、C70を抵抗加熱蒸着により1Å/sで成膜して膜厚10nmのn層(n層(I))30を形成し、その上にC60を抵抗加熱蒸着により1Å/sで成膜して膜厚3nmの正孔障壁層40を形成し、さらにその上にC70を抵抗加熱蒸着により1Å/sで成膜して膜厚30nmのn層(n層(II))50を形成した。その後、バソクプロイン(BCP)を抵抗加熱蒸着により1Å/sで成膜して10nmのバッファー層60とした。
Subsequently, C 70 is deposited at 1 Å / s by resistance heating deposition to form an n layer (n layer (I)) 30 having a thickness of 10 nm, and C 60 is deposited at 1 に よ り by resistance heating deposition. Then, a hole blocking layer 40 having a thickness of 3 nm is formed, and C 70 is further formed thereon by resistance heating vapor deposition at 1 Å / s to form an n layer (n layer (II )) 50 was formed. Thereafter, bathocuproine (BCP) was formed into a 10 nm buffer layer 60 by resistance heating vapor deposition at 1 Å / s.
尚、C60のIpは6.5eVであり、C70のIpは6.4eVである。また、C60の電子移動度は8×10-2cm2/Vsであり、C70の電子移動度は2×10-3cm2/Vsである。Ipは上述の方法により測定した。
尚、C60、C70の電子移動度の値は、R.C.Haddon J.Am.Chem.Soc.1996,118,p.3041-3042による。 Incidentally, Ip of C 60 is 6.5 eV, Ip of C 70 is 6.4 eV. The electron mobility of C 60 is 8 × 10 −2 cm 2 / Vs, and the electron mobility of C 70 is 2 × 10 −3 cm 2 / Vs. Ip was measured by the method described above.
The value of the electron mobility of the C 60, C 70 is, R. C. Haddon J.H. Am. Chem. Soc. 1996, 118, p. 3041-3042.
尚、C60、C70の電子移動度の値は、R.C.Haddon J.Am.Chem.Soc.1996,118,p.3041-3042による。 Incidentally, Ip of C 60 is 6.5 eV, Ip of C 70 is 6.4 eV. The electron mobility of C 60 is 8 × 10 −2 cm 2 / Vs, and the electron mobility of C 70 is 2 × 10 −3 cm 2 / Vs. Ip was measured by the method described above.
The value of the electron mobility of the C 60, C 70 is, R. C. Haddon J.H. Am. Chem. Soc. 1996, 118, p. 3041-3042.
最後に、連続して対向電極70として金属Alを膜厚80nmで蒸着させ、有機薄膜太陽電池1を作製した。素子面積は1.0cm2であった。
Finally, metal Al was continuously deposited as a counter electrode 70 with a film thickness of 80 nm to produce the organic thin film solar cell 1. The element area was 1.0 cm 2 .
作製した有機太陽電池を、AM1.5条件下(光強度(Pin)100mW/cm2)でI-V特性を測定した。開放端電圧(Voc)、短絡電流密度(Jsc)、曲線因子(FF)、光電変換効率(η)を表1に示す。
The IV characteristics of the produced organic solar cell were measured under AM1.5 conditions (light intensity (Pin) 100 mW / cm 2 ). Table 1 shows the open-circuit voltage (Voc), the short-circuit current density (Jsc), the fill factor (FF), and the photoelectric conversion efficiency (η).
光電変換効率(η)は次式によって求めた。
式中、Vocは開放端電圧、Jscは短絡電流密度、FFは曲線因子、Pinは入射光エネルギーである。即ち、同じPinに対して、Voc、Jsc及びFFがいずれも大きな化合物ほど優れた変換効率を示す。
The photoelectric conversion efficiency (η) was obtained by the following formula.
In the equation, Voc is an open circuit voltage, Jsc is a short-circuit current density, FF is a fill factor, and Pin is incident light energy. That is, for the same Pin, a compound having a larger Voc, Jsc, and FF shows better conversion efficiency.
図2に、有機薄膜太陽電池1のエネルギーを模式的に示す。p層20とn層30の界面で生じた正孔の一部はn層30内に移動するが、C70よりIpの大きいC60を含む正孔障壁層40により、正孔が陰極側へ移動することが阻止される。
また、C60はC70よりもAfが小さいが、C60は電子移動度が高く、さらにC60層(正孔障壁層40)が薄いため、p層20とn層30の界面で生じた電子は正孔障壁層40を超えて陰極側へ移動できる。 FIG. 2 schematically shows the energy of the organic thin film solar cell 1. Some of the holes generated at the interface between thep layer 20 and the n layer 30 move into the n layer 30, but the holes are moved to the cathode side by the hole blocking layer 40 containing C 60 having a larger Ip than C 70 . It is prevented from moving.
C 60 has a smaller Af than C 70, but C 60 has higher electron mobility, and the C 60 layer (hole blocking layer 40) is thin, so that it is generated at the interface between thep layer 20 and the n layer 30. Electrons can move beyond the hole barrier layer 40 to the cathode side.
また、C60はC70よりもAfが小さいが、C60は電子移動度が高く、さらにC60層(正孔障壁層40)が薄いため、p層20とn層30の界面で生じた電子は正孔障壁層40を超えて陰極側へ移動できる。 FIG. 2 schematically shows the energy of the organic thin film solar cell 1. Some of the holes generated at the interface between the
C 60 has a smaller Af than C 70, but C 60 has higher electron mobility, and the C 60 layer (hole blocking layer 40) is thin, so that it is generated at the interface between the
実施例2
2つのn層の膜厚をいずれも20nmとした他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Example 2
An organic solar cell was produced and evaluated in the same manner as in Example 1 except that the thickness of each of the two n layers was 20 nm. The results are shown in Table 1.
2つのn層の膜厚をいずれも20nmとした他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Example 2
An organic solar cell was produced and evaluated in the same manner as in Example 1 except that the thickness of each of the two n layers was 20 nm. The results are shown in Table 1.
実施例3
n層(I)の膜厚を30nm、n層(II)の膜厚を10nmとした他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Example 3
An organic solar cell was prepared and evaluated in the same manner as in Example 1 except that the thickness of the n layer (I) was 30 nm and the thickness of the n layer (II) was 10 nm. The results are shown in Table 1.
n層(I)の膜厚を30nm、n層(II)の膜厚を10nmとした他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Example 3
An organic solar cell was prepared and evaluated in the same manner as in Example 1 except that the thickness of the n layer (I) was 30 nm and the thickness of the n layer (II) was 10 nm. The results are shown in Table 1.
比較例1
p層上に、C70を抵抗加熱蒸着により1Å/sで成膜して膜厚40nmのn層とし、正孔障壁層及び他のn層を設けなかった他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Comparative Example 1
on the p layer, an n layer having a thickness of 40nm was deposited at 1 Å / s to C 70 by resistance heating deposition, except that no a hole barrier layer and the other n-layer, in the same manner as in Example 1 An organic solar cell was prepared and evaluated. The results are shown in Table 1.
p層上に、C70を抵抗加熱蒸着により1Å/sで成膜して膜厚40nmのn層とし、正孔障壁層及び他のn層を設けなかった他は、実施例1と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Comparative Example 1
on the p layer, an n layer having a thickness of 40nm was deposited at 1 Å / s to C 70 by resistance heating deposition, except that no a hole barrier layer and the other n-layer, in the same manner as in Example 1 An organic solar cell was prepared and evaluated. The results are shown in Table 1.
比較例2
正孔障壁層の膜厚を10nmとした他は、実施例2と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Comparative Example 2
An organic solar cell was prepared and evaluated in the same manner as in Example 2 except that the thickness of the hole blocking layer was 10 nm. The results are shown in Table 1.
正孔障壁層の膜厚を10nmとした他は、実施例2と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。 Comparative Example 2
An organic solar cell was prepared and evaluated in the same manner as in Example 2 except that the thickness of the hole blocking layer was 10 nm. The results are shown in Table 1.
比較例3
正孔障壁層の膜厚を20nmとした他は、実施例2と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。比較例2、3においては、正孔障壁層が厚すぎるため、電子の陰極への移動が妨げられて変換効率が低下した。 Comparative Example 3
An organic solar cell was prepared and evaluated in the same manner as in Example 2 except that the thickness of the hole blocking layer was 20 nm. The results are shown in Table 1. In Comparative Examples 2 and 3, since the hole blocking layer was too thick, the movement of electrons to the cathode was hindered and the conversion efficiency was lowered.
正孔障壁層の膜厚を20nmとした他は、実施例2と同様にして有機太陽電池を作製し、評価した。結果を表1に示す。比較例2、3においては、正孔障壁層が厚すぎるため、電子の陰極への移動が妨げられて変換効率が低下した。 Comparative Example 3
An organic solar cell was prepared and evaluated in the same manner as in Example 2 except that the thickness of the hole blocking layer was 20 nm. The results are shown in Table 1. In Comparative Examples 2 and 3, since the hole blocking layer was too thick, the movement of electrons to the cathode was hindered and the conversion efficiency was lowered.
実施例4
図3に示す有機太陽電池2を作製した。具体的には、25mm×75mm×0.7mm厚のITO透明電極110付きガラス基板をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間実施した。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず下部電極である透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして、化合物Aを抵抗加熱蒸着により1Å/sで成膜して、膜厚10nmのp層120とした。 Example 4
The organic solar cell 2 shown in FIG. 3 was produced. Specifically, a glass substrate with an ITO transparent electrode 110 having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line as the lower electrode is formed. Was formed by resistance heating vapor deposition at 1 加熱 / s to form a p-layer 120 having a thickness of 10 nm.
図3に示す有機太陽電池2を作製した。具体的には、25mm×75mm×0.7mm厚のITO透明電極110付きガラス基板をイソプロピルアルコール中で超音波洗浄を5分間行なった後、UVオゾン洗浄を30分間実施した。洗浄後の透明電極ライン付きガラス基板を真空蒸着装置の基板ホルダーに装着し、まず下部電極である透明電極ラインが形成されている側の面上に、前記透明電極を覆うようにして、化合物Aを抵抗加熱蒸着により1Å/sで成膜して、膜厚10nmのp層120とした。 Example 4
The organic solar cell 2 shown in FIG. 3 was produced. Specifically, a glass substrate with an ITO transparent electrode 110 having a thickness of 25 mm × 75 mm × 0.7 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. The glass substrate with the transparent electrode line after the cleaning is mounted on a substrate holder of a vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line as the lower electrode is formed. Was formed by resistance heating vapor deposition at 1 加熱 / s to form a p-layer 120 having a thickness of 10 nm.
続いて、p層120上に、化合物Aを0.25Å/sで5nm、C70を1.0Å/sで20nmとなるように同時蒸着し、i層(混合層)130を形成した。次いで、i層130上に、C60を抵抗加熱蒸着により1Å/sで成膜して膜厚1nmの正孔障壁層140を形成し、その上にC70を抵抗加熱蒸着により1Å/sで成膜して膜厚20nmのn層150とした。
Then, on the p-layer 120, 5 nm Compound A at 0.25 Å / s, and co-evaporation so that 20nm to C 70 with 1.0 Å / s, to form the i-layer (mixed layer) 130. Next, C 60 is deposited on the i layer 130 at 1 蒸 着 / s by resistance heating evaporation to form a 1 nm-thick hole barrier layer 140, and C 70 is formed at 1 Å / s on resistance heating evaporation. A film was formed into an n layer 150 having a thickness of 20 nm.
n層150上に、バソクプロイン(BCP)を抵抗加熱蒸着により1Å/sで成膜して膜厚10nmのバッファー層160とした。最後に、連続して対向電極170として金属Alを80nm蒸着させ、有機薄膜太陽電池2を作製した。素子面積は1.0cm2であった。
得られた有機薄膜太陽電池について、実施例1と同様に評価した。結果を表2に示す。 On the n layer 150, bathocuproine (BCP) was deposited at 1 Å / s by resistance heating vapor deposition to form a buffer layer 160 having a thickness of 10 nm. Finally, 80 nm of metal Al was continuously deposited as the counter electrode 170 to produce the organic thin film solar cell 2. The element area was 1.0 cm 2 .
The obtained organic thin film solar cell was evaluated in the same manner as in Example 1. The results are shown in Table 2.
得られた有機薄膜太陽電池について、実施例1と同様に評価した。結果を表2に示す。 On the n layer 150, bathocuproine (BCP) was deposited at 1 Å / s by resistance heating vapor deposition to form a buffer layer 160 having a thickness of 10 nm. Finally, 80 nm of metal Al was continuously deposited as the counter electrode 170 to produce the organic thin film solar cell 2. The element area was 1.0 cm 2 .
The obtained organic thin film solar cell was evaluated in the same manner as in Example 1. The results are shown in Table 2.
実施例5~6
正孔障壁層の膜厚を3nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Examples 5-6
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 3 nm. The results are shown in Table 2.
正孔障壁層の膜厚を3nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Examples 5-6
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 3 nm. The results are shown in Table 2.
実施例7
正孔障壁層の膜厚を10nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Example 7
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 10 nm. The results are shown in Table 2.
正孔障壁層の膜厚を10nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Example 7
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 10 nm. The results are shown in Table 2.
比較例4
正孔障壁層を設けなかった他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Comparative Example 4
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the hole blocking layer was not provided. The results are shown in Table 2.
正孔障壁層を設けなかった他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。 Comparative Example 4
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the hole blocking layer was not provided. The results are shown in Table 2.
比較例5
正孔障壁層の膜厚を20nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。比較例5においては、正孔障壁層が厚すぎるため、電子の陰極への移動が妨げられて変換効率が低下した。 Comparative Example 5
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 20 nm. The results are shown in Table 2. In Comparative Example 5, since the hole barrier layer was too thick, the movement of electrons to the cathode was hindered and the conversion efficiency was lowered.
正孔障壁層の膜厚を20nmとした他は、実施例4と同様にして有機太陽電池を作製し、評価した。結果を表2に示す。比較例5においては、正孔障壁層が厚すぎるため、電子の陰極への移動が妨げられて変換効率が低下した。 Comparative Example 5
An organic solar cell was prepared and evaluated in the same manner as in Example 4 except that the thickness of the hole blocking layer was 20 nm. The results are shown in Table 2. In Comparative Example 5, since the hole barrier layer was too thick, the movement of electrons to the cathode was hindered and the conversion efficiency was lowered.
本発明の有機太陽電池は時計、携帯電話及びモバイルパソコン等の各種装置、電化製品等の電源又は補助電源として使用できる。充電機能のある二次電池と組み合わせ、暗所においても使用可能とし、適用用途を拡げることも可能である。
The organic solar cell of the present invention can be used as a power source or auxiliary power source for various devices such as watches, mobile phones and mobile personal computers, and electrical appliances. Combined with a rechargeable battery with a charging function, it can be used in the dark, and the application can be expanded.
上記に本発明の実施形態及び/又は実施例を幾つか詳細に説明したが、当業者は、本発明の新規な教示及び効果から実質的に離れることなく、これら例示である実施形態及び/又は実施例に多くの変更を加えることが容易である。従って、これらの多くの変更は本発明の範囲に含まれる。
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
この明細書に記載の文献及び本願のパリ優先の基礎となる日本出願明細書の内容を全てここに援用する。 Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The contents of the documents described in this specification and the specification of the Japanese application that is the basis of Paris priority of the present application are all incorporated herein.
Claims (11)
- 第1電極、複数の有機層を含む活性層、第2電極をこの順に含む有機太陽電池であって、前記活性層が下記(A)及び(B)のいずれか一方である有機太陽電池。
(A)p型半導体層、p型半導体材料とn型半導体材料の混合層であるi層、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層の順に積層されてなる活性層
(B)p型半導体層、n型半導体層(I)、正孔の移動を阻止し、電子の移動を妨げない厚さの正孔障壁層、n型半導体層(II)の順に積層されてなる活性層 An organic solar battery including a first electrode, an active layer including a plurality of organic layers, and a second electrode in this order, wherein the active layer is one of the following (A) and (B).
(A) a p-type semiconductor layer, an i-layer that is a mixed layer of a p-type semiconductor material and an n-type semiconductor material, a hole barrier layer having a thickness that prevents hole movement and does not hinder electron movement, and an n-type semiconductor Active layer (B), p-type semiconductor layer, n-type semiconductor layer (I), layered in order of layers, hole-blocking layer with a thickness that prevents hole movement and does not hinder electron movement, n-type semiconductor Active layer that is laminated in the order of layer (II) - 前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより大きい請求項1に記載の有機太陽電池。 2. The ionization potential of a compound contained in the hole barrier layer is higher than an ionization potential of an n-type semiconductor material contained in the i layer or a compound contained in the n-type semiconductor layer (I). Organic solar cells.
- 前記正孔障壁層に含まれる化合物のイオン化ポテンシャルが、前記i層に含まれるn型半導体材料のイオン化ポテンシャル又は前記n型半導体層(I)に含まれる化合物のイオン化ポテンシャルより0.01eV~1.0eV大きい請求項1又は2に記載の有機太陽電池。 The ionization potential of the compound contained in the hole barrier layer is 0.01 eV to 1... From the ionization potential of the n-type semiconductor material contained in the i layer or the ionization potential of the compound contained in the n-type semiconductor layer (I). The organic solar cell according to claim 1, wherein the organic solar cell is 0 eV larger.
- 前記正孔障壁層に含まれる化合物の電子移動度が、前記i層に含まれるn型半導体材料の電子移動度又は前記n型半導体層(I)に含まれる化合物の電子移動度よりも大きい請求項1~3のいずれかに記載の有機太陽電池。 The electron mobility of the compound contained in the hole blocking layer is higher than the electron mobility of the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I). Item 4. The organic solar cell according to any one of Items 1 to 3.
- 前記正孔障壁層に含まれる化合物の電子移動度が1×10-5cm2/Vs以上である請求項1~4のいずれかに記載の有機太陽電池。 5. The organic solar cell according to claim 1, wherein the compound contained in the hole barrier layer has an electron mobility of 1 × 10 −5 cm 2 / Vs or more.
- 前記(A)における正孔障壁層の厚さが0.1~19nmである請求項1~5のいずれかに記載の有機太陽電池。 The organic solar battery according to any one of claims 1 to 5, wherein a thickness of the hole blocking layer in (A) is 0.1 to 19 nm.
- 前記(B)における正孔障壁層の厚さが0.1~9nmである請求項1~5のいずれかに記載の有機太陽電池。 The organic solar battery according to any one of claims 1 to 5, wherein a thickness of the hole barrier layer in (B) is 0.1 to 9 nm.
- 前記(B)におけるn型半導体層(I)の厚さが0.1~40nmである請求項1~5、7のいずれかに記載の有機太陽電池。 The organic solar cell according to any one of claims 1 to 5, wherein the thickness of the n-type semiconductor layer (I) in (B) is 0.1 to 40 nm.
- 前記正孔障壁層に含まれる化合物がフラーレン又はフラーレン誘導体である請求項1~8のいずれかに記載の有機太陽電池。 The organic solar battery according to any one of claims 1 to 8, wherein the compound contained in the hole blocking layer is a fullerene or a fullerene derivative.
- 前記正孔障壁層に含まれる化合物がC60又はその誘導体である請求項9に記載の有機太陽電池。 The organic solar cell according to claim 9, wherein the compound contained in the hole blocking layer is C60 or a derivative thereof.
- 前記i層に含まれるn型半導体材料又はn型半導体層(I)に含まれる化合物がC70又はその誘導体である請求項1~10のいずれかに記載の有機太陽電池。 The organic solar battery according to any one of claims 1 to 10, wherein the n-type semiconductor material contained in the i layer or the compound contained in the n-type semiconductor layer (I) is C70 or a derivative thereof.
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