WO2010140187A1 - Photoelectric conversion element and method for manufacturing the same - Google Patents
Photoelectric conversion element and method for manufacturing the same Download PDFInfo
- Publication number
- WO2010140187A1 WO2010140187A1 PCT/JP2009/002458 JP2009002458W WO2010140187A1 WO 2010140187 A1 WO2010140187 A1 WO 2010140187A1 JP 2009002458 W JP2009002458 W JP 2009002458W WO 2010140187 A1 WO2010140187 A1 WO 2010140187A1
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- WO
- WIPO (PCT)
- Prior art keywords
- photoelectric conversion
- anode
- layer
- conversion element
- cathode
- Prior art date
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 87
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 238000000034 method Methods 0.000 title description 19
- 239000012535 impurity Substances 0.000 claims abstract description 34
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- 239000000872 buffer Substances 0.000 claims abstract description 23
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 42
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 10
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims description 9
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 8
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- 150000002500 ions Chemical class 0.000 claims description 5
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- 229910052581 Si3N4 Inorganic materials 0.000 description 2
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- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/311—Purifying organic semiconductor materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/50—Photovoltaic [PV] devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
- H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
- H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a photoelectric conversion element and a manufacturing method thereof.
- the photoelectric conversion element is an element that converts light into electric energy or an element that converts electric energy into light.
- a typical element using the former photoelectric conversion is a solar cell.
- a typical element using the latter photoelectric conversion is a light emitting element such as a light emitting diode or an electroluminescence (EL) element.
- Patent Document 1 discloses an organic solar cell having a structure in which an anode, a hole transport layer, an organic photoelectric conversion layer, an electron transport layer, and a cathode are laminated in this order.
- Patent Document 2 discloses a light emitting device having a structure in which an anode, a hole injection layer, an organic light emitting layer, an electron transport layer, an electron injection layer, and a cathode are laminated in this order.
- the solar cell and the light emitting element have the same laminated structure in which the photoelectric conversion layer is disposed between the anode and the cathode.
- the hole transport or hole injection layer is one of functional layers provided so that charges are quickly transferred between the anode and the photoelectric conversion layer.
- PDOT-PSS polyethylenedioxythiophene-polystyrenesulfonic acid
- Patent Document 2 describes that polyethylene dioxythiophene-polystyrenesulfonic acid contains 600 ppm to 1000 ppm of Na + (sodium ion) as an impurity.
- Na + (sodium ion) as an impurity is contained in the hole injection layer, the photoelectric conversion efficiency of the light emitting layer may be lowered. Therefore, in the light emitting element of Patent Document 2, the influence of Na + (sodium ions) on the photoelectric conversion layer is obtained by adding a new mixed layer on the cathode side of the light emitting layer and moving the light emitting region away from the hole injection layer. Is made smaller.
- Patent Document 2 it is not preferable to add a mixed layer to change the position of the light emitting region in order to suppress the influence of impurities, not only from the element structure but also from the viewpoint of manufacturing cost.
- the means disclosed in Patent Document 2 may be effective in the case of a light-emitting element that converts electric energy into light, but in the case of a solar cell, charge separation is performed in the entire photoelectric conversion layer. Since it is necessary to cause this, even if a mixed layer is added, a decrease in power generation efficiency may not be suppressed.
- Patent Document 1 which discloses a solar cell, forms a hole transport layer using polyethylenedioxythiophene-polystyrenesulfonic acid, but does not disclose any influence of impurities.
- an object of the present invention is to provide, for example, a photoelectric conversion element that can suppress the influence of impurities and exhibit high photoelectric conversion efficiency and a method for manufacturing the photoelectric conversion element.
- the photoelectric conversion here includes not only the case of converting light into electric energy but also the case of converting electric energy into light.
- the photoelectric conversion element of the present invention is disposed between the anode, the cathode, the photoelectric conversion layer disposed between the anode and the cathode, and the anode and the photoelectric conversion layer as described in claim 1.
- a photoelectric conversion element including at least a hole buffer layer is characterized in that a sodium ion concentration as an impurity contained in the hole buffer layer is 100 ppm or less.
- the photoelectric conversion element of the present invention is disposed between an anode, a cathode, a photoelectric conversion layer disposed between the anode and the cathode, and between the anode and the photoelectric conversion layer.
- the hole buffer layer is formed using a material having a sodium ion concentration of 100 ppm or less as an impurity.
- FF fill factor
- FIG. 1 is a longitudinal sectional view of a photoelectric conversion element configured as a solar cell.
- the solar cell 1 according to the present embodiment includes a substrate 2, an anode 3 as a first electrode, a hole transport layer 4 as a hole buffer layer, a photoelectric that converts light into electrical energy.
- the conversion layer 5 and the cathode 6 as the second electrode are stacked in order.
- a sealing film may be formed so as to cover the upper surface and side surfaces of the stacked structure in order to prevent reaction with moisture and oxygen in the air atmosphere.
- the hole transport layer 4 is disposed for the purpose of improving the planarization of the anode 3 and the current extraction efficiency, for example.
- the concentration of Na + (sodium ion) as an impurity is 100 ppm (mass) or less, and particularly preferably 5 ppm or less.
- the hole transport layer 4 contains sulfur oxide (SOx) ions such as SO 4 as impurities, the preferred concentration of SOx ions is 5 ppm or less.
- SOx sulfur oxide
- the hole transport layer 4 can be formed by, for example, a coating method.
- the film thickness of the hole transport layer 4 is, for example, 10 to 1000 nm.
- positioned between the anode 3 and the photoelectric converting layer 5 is not restricted to the hole transport layer 4, A hole injection layer may be sufficient.
- the hole buffer layer may have a structure in which the hole transport layer 4 and the hole injection layer are laminated from the photoelectric conversion layer 5 toward the anode 3 side. It may be a single layer that also serves as a combination.
- the concentration of Na + (sodium ion) as an impurity contained in the hole buffer layer may be 100 ppm (mass) or less, particularly preferably 5 ppm or less.
- the material for forming the hole transport layer 4 may be any material having hole transport properties. Among these, it is preferable to use polyethylenedioxythiophene (PEDOT). More preferred is polyethylene dioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) obtained by combining polyethylene dioxythiophene (PEDOT) with polystyrene sulfonic acid (PSS). Further, the hole transport layer 4 may contain a material other than PEDOT or PEDOT-PSS. Examples of other materials include fine metal particles and CNT (Carbon Nanotube).
- the material for forming the hole transport layer 4 is not limited to the material containing PEDOT described above.
- examples of other materials include phthalocyanine compounds such as copper phthalocyanine (CuPc), starburst amines such as m-MTDATA, benzidine amine multimers, 4,4′-bis [N- (1-naphthyl) Aromatic tertiary amines such as —N-phenylamino] -biphenyl (NPB) and N-phenyl-p-phenylenediamine (PPD), 4- (di-P-tolylamino) -4 ′-[4- (di Organic materials such as stilbene compounds such as -P-tolylamino) styryl] stilbenzene, triazole derivatives, styrylamine compounds, buckyballs, and fullerenes such as C60 are used.
- a polymer dispersion material in which a low molecular material is dispersed in
- the material for forming the photoelectric conversion layer 5 may be any material that absorbs light and exhibits a photovoltaic action.
- fluorescent organometallic compounds such as (8-hydroxyquinolinato) aluminum complex (Alq3), 4,4′-bis (2,2′-diphenylvinyl) -biphenyl (DPVBi)
- Aromatic dimethylidin compounds such as 1, styrylbenzene compounds such as 1,4-bis (2-methylstyryl) benzene, 3- (4-biphenyl) -4-phenyl-5-t-butylphenyl-1,2,4-
- Fluorescent organic materials such as triazole derivatives such as triazole (TAZ), anthraquinone derivatives and fluorenol derivatives, polymer materials such as polyparafinylene vinylene (PPV), polyfluorene and polyvinylcarbazole (PVK), platinum complexes and iridium
- a phosphorescent organic material such as
- the organic material may not be used, and an inorganic material may be used.
- the material used for the photoelectric conversion layer 5 is preferably a material that absorbs in the visible light region, but even if it is a material that does not absorb in the visible light region, it absorbs in the visible light region by doping with a dye or the like. Can be.
- the photoelectric conversion layer 5 can be formed by, for example, a coating method.
- the film thickness of the photoelectric conversion layer 5 is, for example, 10 to 10,000 nm.
- the material of the substrate 2 is not particularly limited. However, in the case of the solar cell 1 shown in FIG. 1, since the light is taken in from the substrate 2 side, it is preferable to use the substrate 2 formed of a transparent material such as glass or transparent resin. Further, a flexible material such as a transparent film can be used.
- the material for forming the anode 3 can be a metal oxide such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide).
- ITO Indium Tin Oxide
- IZO Indium Zinc Oxide
- Such an anode 3 can be formed, for example, by vapor deposition or sputtering.
- the film thickness of the anode 3 is, for example, 50 to 1000 nm.
- the material for forming the anode 3 may not be a transparent material, and includes, for example, metals such as Al, Cr, Mo, Ni, Pt, Au, Ag, or the like. Materials such as alloys and intermetallic compounds can be used.
- the material for forming the cathode 6 is a single layer or a metal such as Al, Mg, Ag, Au, Ca, Li or a compound thereof, or an alloy containing them. It can be used by laminating.
- a cathode 6 can be formed by, for example, vapor deposition or sputtering.
- the film thickness of the cathode 6 is, for example, 50 to 1000 nm.
- a transparent material such as ITO, ZnO, or IZO.
- a material for forming the sealing film is, for example, a transparent inorganic material having a low water vapor or oxygen permeability. it can.
- silicon nitride (SiNx), silicon nitride oxide (SiOxNy), aluminum oxide (AlOx), aluminum nitride (AlNx), or the like can be used as an example.
- the solar cell 1 shown in FIG. 1 has a structure in which the photoelectric conversion layer 5 and the cathode 6 are adjacent to each other, but the present invention is not limited to this, and an electron transport layer and / or an electron injection layer can be interposed.
- the material for forming the electron transport layer or the electron injection layer may be any material that has high electron transport properties.
- silacyclopentadiene (silole) derivatives such as PyPySPyPy, nitro-substituted fluorenone derivatives, anthraquinodi Organic materials such as methane derivatives, metal complexes of 8-quinolinol derivatives such as tris (8-hydroxyquinolinate) aluminum (Alq3), metal phthalocyanine, 3- (4-biphenyl) -5- (4-t-butylphenyl) ) -4-phenyl-1,2,4-triazole (TAZ) and other triazole compounds, 2- (4-biphenylyl) -5- (4-t-butyl) -1,3,4-oxadiazol ( PBD) oxadiazole-based compounds such as carbon nanotubes, fullerene, LiF, such as Li 2 O It can be used alkali metal compound. However, it is not limited to these materials.
- the anode 3 is formed on the substrate 2 by using, for example, vapor deposition or sputtering. When patterning of the anode 3 is necessary, patterning can be performed using, for example, a photolithography method.
- the liquid material of the hole transport layer 4 is applied on the anode 3, and the solvent and moisture are removed by heating.
- the liquid material is obtained by dissolving or dispersing the material of the hole transport layer 4 as exemplified in an organic solvent, for example.
- the coating method for example, an inkjet method, a spray method, a spin coating method, a dip method, a die coating method, or the like can be used.
- the film thickness can be adjusted by, for example, the application amount and concentration of the liquid material.
- coated at the next process can be performed as needed.
- a crosslinking treatment by a photopolymerization reaction or the like, a hydrophilization treatment, or a hydrophobization treatment can be exemplified.
- a material that is insoluble with respect to the liquid material of the photoelectric conversion layer 5 may be selected.
- the liquid material of the photoelectric conversion layer 5 is applied on the hole transport layer 4 to form a film.
- the liquid material is obtained by dissolving or dispersing the material of the photoelectric conversion layer 5 as exemplified in an organic solvent, for example.
- an inkjet method, a spray method, a spin coating method, a dip method, a die coating method, or the like can be used as the coating method.
- the film thickness can be adjusted by, for example, the application amount and concentration of the liquid material.
- it is not limited to the coating method For example, you may form the photoelectric converting layer 5 with a vapor deposition method or a laser ablation method.
- the cathode 6 is formed on the photoelectric conversion layer 5 by using, for example, vapor deposition or sputtering.
- the solar cell 1 shown in FIG. 1 can be manufactured by performing an annealing process at a temperature of 110 to 165 ° C., for example.
- the annealing treatment may be performed before the cathode 6 is formed, at least after the hole transport layer 4 and the photoelectric conversion layer 5 are formed.
- the diffusion of Na + (sodium ions) can occur not only during photoelectric conversion but also during the manufacturing process. In particular, thermal diffusion is likely to occur during annealing performed at a high temperature. However, if the concentration of Na + (sodium ion) contained as an impurity is 100 ppm or less, it is possible to suppress the influence of Na + (sodium ion) on photoelectric conversion and stably obtain a highly efficient solar cell 1. it can.
- the Na + (sodium ion) concentration as the impurity of the hole transport layer 4 is between 200 ppm and 100 ppm.
- the efficiency of power generation There are three main factors that determine the efficiency of power generation: open-circuit voltage (Voc), short-circuit current (Jsc), and fill factor (FF), but in particular the impurity Na + (sodium ion) It can be seen that it is the fill factor (FF) that is affected and then the short circuit current (Jsc). It can be said that there is almost no influence on the open circuit voltage (Voc).
- the concentration of Na + (sodium ion) contained as an impurity in the hole transport layer 4 is set to 100 ppm or less, the influence of Na + (sodium ion) is suppressed and high photoelectric conversion efficiency is exhibited.
- the photoelectric conversion element which can be realized is realizable.
- Table 1 below shows test results using commercially available PEDOT-PSS as the material of the hole transport layer 4.
- 3 and 4 are graphs of the results of Table 1.
- Commercially available PEDOT-PSS often contains Na + (sodium ions) in the production process, and product grades are classified according to the concentration of Na + (sodium ions). In the test, these commercially available PEDOT-PSSs were used so that the concentrations of Na + (sodium ions) were 3.4 ppm, 50 ppm, 100 ppm, 200 ppm, and 360 ppm. The concentration of SO 4 ions contained as impurities was 5 ppm.
- a bulk heterostructure (film thickness: 120 nm) using P3HT and PCBM is used as the material of the photoelectric conversion layer 5
- ITO film thickness: 110 nm
- Al material
- the solar cell 1 of the present embodiment can suppress the influence of impurities on photoelectric conversion. Therefore, there is an advantage that a function film (mixed film) for suppressing the influence of impurities as in Patent Document 2 need not be newly added.
- the concentration of sulfur oxide (SOx) ions contained as impurities to 5 ppm or less, the influence of the impurities can be suppressed and high power generation efficiency can be obtained. It is particularly preferable that the concentrations of Na + (sodium ion) and sulfur oxide (SOx) ion are both 5 ppm.
- This embodiment is a modification of the first embodiment and relates to a photoelectric conversion element configured as a light emitting element.
- the light emitting element of the present embodiment has a configuration in which power is supplied to the anode 3 and the cathode 6, and electric energy is converted into light by the photoelectric conversion layer 5 to emit light. Except for the effect of converting electrical energy into light in this way, a structure similar to that shown in FIG. 1 can be obtained. Further, it can be manufactured by the process shown in FIG. However, in the case of a light emitting element, the annealing temperature may be lowered to about 100 ° C., for example. Even in the case of such a light-emitting element, the influence of impurities on photoelectric conversion can be suppressed as in the case of the first embodiment. As a result, light can be emitted with high efficiency.
- the anode, the cathode, the photoelectric conversion layer arranged between the anode and the cathode, and the anode and the photoelectric conversion layer are arranged.
- a concentration of Na + (sodium ion) as an impurity included in the hole buffer layer is 100 ppm or less.
- the hole buffer layer is formed using a material having a sodium ion concentration of 100 ppm or less as an impurity, thereby suppressing the influence of the impurity and increasing the photoelectric conversion element. It becomes possible to manufacture a photoelectric conversion element that can exhibit conversion efficiency.
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Abstract
Provided is a photoelectric conversion element which can exhibit a high photoelectric conversion efficiency by suppressing affects of impurities.
The photoelectric conversion element includes: an anode; a cathode; a photoelectric conversion layer arranged between the anode and the cathode; and an electron hole buffer layer arranged between the anode and the photoelectric conversion layer. The concentration of the sodium ion as impurities contained in the electron hole buffer layer is set to 100 ppm or below. This suppresses the affect of the impurities to the photoelectric conversion and increases the photoelectric conversion efficiency.
Description
本発明は、光電変換素子及びその製造方法に関する。
The present invention relates to a photoelectric conversion element and a manufacturing method thereof.
光電変換素子とは、光を電気エネルギーに変換する素子、又は電気エネルギーを光に変換する素子である。前者の光電変換を利用する代表的な素子は、太陽電池である。また、後者の光電変換を利用する代表的な素子は、発光ダイオードやエレクトロルミネッセンス（ＥＬ）素子などの発光素子である。
The photoelectric conversion element is an element that converts light into electric energy or an element that converts electric energy into light. A typical element using the former photoelectric conversion is a solar cell. A typical element using the latter photoelectric conversion is a light emitting element such as a light emitting diode or an electroluminescence (EL) element.
特許文献１には、陽極、正孔輸送層、有機光電変換層、電子輸送層、陰極の順に積層された構造の有機太陽電池が開示されている。一方、特許文献２には、陽極、正孔注入層、有機発光層、電子輸送層、電子注入層、陰極の順に積層された構造の発光素子が開示されている。このように、太陽電池と発光素子は、陽極と陰極の間に光電変換層を配置した同様の積層構造を有している。
Patent Document 1 discloses an organic solar cell having a structure in which an anode, a hole transport layer, an organic photoelectric conversion layer, an electron transport layer, and a cathode are laminated in this order. On the other hand, Patent Document 2 discloses a light emitting device having a structure in which an anode, a hole injection layer, an organic light emitting layer, an electron transport layer, an electron injection layer, and a cathode are laminated in this order. As described above, the solar cell and the light emitting element have the same laminated structure in which the photoelectric conversion layer is disposed between the anode and the cathode.
正孔輸送又は正孔注入層は、陽極と光電変換層との間で電荷が速やかに受け渡しされるように設けられる機能層の一つである。特許文献１の太陽電池である場合および特許文献２の発光素子である場合のいずれも、正孔輸送層又は正孔注入層を形成する材料としてポリエチレンジオキシチオフェン－ポリスチレンスルホン酸（ＰＥＤＯＴ－ＰＳＳ）を用いることが記載されている。
The hole transport or hole injection layer is one of functional layers provided so that charges are quickly transferred between the anode and the photoelectric conversion layer. In both the case of the solar cell of Patent Document 1 and the case of the light emitting device of Patent Document 2, polyethylenedioxythiophene-polystyrenesulfonic acid (PEDOT-PSS) is used as a material for forming the hole transport layer or the hole injection layer. Is described.
特許文献２には、ポリエチレンジオキシチオフェン－ポリスチレンスルホン酸に不純物としてＮａ＋（ナトリウムイオン）が６００ｐｐｍ～１０００ｐｐｍ含まれていることが記載されている。不純物となるＮａ＋（ナトリウムイオン）が正孔注入層に含まれる場合、発光層の光電変換効率が低下してしまう場合がある。そのため、特許文献２の発光素子は、発光層の陰極側に混合層を新たに追加して、発光領域を正孔注入層から遠ざけることにより、Ｎａ＋（ナトリウムイオン）が光電変換層へ与える影響を小さくしている。
Patent Document 2 describes that polyethylene dioxythiophene-polystyrenesulfonic acid contains 600 ppm to 1000 ppm of Na + (sodium ion) as an impurity. When Na + (sodium ion) as an impurity is contained in the hole injection layer, the photoelectric conversion efficiency of the light emitting layer may be lowered. Therefore, in the light emitting element of Patent Document 2, the influence of Na + (sodium ions) on the photoelectric conversion layer is obtained by adding a new mixed layer on the cathode side of the light emitting layer and moving the light emitting region away from the hole injection layer. Is made smaller.
しかしながら、特許文献２のように、不純物の影響を抑制するために混合層を追加して発光領域の位置を変えることは、素子構造だけでなく製作コストの観点からも決して好ましいとは言えない。さらに、特許文献２に開示されている手段は、電気エネルギーを光に変換する発光素子の場合には有効であるかもしれないが、太陽電池の場合は光電変換層の層中全域で電荷分離を起こす必要があるため、混合層を追加しても発電効率の低下を抑制できない場合がある。太陽電池について開示する特許文献１も、ポリエチレンジオキシチオフェン－ポリスチレンスルホン酸を用いて正孔輸送層を形成しているが、不純物の影響については何ら開示していない。
However, as in Patent Document 2, it is not preferable to add a mixed layer to change the position of the light emitting region in order to suppress the influence of impurities, not only from the element structure but also from the viewpoint of manufacturing cost. Further, the means disclosed in Patent Document 2 may be effective in the case of a light-emitting element that converts electric energy into light, but in the case of a solar cell, charge separation is performed in the entire photoelectric conversion layer. Since it is necessary to cause this, even if a mixed layer is added, a decrease in power generation efficiency may not be suppressed. Patent Document 1, which discloses a solar cell, forms a hole transport layer using polyethylenedioxythiophene-polystyrenesulfonic acid, but does not disclose any influence of impurities.
すなわち、本発明が解決しようとする課題には、上述した問題が一例として挙げられる。よって本発明の目的は、不純物の影響を抑制して、高い光電変換効率を発揮することのできる光電変換素子及びその製造方法を提供することが一例として挙げられる。ここでいう光電変換には、光を電気エネルギーに変換する場合のみならず、電気エネルギーを光に変換する場合も含まれる。
That is, the above-described problem is given as an example of the problem to be solved by the present invention. Therefore, an object of the present invention is to provide, for example, a photoelectric conversion element that can suppress the influence of impurities and exhibit high photoelectric conversion efficiency and a method for manufacturing the photoelectric conversion element. The photoelectric conversion here includes not only the case of converting light into electric energy but also the case of converting electric energy into light.
本発明の光電変換素子は、請求項１に記載のように、陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子において、前記正孔バッファ層に含まれる不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下であることを特徴とする。
The photoelectric conversion element of the present invention is disposed between the anode, the cathode, the photoelectric conversion layer disposed between the anode and the cathode, and the anode and the photoelectric conversion layer as described in claim 1. A photoelectric conversion element including at least a hole buffer layer is characterized in that a sodium ion concentration as an impurity contained in the hole buffer layer is 100 ppm or less.
本発明の光電変換素子は、請求項５に記載のように、陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子の製造方法において、不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下である材料を用いて前記正孔バッファ層を形成することを特徴とする。
The photoelectric conversion element of the present invention, as described in claim 5, is disposed between an anode, a cathode, a photoelectric conversion layer disposed between the anode and the cathode, and between the anode and the photoelectric conversion layer. In the method for manufacturing a photoelectric conversion element including at least a hole buffer layer, the hole buffer layer is formed using a material having a sodium ion concentration of 100 ppm or less as an impurity.
１ 太陽電池
２ 基板
３ 陽極
４ 正孔輸送層
５ 光電変換層
６ 陰極 DESCRIPTION OFSYMBOLS 1 Solar cell 2 Substrate 3 Anode 4 Hole transport layer 5 Photoelectric conversion layer 6 Cathode
２ 基板
３ 陽極
４ 正孔輸送層
５ 光電変換層
６ 陰極 DESCRIPTION OF
以下、本発明の好ましい実施形態による表示装置について、添付図面を参照しながら詳しく説明する。但し、以下に説明する実施形態によって本発明の技術的範囲は何ら限定解釈されることはない。
Hereinafter, a display device according to a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings. However, the technical scope of the present invention is not construed as being limited by the embodiments described below.
（第１の実施形態）
図１は、太陽電池として構成した光電変換素子の縦断面図を示す。
図１に示すように、本実施形態による太陽電池１は、基板２の上に、第１電極である陽極３、正孔バッファ層としての正孔輸送層４、光を電気エネルギーに変換する光電変換層５、第２電極である陰極６が順に積層された構造である。なお、図示は省略するが、大気雰囲気中の水分や酸素と反応することを防止するために、積層構造の上面及び側面を覆うように封止膜を形成してもよい。 (First embodiment)
FIG. 1 is a longitudinal sectional view of a photoelectric conversion element configured as a solar cell.
As shown in FIG. 1, thesolar cell 1 according to the present embodiment includes a substrate 2, an anode 3 as a first electrode, a hole transport layer 4 as a hole buffer layer, a photoelectric that converts light into electrical energy. The conversion layer 5 and the cathode 6 as the second electrode are stacked in order. Although illustration is omitted, a sealing film may be formed so as to cover the upper surface and side surfaces of the stacked structure in order to prevent reaction with moisture and oxygen in the air atmosphere.
図１は、太陽電池として構成した光電変換素子の縦断面図を示す。
図１に示すように、本実施形態による太陽電池１は、基板２の上に、第１電極である陽極３、正孔バッファ層としての正孔輸送層４、光を電気エネルギーに変換する光電変換層５、第２電極である陰極６が順に積層された構造である。なお、図示は省略するが、大気雰囲気中の水分や酸素と反応することを防止するために、積層構造の上面及び側面を覆うように封止膜を形成してもよい。 (First embodiment)
FIG. 1 is a longitudinal sectional view of a photoelectric conversion element configured as a solar cell.
As shown in FIG. 1, the
太陽電池１の場合、正孔輸送層４は、例えば陽極３の平坦化及び電流の取り出し効率を改善することを目的の一つとして配置される。本実施形態の正孔輸送層４は、不純物としてのＮａ＋（ナトリウムイオン）の濃度が１００ｐｐｍ（質量）以下であり、特に好ましくは５ｐｐｍ以下である。さらに、正孔輸送層４に不純物として例えばＳＯ４などの硫黄酸化物（ＳＯｘ）イオンが含まれる場合、ＳＯｘイオンの好ましい濃度は５ｐｐｍ以下である。正孔輸送層４は、例えば塗布法によって成膜することができる。また、正孔輸送層４の膜厚は、例えば１０～１０００ｎｍである。
In the case of the solar cell 1, the hole transport layer 4 is disposed for the purpose of improving the planarization of the anode 3 and the current extraction efficiency, for example. In the hole transport layer 4 of the present embodiment, the concentration of Na + (sodium ion) as an impurity is 100 ppm (mass) or less, and particularly preferably 5 ppm or less. Furthermore, when the hole transport layer 4 contains sulfur oxide (SOx) ions such as SO 4 as impurities, the preferred concentration of SOx ions is 5 ppm or less. The hole transport layer 4 can be formed by, for example, a coating method. The film thickness of the hole transport layer 4 is, for example, 10 to 1000 nm.
なお、陽極３と光電変換層５の間に配置する正孔バッファ層は、正孔輸送層４に限られず、正孔注入層であってもよい。或いは、正孔バッファ層は、光電変換層５から陽極３側に向かって正孔輸送層４と正孔注入層が積層された構造であってもよく、正孔輸送層４と正孔注入層を兼用する単一層であってもよい。いずれの態様であっても、正孔バッファ層に含まれる不純物としてのＮａ＋（ナトリウムイオン）の濃度が、１００ｐｐｍ（質量）以下、特に好ましくは５ｐｐｍ以下であればよい。
In addition, the hole buffer layer arrange | positioned between the anode 3 and the photoelectric converting layer 5 is not restricted to the hole transport layer 4, A hole injection layer may be sufficient. Alternatively, the hole buffer layer may have a structure in which the hole transport layer 4 and the hole injection layer are laminated from the photoelectric conversion layer 5 toward the anode 3 side. It may be a single layer that also serves as a combination. In any embodiment, the concentration of Na + (sodium ion) as an impurity contained in the hole buffer layer may be 100 ppm (mass) or less, particularly preferably 5 ppm or less.
正孔輸送層４を形成する材料は、正孔の輸送特性を有する材料であればよい。その中でも、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）を用いるのが好ましい。さらに好ましくは、ポリエチレンジオキシチオフェン（ＰＥＤＯＴ）にポリスチレンスルホン酸（ＰＳＳ）を組み合わせた、ポリエチレンジオキシチオフェン－ポリスチレンスルホン酸（ＰＥＤＯＴ－ＰＳＳ）である。また、正孔輸送層４は、ＰＥＤＯＴ又はＰＥＤＯＴ－ＰＳＳ以外の材料を含んでいてもよい。その他の材料としては、金属微粒子やＣＮＴ（Carbon nanotube）などが一例として挙げられる。
The material for forming the hole transport layer 4 may be any material having hole transport properties. Among these, it is preferable to use polyethylenedioxythiophene (PEDOT). More preferred is polyethylene dioxythiophene-polystyrene sulfonic acid (PEDOT-PSS) obtained by combining polyethylene dioxythiophene (PEDOT) with polystyrene sulfonic acid (PSS). Further, the hole transport layer 4 may contain a material other than PEDOT or PEDOT-PSS. Examples of other materials include fine metal particles and CNT (Carbon Nanotube).
但し、正孔輸送層４を形成する材料は、前述のＰＥＤＯＴを含む材料に限定されることはない。他の材料としては、一例として、銅フタロシアニン（ＣｕＰｃ）などのフタロシアニン化合物、ｍ－ＭＴＤＡＴＡ等のスターバースト型アミン、ベンジジン型アミンの多量体、４，４’－ビス［Ｎ－（１－ナフチル）－Ｎ－フェニルアミノ］－ビフェニル（ＮＰＢ）、Ｎ－フェニル－ｐ－フェニレンジアミン（ＰＰＤ）等の芳香族第三級アミン、４－（ジ－Ｐ－トリルアミノ）－４’－［４－（ジ－Ｐ－トリルアミノ）スチリル］スチルベンゼン等のスチルベン化合物、トリアゾール誘導体、スチリルアミン化合物、バッキーボール、Ｃ60等のフラーレンなどの有機材料が用いられる。また、ポリカーボネート等の高分子材料中に低分子材料を分散させた高分子分散系の材料を使用してもよい。但し、これらの材料に限定されることはない。
However, the material for forming the hole transport layer 4 is not limited to the material containing PEDOT described above. Examples of other materials include phthalocyanine compounds such as copper phthalocyanine (CuPc), starburst amines such as m-MTDATA, benzidine amine multimers, 4,4′-bis [N- (1-naphthyl) Aromatic tertiary amines such as —N-phenylamino] -biphenyl (NPB) and N-phenyl-p-phenylenediamine (PPD), 4- (di-P-tolylamino) -4 ′-[4- (di Organic materials such as stilbene compounds such as -P-tolylamino) styryl] stilbenzene, triazole derivatives, styrylamine compounds, buckyballs, and fullerenes such as C60 are used. Further, a polymer dispersion material in which a low molecular material is dispersed in a polymer material such as polycarbonate may be used. However, it is not limited to these materials.
光電変換層５を形成する材料は、光を吸収して光起電力作用を発現する材料であればよい。そのような材料の一例としては、（８－ヒドロキシキノリナート）アルミニウム錯体（Ａｌｑ3）などの蛍光性有機金属化合物、４，４’－ビス（２，２’－ジフェニルビニル）－ビフェニル（ＤＰＶＢｉ）などの芳香族ジメチリディン化合物、１，４－ビス（２－メチルスチリル）ベンゼンなどのスチリルベンゼン化合物、３－（４－ビフェニル）－４－フェニル－５－ｔ－ブチルフェニル－１，２，４－トリアゾール（ＴＡＺ）などのトリアゾール誘導体、アントラキノン誘導体、フルオノレン誘導体等の蛍光性有機材料、ポリパラフィニレンビニレン（ＰＰＶ）系、ポリフルオレン系、ポリビニルカルバゾール（ＰＶＫ）系などの高分子材料、白金錯体やイリジウム錯体などの燐光性有機材料を用いることができる。但し、これらの材料に限定されることはない。また、有機材料でなくともよく、無機材料を用いてもよい。光電変換層５に用いる材料は、可視光領域に吸収を示す材料が好ましいが、可視光領域に吸収を示さない材料であっても、色素などをドープすることによって可視光領域に吸収を示すようにすることができる。用いる材料の種類にもよるが、光電変換層５は、例えば塗布法によって成膜することができる。また、光電変換層５の膜厚は、例えば１０～１００００ｎｍである。
The material for forming the photoelectric conversion layer 5 may be any material that absorbs light and exhibits a photovoltaic action. Examples of such materials include fluorescent organometallic compounds such as (8-hydroxyquinolinato) aluminum complex (Alq3), 4,4′-bis (2,2′-diphenylvinyl) -biphenyl (DPVBi) Aromatic dimethylidin compounds such as 1, styrylbenzene compounds such as 1,4-bis (2-methylstyryl) benzene, 3- (4-biphenyl) -4-phenyl-5-t-butylphenyl-1,2,4- Fluorescent organic materials such as triazole derivatives such as triazole (TAZ), anthraquinone derivatives and fluorenol derivatives, polymer materials such as polyparafinylene vinylene (PPV), polyfluorene and polyvinylcarbazole (PVK), platinum complexes and iridium A phosphorescent organic material such as a complex can be used. However, it is not limited to these materials. Further, the organic material may not be used, and an inorganic material may be used. The material used for the photoelectric conversion layer 5 is preferably a material that absorbs in the visible light region, but even if it is a material that does not absorb in the visible light region, it absorbs in the visible light region by doping with a dye or the like. Can be. Depending on the type of material used, the photoelectric conversion layer 5 can be formed by, for example, a coating method. The film thickness of the photoelectric conversion layer 5 is, for example, 10 to 10,000 nm.
基板２の材料についても、特に限定されることはない。但し、図１に示す太陽電池１の場合、基板２側から光を取り込む構造としているので、ガラスや透明樹脂のような透明材料で形成された基板２を用いるのが好ましい。さらに、透明フィルムなどの可撓性材料を用いることもできる。
The material of the substrate 2 is not particularly limited. However, in the case of the solar cell 1 shown in FIG. 1, since the light is taken in from the substrate 2 side, it is preferable to use the substrate 2 formed of a transparent material such as glass or transparent resin. Further, a flexible material such as a transparent film can be used.
さらに、基板２側から光を取り込む構造の場合、陽極３を形成する材料は、例えばＩＴＯ（Indium Tin Oxide）やＩＺＯ（Indium Zinc Oxide）などの金属酸化物等を用いることができる。このような陽極３は、例えば蒸着やスパッタ法などで形成することができる。また、陽極３の膜厚は、例えば５０～１０００ｎｍである。但し、例えば陰極６側から光を取り込む構造とする場合、陽極３を形成する材料は透明材料でなくともよく、例えばＡｌ、Ｃｒ、Ｍｏ、Ｎｉ、Ｐｔ、Ａｕ、Ａｇなどの金属またはそれらを含む合金や金属間化合物などの材料を用いることができる。
Furthermore, in the case of a structure for taking in light from the substrate 2 side, the material for forming the anode 3 can be a metal oxide such as ITO (Indium Tin Oxide) or IZO (Indium Zinc Oxide). Such an anode 3 can be formed, for example, by vapor deposition or sputtering. The film thickness of the anode 3 is, for example, 50 to 1000 nm. However, for example, in the case of a structure for taking in light from the cathode 6 side, the material for forming the anode 3 may not be a transparent material, and includes, for example, metals such as Al, Cr, Mo, Ni, Pt, Au, Ag, or the like. Materials such as alloys and intermetallic compounds can be used.
さらに、基板２側から光を取り込む構造の場合、陰極６を形成する材料は、例えばＡｌ、Ｍｇ、Ａｇ、Ａｕ、Ｃａ、Ｌｉなどの金属またはその化合物、あるいはそれらを含む合金などを単層あるいは積層して用いることができる。このような陰極６は、例えば蒸着やスパッタ法などで形成することができる。また、陰極６の膜厚は、例えば５０～１０００ｎｍである。但し、例えば陰極６側から光を取り込む構造とする場合は、例えばＩＴＯ、ＺｎＯやＩＺＯなどの透明材料を用いるのが好ましい。
Further, in the case of a structure for taking in light from the substrate 2 side, the material for forming the cathode 6 is a single layer or a metal such as Al, Mg, Ag, Au, Ca, Li or a compound thereof, or an alloy containing them. It can be used by laminating. Such a cathode 6 can be formed by, for example, vapor deposition or sputtering. The film thickness of the cathode 6 is, for example, 50 to 1000 nm. However, for example, when the light is taken in from the cathode 6 side, it is preferable to use a transparent material such as ITO, ZnO, or IZO.
なお、図１では図示を省略しているが、必要に応じて封止膜を設ける場合、封止膜を形成する材料は、例えば水蒸気や酸素の透過率が小さい透明の無機材料を用いることができる。そのような材料としては、一例として窒化ケイ素（ＳｉＮｘ）、窒化酸化ケイ素（ＳｉＯｘＮｙ）、酸化アルミニウム（ＡｌＯｘ）、窒化アルミニウム（ＡｌＮｘ）などを用いることができる。
Although not shown in FIG. 1, when a sealing film is provided as necessary, a material for forming the sealing film is, for example, a transparent inorganic material having a low water vapor or oxygen permeability. it can. As such a material, silicon nitride (SiNx), silicon nitride oxide (SiOxNy), aluminum oxide (AlOx), aluminum nitride (AlNx), or the like can be used as an example.
さらに、図１に示す太陽電池１は、光電変換層５と陰極６が隣接した構造であるが、これに限定されることはなく、電子輸送層及び／又は電子注入層を介在させることができる。電子輸送層や電子注入層を形成する材料は、電子の輸送特性が高い材料で形成されていればよく、一例として、ＰｙＰｙＳＰｙＰｙ等のシラシクロペンタジエン（シロール）誘導体、ニトロ置換フルオレノン誘導体、アントラキノジメタン誘導体などの有機材料、トリス（８－ヒドロキシキノリナート）アルミニウム（Ａｌｑ3）などの８－キノリノール誘導体の金属錯体、メタルフタロシアニン、３－（４－ビフェニル）－５－（４－ｔ－ブチルフェニル）－４－フェニル－１，２，４－トリアゾール（ＴＡＺ）などのトリアゾール系化合物、２－（４－ビフェニリル）－５－（４－ｔ－ブチル）－１，３，４－オキサジアゾ－ル（ＰＢＤ）などのオキサジアゾール系化合物、カーボンナノチューブ、フラーレン、ＬｉＦ、Ｌｉ２Ｏなどのアルカリ金属化合物を使用することができる。但し、これらの材料に限定されることはない。
Furthermore, the solar cell 1 shown in FIG. 1 has a structure in which the photoelectric conversion layer 5 and the cathode 6 are adjacent to each other, but the present invention is not limited to this, and an electron transport layer and / or an electron injection layer can be interposed. . The material for forming the electron transport layer or the electron injection layer may be any material that has high electron transport properties. For example, silacyclopentadiene (silole) derivatives such as PyPySPyPy, nitro-substituted fluorenone derivatives, anthraquinodi Organic materials such as methane derivatives, metal complexes of 8-quinolinol derivatives such as tris (8-hydroxyquinolinate) aluminum (Alq3), metal phthalocyanine, 3- (4-biphenyl) -5- (4-t-butylphenyl) ) -4-phenyl-1,2,4-triazole (TAZ) and other triazole compounds, 2- (4-biphenylyl) -5- (4-t-butyl) -1,3,4-oxadiazol ( PBD) oxadiazole-based compounds such as carbon nanotubes, fullerene, LiF, such as Li 2 O It can be used alkali metal compound. However, it is not limited to these materials.
続いて、図１に示す構造の太陽電池１を製造する工程について、図２の工程図を参照しながら説明する。
Subsequently, the process of manufacturing the solar cell 1 having the structure shown in FIG. 1 will be described with reference to the process diagram of FIG.
まず、図２の工程１００に示すように、例えば蒸着やスパッタ法などを用いて陽極３を基板２上に成膜する。陽極３のパターニングが必要な場合は、例えばフォトリソグラフィー法を用いてパターニングすることができる。次に、図２の工程１１０に示すように、正孔輸送層４の液体材料を、陽極３上に塗布し、加熱により溶媒や水分を除去する。液体材料は、例示したような正孔輸送層４の材料を、例えば有機溶媒に溶解又は分散させたものである。塗布方法としては、例えばインクジェット法、スプレー法、スピンコート法、ディップ法、ダイコート法などを用いることができる。膜厚は、例えば液体材料の塗布量や濃度によって調整することができる。また、必要に応じて、次の工程で塗布される光電変換層５の液体材料に対する不溶化処理を行うことができる。不溶化処理の一例としては、光重合反応等による架橋化処理、親水化処理或いは疎水化処理などを挙げることができる。また、光電変換層５の液体材料に対して不溶性の材料を選定するようにしてもよい。
First, as shown in Step 100 of FIG. 2, the anode 3 is formed on the substrate 2 by using, for example, vapor deposition or sputtering. When patterning of the anode 3 is necessary, patterning can be performed using, for example, a photolithography method. Next, as shown in Step 110 of FIG. 2, the liquid material of the hole transport layer 4 is applied on the anode 3, and the solvent and moisture are removed by heating. The liquid material is obtained by dissolving or dispersing the material of the hole transport layer 4 as exemplified in an organic solvent, for example. As the coating method, for example, an inkjet method, a spray method, a spin coating method, a dip method, a die coating method, or the like can be used. The film thickness can be adjusted by, for example, the application amount and concentration of the liquid material. Moreover, the insolubilization process with respect to the liquid material of the photoelectric converting layer 5 apply | coated at the next process can be performed as needed. As an example of the insolubilization treatment, a crosslinking treatment by a photopolymerization reaction or the like, a hydrophilization treatment, or a hydrophobization treatment can be exemplified. Further, a material that is insoluble with respect to the liquid material of the photoelectric conversion layer 5 may be selected.
次に、図２の工程１２０に示すように、光電変換層５の液体材料を、正孔輸送層４上に塗布し、成膜する。液体材料は、例示したような光電変換層５の材料を、例えば有機溶媒に溶解又は分散させたものである。塗布方法としては、例えばインクジェット法、スプレー法、スピンコート法、ディップ法、ダイコート法などを用いることができる。膜厚は、例えば液体材料の塗布量や濃度によって調整することができる。但し、塗布法に限定されることはなく、例えば蒸着法やレーザーアブレーション法によって光電変換層５を形成してもよい。
Next, as shown in step 120 of FIG. 2, the liquid material of the photoelectric conversion layer 5 is applied on the hole transport layer 4 to form a film. The liquid material is obtained by dissolving or dispersing the material of the photoelectric conversion layer 5 as exemplified in an organic solvent, for example. As the coating method, for example, an inkjet method, a spray method, a spin coating method, a dip method, a die coating method, or the like can be used. The film thickness can be adjusted by, for example, the application amount and concentration of the liquid material. However, it is not limited to the coating method, For example, you may form the photoelectric converting layer 5 with a vapor deposition method or a laser ablation method.
次に、図２の工程１３０に示すように、例えば蒸着法やスパッタ法を用いて、光電変換層５上に、陰極６を形成する。次に、図２の工程１４０に示すように、例えば１１０～１６５℃の温度にてアニール処理を行うことによって、図１に示した太陽電池１を製造することができる。アニール処理は、少なくとも正孔輸送層４と光電変換層５を形成した後であれば、陰極６を形成する前に行ってもよい。
Next, as shown in Step 130 of FIG. 2, the cathode 6 is formed on the photoelectric conversion layer 5 by using, for example, vapor deposition or sputtering. Next, as shown in step 140 of FIG. 2, the solar cell 1 shown in FIG. 1 can be manufactured by performing an annealing process at a temperature of 110 to 165 ° C., for example. The annealing treatment may be performed before the cathode 6 is formed, at least after the hole transport layer 4 and the photoelectric conversion layer 5 are formed.
上述の実施形態によれば、不純物として含まれるＮａ＋（ナトリウムイオン）濃度が１００ｐｐｍ以下、特に好ましくは５ｐｐｍ以下である正孔輸送層４を、光電変換層５と隣接して配置したことにより、光電変換層５の膜中にＮａ＋（ナトリウムイオン）が拡散して、励起子の失活やキャリアーとの再結合を起こすことを格段に抑制することができる。その結果、当該太陽電池１は、光電変換層５の膜中全域で電荷分離が行われ、高い効率で発電することができる。
According to the above-described embodiment, by arranging the hole transport layer 4 having a Na + (sodium ion) concentration contained as an impurity of 100 ppm or less, particularly preferably 5 ppm or less, adjacent to the photoelectric conversion layer 5, It is possible to markedly suppress the diffusion of Na + (sodium ions) in the film of the photoelectric conversion layer 5 and the deactivation of excitons and the recombination with carriers. As a result, the solar cell 1 is capable of generating power with high efficiency because charge separation is performed throughout the film of the photoelectric conversion layer 5.
Ｎａ＋（ナトリウムイオン）の拡散は、光電変換中だけでなく、製造過程でも起こり得る。特に、高温で処理するアニール処理中に熱拡散し易い。しかしながら、不純物として含まれるＮａ＋（ナトリウムイオン）の濃度が１００ｐｐｍ以下であれば、Ｎａ＋（ナトリウムイオン）が光電変換に与える影響を抑制し、効率の高い太陽電池１を安定的に得ることができる。
The diffusion of Na + (sodium ions) can occur not only during photoelectric conversion but also during the manufacturing process. In particular, thermal diffusion is likely to occur during annealing performed at a high temperature. However, if the concentration of Na + (sodium ion) contained as an impurity is 100 ppm or less, it is possible to suppress the influence of Na + (sodium ion) on photoelectric conversion and stably obtain a highly efficient solar cell 1. it can.
すなわち、下記の表１並びに図３及び図４に示す試験結果の一例から明らかなように、正孔輸送層４の不純物としてのＮａ＋（ナトリウムイオン）濃度が２００ｐｐｍから１００ｐｐｍの間に、発電の効率が格段に向上する分岐点がある。発電の効率を決定する一般的な主要因としては、開放電圧（Ｖｏｃ），短絡電流（Ｊｓｃ），フィルファクタ（ＦＦ）の３つの要素があるが、特に不純物であるＮａ＋（ナトリウムイオン）の影響を受けるのはフィルファクタ（ＦＦ）であり、次いで短絡電流（Ｊｓｃ）であることが分かる。開放電圧（Ｖｏｃ）については殆ど影響がないと言える。従って、正孔輸送層４に不純物として含まれるＮａ＋（ナトリウムイオン）の濃度を１００ｐｐｍ以下とすることによって、Ｎａ＋（ナトリウムイオン）の影響を抑制して、高い光電変換効率を発揮することのできる光電変換素子を実現できるのである。
That is, as apparent from the example of the test results shown in Table 1 below and FIG. 3 and FIG. 4, the Na + (sodium ion) concentration as the impurity of the hole transport layer 4 is between 200 ppm and 100 ppm. There is a turning point where efficiency is dramatically improved. There are three main factors that determine the efficiency of power generation: open-circuit voltage (Voc), short-circuit current (Jsc), and fill factor (FF), but in particular the impurity Na + (sodium ion) It can be seen that it is the fill factor (FF) that is affected and then the short circuit current (Jsc). It can be said that there is almost no influence on the open circuit voltage (Voc). Therefore, by setting the concentration of Na + (sodium ion) contained as an impurity in the hole transport layer 4 to 100 ppm or less, the influence of Na + (sodium ion) is suppressed and high photoelectric conversion efficiency is exhibited. The photoelectric conversion element which can be realized is realizable.
なお、下記の表１は、正孔輸送層４の材料として市販のＰＥＤＯＴ－ＰＳＳを用いた試験結果である。図３及び図４は、表１の結果をグラフ化したものである。市販のＰＥＤＯＴ－ＰＳＳは、製造過程でＮａ＋（ナトリウムイオン）が含有されることが多く、Ｎａ＋（ナトリウムイオン）の濃度によって製品グレードが分類されている。試験では、それら市販のＰＥＤＯＴ－ＰＳＳを用いて、Ｎａ＋（ナトリウムイオン）の濃度が、３．４ｐｐｍ，５０ｐｐｍ，１００ｐｐｍ，２００ｐｐｍ，３６０ｐｐｍとなるように調製した。また、不純物として含まれるＳＯ４イオンの濃度は、５ｐｐｍであった。さらに、試験では光電変換層５の材料にＰ３ＨＴとＰＣＢＭを用いたバルクヘテロ構造（膜厚；１２０ｎｍ）を用い、陽極３の材料にＩＴＯ（膜厚；１１０ｎｍ）を用い、陰極６の材料にＡｌ（膜厚；１００ｎｍ）を用いた。
Table 1 below shows test results using commercially available PEDOT-PSS as the material of the hole transport layer 4. 3 and 4 are graphs of the results of Table 1. Commercially available PEDOT-PSS often contains Na + (sodium ions) in the production process, and product grades are classified according to the concentration of Na + (sodium ions). In the test, these commercially available PEDOT-PSSs were used so that the concentrations of Na + (sodium ions) were 3.4 ppm, 50 ppm, 100 ppm, 200 ppm, and 360 ppm. The concentration of SO 4 ions contained as impurities was 5 ppm. Further, in the test, a bulk heterostructure (film thickness: 120 nm) using P3HT and PCBM is used as the material of the photoelectric conversion layer 5, ITO (film thickness: 110 nm) is used as the material of the anode 3, and Al (material) is used as the material of the cathode 6. Film thickness: 100 nm) was used.
このような理由により、本実施形態の太陽電池１は不純物が光電変換に及ぼす影響を抑制できる。従って、特許文献２のような、不純物の影響を抑制するための機能膜（混合膜）を新たに追加しなくともよいという利点がある。
For this reason, the solar cell 1 of the present embodiment can suppress the influence of impurities on photoelectric conversion. Therefore, there is an advantage that a function film (mixed film) for suppressing the influence of impurities as in Patent Document 2 need not be newly added.
さらに上述の実施形態によれば、不純物として含まれる硫黄酸化物（ＳＯｘ）イオンの濃度を５ｐｐｍ以下とすることにより、当該不純物の影響を抑制して、高い発電効率を得ることができる。Ｎａ＋（ナトリウムイオン）と硫黄酸化物（ＳＯｘ）イオンの濃度を共に５ｐｐｍにすることが特に好ましい。
Furthermore, according to the above-described embodiment, by setting the concentration of sulfur oxide (SOx) ions contained as impurities to 5 ppm or less, the influence of the impurities can be suppressed and high power generation efficiency can be obtained. It is particularly preferable that the concentrations of Na + (sodium ion) and sulfur oxide (SOx) ion are both 5 ppm.
（第２の実施形態）
本実施形態は、第１の実施形態の変形例であり、発光素子として構成した光電変換素子に関する。 (Second Embodiment)
This embodiment is a modification of the first embodiment and relates to a photoelectric conversion element configured as a light emitting element.
本実施形態は、第１の実施形態の変形例であり、発光素子として構成した光電変換素子に関する。 (Second Embodiment)
This embodiment is a modification of the first embodiment and relates to a photoelectric conversion element configured as a light emitting element.
本実施形態の発光素子は、陽極３及び陰極６に電力を供給して、光電変換層５にて電気エネルギーを光に変換して発光させる構成である。このように電気エネルギーを光に変換する作用を発揮させることを除けば、図１と同様の構造とすることができる。また、図２に示した工程によって製造することができる。但し、発光素子の場合には、アニール処理の温度を例えば１００℃程度に低くしてもよい。このような発光素子の場合であっても、第１の実施形態の場合と同様に、不純物が光電変換に及ぼす影響を抑制することができる。その結果、高い効率で発光することができる。
The light emitting element of the present embodiment has a configuration in which power is supplied to the anode 3 and the cathode 6, and electric energy is converted into light by the photoelectric conversion layer 5 to emit light. Except for the effect of converting electrical energy into light in this way, a structure similar to that shown in FIG. 1 can be obtained. Further, it can be manufactured by the process shown in FIG. However, in the case of a light emitting element, the annealing temperature may be lowered to about 100 ° C., for example. Even in the case of such a light-emitting element, the influence of impurities on photoelectric conversion can be suppressed as in the case of the first embodiment. As a result, light can be emitted with high efficiency.
以上のように、第１及び第２の実施形態によれば、陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子において、前記正孔バッファ層に含まれる不純物としてのＮａ＋（ナトリウムイオン）の濃度が１００ｐｐｍ以下である構成とする。その結果、不純物の影響を抑制して、高い光電変換効率を発揮することのできる光電変換素子を得ることが可能となる。
As described above, according to the first and second embodiments, the anode, the cathode, the photoelectric conversion layer arranged between the anode and the cathode, and the anode and the photoelectric conversion layer are arranged. In the photoelectric conversion element including at least a hole buffer layer, a concentration of Na + (sodium ion) as an impurity included in the hole buffer layer is 100 ppm or less. As a result, it is possible to obtain a photoelectric conversion element that can suppress the influence of impurities and exhibit high photoelectric conversion efficiency.
さらに、第１及び第２の実施形態によれば、陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子の製造方法において、不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下である材料を用いて前記正孔バッファ層を形成することにより、不純物の影響を抑制して、高い光電変換効率を発揮することのできる光電変換素子を製造することが可能となる。
Furthermore, according to the first and second embodiments, the anode, the cathode, the photoelectric conversion layer disposed between the anode and the cathode, and the hole buffer disposed between the anode and the photoelectric conversion layer. In the method of manufacturing a photoelectric conversion element including at least a layer, the hole buffer layer is formed using a material having a sodium ion concentration of 100 ppm or less as an impurity, thereby suppressing the influence of the impurity and increasing the photoelectric conversion element. It becomes possible to manufacture a photoelectric conversion element that can exhibit conversion efficiency.
以上、本発明を具体的な実施形態に則して詳細に説明したが、形式や細部についての種々の置換、変形、変更等が、特許請求の範囲の記載により規定されるような本発明の精神及び範囲から逸脱することなく行われることが可能であることは、当該技術分野における通常の知識を有する者には明らかである。従って、本発明の範囲は、前述の実施形態及び添付図面に限定されるものではなく、特許請求の範囲の記載及びこれと均等なものに基づいて定められるべきである。
Although the present invention has been described in detail with reference to specific embodiments, various substitutions, modifications, changes, etc. in form and detail are defined in the claims. It will be apparent to those skilled in the art that this can be done without departing from the spirit and scope. Therefore, the scope of the present invention should not be limited to the above-described embodiments and the accompanying drawings, but should be determined based on the description of the claims and equivalents thereof.
Claims (6)
- 陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子において、
前記正孔バッファ層に含まれる不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下であることを特徴とする光電変換素子。 In a photoelectric conversion element including at least an anode, a cathode, a photoelectric conversion layer disposed between the anode and the cathode, and a hole buffer layer disposed between the anode and the photoelectric conversion layer,
The photoelectric conversion element characterized by the sodium ion concentration as an impurity contained in the said hole buffer layer being 100 ppm or less. - 前記正孔バッファ層に含まれる不純物としての硫黄酸化物（ＳＯｘ）イオン濃度が５ｐｐｍ以下であることを特徴とする請求項１に記載の光電変換素子。 The photoelectric conversion element according to claim 1, wherein a concentration of sulfur oxide (SOx) ions as impurities contained in the hole buffer layer is 5 ppm or less.
- 前記正孔バッファ層がポリエチレンジオキシチオフェン（ＰＥＤＯＴ）を含む材料で形成されていることを特徴とする請求項１に記載の光電変換素子。 The photoelectric conversion element according to claim 1, wherein the hole buffer layer is formed of a material containing polyethylene dioxythiophene (PEDOT).
- 前記光電変換素子が太陽電池であることを特徴とする請求項１に記載の光電変換素子。 The photoelectric conversion element according to claim 1, wherein the photoelectric conversion element is a solar cell.
- 陽極と、陰極と、前記陽極と陰極の間に配置される光電変換層と、前記陽極と光電変換層の間に配置される正孔バッファ層と、を少なくとも含む光電変換素子の製造方法において、
不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下である材料を用いて前記正孔バッファ層を形成することを特徴とする光電変換素子の製造方法。 In a method for producing a photoelectric conversion element comprising at least an anode, a cathode, a photoelectric conversion layer disposed between the anode and the cathode, and a hole buffer layer disposed between the anode and the photoelectric conversion layer,
A method for producing a photoelectric conversion element, wherein the hole buffer layer is formed using a material having a sodium ion concentration of 100 ppm or less as an impurity. - 前記正孔バッファ層は、不純物としてのナトリウムイオン濃度が１００ｐｐｍ以下であるポリエチレンジオキシチオフェン（ＰＥＤＯＴ）を用いて塗布法によって成膜し、少なくとも前記光電変換層を成膜した後に、アニール処理を行うことを特徴とする請求項５に記載の光電変換素子の製造方法。 The hole buffer layer is formed by a coating method using polyethylenedioxythiophene (PEDOT) having a sodium ion concentration of 100 ppm or less as an impurity, and at least after the photoelectric conversion layer is formed, an annealing treatment is performed. The manufacturing method of the photoelectric conversion element of Claim 5 characterized by the above-mentioned.
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