JP6359519B2 - Silicon substrate surface treatment method, semiconductor device manufacturing method, semiconductor manufacturing device, transfer member and manufacturing method thereof, solar cell, and solar cell manufacturing method - Google Patents
Silicon substrate surface treatment method, semiconductor device manufacturing method, semiconductor manufacturing device, transfer member and manufacturing method thereof, solar cell, and solar cell manufacturing method Download PDFInfo
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- 229910052710 silicon Inorganic materials 0.000 title claims description 94
- 239000010703 silicon Substances 0.000 title claims description 94
- 238000012546 transfer Methods 0.000 title claims description 58
- 238000000034 method Methods 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000004065 semiconductor Substances 0.000 title claims description 15
- 239000000758 substrate Substances 0.000 title description 101
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title description 85
- 238000004381 surface treatment Methods 0.000 title description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 65
- 239000002159 nanocrystal Substances 0.000 claims description 58
- 229910052751 metal Inorganic materials 0.000 claims description 49
- 239000002184 metal Substances 0.000 claims description 49
- 239000004332 silver Substances 0.000 claims description 38
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- 230000003197 catalytic effect Effects 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 11
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- 230000001590 oxidative effect Effects 0.000 claims description 9
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- 239000000243 solution Substances 0.000 description 35
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 33
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- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 18
- 239000000126 substance Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 239000011259 mixed solution Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000002253 acid Substances 0.000 description 8
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- UKCBKQLNTLMFAA-UHFFFAOYSA-N F.[F] Chemical compound F.[F] UKCBKQLNTLMFAA-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 239000011888 foil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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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
- H01L31/0236—Special surface textures
- H01L31/02363—Special surface textures of the semiconductor body itself, e.g. textured active layers
-
- 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
- Y02E10/546—Polycrystalline silicon PV cells
Description
本発明は、シリコン基板の表面に微細なナノクリスタル構造層を形成することに係る、シリコン基板の表面処理方法、半導体装置の製造方法、半導体の製造装置、転写用部材およびその製造方法、太陽電池および太陽電池の製造方法に関するものである。 The present invention relates to a silicon substrate surface treatment method, a semiconductor device manufacturing method, a semiconductor manufacturing device, a transfer member and a manufacturing method thereof, and a solar cell, which are related to forming a fine nanocrystal structure layer on the surface of a silicon substrate. And a method for manufacturing a solar cell.
従来、シリコン基板（Ｓｉウェハ）に対して、白金等の触媒金属の微細粒子が共存するフッ化水素酸・過酸化水素水（ＨＦ・Ｈ２Ｏ２）混合溶液に作用させると、Ｓｉウェハの表面に、上記触媒金属の存在によって、開孔及びその開孔周辺での微細な多孔質層が形成されること、そして、この技術を太陽電池の受光面に適用することにより、光反射率を低減させて、太陽電池の変換効率を向上させることの可能なことが知られている（特許文献１）。Conventionally, when a silicon substrate (Si wafer) is allowed to act on a mixed solution of hydrofluoric acid / hydrogen peroxide (HF / H 2 O 2 ) in which fine particles of catalyst metal such as platinum coexist, Due to the presence of the catalytic metal on the surface, an opening and a fine porous layer around the opening are formed, and by applying this technique to the light receiving surface of the solar cell, the light reflectance is reduced. It is known that the conversion efficiency of a solar cell can be improved by reducing it (Patent Document 1).
しかし、一方で、上述の従来技術では、その処理後に、上記溶液中の白金等の触媒金属がＳｉウェハの表面に付着・残存したままで、これが、例えば半導体表面のキャリア特性を低下させる要因となることが懸念され、太陽電池の性能向上には、かかる要因の影響を除くことを含め、解決すべき課題がある。 However, on the other hand, in the above-described conventional technology, after the treatment, the catalyst metal such as platinum in the solution remains attached to the surface of the Si wafer, which is a factor that deteriorates the carrier characteristics of the semiconductor surface, for example. There is a problem to be solved, including removing the influence of such factors, in improving the performance of solar cells.
本願の発明者は、先に、白金メッシュ等をローラーに装着して用いて、シリコン基板を酸化しかつ溶解し得る、例えば上述のフッ化水素酸・過酸化水素水（ＨＦ・Ｈ２Ｏ２）混合溶液等の処理溶液中で、上記白金メッシュ等を処理対象のシリコン基板に対向配置して接触又は近接させたとき、同白金メッシュ等が、その表面形状を処理対象のシリコン基板表面の広い面積において、酸化と溶解との反応における触媒作用をなして、短時間に、そのシリコン基板表面を微細なナノクリスタル構造層に作り替える、転写用部材となること、すなわち、同白金メッシュ等を転写用部材として利用する技術（以下、この種の技術を化学的構造転写法と称する）を提示し、それにより、シリコン基板を低反射光特性の表面になして、高い光電変換性能の太陽電池を製造することを提案している（特許文献２）。
また、本願の発明者は、転写用部材の形状として、メッシュに限らず、貫通孔及び／又は非貫通孔が形成された触媒材、アイランド状の触媒材あるいは平板状の触媒材を用い得ること、さらに、上述の処理溶液中に１％以下の銀イオンなど少量の金属イオンが含まれていてもよいことを提示した（特許文献３）。The inventor of the present application can first oxidize and dissolve the silicon substrate using a platinum mesh or the like mounted on a roller, for example, the above-described hydrofluoric acid / hydrogen peroxide solution (HF / H 2 O 2). ) When the platinum mesh or the like is placed in contact with or in close proximity to the silicon substrate to be processed in a processing solution such as a mixed solution, the surface shape of the platinum mesh or the like is wide on the surface of the silicon substrate to be processed. In the area, it becomes a transfer member that catalyzes the reaction between oxidation and dissolution, and in a short time, the surface of the silicon substrate is changed to a fine nanocrystal structure layer. Presenting a technology to be used as a member (hereinafter, this type of technology is referred to as a chemical structure transfer method), thereby making a silicon substrate a surface with low reflected light characteristics and high photoelectric conversion performance Has been proposed (Patent Literature 2).
Further, the inventor of the present application is not limited to the mesh as the shape of the transfer member, but may use a catalyst material in which a through hole and / or a non-through hole is formed, an island-shaped catalyst material, or a flat plate-shaped catalyst material. Furthermore, it has been suggested that a small amount of metal ions such as 1% or less of silver ions may be contained in the above-described treatment solution (Patent Document 3).
かかる化学的構造転写法を用いる場合においても、極低反射率を持ったシリコン基板表面を、迅速、確実に形成すること、並びにそのシリコン基板表面部におけるキャリア特性を安定に維持すること、また、それらを実現するための方策、手法として、上述の転写用部材の形状、構造、製作手法等には、更なる創意工夫が求められる。 Even when such a chemical structure transfer method is used, it is possible to quickly and surely form a silicon substrate surface having an extremely low reflectance, and to stably maintain carrier characteristics in the silicon substrate surface portion. As measures and methods for realizing them, further ingenuity is required for the shape, structure, manufacturing method and the like of the above-mentioned transfer member.
本発明の目的は、上述の従来例のような転写用部材の機能を一層高めることで、迅速に、シリコン表面を極薄、微細なナノクリスタル構造層に形成するための、シリコン基板の表面処理方法及び半導体装置の製造方法、並びに太陽電池およびその製造方法を提供すること、さらには、その微細なナノクリスタル構造層形成に利用する転写用部材並びにナノクリスタル構造層を有するシリコン基板自体を実現することにある。 The object of the present invention is to further improve the function of a transfer member as in the above-described conventional example, thereby quickly forming a silicon surface into a very thin and fine nanocrystal structure layer. The present invention provides a method, a method for manufacturing a semiconductor device, a solar cell, and a method for manufacturing the solar cell, and further realizes a transfer member used for forming the fine nanocrystal structure layer and the silicon substrate itself having the nanocrystal structure layer. There is.
本発明の要旨は、化学的構造転写法において利用する触媒機能を有する第１の金属による転写用部材の表面に、微量の触媒機能を有する第２の金属を担持させて用いること、または上記転写用部材を、微量の第２の金属を含む混合水溶液中でシリコン基板に接触させて用いることにある。 The gist of the present invention is that the surface of the transfer member made of the first metal having a catalytic function used in the chemical structure transfer method is used by supporting a small amount of the second metal having the catalytic function, or the transfer described above. The member for use is in contact with the silicon substrate in a mixed aqueous solution containing a trace amount of the second metal.
詳細には、化学的構造転写法において、例えば、第１の金属による転写用部材に微量の第２の金属を担持させて、シリコンを酸化しかつ溶解し得る処理溶液中で、シリコン基板の表面に接触乃至接近させることにより、または、上記第１の金属による転写用部材の表面を、シリコンを酸化しかつ溶解し得る処理溶液中に微量の第２の金属を含ませて、シリコン基板の表面に接触乃至接近させることにより、同シリコン基板の最表部に極薄、微細なナノクリスタル構造層を形成する、シリコン基板の表面処理方法及び半導体装置の製造方法である。 Specifically, in the chemical structure transfer method, for example, the surface of the silicon substrate is treated in a treatment solution that can oxidize and dissolve silicon by supporting a small amount of the second metal on the first metal transfer member. A surface of the silicon substrate by bringing a trace amount of the second metal into the treatment solution capable of oxidizing and dissolving the surface of the transfer member made of the first metal by contacting or approaching the surface. A surface treatment method for a silicon substrate and a method for manufacturing a semiconductor device, in which an ultrathin and fine nanocrystal structure layer is formed on the outermost surface of the silicon substrate by contacting or approaching the substrate.
本発明では、触媒機能を有する第１の金属による転写用部材の表面に微量の触媒機能を有する第２の金属を担持して存在させるか、あるいは、シリコンを酸化しかつ溶解し得る処理溶液中に第２の金属を溶解して存在させることにより、上記触媒機能を有する第１の金属による転写用部材を、上記シリコンを酸化しかつ溶解し得る処理溶液中で、シリコン基板の表面に接触ないし接近させて、上記シリコン基板の表面に極薄、微細なナノクリスタル構造層をシリコン基板全面に一様に形成することに特徴がある。 In the present invention, a transfer metal member having a catalytic function is supported on the surface of the transfer member by a small amount of the second metal having a catalytic function, or in a processing solution capable of oxidizing and dissolving silicon. When the second metal is dissolved and present in the substrate, the transfer member made of the first metal having the catalytic function is brought into contact with the surface of the silicon substrate in a treatment solution capable of oxidizing and dissolving the silicon. It is characterized in that an ultrathin and fine nanocrystal structure layer is uniformly formed on the entire surface of the silicon substrate.
本発明で、上記第１の金属は、白金（Ｐｔ）、銀（Ａｇ）、パラジウム（Ｐｄ）、金（Ａｕ）、ロジウム（Ｒｈ）およびこれらを含む他の金属との合金の群から選ばれる。また上記第２の金属は、銀（Ａｇ）のほか、Ｎｉ、Ｆｅ、Ｃｕ、Ｐｄの群から選ばれる。 In the present invention, the first metal is selected from the group of platinum (Pt), silver (Ag), palladium (Pd), gold (Au), rhodium (Rh) and alloys with other metals containing these. . The second metal is selected from the group of Ni, Fe, Cu, and Pd in addition to silver (Ag).
本発明では、第１例として、上記第１の金属でなる転写用部材に、上記第２の金属を溶解させて調製した溶液に浸漬して引揚げて、同転写用部材の面に微量の上記第２の金属を担持させて、この転写用部材を所定のローラーに装着して用いて、シリコンを酸化しかつ溶解し得る、所定の処理溶液中で、シリコン基板に接触乃至近接させながらローラーごと回転移動させることにより、上記シリコン基板の表面に微細なナノクリスタル構造層を形成する過程を備える。 In the present invention, as a first example, the transfer member made of the first metal is dipped in a solution prepared by dissolving the second metal and pulled up, and a small amount of trace is formed on the surface of the transfer member. A roller that supports the second metal and attaches the transfer member to a predetermined roller and uses it to oxidize and dissolve silicon while contacting or approaching the silicon substrate in a predetermined processing solution. And a process of forming a fine nanocrystal structure layer on the surface of the silicon substrate.
また、本発明では、第２例として、上述のシリコンを酸化しかつ溶解し得る所定の処理溶液に上記第２の金属を微量溶解させて用い、その溶液中に、上記の転写用部材を、所定のシリコン基板に接触乃至接近させることにより、上記シリコン基板の表面に極薄、微細なナノクリスタル構造層を形成する過程を備えることを含む。 Further, in the present invention, as a second example, the above-mentioned transfer member is used by dissolving a small amount of the above-mentioned second metal in a predetermined processing solution capable of oxidizing and dissolving the above-described silicon. A step of forming an ultrathin and fine nanocrystal structure layer on the surface of the silicon substrate by contacting or approaching a predetermined silicon substrate.
なお、上述のシリコンを酸化しかつ溶解し得る処理溶液は、例えば、５０ｗｔ％濃度のフッ化水素酸（ＨＦ）水と３０ｗｔ％濃度の過酸化水素水（Ｈ２Ｏ２）とを適宜な体積比で混合したフッ化水素酸・過酸化水素水の混合溶液が用いられる。The above-mentioned treatment solution capable of oxidizing and dissolving silicon includes, for example, an appropriate volume of 50 wt% hydrofluoric acid (HF) water and 30 wt% hydrogen peroxide (H 2 O 2 ). A mixed solution of hydrofluoric acid and hydrogen peroxide water mixed in a ratio is used.
本発明では、上記第１例の実施事例として、例えば、５０ｗｔ％濃度のフッ化水素酸（ＨＦ）水と３０ｗｔ％濃度の過酸化水素水（Ｈ２Ｏ２）とを体積比１：１で混合したフッ化水素酸・過酸化水素水の混合溶液に銀（Ａｇ）を１００ｐｐｍ程度溶解させて調製し、これに短時間浸漬して引揚げ、さらに所定の熱処理を行うことで、少量の銀を担持した転写用部材を形成する過程も含まれ、さらに、この転写用部材を所定のローラーに装着して所定のシリコン基板に接触乃至接近させながら、ローラーを回転して移動させることにより、上記シリコン基板の表面に微細なナノクリスタル構造層を形成する過程を備えることも含まれる。In the present invention, as an implementation example of the first example, for example, 50 wt% concentration of hydrofluoric acid (HF) water and 30 wt% concentration of hydrogen peroxide water (H 2 O 2 ) are used at a volume ratio of 1: 1. A small amount of silver is prepared by dissolving about 100 ppm of silver (Ag) in a mixed solution of hydrofluoric acid and hydrogen peroxide, and then immersing it in it for a short period of time. Forming a transfer member carrying the transfer member, and by rotating the roller while moving the roller member while contacting or approaching the predetermined silicon substrate while mounting the transfer member on the predetermined roller, It also includes providing a process of forming a fine nanocrystal structure layer on the surface of the silicon substrate.
転写用部材への微量の第２の金属を担持させるに際しては、上述の銀（Ａｇ）を溶解させた、フッ化水素酸・過酸化水素水の混合溶液を用いる場合に限らず、それとは別の溶液に所定適量の第２の金属が溶解されているものに、前記第１の金属でなる転写用部材を浸漬して引揚げることで、この転写用部材に第２の金属を微量担持して利用することも可能である。 When a small amount of the second metal is supported on the transfer member, it is not limited to using a mixed solution of hydrofluoric acid and hydrogen peroxide water in which the above silver (Ag) is dissolved. The transfer member made of the first metal is dipped into a solution in which a predetermined appropriate amount of the second metal is dissolved in the solution, and lifted, so that a small amount of the second metal is supported on the transfer member. Can also be used.
本発明は、シリコン基板として、単結晶シリコン、多結晶シリコン、非結晶性シリコン、疑似単結晶シリコンおよびシリコン化合物半導体（シリコンカーバイト、シリコンゲルマニウム等を含む）から選ばれるシリコン基材を選択的に使用することができる。 In the present invention, a silicon substrate selected from single crystal silicon, polycrystalline silicon, amorphous silicon, pseudo single crystal silicon, and silicon compound semiconductor (including silicon carbide, silicon germanium, etc.) is selectively used as the silicon substrate. Can be used.
本発明の上述第１の実施亊例によると、化学的構造転写法において、微量の触媒機能を有する第２の金属類の担持された転写用部材を実現して、これを用いて、シリコンを酸化しかつ溶解し得る処理溶液内で所定のシリコン基板に接触乃至接近させることにより、そのシリコン基板表面には、シリコンナノクリスタル構造層が、その形成速度をいっそう高めて、形成されて、極低反射率のシリコン表面を形成し得る。形成された一様な極薄、微細なナノクリスタル構造層の光学反射特性は平均値で５％以下の低反射率特性が得られ、これを用いて製造した太陽電池では、変換効率を一段と向上させることできる。 According to the first embodiment of the present invention, in the chemical structure transfer method, a transfer member loaded with a second metal having a trace amount of catalytic function is realized, and this is used to form silicon. By contacting or approaching a predetermined silicon substrate in an oxidizing and dissolving processing solution, a silicon nanocrystal structure layer is formed on the surface of the silicon substrate at a further increased rate of formation. A reflective silicon surface may be formed. The formed ultra-thin and fine nanocrystal structure layer has a low optical reflectance characteristic with an average value of 5% or less, and solar cells manufactured using it have a much higher conversion efficiency. Can be made.
１ Ｐ型シリコン基板
２ ナノクリスタル構造層
３ アルミニウム蒸着層
１１ 多結晶シリコン基板
１２ ナノクリスタル構造層
１３ アルミニウム蒸着層DESCRIPTION OF SYMBOLS 1 P-type silicon substrate 2 Nanocrystal structure layer 3 Aluminum vapor deposition layer 11 Polycrystalline silicon substrate 12 Nanocrystal structure layer 13 Aluminum vapor deposition layer
［実施例１］
つぎに、本発明を、実施の形態である各実施例により、図面を参照して詳細に述べる。[Example 1]
Next, the present invention will be described in detail with reference to the drawings by examples of embodiments.
フッ素樹脂のトレーに５０ｗｔ％濃度のフッ化水素酸（ＨＦ）と３０ｗｔ％濃度の過酸化水素水（Ｈ２Ｏ２）とを体積比１：１で混合したフッ化水素酸と過酸化水素水との混合溶液２００ｍｌを用いて、銀の粒子を１００ｐｐｍ溶解させて調製した。その溶液に２００メッシュの白金メッシュを室温で１０秒間浸漬した後、このメッシュを取り出し、流水で２分間洗浄し、同白金メッシュ体に微量の銀を担持させる。Hydrofluoric acid and hydrogen peroxide solution in which 50 wt% concentration of hydrofluoric acid (HF) and 30 wt% concentration of hydrogen peroxide (H 2 O 2 ) are mixed at a volume ratio of 1: 1 in a fluororesin tray. The silver particles were prepared by dissolving 100 ppm using 200 ml of the mixed solution. A 200-mesh platinum mesh is immersed in the solution at room temperature for 10 seconds, and then the mesh is taken out and washed with running water for 2 minutes to allow a trace amount of silver to be supported on the platinum mesh body.
化学的構造転写法において、微量の銀を担持した上記白金メッシュを用いて、５０ｗｔ％濃度のフッ化水素酸（ＨＦ）と３０ｗｔ％濃度の過酸化水素水（Ｈ２Ｏ２）とを体積比でフッ化水素酸（ＨＦ）水：過酸化水素水（Ｈ２Ｏ２）＝１：３，１：１，３：１，５：１，１０：１のそれぞれに混合したフッ化水素酸水と過酸化水素水との混合溶液５００ｍｌのフッ素樹脂容器内において、ｐ型で面方位（１００）の片面ミラー面、比抵抗：１〜２０Ωｃｍの５ｃｍ角に切断した単結晶シリコン基板を、その銀担持白金メッシュを、所定のローラー面に装着して、室温で約３０秒間のローラーによる数度の回転処理で接触させ、流水洗浄し、窒素ブロー処理後、図１〜図５の各ＳＥＭ（写真）図に見られるように、いずれの場合にも上記シリコン基板面にシリコンナノクリスタル層の形成されていることが確認できた。In the chemical structure transfer method, a volume ratio of 50 wt% concentration of hydrofluoric acid (HF) and 30 wt% concentration of hydrogen peroxide (H 2 O 2 ) using the platinum mesh supporting a small amount of silver. Hydrofluoric acid (HF) water: hydrogen peroxide water (H 2 O 2 ) = 1: 3, 1: 1, 3: 1, 5: 1, 10: 1 mixed with hydrofluoric acid water In a fluororesin container of 500 ml of a mixed solution of hydrogen peroxide and water, a single-crystal silicon substrate cut into a 5 cm square of p-type, single-sided mirror surface with a plane orientation (100), specific resistance: 1 to 20 Ωcm, A supported platinum mesh is mounted on a predetermined roller surface, brought into contact with the roller by rotating it several times with a roller at room temperature for about 30 seconds, washed with running water, treated with nitrogen blow, and then each SEM shown in FIGS. ) As shown in the figure, the above It was confirmed that a silicon nanocrystal layer was formed on the recon substrate surface.
図６及び図７は、本実施例により得られた事例２つ（体積比でフッ化水素酸：過酸化水素水＝３：１、及び同１０：１のそれぞれに混合したフッ化水素酸と過酸化水素水との混合溶液を使用した場合）の単結晶シリコン基板の表面近傍の断面ＴＥＭ（透過電子顕微鏡）の各写真図であり、図６及び図７で見ると、シリコン基板１の表面には約１００ｎｍのシリコンナノクリスタル構造層２が形成されていることが分かる。 6 and 7 show two examples obtained by this example (hydrofluoric acid mixed in a volume ratio of hydrofluoric acid: hydrogen peroxide = 3: 1 and 10: 1, respectively) FIG. 6 is a photographic view of a cross-sectional TEM (transmission electron microscope) in the vicinity of the surface of a single crystal silicon substrate (when a mixed solution with hydrogen peroxide water is used). It can be seen that a silicon nanocrystal structure layer 2 of about 100 nm is formed.
なお、図６及び図７でアルミニウム蒸着層３は、ＴＥＭ（透過電子顕微鏡）観察に際して、上記シリコンナノクリスタル構造層２の表面界域を明示するために設けたものであり、完成の装置にそのまま存在させるものではない。 In FIGS. 6 and 7, the aluminum vapor deposition layer 3 is provided to clearly indicate the surface boundary area of the silicon nanocrystal structure layer 2 when observed with a TEM (transmission electron microscope), and is used as it is in a completed apparatus. It does not exist.
図８は、シリコンナノクリスタル構造層２の領域の断面を主体的に示す部分拡大のＴＥＭ（写真）図であり、これによって、シリコンナノクリスタル構造層２の内部には、同図中の矢印先端にみられる通りの、約２〜８ｎｍの粒径で、単結晶シリコン基板１の領域にみられるものと同様に結晶構造が揃って観察される。すなわち、単結晶シリコン基板１に対して、上記フッ化水素酸と過酸化水素水との混合溶液を使用して化学的構造転写法を適用した場合、シリコンナノクリスタル構造層２内に微細な粒径の結晶構造が揃って存在する態様が明らかであり、これにより、このシリコンナノクリスタル構造層２のなかの、まさしくナノクリスタル構造の微細な粒径結晶が存在することを確認できる。 FIG. 8 is a partially enlarged TEM (photograph) diagram mainly showing a cross section of the region of the silicon nanocrystal structure layer 2, whereby the tip of the arrow in FIG. As can be seen, the crystal structure is observed with a grain size of about 2 to 8 nm as in the region of the single crystal silicon substrate 1. That is, when the chemical structure transfer method is applied to the single crystal silicon substrate 1 using the mixed solution of hydrofluoric acid and hydrogen peroxide, fine particles are formed in the silicon nanocrystal structure layer 2. It is clear that the crystal structures having the same diameter are present, and thus, it can be confirmed that the fine crystal grains having the nanocrystal structure are present in the silicon nanocrystal structure layer 2.
上記ナノクリスタル構造層を形成して、株式会社コベルコ科研製のライフタイム測定装置ＬＴＡ―１５１０を用いて、少数キャリアの１／ｅ２ライフタイムを測定したところ、その値が、上記ナノクリスタル構造層形成直後には１０μｓであり、引続き９００℃，１０分の熱酸化を行ったところ、１５μｓへ、さらに、４５０℃，５％水素／９５％窒素中のアニール処理４５分で１７４μｓ以上へと、大きく改善されることが分かった。また、同様の試料で、上記熱酸化に代えて、濃度７０ｗｔ％の硝酸中で、７０℃，１０分の硝酸処理を行うと、ライフタイムは、硝酸処理前の９μｓから、処理後に１０μｓへ、さらに、４５０℃，５％水素／９５％窒素中のアニール処理で１７μｓへと、ほぼ２倍の改善が見られた。When the nanocrystal structure layer was formed and the 1 / e 2 lifetime of minority carriers was measured using a lifetime measuring device LTA-1510 manufactured by Kobelco Research Institute, Inc., the value was determined as the nanocrystal structure layer. Immediately after the formation, it was 10 μs, and when thermal oxidation was subsequently performed at 900 ° C. for 10 minutes, it was greatly increased to 15 μs and further to 174 μs or more in 45 minutes at 450 ° C., annealing in 5% hydrogen / 95% nitrogen. It turns out that it improves. In addition, when a nitric acid treatment is performed at 70 ° C. for 10 minutes in nitric acid having a concentration of 70 wt% instead of the thermal oxidation with the same sample, the lifetime is changed from 9 μs before nitric acid treatment to 10 μs after the treatment. Furthermore, the annealing treatment at 450 ° C., 5% hydrogen / 95% nitrogen showed an almost double improvement to 17 μs.
これらの透過電子顕微鏡（ＴＥＭ）の写真図からは、シリコンナノクリスタル構造層の表面及び層内に微細な細孔や金属微粒子の存在は認められない。シリコンナノクリスタル構造層の厚みは約１００ｎｍであるが、かかる厚みは処理時間を制御することにより、３０ｎｍから５００ｎｍ程度が可能である。 From these transmission electron microscope (TEM) photographs, the presence of fine pores and fine metal particles in the surface of the silicon nanocrystal structure layer and in the layer are not recognized. The thickness of the silicon nanocrystal structure layer is about 100 nm, and the thickness can be about 30 nm to 500 nm by controlling the processing time.
加えて、本実施例で得られたシリコンナノクリスタル構造層は、３６５ｎｍの紫外光照射で概ね６００ｎｍ〜８００ｎｍ波長のオレンジ色発光が観察されることから、バンドギャップが、通常のシリコンの場合の１．１ｅＶより大きい、約２ｅＶから約１．５ｅＶに拡大していることを確認することができた。上記オレンジ色の発光は、ＴＥＭで見られた数ｎｍ程度の粒径の微細結晶構造からの発光と考えられる。 In addition, since the silicon nanocrystal structure layer obtained in this example exhibits orange emission of about 600 nm to 800 nm wavelength when irradiated with ultraviolet light at 365 nm, the band gap is 1 in the case of normal silicon. It was confirmed that the magnification was increased from about 2 eV to about 1.5 eV, which is larger than .1 eV. The orange light emission is considered to be light emission from a fine crystal structure having a particle size of about several nanometers as seen by TEM.
また、銀を担持させて、流水洗浄したが、流水洗浄後に数百度の加熱処理を行い、
銀粒子と白金メッシュの付着強度を上げることも有効である。Also, silver was supported and washed with running water, but after washing with running water, heat treatment was performed at several hundred degrees,
It is also effective to increase the adhesion strength between silver particles and platinum mesh.
なお、上記白金メッシュには、白金と銀との合金あるいはニッケル（Ｎｉ）−白金−銀の合金のメッシュを用いることによっても、シリコン表面に所望のナノクリスタル構造層を形成することができる。 In addition, a desired nanocrystal structure layer can be formed on the silicon surface by using an alloy of platinum and silver or a nickel (Ni) -platinum-silver alloy mesh for the platinum mesh.
さらに、転写用部材の母体には、白金と白金以外の触媒機能を有する他金属との合金、同触媒機能を有する金属と溶液に不溶の別金属との合金、同触媒機能を有する金属を含む不織布等の合成体を用いることができる。いずれの場合も、母体の転写用部材の表面部には微量かつ適度の銀を担持し得るものが利用可能である。 Furthermore, the base material of the transfer member includes platinum and an alloy of another metal having a catalytic function other than platinum, an alloy of the metal having the catalytic function and another metal insoluble in a solution, and a metal having the catalytic function. A synthetic material such as a nonwoven fabric can be used. In any case, the surface portion of the base transfer member can use a trace amount of moderate silver.
図９は、本実施例による光波長域３００〜８００ｎｍでの表面反射率特性を示し、反射特性では表面反射率が５％以下の低反射率特性である。これは、表面のナノクリスタル構造層の存在により、通常のシリコン基板にくらべて、表面反射率が顕著に低減されていることを示している。
［実施例２］FIG. 9 shows the surface reflectance characteristics in the light wavelength region of 300 to 800 nm according to the present embodiment, which is a low reflectance characteristic with a surface reflectance of 5% or less. This indicates that the surface reflectance is remarkably reduced as compared with a normal silicon substrate due to the presence of the nanocrystal structure layer on the surface.
[Example 2]
つぎに、本発明を、実施の形態である多結晶シリコン基板の表面処理過程により、図面を参照して詳細に述べる。 Next, the present invention will be described in detail with reference to the drawings by the surface treatment process of the polycrystalline silicon substrate according to the embodiment.
４００メッシュの白金の構造体を転写用部材として、この転写用部材を過酸化水素（Ｈ２Ｏ２）水とフッ化水素（ＨＦ）酸との混合水溶液中で多結晶シリコン基板に接触させて、その多結晶シリコン基板表面にシリコンナノクリスタル構造層を形成した。詳細には、上記多結晶シリコン基板として、ｐ型のアズスライス，比抵抗１〜２０Ωｃｍ，基板の大きさ５ｃｍ×５ｃｍ（５ｃｍ角），厚さ約２００μｍを、予め、表面のアルカリエッチ（ＫＯＨ：２１ｗｔ％水溶液の５００ｍｌ中，フッ素樹脂容器内で実施）で８０℃１０分間の処理後、水洗２分を２回、窒素（Ｎ２）ブロー乾燥した。次に、５０ｗｔ％濃度のフッ化水素（ＨＦ）酸と３０ｗｔ％濃度の過酸化水素（Ｈ２Ｏ２）水とを体積比３：１で混合して銀イオンを１ｐｐｍ程度含ませた、フッ化水素（ＨＦ）酸と過酸化水素（Ｈ２Ｏ２）水との混合水溶液内（フッ素樹脂のトレー内の２００ｍｌを使用）で、上記転写用部材を所定のローラーに装着して、上記多結晶シリコン基板の主表面に約１０秒間接触させる。その後、流水洗浄及び窒素（Ｎ２）ブロー乾燥を行った。A 400 mesh platinum structure is used as a transfer member, and the transfer member is brought into contact with a polycrystalline silicon substrate in a mixed aqueous solution of hydrogen peroxide (H 2 O 2 ) water and hydrogen fluoride (HF) acid. A silicon nanocrystal structure layer was formed on the surface of the polycrystalline silicon substrate. Specifically, as the polycrystalline silicon substrate, a p-type as-slice, a specific resistance of 1 to 20 Ωcm, a substrate size of 5 cm × 5 cm (5 cm square), and a thickness of about 200 μm are preliminarily formed on the surface by alkaline etching (KOH: After carrying out treatment at 80 ° C. for 10 minutes in 500 ml of a 21 wt% aqueous solution in a fluororesin container, it was blown dry with nitrogen (N 2 ) twice for 2 minutes with water. Next, 50 wt% concentration of hydrofluoric acid (HF) acid and 30 wt% concentration of hydrogen peroxide (H 2 O 2 ) water were mixed at a volume ratio of 3: 1 to contain about 1 ppm of silver ions. In a mixed aqueous solution of hydrofluoric acid (HF) acid and hydrogen peroxide (H 2 O 2 ) water (using 200 ml in a fluororesin tray), the transfer member is mounted on a predetermined roller, and The main surface of the crystalline silicon substrate is contacted for about 10 seconds. Then, running water washing and nitrogen (N 2 ) blow drying were performed.
上述の処理の結果、図１０のＳＥＭ写真図から、その多結晶シリコン基板の表面は数十ｎｍ以下の微細な粒子状結晶構造群からなっていることが観察された。 As a result of the above processing, it was observed from the SEM photograph of FIG. 10 that the surface of the polycrystalline silicon substrate was composed of a group of fine particulate crystal structures of several tens of nm or less.
図１１は断面の透過電子顕微鏡写真（ＴＥＭ像）であり、多結晶シリコン基板１１上の形成されたシリコンナノクリスタル構造層１２と、これにアルミニウム蒸着層１３を設けた断面を表している。図１１の透過電子顕微鏡（ＴＥＭ）写真で示されるように、シリコンナノクリスタル構造層１２の厚さは約１００ｎｍ以上であることが分かる。また、シリコンナノクリスタル構造層１２内には、単結晶と同様に、数ｎｍ程度の微細な結晶構造が見られた。 FIG. 11 is a transmission electron micrograph (TEM image) of the cross section, showing a cross section in which the silicon nanocrystal structure layer 12 formed on the polycrystalline silicon substrate 11 and the aluminum vapor deposition layer 13 are provided thereon. As shown in the transmission electron microscope (TEM) photograph of FIG. 11, it can be seen that the thickness of the silicon nanocrystal structure layer 12 is about 100 nm or more. In addition, a fine crystal structure of about several nm was observed in the silicon nanocrystal structure layer 12 as in the case of the single crystal.
本実施例で得られたシリコンナノクリスタル構造層は、紫外光照射（例えば、ＵＶブラックライトによる照射）で単結晶シリコンの場合と同様に、概ね６００ｎｍ〜８００ｎｍ波長のオレンジ色発光が観察された。 The silicon nanocrystal structure layer obtained in this example was observed to emit orange light having a wavelength of approximately 600 nm to 800 nm, as in the case of single crystal silicon, when irradiated with ultraviolet light (for example, irradiation with UV black light).
図１２では、シリコン基板表面の反射率を比較して表しており、図中の特性曲線（ａ）は本実施例の化学的構造転写法を実施する以前の多結晶シリコン基板の反射率特性、図中の特性曲線（ｂ）は本実施例後の化学的構造転写法による多結晶シリコン基板の反射率、さらに図中の特性曲線（ｃ）は、比較例として、面方位（１００）単結晶シリコンに異方性アルカリエッチングを行って得たマットテキスチャー面の反射率を示した。 In FIG. 12, the reflectance of the silicon substrate surface is compared and represented, and the characteristic curve (a) in the figure shows the reflectance characteristics of the polycrystalline silicon substrate before the chemical structure transfer method of this embodiment, The characteristic curve (b) in the figure is the reflectivity of the polycrystalline silicon substrate by the chemical structure transfer method after this example, and the characteristic curve (c) in the figure is a plane orientation (100) single crystal as a comparative example. The reflectance of the mat texture surface obtained by performing anisotropic alkali etching on silicon is shown.
本実施例によると、図１２中の特性（ｂ）に示される通り、フッ化水素酸と過酸化水素水との混合水溶液に微量の銀が含まれた溶液内で所定の白金ローラーに装着した上記転写用部材を多結晶シリコン基板に接触させて、その多結晶シリコン基板表面にシリコンナノクリスタル構造層を形成した場合には、同多結晶シリコン基板の反射率特性が、波長３００−８００ｎｍの光波長域において、平均値で３％以下と、顕著な低レベルになっており、シリコンナノクリスタル構造層の生成により、この光波長領域における光吸収率を向上させて、太陽電池の変換効率向上に寄与できる。 According to the present embodiment, as shown in the characteristic (b) in FIG. 12, a predetermined platinum roller was mounted in a solution containing a trace amount of silver in a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide. When the transfer member is brought into contact with a polycrystalline silicon substrate and a silicon nanocrystal structure layer is formed on the surface of the polycrystalline silicon substrate, the polycrystalline silicon substrate has a reflectance characteristic of light having a wavelength of 300 to 800 nm. In the wavelength region, the average value is not more than 3%, which is a remarkably low level. By generating a silicon nanocrystal structure layer, the light absorption rate in this light wavelength region is improved and the conversion efficiency of the solar cell is improved. Can contribute.
加えて、少数キャリアのライフタイム測定で、そのライフタイムは、シリコンナノクリスタル構造層の形成後には約５μｓ（１０−６秒）であることがわかり、形成前の約１μｓであったことと比較して、約５倍に増大していることが認められた。In addition, minority carrier lifetime measurements show that the lifetime is about 5 μs (10 −6 seconds) after the formation of the silicon nanocrystal structure layer, compared to about 1 μs before formation. Thus, it was observed that the increase was about 5 times.
更に、転写用部材には、前記実施例１で述べたような、銀を担持させた白金メッシュを用いても良い。
［実施例３］Furthermore, a platinum mesh carrying silver as described in the first embodiment may be used for the transfer member.
[Example 3]
つぎに、本発明の他の実施の形態を実施例により、詳細に述べる。 Next, another embodiment of the present invention will be described in detail by way of examples.
まず、５０ｗｔ％濃度のフッ化水素酸（ＨＦ）と３０ｗｔ％濃度の過酸化水素水（Ｈ２Ｏ２）とを体積比でフッ化水素酸（ＨＦ）水 ： 過酸化水素水（Ｈ２Ｏ２）＝１：１に混合したフッ化水素酸水と過酸化水素水との混合溶液内に、銀の粒子を１ｐｐｍ溶解させて処理用溶液を調製した。First, hydrofluoric acid (HF) water: hydrogen peroxide water (H 2 O) in a volume ratio of 50 wt% hydrofluoric acid (HF) and 30 wt% hydrogen peroxide water (H 2 O 2 ). 2 ) = 1 ppm of silver particles was dissolved in a mixed solution of hydrofluoric acid water and hydrogen peroxide water mixed at 1: 1 to prepare a treatment solution.
つぎに、厚さ約２０ミクロン（μｍ）の白金箔を所定のローラーに卷きつけてなる白金の構造体を化学的構造転写法における転写用部材として用い、この転写用部材を、フッ素樹脂容器（容量約５００ｍｌのトレー）内の、上記銀の粒子を１ｐｐｍ溶解させた処理用溶液２００ｍｌ中おいて、ｐ型で面方位（１００）の片面ミラー面、比抵抗：１〜２０Ωｃｍの５ｃｍ角に切断した単結晶シリコン基板面に対して、室温で、ローラーを回しながらの移動処理を６回反復して接触させた。その間の所要時間は約３０秒であった。 Next, a platinum structure in which a platinum foil having a thickness of about 20 microns (μm) is wound on a predetermined roller is used as a transfer member in the chemical structure transfer method, and this transfer member is used as a fluororesin container ( In a 200 ml treatment solution in which 1 ppm of the above silver particles is dissolved in a tray having a capacity of about 500 ml, the p-type single-sided mirror surface with a plane orientation (100) is cut into a 5 cm square with a specific resistance of 1 to 20 Ωcm. The moving process while rotating the roller was brought into contact with the single crystal silicon substrate surface 6 times at room temperature. The time required during that time was about 30 seconds.
その後、上記単結晶シリコン基板面を流水洗浄し、次いで窒素ブロー処理した後に上記単結晶シリコン基板面を観察したＳＥＭ図（写真）を図１３に示す。これは、上述の実施例２で得られた結果、すなわち、図５のＳＥＭ（写真）図とほとんど同様である。 Thereafter, an SEM view (photograph) of the surface of the single crystal silicon substrate observed after the surface of the single crystal silicon substrate was washed with running water and then blown with nitrogen is shown in FIG. This is almost the same as the result obtained in Example 2 described above, that is, the SEM (photograph) diagram of FIG.
また、図１４は断面の透過電子顕微鏡写真（ＴＥＭ像）であり、本実施例の場合も、実施例２で述べた図７の透過電子顕微鏡写真（ＴＥＭ図）と同様に、シリコンナノクリスタル構造層の厚さは約１００ｎｍ以上であることが分かる。 FIG. 14 is a cross-sectional transmission electron micrograph (TEM image). In the case of this example as well, as in the transmission electron micrograph (TEM diagram) of FIG. It can be seen that the thickness of the layer is about 100 nm or more.
本実施例では、単結晶シリコン基板を用いたが、多結晶シリコン基板を用いた場合にも、そのシリコン基板の表面にナノクリスタル層を形成することが可能である。 In this embodiment, a single crystal silicon substrate is used. However, even when a polycrystalline silicon substrate is used, a nanocrystal layer can be formed on the surface of the silicon substrate.
なお、本実施例でのローラーへの印加圧力は、ローラーの自重のみで付加圧を与えていないが、経験的に適宜設定したものであり、同ローラーの移動速度並びに移動処理反復回数等と兼ね合わせて、対象のシリコン基板や対応装置の大きさ、温度等の環境に応じて、最適条件に設定し得ることは当然である。 In addition, although the applied pressure to the roller in this example does not give an additional pressure only by its own weight, it is appropriately set empirically, and also serves as the moving speed of the roller and the number of repetitions of moving processing, etc. In addition, it is a matter of course that optimum conditions can be set according to the environment such as the size and temperature of the target silicon substrate and corresponding device.
処理用溶液の調製にあたり、本実施例の５０ｗｔ％濃度のフッ化水素（ＨＦ）酸と３０ｗｔ％濃度の過酸化水素（Ｈ２Ｏ２）水とを体積比でフッ化水素酸（ＨＦ）水 ： 過酸化水素水（Ｈ２Ｏ２）＝１：１に混合したフッ化水素酸と過酸化水素水との混合溶液以外に、前述の実施例１の場合のように、５０ｗｔ％濃度のフッ化水素（ＨＦ）酸と３０ｗｔ％濃度の過酸化水素（Ｈ２Ｏ２）水とを体積比でフッ化水素酸（ＨＦ）水 ： 過酸化水素（Ｈ２Ｏ２）水＝１：３，３：１，５：１，１０：１のそれぞれに混合したフッ化水素酸と過酸化水素水との混合溶液のいずれかを用いること、或いはフッ化水素酸と過酸化水素水との混合比を適宜変えて利用することも可能である。In preparing the treatment solution, hydrofluoric acid (HF) water in a volume ratio of 50 wt% concentration of hydrofluoric acid (HF) acid and 30 wt% concentration of hydrogen peroxide (H 2 O 2 ) water of this example was used. In addition to the mixed solution of hydrofluoric acid and hydrogen peroxide mixed in a hydrogen peroxide solution (H 2 O 2 ) = 1: 1, as in the case of Example 1 described above, a 50 wt% concentration of fluorine Hydrofluoric acid (HF) acid and 30 wt% hydrogen peroxide (H 2 O 2 ) water in a volume ratio of hydrofluoric acid (HF) water: hydrogen peroxide (H 2 O 2 ) water = 1: 3 Use one of the mixed solutions of hydrofluoric acid and hydrogen peroxide mixed in 3: 1, 5: 1, and 10: 1, respectively, or the mixing ratio of hydrofluoric acid and hydrogen peroxide It is also possible to change and use as appropriate.
図１５は、本実施例によるナノクリスタル層を有するシリコン基板の光波長域３００〜８００ｎｍでの表面反射率特性を示し、反射特性では表面反射率が概ね３％以下の低反射率特性である。これは、前述の実施例１の場合と対比しても、一層安定な低反射特性であり、転写用部材が白金箔であること、及び銀を１ｐｐｍ溶解させた処理用溶液を用いたことによる作用で、表面の全域にナノクリスタル構造層が形成されたことによるものである。 FIG. 15 shows the surface reflectance characteristics in the light wavelength region of 300 to 800 nm of the silicon substrate having the nanocrystal layer according to the present embodiment, and the reflectance characteristics are low reflectance characteristics where the surface reflectance is approximately 3% or less. This is due to the fact that the low reflection characteristic is more stable even when compared with the case of Example 1 described above, the transfer member is a platinum foil, and the use of a processing solution in which 1 ppm of silver is dissolved. This is because the nanocrystal structure layer is formed over the entire surface by the action.
なお、上記白金箔には、白金と銀との合金あるいはニッケル（Ｎｉ）−白金−銀の合金箔、あるいは白金と金属等との混合乃至積層構造体からなるものを用いることによっても、シリコン表面に所望のナノクリスタル構造層を形成することができる。 Note that the platinum surface can be obtained by using an alloy of platinum and silver, an alloy foil of nickel (Ni) -platinum-silver, or a mixed or laminated structure of platinum and metal. In addition, a desired nanocrystal structure layer can be formed.
さらに、転写用部材の母体には、触媒機能を有する白金以外の金属との合金、同触媒機能を有する金属と溶液に不溶の金属との合金、耐薬品性を有する薄膜の樹脂や不織布等の合成体を用いることもできる。そして、上記転写用部材は、ローラーに巻きつけての加圧や薬液中での移動による耐薬品性などの耐用性の面から、白金部分が少なくとも１μｍ以上であり、白金以外の構造も含めて、全体の厚みが１０〜５０μｍであれば十分に利用可能である。
［実施例４］Furthermore, the base material of the transfer member includes an alloy of a metal other than platinum having a catalytic function, an alloy of a metal having the catalytic function and an insoluble metal in a solution, a thin film resin or nonwoven fabric having chemical resistance, etc. A composite can also be used. The transfer member has a platinum portion of at least 1 μm or more from the viewpoint of durability such as chemical resistance due to pressure applied around a roller or movement in a chemical solution, and includes structures other than platinum. If the total thickness is 10 to 50 μm, it can be used sufficiently.
[Example 4]
つぎに、本発明の他の実施例として、太陽電池及びその製造方法について詳細を述べる。
まず、ｐ型単結晶シリコン基板（ｐ−Ｓｉ（１００）、厚さ７２５μｍ、比抵抗７〜１１Ωｃｍ、面積５×５ｃｍ２を５枚単位で処理）を用い、フッ素樹脂製の容器内で、同基板を１００ｍｌの濃度５ｗｔ％のフッ化水素（ＨＦ）酸中、室温で、２分間の洗浄処理を行った。Next, as another embodiment of the present invention, a solar cell and a method for manufacturing the solar cell will be described in detail.
First, using a p-type single crystal silicon substrate (p - Si (100), thickness 725 μm, specific resistance 7 to 11 Ωcm, area 5 × 5 cm 2 processed in units of 5 sheets), the same The substrate was washed in 100 ml of 5 wt% concentration of hydrofluoric acid (HF) acid at room temperature for 2 minutes.
つづいて、塩化ビニール製の容器内で、濃度５０ｗｔ％のフッ化水素（ＨＦ）水１００ｍｌと濃度３０ｗｔ％の過酸化水素（Ｈ２Ｏ２）水溶液１００ｍｌとの混合液を１容器中に準備し、これに銀（Ａｇ）の溶解した薬液（上記同様のフッ化水素（ＨＦ）水と過酸化水素（Ｈ２Ｏ２）水との１：１混合比の溶液）を、銀（Ａｇ）量が１ｐｐｍとなるように注入して処理液を調製し、この処理液中で、ローラーに厚さ約２０μｍの白金箔を巻きつけた状態で、その白金箔を上記シリコン基板表面に接触させる。上記ローラー及び白金箔の接触操作は、ローラーの自重のほかには外部加重はなしで、上記シリコン基板の表面を、白金箔面の移動速度１ｃｍ／ｓで、約３０秒間に６回（往復３度）程度接触させるように反復移動させた。なお、上記薬液中のフッ酸（ＨＦ）の代りに、フッ化アンモニウム溶液あるいはその混合物を用いてもよい。また、銀（Ａｇ）添加に際しては、銀粒子のほか、塩化銀或いは硝酸銀等、或いはその他の化合物乃至は銀の錯体又は銀錯体イオンでもよく、銀添加量も０．１〜５０ｐｐｍの範囲で選択できる。Next, a mixture of 100 ml of 50 wt% hydrogen fluoride (HF) water and 100 ml of 30 wt% hydrogen peroxide (H 2 O 2 ) aqueous solution was prepared in one container in a vinyl chloride container. Then, a chemical solution in which silver (Ag) is dissolved (a solution having the same mixing ratio of hydrogen fluoride (HF) water and hydrogen peroxide (H 2 O 2 ) as in the above) is added to silver (Ag). A treatment liquid is prepared by injecting to a concentration of 1 ppm. In this treatment liquid, a platinum foil having a thickness of about 20 μm is wound around a roller, and the platinum foil is brought into contact with the surface of the silicon substrate. The contact operation between the roller and the platinum foil is 6 times in about 30 seconds (3 degrees reciprocation) on the surface of the silicon substrate at a moving speed of 1 cm / s on the surface of the platinum foil without any external load in addition to the weight of the roller. ) It was moved repeatedly so as to make contact. Instead of hydrofluoric acid (HF) in the chemical solution, an ammonium fluoride solution or a mixture thereof may be used. When silver (Ag) is added, in addition to silver particles, silver chloride, silver nitrate, etc., or other compounds or silver complexes or silver complex ions may be used, and the silver addition amount is selected within the range of 0.1 to 50 ppm. it can.
この操作過程によって、上記処理液中では白金及び銀による触媒作用で、シリコン基板表面の結晶層が微細構造化する、いわゆる化学的構造転写（Ｓｕｒｆａｃｅ Ｓｔｒｕｃｔｕｒｅ Ｃｈｅｍｉｃａｌ Ｔｒａｎｓｆｅｒ、以下、ＳＳＣＴと略記）呼ばれる化学的反応が生じ、同シリコン基板の表面領域では約２００ｎｍの深さでシリコンナノクリスタル構造層が形成されることが見出された。 Through this operation process, the crystal layer on the surface of the silicon substrate is microstructured by the catalytic action of platinum and silver in the above treatment liquid, so-called chemical structure transfer (hereinafter abbreviated as SSCT). It was found that a reaction occurred and a silicon nanocrystal structure layer was formed at a depth of about 200 nm in the surface region of the silicon substrate.
次に、上記シリコン基板のナノクリスタル構造層表面を、フッ素樹脂容器内で、１００ｍｌの濃度７０ｗｔ％の硝酸（ＨＮＯ３）水溶液中、室温で１０分間処理して、上記ナノクリスタル構造層内に残留した銀を溶解し、さらに濃度５ｗｔ％のフッ化水素（ＨＦ）酸で２分間処理後、水洗処理を行った。Next, the surface of the nanocrystal structure layer of the silicon substrate is treated in a 100 ml concentration of 70 wt% nitric acid (HNO 3 ) aqueous solution at room temperature for 10 minutes in a fluororesin container, and remains in the nanocrystal structure layer. The obtained silver was dissolved, and further treated with hydrogen fluoride (HF) acid having a concentration of 5 wt% for 2 minutes, and then washed with water.
その後は、上記面積５×５ｃｍ２（５ｃｍ角）のｐ型単結晶シリコン基板を、その各端をダイヤモンドペンカッターで更に切断して、中央部の面積２．５×２、５ｃｍ２の領域を取り出し、そのｐ型単結晶シリコン基板を、フッ素樹脂容器内で１００ｍｌの濃度７０ｗｔ％の硝酸（ＨＮＯ３）溶液中、室温で１０分間処理して引揚げ、さらに上記ナノクリスタル構造層表面にＰ２Ｏ５含有の有機ケイ酸からなる被膜形成用コート剤（溶液）を滴下、スピンコート（３０００ｒｐｍ，３０分）後、空気中１５０℃の乾燥処理で、リンケイ酸被膜を形成した。Thereafter, the p-type single crystal silicon substrate having an area of 5 × 5 cm 2 (5 cm square) is further cut at each end with a diamond pen cutter to obtain a region having an area of 2.5 × 2 , 5 cm 2 at the center. The p-type single crystal silicon substrate was taken out and treated for 10 minutes at room temperature in a 100 ml nitric acid (HNO 3 ) solution with a concentration of 70 wt% in a fluororesin container. Further, P 2 was deposited on the surface of the nanocrystal structure layer. A coating agent (solution) for forming a film composed of O 5 -containing organic silicic acid was dropped, spin-coated (3000 rpm, 30 minutes), and then a phosphosilicate film was formed by drying at 150 ° C. in air.
他方、同ｐ型単結晶シリコン基板の裏面側には、別の同形の単結晶シリコン基板表面にＢ２Ｏ３含有の有機ケイ酸からなる被膜形成用コート剤（溶液）を滴下、スピンコート（３０００ｒｐｍ，３０分）後、空気中１５０℃の乾燥処理でホウ素ケイ酸被膜を形成して、そのホウ素ケイ酸被膜面を重ねて接触（貼り合せ）して配置した。On the other hand, on the back side of the same p-type single crystal silicon substrate, a coating agent (solution) for forming a film made of organic silicic acid containing B 2 O 3 is dropped on the surface of another single crystal silicon substrate having the same shape, and spin coating ( (3000 rpm, 30 minutes), a boron silicate coating film was formed by a drying process at 150 ° C. in air, and the boron silicate coating surface was stacked and contacted (bonded).
そして、上述の２枚のシリコン基板を横置きに重ねて接触（貼り合せ）して配置した状態で、一旦、両者の単結晶シリコン基板を酸素中、６００℃、３０分間の積層処理でそれぞれの被膜のガラス化（ＰＳＧ，ＢＳＧ）処理を行った後、さらに、（窒素（Ｎ２）中、９７０℃で１５分間の同時拡散処理を行って、表面側にｎ＋型領域及び裏面側にｐ＋領域を形成した。
なお、この一連の処理過程では、上述の２枚のシリコン基板が互いに付着することはなく、簡単に剥がして外すことができる。Then, in a state where the above-described two silicon substrates are placed horizontally in contact with each other (bonded), both single-crystal silicon substrates are temporarily laminated in oxygen at 600 ° C. for 30 minutes. After the vitrification (PSG, BSG) treatment of the coating, it was further subjected to simultaneous diffusion treatment at 970 ° C. for 15 minutes in (nitrogen (N 2 ), and the n + type region on the front side and the p side on the back side A + region was formed.
In this series of processing steps, the two silicon substrates described above do not adhere to each other, and can be easily removed by peeling.
次に、表面側にｎ＋型領域及び裏面側にｐ＋領域の形成された、上記ｐ型単結晶シリコン基板は、その各端面にｐ＋及びｎ＋層が回り込んで拡散されているので、その部分をダイヤモンドやすりで削り取った。Next, in the p-type single crystal silicon substrate in which the n + type region is formed on the front surface side and the p + region is formed on the back surface side, the p + and n + layers wrap around the respective end surfaces and are diffused. The part was shaved off with a diamond file.
最後に、フッ素樹脂製の容器内で、同基板を１００ｍｌの濃度５ｗｔ％のフッ化水素（ＨＦ）酸中、室温で、２分間の洗浄処理を行った後に、表面側のｎ＋型領域に厚さ１μｍの銀（Ａｇ）層の標準的ストライプ型表面電極をパターン蒸着により設け、他方の裏面側のｐ＋型領域には厚さ１μｍのアルミニウム（Ａｌ）層の裏面（全域）電極を蒸着により設けた後、窒素中２００℃で４５分間のアニール処理を行って、ｐｎ接合型太陽電池を作製した。Finally, the substrate was washed in 100 ml of 5 wt% hydrofluoric acid (HF) acid at room temperature for 2 minutes in a fluororesin container, and then the n + type region on the surface side was formed. A standard stripe-type surface electrode with a silver (Ag) layer having a thickness of 1 μm is provided by pattern deposition, and a back surface (entire area) electrode of an aluminum (Al) layer with a thickness of 1 μm is deposited on the p + type region on the other back side. After that, annealing treatment was performed in nitrogen at 200 ° C. for 45 minutes to produce a pn junction solar cell.
図１６は本実施例によるナノクリスタル構造層を有するシリコン基板の上記表面側のｎ＋型領域前の光波長域３００〜８００ｎｍで約２％以下の表面反射率特性図であり、先述の実施例３で述べた図１５の場合と比べると、シリコン基板の比抵抗の違いによる多少の差異がみられるものの、極低反射率特性が安定して得られていることが分かった。FIG. 16 is a surface reflectance characteristic diagram of about 2% or less in the light wavelength region 300 to 800 nm before the n + type region on the surface side of the silicon substrate having the nanocrystal structure layer according to this example. Compared with the case of FIG. 15 described in FIG. 3, it was found that the ultra-low reflectance characteristic was stably obtained although there was some difference due to the difference in specific resistance of the silicon substrate.
図１７は、本実施例により得られたｐｎ接合型太陽電池のＡＭ１．５の光照射で得られた電流密度（ｍＡ／ｃｍ２）―電圧特性図であり、図中、実線の特性が本実施例のシリコンナノクリスタル層表面構造を有するもの、図中、点線の特性が同表面構造の形成を行わなかったものである。図１７の特性図から、本実施例の太陽電池では、光電流密度は４０．３ｍＡ／ｃｍ２、Ｖｏｃは５８９ｍＶ、変換効率は１７．６％と、それぞれ高性能が得られた。因みに、図１７の特性図中の点線の特性に示したように、表面構造の形成を行わなかったものでは、光電流密度が２８．０ｍＡ／ｃｍ２、Ｖｏｃが５８２ｍＶ、変換効率が１２．５％であり、これに比較して、本実施例により得られたｐｎ接合型太陽電池の場合は、実線の特性に見られるように、光電流密度大きく増加しており、変換効率の増大も顕著であることが明白であった。FIG. 17 is a current density (mA / cm 2 ) -voltage characteristic diagram obtained by light irradiation of AM1.5 of the pn junction solar cell obtained in this example. The silicon nanocrystal layer surface structure of the example, the dotted line in the figure is the same surface structure was not formed. From the characteristic diagram of FIG. 17, in the solar cell of this example, high performance was obtained with a photocurrent density of 40.3 mA / cm 2 , Voc of 589 mV, and conversion efficiency of 17.6%. Incidentally, as shown in the characteristic of the dotted line in the characteristic diagram of FIG. 17, when the surface structure is not formed, the photocurrent density is 28.0 mA / cm 2 , Voc is 582 mV, and the conversion efficiency is 12.5. In comparison with this, in the case of the pn junction type solar cell obtained in this example, the photocurrent density is greatly increased as seen from the characteristics of the solid line, and the increase in conversion efficiency is also remarkable. It was clear that
この特性は、表面に反射防止膜をそなえていないこと、表面のパッシベーション処理や、バックサーフェースフィールド（ＢＳＦ）の形成及び最適化も行っていないときの事例であり、それらを適切に施すことで、最終製品化においては、太陽電池の変換効率をさらに高め得ることが十分に期待できる。 This characteristic is an example when the surface is not provided with an anti-reflective coating, the surface is not passivated, and the back surface field (BSF) is not formed and optimized. In the final product, it can be sufficiently expected that the conversion efficiency of the solar cell can be further increased.
本実施例では、ｐ型シリコン基板を用いたが、ｎ型基板を用いて同様に太陽電池を作製することも可能である。 In this example, a p-type silicon substrate was used, but a solar cell can be similarly manufactured using an n-type substrate.
本発明は、シリコン基板の表面に対して、シリコンを酸化しかつ溶解し得る処理溶液、例えばフッ酸および過酸化水素水の混合の処理溶液中で転写用部材の表面で触媒金属を作用させて、または触媒機能を有する第１の金属による転写用部材を、シリコンを酸化しかつ溶解し得る処理溶液中に微量の触媒機能を有する第２の金属を含ませた、処理溶液中でシリコン基板上に接触ないし接近させることにより、上記シリコン基板の表面にナノクリスタル構造層を形成する過程を持つ、すべての半導体装置の製造方法に利用することができるシリコン基板の表面処理溶液剤を利用すること、並びに、少なくともｐｎ接合を有する太陽電池、光電変換作用を利用する半導体デバイスで、表面反射率の低減を図り、併せて、そのデバイスの高性能化を得るように、広範囲の半導体機能デバイスおよびその製造方法への利用、応用が可能である。 According to the present invention, a catalytic metal is allowed to act on the surface of a transfer member in a processing solution capable of oxidizing and dissolving silicon, for example, a mixed processing solution of hydrofluoric acid and hydrogen peroxide solution. Or a transfer member made of a first metal having a catalytic function on a silicon substrate in a processing solution containing a trace amount of a second metal having a catalytic function in a processing solution capable of oxidizing and dissolving silicon. Using a silicon substrate surface treatment solution that can be used in any method of manufacturing a semiconductor device, having a process of forming a nanocrystal structure layer on the surface of the silicon substrate by contacting or approaching the substrate. In addition, at least solar cells that have a pn junction and semiconductor devices that use photoelectric conversion, reduce surface reflectance, and improve the performance of the devices. In so that the use of the wide range of semiconductor functional device and a manufacturing method thereof, and applications are possible.
Claims (11)
ナノクリスタル構造層形成用転写用部材。 To the mother of the first metallic having a catalytic function, it was supported a second metal having a catalytic function,
Transfer member for nanocrystal structure layer formation .
前記第２の金属が、銀である、The second metal is silver;
請求項１に記載の転写用部材。The transfer member according to claim 1.
ナノクリスタル構造層形成用転写用部材の製造方法。 The maternal first metallic having a catalytic function, the repatriation isosamples immersed in a solution prepared by dissolving a second metal having a catalytic function, carrying said second metal to the mother of the rolling Utsushiyo member Including the step of
A method for producing a transfer member for forming a nanocrystal structure layer .
前記第２の金属が、銀である、The second metal is silver;
請求項３に記載の転写用部材の製造方法。A method for manufacturing the transfer member according to claim 3.
半導体装置の製造方法。 To the mother of the first metallic having a catalytic function, with the second transfer member which metal is supported with having a catalytic function, to oxidize the silicon and the processing solution capable of dissolving the surface of the silicon down by contact with or in proximity, comprising forming a nanocrystal structure layer on the surface portion of the silicon down,
A method for manufacturing a semiconductor device.
前記第２の金属が、銀である、The second metal is silver;
請求項５に記載の半導体装置の製造方法。A method for manufacturing a semiconductor device according to claim 5.
請求項５又は請求項６に記載の半導体装置の製造方法。 The nanocrystal structure layer includes crystal particles having a size of 2 nm to 8 nm;
A method for manufacturing a semiconductor device according to claim 5.
太陽電池の製造方法。 To the mother of the first metallic having a catalytic function, with the second transfer member which metal is supported with having a catalytic function, to oxidize the silicon and the processing solution capable of dissolving, a surface of the silicon down by contacting with or close to, comprising the step of forming a nanocrystal structure layer on the surface portion of the silicon down,
A method for manufacturing a solar cell.
請求項８に記載の太陽電池の製造方法。 The nanocrystal structure layer includes crystal particles having a size of 2 nm to 8 nm ;
The manufacturing method of the solar cell of Claim 8.
請求項８又は請求項９に記載の太陽電池の製造方法。 The nanocrystal structure layer has a thickness of 30 nm to 500 nm .
The manufacturing method of the solar cell of Claim 8 or Claim 9.
触媒機能を有する第１の金属の母体の表面に触媒機能を有する第２の金属を担持させた転写用部材と、
前記容器内の前記シリコンの表面に前記転写用部材を接触又は接近させて前記シリコンの表面部にナノクリスタル構造層を形成する接触又は接近機構と、を備える、
半導体の製造装置。 A container for containing a treatment solution capable of oxidizing and dissolving silicon;
A transfer member having supported thereon a second metal having a catalytic function in the first metallic surface of the base having a catalytic function,
And a contact or approximation mechanism forms a nanocrystal structure layer on the surface portion of the silicon the silicon down of the transfer member in contact with or approximated allowed on the surface of the container,
Semiconductor manufacturing equipment.
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