WO2009154137A1 - 太陽電池およびその製造方法 - Google Patents
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- WO2009154137A1 WO2009154137A1 PCT/JP2009/060700 JP2009060700W WO2009154137A1 WO 2009154137 A1 WO2009154137 A1 WO 2009154137A1 JP 2009060700 W JP2009060700 W JP 2009060700W WO 2009154137 A1 WO2009154137 A1 WO 2009154137A1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/056—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means the light-reflecting means being of the back surface reflector [BSR] type
-
- 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
- Y02E10/52—PV systems with concentrators
Definitions
- the present invention relates to a solar cell having an alloy electrode and a manufacturing method thereof.
- This application claims priority based on Japanese Patent Application No. 2008-157713 for which it applied to Japan on June 17, 2008, and uses the content here.
- solar cells have been widely used as photoelectric conversion devices.
- this type of solar cell there are a crystalline silicon solar cell using single crystal silicon or polysilicon as a semiconductor layer (photoelectric conversion layer), and a thin film silicon solar cell using amorphous silicon and / or microcrystalline silicon. is there.
- a transparent electrode is formed as a first electrode (surface transparent electrode) on a glass substrate; silicon (amorphous silicon and / or / Alternatively, a semiconductor layer (photoelectric conversion layer) of microcrystal silicon) and a light-transmitting buffer layer are formed in order; a reflective pure metal electrode (reflecting electrode) is formed on the buffer layer as a second electrode. It is formed as (back metal electrode); and further has a configuration in which a protective layer is formed on the second electrode (see, for example, Patent Document 1).
- the silicon photoelectric conversion layer has a pin junction structure or an nip structure in which an i-type silicon film that is mainly excited by incident light to generate electrons and holes is sandwiched between p-type and n-type silicon films. It has a p-junction structure.
- a tandem structure in which an amorphous silicon photoelectric conversion layer and a microcrystal silicon photoelectric conversion layer are stacked in order to improve the conversion rate is known.
- Sunlight incident on the glass substrate first passes through the surface transparent electrode and enters the photoelectric conversion layer.
- i-type silicon When energetic particles called photons contained in sunlight hit i-type silicon, electrons and holes are generated by the photovoltaic effect. Electrons move toward n-type silicon and holes move toward p-type silicon. By extracting these electrons and holes from the front transparent electrode and the back metal electrode, light energy can be converted into electric energy.
- the light transmitted through the photoelectric conversion layer is reflected by the surface of the back metal electrode and travels again to the photoelectric conversion layer. As a result, electrons and holes are generated again in the photoelectric conversion layer to convert light energy into electric energy.
- a silver (Ag) electrode having low resistance and high light reflectance is formed by a sputtering method.
- the buffer layer for example, an AZO (Al-added ZnO) film or a GZO (Ga-added ZnO) film is formed. This buffer layer functions as a barrier layer between the photoelectric conversion layer and the back surface metal electrode.
- an Ag electrode using Ag as the back surface metal electrode material is used.
- silver oxide is formed at the interface with the buffer layer that is an oxide and the light reflectivity is lowered. Therefore, the light transmitted through the photoelectric conversion layer may not be sufficiently reflected.
- the Ag electrode may form pores at the interface with the buffer layer due to a difference in expansion coefficient from the buffer layer positioned on the Ag electrode. If the adhesiveness with the buffer layer becomes insufficient and the contact resistance increases, there arises a problem that the photoelectric conversion efficiency of the solar cell is reduced. That is, the conventional solar cell has a problem that the curve factor and reliability of the solar cell may be reduced due to the Ag electrode as the second electrode.
- the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a solar cell capable of improving photoelectric conversion efficiency and reliability and a method for manufacturing the solar cell.
- the solar cell of the present invention includes a first electrode having light permeability; a photoelectric conversion layer made of silicon; a buffer layer having light permeability; a second electrode made of an alloy having light reflectivity;
- the second electrode is made of a silver alloy containing at least one of tin (Sn) and gold (Au) and containing silver (Ag) as a main component.
- the silver alloy contains Sn containing Sn in the range of 0.1 ⁇ Sn ⁇ 2.5 in atomic% units (at%) as a main component. It may be made of a material to be used.
- the silver alloy contains Au in the atomic percent unit (at%) in a range of 0.1 ⁇ Au ⁇ 4.0, Ag as a main component. It may be made of a material to be used.
- the silver alloy includes Sn in a range of 0.1 ⁇ Sn ⁇ 2.5 in atomic percent units (at%) and 0.1 ⁇ Au ⁇ 4. It may be made of a material containing Ag as a main component and containing Au in the range of 0.
- a method for manufacturing a solar cell according to the present invention is a method for manufacturing the solar cell according to (1) above, wherein the second electrode is a target including at least one of Sn and Au and Ag. And a step of forming by a sputtering method.
- the target mainly includes Ag containing Sn in the range of 0.1 ⁇ Sn ⁇ 2.5 in atomic% units (at%). It is good also as what consists of the raw material used as a component.
- the target mainly includes Ag containing Au in the range of 0.1 ⁇ Au ⁇ 4.0 in atomic% units (at%).
- the material of the second electrode is an alloy containing Ag as a main component and at least one of Sn and Au added thereto.
- FIG. 1 is a partial cross-sectional view showing a configuration of a solar cell according to the present embodiment.
- a solar cell 10 according to this embodiment includes a substrate 11 having optical transparency, a first electrode (surface transparent electrode) 13 having optical transparency, and a semiconductor layer (photoelectric conversion) made of silicon. Layer) 14, a light-transmitting buffer layer 15, a second electrode (back surface alloy electrode) 16, and a protective layer 17.
- the first electrode 13, the photoelectric conversion layer 14, the buffer layer 15, and the second electrode 16 that are sequentially stacked on one surface (back surface) 11 a of the substrate 11 constitute the photoelectric conversion body 12. is doing.
- the substrate 11 is formed of an insulating material having excellent sunlight permeability and durability, such as glass and transparent resin.
- sunlight is incident from the opposite side of the photoelectric conversion body 12, that is, the other surface (front surface) 11 b side of the substrate 11 with the substrate 11 interposed therebetween.
- the first electrode (surface electrode) 13 is a metal oxide having optical transparency, for example, TCO (Transparent Conducting) such as AZO (ZnO to which Al is added), GZO (ZnO to which Ga is added), ITO (Indium Tin Oxide) or the like. Oxide) and is formed on the back surface 11a of the substrate 11.
- TCO Transparent Conducting
- AZO ZnO to which Al is added
- GZO ZnO to which Ga is added
- ITO Indium Tin Oxide
- a photoelectric conversion layer (semiconductor layer) 14 made of silicon is formed on the first electrode 13.
- the photoelectric conversion layer 14 includes an i-type silicon film (amorphous) between a p-type silicon film (amorphous silicon film and / or microcrystal silicon) and an n-type silicon film (amorphous silicon film and / or microcrystal silicon).
- the photoelectric conversion layer 14 is formed by sequentially stacking a p-type amorphous silicon film, an i-type amorphous silicon film, and an n-type amorphous silicon film from the surface transparent electrode 13 side.
- the pin junction structure or the nip junction structure of microcrystal silicon may be stacked on the pin junction structure or the nip junction structure of amorphous silicon.
- the buffer layer 15 is made of a light-transmitting low-resistance metal oxide (for example, TCO (Transparent Conducting Oxide) such as AZO (Al-added ZnO) or GZO (Ga-added ZnO) having a film thickness of about 40 to 100 nm. )), And is formed between the photoelectric conversion layer 14 and the second electrode 16.
- TCO Transparent Conducting Oxide
- AZO Al-added ZnO
- GZO Ga-added ZnO
- This buffer layer 15 prevents the silicon film of the photoelectric conversion layer 14 from being damaged by forming the second electrode 16 by a sputtering method, and silver (Ag) as a constituent material of the second electrode 16 is silicon. Functions as a barrier layer to prevent alloying.
- the buffer layer 15 is provided in the hole movement path in order to take out holes generated in the i-type silicon by photoelectric conversion from the first electrode 13. Therefore, the buffer layer 15 is made of a material having conductivity that keeps conduction between the photoelectric conversion layer 14 and the first electrode 16 and low contact resistance so as not to lower the photoelectric conversion efficiency of the solar cell 10. It is desirable. Further, when a texture structure is adopted for the photoelectric conversion layer 14, it is desirable that the film has excellent coverage during film formation.
- the second electrode (back alloy electrode) 16 is an alloy electrode made of a silver alloy containing tin (Sn), gold (Au), and silver (Ag), and is formed on the buffer layer 15. More specifically, the alloy electrode 16 is formed by sputtering an alloy containing Ag as a main component and adding Sn and Au to a thickness of, for example, 200 to 250 nm by a sputtering method.
- the alloy electrode 16 has a function as an electrode for extracting holes generated in the photoelectric conversion layer 14. Further, the alloy electrode 16 is incident on the photoelectric conversion layer 14 through the substrate 11 and the transparent electrode 13, further reflects the light transmitted through the photoelectric conversion layer 14 and the buffer layer 15, and returns to the photoelectric conversion layer 14. It also has a function that contributes to conversion.
- the ASA (Ag—Sn—Au) film constituting the alloy electrode (second electrode) 16 has Sn in the range of 0.1 ⁇ Sn ⁇ 2.5 in atomic% units (at%), 0.1% It is desirable that it is composed of Au in the range of ⁇ Au ⁇ 4.0 and the remainder Ag.
- the Au content 0.1 at% to 4.0 at% the reflectance on the long wavelength side of the light incident on the second electrode 16 can be significantly improved as compared with the conventional Ag electrode.
- the corrosion resistance of the alloy electrode can be remarkably improved. This is because if the Au content is less than 0.1 at%, the effect of improving the reflectance is not significant, and if it exceeds 4.0 at%, a problem of an increase in cost occurs and the above effect is offset. .
- the Sn content is set to 0.1 at% to 2.5 at%, so that the adhesiveness with the buffer layer 15 is higher than that of the conventional Ag electrode. It can be remarkably improved. This is because if the Sn content is less than 0.1 at%, the effect of improving the adhesion is not remarkable, and if it exceeds 2.5 at%, the resistance of the ASA film increases.
- a method for manufacturing the solar cell 10 of FIG. 1 will be described below.
- the substrate 11 is prepared, and a TCO film to be the first electrode (surface transparent electrode) 13 is formed on the back surface 11 a of the substrate 11. Since a glass substrate with TCO is commercially available, it may be procured, but an AZO film or a GZO film may be formed on the glass substrate by a sputtering method.
- a ZnO sintered body to which Al or Ga is added is used as a target, argon gas is used as a sputtering gas under reduced pressure, or oxygen gas is added to argon gas and sputtering gas is used.
- a ZnO film is formed under reduced pressure.
- a p-type silicon film, an i-type silicon film, and an n-type silicon film to be the photoelectric conversion layer 14 are stacked on the first electrode 13 by a CVD method. Further, an AZO film or a GZO film to be the buffer layer 15 is formed on the silicon laminated film by sputtering.
- an ASA film to be the alloy electrode (second electrode) 16 is formed on the GZO film to be the buffer layer 15 by a sputtering method.
- a target consisting of Sn in the range of 0.1 ⁇ Sn ⁇ 2.5, Au in the range of 0.1 ⁇ Au ⁇ 4.0, and the balance Ag (
- a silver alloy target with 0.1 at% to 2.5 at% of Sn added and 0.1 at% to 4.0 at% of Au is used to form an ASA film under reduced pressure using argon gas as a sputtering gas.
- the formed ASA film becomes a silver alloy film to which Sn is added at 0.1 at% to 2.5 at% and Au is added at 0.1 at% to 4.0 at%.
- the first electrode 13 is exposed by removing a part of the protective film 17, the alloy electrode (second electrode) 16, the buffer layer 15, and the photoelectric conversion layer 14 to expose a part of the back surface of the first electrode 13.
- An area for wire bonding or the like is secured on 13.
- a region for wire bonding or the like is secured on the second electrode 16.
- FIG. 2 is a graph showing the reflectance characteristics with respect to the incident light wavelength in the ASA film constituting the second electrode 16 of the solar cell 10.
- the reflectance characteristic with respect to the incident light wavelength in the Ag film constituting the second electrode of the conventional solar cell is also shown as a comparative example.
- an ASA film used in the present invention and an Ag film used in a conventional solar cell are formed on a glass substrate with the same film thickness.
- the wavelength of light contributing to photoelectric conversion is 300 nm to 800 nm.
- the light reflectance of the ASA film is higher than that of the conventional Ag film on the longer wavelength side where the wavelength of incident light is 600 nm or more.
- the light reflectance of the Ag film is 90 to 92%, and the light reflectance of the ASA film is 94 to 96%.
- the effect of improving the light reflectance on the long wavelength side is obtained by adding Au. Therefore, even if an Ag alloy film containing Ag as a main component without adding Sn without adding Sn is used, the above-described light reflectance improvement effect can be obtained.
- the light reflectance of the ASA film is equivalent to that of the conventional Ag film for incident wavelengths shorter than 600 nm. Therefore, in the solar cell 10 of this embodiment in which the second electrode 16 is made of an ASA alloy, the light reflectance on the short wavelength side of the second electrode 16 is kept equal to the light reflectance of the conventional Ag electrode, while being long. The light reflectance on the wavelength side can be improved as compared with the light reflectance of the conventional Ag electrode.
- the solar cell among the light incident from the substrate side, mainly the light on the short wavelength side is directly absorbed in the photoelectric conversion layer and contributes to the photoelectric conversion, so that it does not reach the second electrode and the remaining long wavelength side Light passes through the photoelectric conversion layer and the buffer layer and reaches the second electrode.
- the fact that the light reflection on the long wavelength side of the second electrode 16 is high means that the light transmitted through the photoelectric conversion layer 14 can be efficiently returned to the photoelectric conversion layer 14, and the photoelectric conversion is surely performed. Efficiency can be improved.
- the second electrode 16 by forming the second electrode 16 with an alloy in which Sn and Au are added to Ag as the main component, the reflectance on the long wavelength side is increased, and the amount of reflected light incident on the photoelectric conversion layer 14 is increased. Therefore, the photoelectric conversion efficiency of the solar cell 10 can be improved.
- high light reflectance on the long wavelength side is particularly effective in a tandem structure in which amorphous silicon and microcrystalline silicon are stacked. This is because microcrystalline silicon generates power with light on the long wavelength side.
- FIGS. 3A to 3D are diagrams for explaining a peel test (seal test) for evaluating the adhesion of the ASA film constituting the second electrode 16 of the solar cell 10.
- FIG. 3A is a cross-sectional view of a sample A in which an ASA film 21 is formed on a glass substrate 20 by a sputtering method.
- FIG. 3B is a cross-sectional view of Sample B in which an Ag film 201 having the same thickness as the ASA film is formed on a glass substrate 200 (the same as the glass substrate 20) by a sputtering method.
- 3C is a plan view showing the result of the peel test of the sample A
- FIG. 3D is a plan view showing the result of the peel test of the sample B.
- Sn enhances adhesion by forming an oxide at the interface with the buffer layer 15. Moreover, since SnO is transparent and conductive, the influence on the reflectance is small and the resistance hardly decreases. Therefore, even if an Ag alloy film mainly composed of Ag added with Sn without adding Au is used, the effect of improving the adhesion can be obtained.
- the second electrode 16 by forming the second electrode 16 with an alloy in which Sn and Au are added to Ag as the main component, the adhesion of the second electrode 16 to the buffer layer 15 can be improved. As a result, the contact resistance (interface resistance) at the interface with the buffer layer 15 can be reduced, so that the photoelectric conversion efficiency of the solar cell can be improved.
- Photoelectric conversion efficiency of solar cell 10 When performing a sputtering method for forming an alloy electrode (second electrode 16) in which Sn and Au are added to Ag, a plurality of solar cells 10 were manufactured by changing the flow rate of argon gas. In some of the solar cells 10, the photoelectric conversion efficiency is improved by about 7% as compared with the conventional solar cell in which the second electrode 16 is an Ag electrode. In addition, as shown in Table 1 below, the short-circuit current, the open-circuit voltage, and the fill factor were also confirmed to be equal to or improved with respect to the prior art. Table 1 shows the value of the solar cell of the present embodiment in which the second electrode 16 is an ASA electrode, where the value of the conventional solar cell in which the second electrode 16 is an Ag electrode is 100 (%). It is written.
- the saline solution reacted with Ag, and corrosion portions were observed in the Ag film.
- the sample A in which the ASA film 21 forming the second electrode (alloy electrode) 16 of the present embodiment was formed no corrosion portion was observed in the ASA film 21 and it was confirmed that there was no corrosion change. .
- the effect of improving the corrosion resistance is achieved by adding Au. Therefore, even if an Ag alloy film containing Ag as a main component without adding Sn without adding Sn is used, the effect of improving the corrosion resistance can be obtained.
- the corrosion resistance of the second electrode (alloy electrode) 16 can be improved. Therefore, it is possible to prevent the reflectance from being lowered due to the corrosion of the alloy electrode 16 and to prevent the contact resistance from being lowered due to the deterioration of the adhesion at the interface with the buffer layer 15. As a result, it is possible to secure a stable high reflectivity with little deterioration, and it is possible to secure stable adhesion without deterioration.
- a second electrode (alloy electrode) 16 composed of a first electrode (transparent electrode) 13 constituting the photoelectric conversion body 12, a nip silicon film of the photoelectric conversion layer 14, a buffer layer 15, and an ASA film 21. It is preferable that each of the layers has a texture structure in which irregularities are formed on the front and back surfaces. In this case, the prism effect for extending the optical path of sunlight incident on each layer and the light confinement effect can be obtained, so that the photoelectric conversion efficiency of the solar cell 10 can be further improved.
- the coverage of the ASA film formed on the buffer layer 15 having such a texture structure is inferior to that of the conventional Ag film, the adhesiveness with the buffer layer 15 is reduced.
- the ASA film 21 used as the second electrode 16 in this embodiment is formed on the buffer layer 15 having a texture structure, the same coverage as that of the conventional Ag film can be obtained. Therefore, it is possible to ensure the same or better adhesion with the buffer layer 15 having the texture structure.
- the solar cell 10 in FIG. 1 is a single type solar cell in which the photoelectric conversion layer 14 has a single structure, but the present invention is also applicable to a tandem type solar cell in which the photoelectric conversion layer has a tandem structure.
- the solar cell 10 has been illustrated as a so-called super straight type in which light is incident from the transparent substrate side.
- an alloy electrode (second electrode) 16 and a glass, insulator, or film substrate are provided on the substrate.
- the alloy electrode (second electrode) 16 of this embodiment can also be applied to a so-called substrate type in which the buffer layer 15, the photoelectric conversion layer 14, and the first electrode (surface transparent electrode) 13 are formed.
- the buffer layer 15 can be formed of a low refractive index conductive material.
- the refractive index of the GZO film is 2.05, but it can be formed of a material having a refractive index of 2.0 or less.
- the buffer layer 15 made of a GZO film also functions as a reflective layer that reflects a part of light that has been transmitted through the photoelectric conversion layer 14 and reflected toward the photoelectric conversion layer 14 without being directed toward the alloy electrode 16.
- the refractive index of the silicon film constituting the photoelectric conversion layer 14 is 3.8 to 4.0, the light that can be reflected is limited to those having a small incident angle. Therefore, by reducing the refractive index of the buffer layer 15 and increasing the refractive index difference from the silicon film, part of the light incident from the photoelectric conversion layer 14 at a small incident angle can also be reflected. As a result, it is possible to further improve the photoelectric conversion efficiency without reflecting such light by the alloy electrode 16.
- a low refractive index buffer layer 15 for example, when formed on an n-type amorphous silicon film, phosphorus (P), arsenic (As), antimony (Sb), bismuth (Bi), lithium (Li There is a silicon oxide film doped with an n-type impurity such as magnesium (Mg). Further, for example, when formed on a p-type amorphous silicon film, p-type impurities such as boron (B), gallium (Ga), aluminum (Al), indium (In), thallium (Tl), and beryllium (Be) There is a silicon oxide film doped with.
- the material of the second electrode is an alloy containing Ag as a main component and Sn and Au added.
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Abstract
Description
本願は、2008年6月17日に、日本国に出願された特願2008-157713号に基づき優先権を主張し、その内容をここに援用する。
(1)本発明の太陽電池は、光透過性を有する第1電極と;シリコンからなる光電変換層と;光透過性を有するバッファ層と;光反射性を有する合金からなる第2電極と;を有し、前記第2電極が、錫(Sn)及び金(Au)の少なくとも一方を含有してかつ、銀(Ag)を主成分とする銀合金からなる。
(2)上記(1)に記載の太陽電池では、前記銀合金が、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnを含有する、Agを主成分とする素材からなるものとしてもよい。
(3)上記(1)に記載の太陽電池では、前記銀合金が、原子%単位(at%)で0.1≦Au≦4.0の範囲にあるAuを含有する、Agを主成分とする素材からなるものとしてもよい。
(4)上記(1)に記載の太陽電池では、前記銀合金が、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnと0.1≦Au≦4.0の範囲にあるAuとを含有する、Agを主成分とする素材からなるものとしてもよい。
(6)上記(5)に記載の太陽電池の製造方法では、前記ターゲットが、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnを含有する、Agを主成分とする素材からなるものとしてもよい。
(7)上記(5)に記載の太陽電池の製造方法では、前記ターゲットが、原子%単位(at%)で0.1≦Au≦4.0の範囲にあるAuを含有する、Agを主成分とする素材からなるものとしてもよい。
(8)上記(5)に記載の太陽電池の製造方法では、前記ターゲットが、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnと、0.1≦Au≦4.0の範囲にあるAuとを含有する、Agを主成分とする素材からなるものとしてもよい。
基板11は、例えば、ガラスや透明樹脂等の、太陽光の透過性に優れてかつ耐久性のある絶縁材料で形成されている。この太陽電池10では、基板11を間に挟んで光電変換体12の反対側、つまり基板11の他方の面(表面)11b側から太陽光を入射させる。
第1電極(表面電極)13は、光透過性を有する金属酸化物、例えばAZO(Alを添加したZnO)やGZO(Gaを添加したZnO)やITO(Indium Tin Oxide)等のTCO(Transparent Conducting Oxide)によって構成されており、基板11の裏面11a上に形成されている。
シリコンからなる光電変換層(半導体層)14は、第1電極13上に形成されている。この光電変換層14は、p型シリコン膜(アモルファスシリコン膜および/またはマイクロクリスタルシリコン)と、n型シリコン膜(アモルファスシリコン膜および/またはマイクロクリスタルシリコン)との間に、i型シリコン膜(アモルファスシリコン膜および/またはマイクロクリスタルシリコン)を挟んだp-i-n接合構造またはn-i-p接合構造を有している。この光電変換層14は、例えば、表面透明電極13側からp型アモルファスシリコン膜、i型アモルファスシリコン膜、n型アモルファスシリコン膜が順次積層されたものである。また、アモルファスシリコンのp-i―n接合構造もしくはn-i―p接合構造に、マイクロクリスタルシリコンのp-i―n接合構造もしくはn-i―p接合構造を積層しても良い。
バッファ層15は、光透過性を有する低抵抗の金属酸化物(例えば膜厚がおよそ40~100nmのAZO(Alを添加したZnO)もしくはGZO(Gaを添加したZnO)等のTCO(Transparent Conducting Oxide))によって構成されており、光電変換層14と第2電極16との間に形成されている。このバッファ層15は、第2電極16をスパッタリング法で形成することにより、光電変換層14のシリコン膜にダメージを与えるのを防ぐとともに、第2電極16の構成材料である銀(Ag)がシリコンと合金化してしまうのを防ぐためのバリア層として機能する。
第2電極(裏面合金電極)16は、錫(Sn)と金(Au)と銀(Ag)とを含む銀合金からなる合金電極であり、バッファ層15上に形成されている。さらに具体的には、この合金電極16は、Agを主成分としてSnおよびAuを添加した合金を、スパッタリング法により、例えば200~250nmの膜厚に形成したものである。
図1の太陽電池10の製造方法について以下に説明する。まず、基板11を用意し、この基板11の裏面11a上に、第1電極(表面透明電極)13となるTCO膜を形成する。
TCO付きガラス基板が市販されているのでこれを調達しても良いが、ガラス基板上にスパッタリング法によりAZO膜やGZO膜を形成しても良い。AZO成膜スパッタリングもしくはGZO成膜スパッタリングでは、AlもしくはGaを添加したZnO焼結体をターゲットとして使用し、アルゴンガスをスパッタリングガスとした減圧下、あるいはアルゴンガスに酸素ガスを添加してスパッタリングガスとした減圧下においてZnO膜を形成する。
図2は、太陽電池10の第2電極16を構成するASA膜における、入射光波長に対する反射率特性を示すグラフである。なお、図2には、従来の太陽電池の第2電極を構成するAg膜における、入射光波長に対する反射率特性も比較例として示してある。サンプルは、ガラス基板上に、本発明に用いるASA膜、従来の太陽電池に用いるAg膜をそれぞれ同じ膜厚で形成したものである。
図3A~3Dは、太陽電池10の第2電極16を構成するASA膜の密着性を評価する剥離試験(シール試験)を説明する図である。図3Aは、ガラス基板20上に、スパッタリング法によってASA膜21を形成したサンプルAの断面図である。図3Bは、ガラス基板200(ガラス基板20と同じもの)上に、スパッタリング法によって上記ASA膜と同じ膜厚のAg膜201を形成したサンプルBの断面図である。また、図3Cは、上記サンプルAの剥離試験の結果を示す平面図であり、図3Dは、上記サンプルBの剥離試験の結果を示す平面図である。
AgにSnおよびAu添加した合金電極(第2電極16)を形成するスパッタリング法を行うに際し、アルゴンガスの流量を変化させて複数の太陽電池10を作製した。それらのうちのいくつかの太陽電池10では、第2電極16がAg電極である従来の太陽電池に比較して、光電変換効率がおよそ7%向上した。また、下記表1に示す通り、短絡電流、開放電圧、曲線因子も、従来に対して同等もしくは向上が確認された。
なお、表1は、第2電極16がAg電極である従来の太陽電池での値を100(%)とした場合の、第2電極16がASA電極である本実施形態の太陽電池の値を表記している。
ASA膜の耐蝕性を確認するために、図3Aに示すサンプルA(ガラス基板20上にスパッタリング法によってASA膜21を形成したもの)と、比較例として上記図3Bに示すサンプルB(サンプルAと同じガラス基板上にサンプルAのASA膜と同じ膜厚のAg膜を形成したもの)とを用意した。そして、これらサンプルを塩分5%の食塩水に96時間浸漬した後、両サンプルの表面を目視によって観察した。
光電変換体12を構成する第1電極(透明電極)13と、光電変換層14のn-i-pシリコン膜と、バッファ層15と、ASA膜21とからなる第2電極(合金電極)16のそれぞれの層を、その表裏面に凹凸が形成されたテクスチャ構造にするのが好ましい。この場合、それぞれの層に入射した太陽光の光路を伸ばすプリズム効果と光の閉じ込め効果とを得ることができるので、太陽電池10の光電変換効率をさらに向上させることができる。
しかし、本実施形態において第2電極16として用いるASA膜21は、テクスチャ構造を有するバッファ層15上に形成しても、従来のAg膜との同等のカバレッジが得られる。よって、テクスチャ構造を有するバッファ層15との間で従来と同等以上の密着性を確保できる。
また、図1の太陽電池10において、バッファ層15を、低屈折率の導電性材料で形成することも可能である。例えば、バッファ層15をGZOとした場合、GZO膜の屈折率は2.05であるが、屈折率2.0以下の材料で形成することも可能である。
しかし、光電変換層14を構成するシリコン膜の屈折率が3.8~4.0であるため、反射できる光は、その入射角が小さなものに限られる。そこで、バッファ層15の屈折率を低くしてシリコン膜との屈折率差を大きくすることにより、光電変換層14から小さな入射角で入射する光の一部をも、反射させることができる。その結果、このような光を合金電極16で反射させるまでもなく、さらに光電変換効率を向上させることができる。
11 基板
11a 基板の裏面
11b 基板の表面
12 光電変換体
13 第1電極(表面電極)
14 半導体層(光電変換層)
15 バッファ層
16 第2電極(裏面合金電極)
17 保護層
Claims (8)
- 光透過性を有する第1電極と;
シリコンからなる光電変換層と;
光透過性を有するバッファ層と;
光反射性を有する合金からなる第2電極と;
を有し、
前記第2電極が、錫(Sn)及び金(Au)の少なくとも一方を含有してかつ、銀(Ag)を主成分とする銀合金からなる
ことを特徴とする太陽電池。 - 前記銀合金が、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnを含有する、Agを主成分とする素材からなることを特徴とする請求項1に記載の太陽電池。
- 前記銀合金が、原子%単位(at%)で0.1≦Au≦4.0の範囲にあるAuを含有する、Agを主成分とする素材からなることを特徴とする請求項1に記載の太陽電池。
- 前記銀合金が、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnと0.1≦Au≦4.0の範囲にあるAuとを含有する、Agを主成分とする素材からなることを特徴とする請求項1に記載の太陽電池。
- 請求項1に記載の太陽電池を製造する方法であって、
前記第2電極を、Sn及びAuの少なくとも一方とAgとを含むターゲットを用いて、スパッタリング法により形成する工程を有する
ことを特徴とする太陽電池の製造方法。 - 前記ターゲットが、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnを含有する、Agを主成分とする素材からなることを特徴とする請求項5に記載の太陽電池の製造方法。
- 前記ターゲットが、原子%単位(at%)で0.1≦Au≦4.0の範囲にあるAuを含有する、Agを主成分とする素材からなることを特徴とする請求項5に記載の太陽電池の製造方法。
- 前記ターゲットが、原子%単位(at%)で0.1≦Sn≦2.5の範囲にあるSnと、0.1≦Au≦4.0の範囲にあるAuとを含有する、Agを主成分とする素材からなることを特徴とする請求項5に記載の太陽電池の製造方法。
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JPWO2015060432A1 (ja) * | 2013-10-25 | 2017-03-09 | シャープ株式会社 | 光電変換装置 |
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Cited By (5)
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US20110247685A1 (en) * | 2010-03-16 | 2011-10-13 | Fuji Electric Holdings Co., Ltd. | Thin-film solar cell and method for manufacturing the same |
KR101273179B1 (ko) * | 2011-09-20 | 2013-06-17 | 엘지이노텍 주식회사 | 태양전지 및 이의 제조방법 |
JP2016518720A (ja) * | 2013-05-03 | 2016-06-23 | サン−ゴバン グラス フランス | 光電池又は光電池モジュール用のバックコンタクト基材 |
JPWO2015060432A1 (ja) * | 2013-10-25 | 2017-03-09 | シャープ株式会社 | 光電変換装置 |
US11227961B2 (en) | 2013-10-25 | 2022-01-18 | Sharp Kabushiki Kaisha | Photoelectric conversion device |
Also Published As
Publication number | Publication date |
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KR20100115369A (ko) | 2010-10-27 |
JPWO2009154137A1 (ja) | 2011-12-01 |
TW201010100A (en) | 2010-03-01 |
CN101971357A (zh) | 2011-02-09 |
EP2293344A4 (en) | 2013-03-06 |
KR101153435B1 (ko) | 2012-06-07 |
EP2293344A1 (en) | 2011-03-09 |
US20110108114A1 (en) | 2011-05-12 |
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