JP2017504179A - Surface texture structure of crystalline silicon solar cell and manufacturing method thereof - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- 229910021419 crystalline silicon Inorganic materials 0.000 title claims abstract description 26
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 65
- 239000010703 silicon Substances 0.000 claims abstract description 65
- 238000004140 cleaning Methods 0.000 claims abstract description 61
- 238000005530 etching Methods 0.000 claims abstract description 30
- 238000012937 correction Methods 0.000 claims abstract description 21
- 238000003486 chemical etching Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 10
- 239000002923 metal particle Substances 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 68
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 18
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 18
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- -1 gold ions Chemical class 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 229910052709 silver Inorganic materials 0.000 claims 1
- 239000004332 silver Substances 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 8
- 101710134784 Agnoprotein Proteins 0.000 description 7
- 238000010586 diagram Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000010329 laser etching Methods 0.000 description 2
- 239000002110 nanocone Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910021418 black silicon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 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
Abstract
結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、（１）シリコンウエハを洗浄して、テクスチャリングする工程と、（２）シリコンウエハを金属イオンを含有する溶液に浸漬して、シリコンウエハの表面に金属ナノ粒子層をコーティングする工程と、（３）シリコンウエハの表面を腐食して、ナノレベルの表面テクスチャ構造を形成する工程と、（４）シリコンウエハを洗浄して、金属粒子を除去する工程と、（５）シリコンウエハを第２化学エッチング液に浸漬して、微細構造に対し修正エッチングを行う工程と、（６）シリコンウエハを洗浄して、スピン乾燥させる工程と、を含む結晶シリコン太陽電池の表面テクスチャ構造の製造方法。試験によれば、本発明に係る表面テクスチャ構造は、サイズが１００〜５００ｎｍであり、孔径が大きく深さが浅いナノ孔状又は角付きのナノピラミッド又は角付きのナノ円錐体又は角付きのナノピット状構造である。ＣＮ１０２６１０６９２Ａに開示されているナノ—ミクロン複合テクスチャ構造に比べて、セルの変換効率を０．２〜０．５％程度向上させ、予想できない効果を取得した。A method for producing a surface texture structure of a crystalline silicon solar cell, comprising: (1) a step of cleaning and texturing a silicon wafer; and (2) dipping the silicon wafer in a solution containing metal ions. Coating the surface of the substrate with a metal nanoparticle layer; (3) corroding the surface of the silicon wafer to form a nano-level surface texture structure; and (4) cleaning the silicon wafer to remove the metal particles. A step of removing, (5) a step of immersing the silicon wafer in a second chemical etching solution to perform correction etching on the fine structure, and (6) a step of cleaning the silicon wafer and spin-drying. A method for producing a surface texture structure of a crystalline silicon solar cell. According to tests, the surface texture structure according to the present invention is a nanoporous or angular nanopyramid or angular nanoconical or angular nanopit having a size of 100 to 500 nm and a large pore diameter and shallow depth. It is a shape structure. Compared with the nano-micron composite texture structure disclosed in CN102610692A, the cell conversion efficiency was improved by about 0.2 to 0.5%, and an unexpected effect was obtained.
Description
本発明は、結晶シリコン太陽電池の表面テクスチャ構造及びその製造方法に関し、太陽エネルギー利用技術の分野に属する。 The present invention relates to a surface texture structure of a crystalline silicon solar cell and a manufacturing method thereof, and belongs to the field of solar energy utilization technology.
太陽電池モジュールの幅広く応用につれて、太陽光発電がニューエナジーの分野において益々大きな割合を占め、急速に発展している。現在実用化されている太陽電池製品のうち、結晶シリコン（単結晶シリコンと多結晶シリコン）太陽電池は、マーケットシェアが最大であり、８５％以上の市場占有率を維持している。 With the wide application of solar cell modules, photovoltaic power generation is increasingly growing in the field of new energy and is developing rapidly. Of the solar cell products currently in practical use, crystalline silicon (single crystal silicon and polycrystalline silicon) solar cells have the largest market share and maintain a market share of 85% or more.
従来、太陽電池の生産プロセスにおいて、シリコンウエハの表面におけるテクスチャ構造は、太陽電池の表面反射率を効果的に低下でき、太陽電池の光電変換効率に影響する要因の一つとなる。結晶シリコン太陽電池の表面に優れたテクスチャ構造を形成して、良好な反射防止効果を実現するために、多くの方法を試してみた。機械彫刻法、レーザエッチング法、反応性イオンエッチング法（ＲＩＥ）、化学エッチング法（即ちウェットエッチング）等が一般的な方法である。その中で、機械彫刻法は、低表面反射率が得られるが、該方法ではシリコンウエハの表面に対する機械的損傷が深刻であり、且つ歩留まりが悪く、そのため、工業生産において使用されることが少ない。レーザエッチング法は、レーザにより異なる彫刻模様が製造され、縞状、逆ピラミッド状の表面が既に形成され、その反射率が８．３％へと低下するが、それにより製造される電池の効率が低く、生産へ効果的に応用できない。ＲＩＥ方法は、異なるテンプレートを使用してエッチングすることができ、エッチングとして一般的にドライエッチングが使用され、シリコンウエハの表面にいわゆる「ブラックシリコン」構造を形成することができ、その反射率が７．９％、更に４％へと低下することができるが、装置が高価であり、生産コストが高まるため、工業生産への使用が少ない。化学エッチング法は、プロセスが簡単であり、安価で品質が高く、従来のプロセスとの互換性が良い等の特徴を有し、現在、工業において最も多く使用される方法となる。 Conventionally, in the production process of a solar cell, the texture structure on the surface of the silicon wafer can effectively reduce the surface reflectance of the solar cell, and is one of the factors affecting the photoelectric conversion efficiency of the solar cell. A number of methods have been tried to form an excellent texture structure on the surface of a crystalline silicon solar cell to achieve a good antireflection effect. A mechanical engraving method, a laser etching method, a reactive ion etching method (RIE), a chemical etching method (that is, wet etching), etc. are common methods. Among them, the mechanical engraving method can obtain a low surface reflectance, but in this method, mechanical damage to the surface of the silicon wafer is serious and the yield is poor, and therefore, it is rarely used in industrial production. . In the laser etching method, different engraving patterns are manufactured by laser, and a striped and inverted pyramid-shaped surface is already formed, and its reflectance is reduced to 8.3%. Low and cannot be effectively applied to production. The RIE method can be etched using different templates, and dry etching is generally used as the etching, so that a so-called “black silicon” structure can be formed on the surface of the silicon wafer, and its reflectance is 7 Although it can be reduced to 0.9% and further 4%, the apparatus is expensive and the production cost is increased, so that it is less used for industrial production. The chemical etching method has features such as a simple process, low cost, high quality, and good compatibility with conventional processes, and is currently the most frequently used method in industry.
従来、ウェットエッチング法により製造される結晶シリコン太陽電池の表面テクスチャ構造は、一般的にミクロンレベルとなる。現在の通常手法は、以前と同じようにその表面反射率を更に低下させる。中国特許出願公開第１０２６１０６９２号明細書（特許文献１）において、結晶シリコンのナノ−ミクロン複合テクスチャの製造方法が開示されている。その製造プロセスは、（１）結晶シリコンウエハを洗浄し腐食して、ミクロンレベルの表面テクスチャ構造を形成する工程と、（２）シリコンウエハの表面に、非連続的な貴金属ナノ粒子層を均一にコーティングする工程と、（３）化学エッチング液でシリコンウエハの表面を選択的に腐食して、ナノレベルの表面テクスチャ構造を形成する工程と、（４）化学溶液で貴金属粒子を除去するする工程と、を含む。しかしながら、上記製造方法により製造されるナノ−ミクロン複合テクスチャでは、そのナノ構造がナノ孔状となり、即ち、その孔径が小さく、深さが深い。文献報告及び試験によれば、このような複合テクスチャ構造は、その表面反射率が１２％以下まで低下するが、その後の表面不動態化に不利であり、且つ製造されるセルは、生産ラインで通常のテクスチャリング方法を用いたセルより変換効率が低いことが確証した。 Conventionally, the surface texture structure of a crystalline silicon solar cell manufactured by a wet etching method is generally on the micron level. The current normal approach further reduces its surface reflectivity as before. In Chinese Patent Application No. 1026161092 (Patent Document 1), a method for producing a nano-micron composite texture of crystalline silicon is disclosed. The manufacturing process consists of (1) cleaning and corroding the crystalline silicon wafer to form a micron-level surface texture structure, and (2) uniformly discontinuous noble metal nanoparticle layer on the surface of the silicon wafer. Coating, (3) selectively corroding the surface of the silicon wafer with a chemical etching solution to form a nano-level surface texture structure, and (4) removing noble metal particles with the chemical solution. ,including. However, in the nano-micron composite texture produced by the above production method, the nanostructure is nanoporous, that is, the pore diameter is small and the depth is deep. According to literature reports and tests, such composite texture structures have their surface reflectivity reduced to below 12%, but are disadvantageous for subsequent surface passivation, and the cells produced are It is confirmed that the conversion efficiency is lower than that of the cell using the normal texturing method.
本発明は、結晶シリコン太陽電池の表面テクスチャ構造及びその製造方法を提供することを目的とする。 An object of this invention is to provide the surface texture structure of a crystalline silicon solar cell, and its manufacturing method.
上記目的を達成するために、本発明に係る技術的手段として、結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、以下の工程を含む結晶シリコン太陽電池の表面テクスチャ構造の製造方法を提供する。
（１）多結晶シリコンウエハを洗浄し、腐食してミクロンレベルの表面テクスチャ構造を形成する工程。
（２）上記シリコンウエハを金属イオンを含有する溶液に浸漬して、シリコンウエハの表面に金属ナノ粒子層をコーティングする工程。
ただし、前記金属イオンは、金イオン、銀イオン及び銅イオンから選ばれる１種である。
（３）第１化学エッチング液でシリコンウエハの表面を腐食して、ナノレベルの表面テクスチャ構造を形成する工程。
ただし、前記第１化学エッチング液は、ＨＦとＨ２Ｏ２の混合溶液、ＨＦとＨＮＯ３の混合溶液、ＨＦとＨ２ＣｒＯ４の混合溶液から選ばれる１種であり、
ＨＦの濃度は１〜１５ｍｏｌ／Ｌであり、Ｈ２Ｏ２、ＨＮＯ３又はＨ２ＣｒＯ４の濃度は０．０５〜０．５ｍｏｌ／Ｌである。
（４）それぞれ第１洗浄液、第２洗浄液、脱イオン水を使用して上記シリコンウエハを洗浄して、金属粒子を除去する工程。
ただし、前記第１洗浄液は２７〜６９質量％の硝酸溶液であり、洗浄時間は６０〜１２００秒であり、洗浄温度は５〜８５℃であり、
前記第２洗浄液は１〜１０質量％のフッ化水素酸溶液であり、洗浄時間は６０〜６００秒であり、洗浄温度は５〜４５℃である。
（５）上記シリコンウエハを第２化学エッチング液に浸漬して、微細構造の修正エッチングを行う工程。
ただし、前記第２化学エッチング液は、ＮａＯＨ溶液、ＫＯＨ溶液、テトラメチルアンモニウムヒドロキシド溶液、ＨＮＯ３とＨＦ酸の混合溶液から選ばれる１種であり、
前記第２化学エッチング液はＮａＯＨ溶液である場合、その濃度は０．００１〜０．１ｍｏｌ／Ｌであり、反応時間は１０〜１０００秒であり、反応温度は５〜８５℃であり、
前記第２化学エッチング液はＫＯＨ溶液である場合、その濃度は０．００１〜０．１ｍｏｌ／Ｌであり、反応時間は１０〜１０００秒であり、反応温度は５〜８５℃であり、
前記第２化学エッチング液はテトラメチルアンモニウムヒドロキシド溶液である場合、その濃度は０．００１〜０．１ｍｏｌ／Ｌであり、反応時間は１０〜１０００秒であり、反応温度は５〜８５℃であり、
前記第２化学エッチング液はＨＮＯ３とＨＦ酸の混合溶液である場合、ＨＦとＨＮＯ３の濃度は、それぞれ０．０５〜０．５ｍｏｌ／Ｌ、１〜１０ｍｏｌ／Ｌであり、反応時間は１０〜１０００秒であり、反応温度は５〜４５℃である。
（６）上記シリコンウエハを洗浄して、スピン乾燥し、結晶シリコン太陽電池の表面テクスチャ構造を得る工程。
In order to achieve the above object, as a technical means according to the present invention, there is provided a method for producing a surface texture structure of a crystalline silicon solar cell, the method comprising: To do.
(1) A process in which a polycrystalline silicon wafer is cleaned and corroded to form a micron level surface texture structure.
(2) A step of immersing the silicon wafer in a solution containing metal ions to coat the surface of the silicon wafer with a metal nanoparticle layer.
However, the said metal ion is 1 type chosen from a gold ion, a silver ion, and a copper ion.
(3) A step of corroding the surface of the silicon wafer with the first chemical etching solution to form a nano-level surface texture structure.
However, the first chemical etching solution is one selected from a mixed solution of HF and H 2 O 2, a mixed solution of HF and HNO 3, and a mixed solution of HF and H 2 CrO 4 .
The concentration of HF is 1 to 15 mol / L, and the concentration of H 2 O 2 , HNO 3 or H 2 CrO 4 is 0.05 to 0.5 mol / L.
(4) A step of removing the metal particles by cleaning the silicon wafer using a first cleaning liquid, a second cleaning liquid, and deionized water, respectively.
However, the first cleaning liquid is a 27-69 mass% nitric acid solution, the cleaning time is 60-1200 seconds, the cleaning temperature is 5-85 ° C.,
The second cleaning liquid is a 1 to 10% by mass hydrofluoric acid solution, the cleaning time is 60 to 600 seconds, and the cleaning temperature is 5 to 45 ° C.
(5) A step of performing a correction etching of the fine structure by immersing the silicon wafer in a second chemical etching solution.
However, the second chemical etching solution is one selected from a NaOH solution, a KOH solution, a tetramethylammonium hydroxide solution, and a mixed solution of HNO 3 and HF acid,
When the second chemical etching solution is a NaOH solution, the concentration thereof is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, the reaction temperature is 5 to 85 ° C.,
When the second chemical etching solution is a KOH solution, the concentration thereof is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, the reaction temperature is 5 to 85 ° C.,
When the second chemical etching solution is a tetramethylammonium hydroxide solution, the concentration is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, and the reaction temperature is 5 to 85 ° C. Yes,
When the second chemical etching solution is a mixed solution of HNO 3 and HF acid, the concentrations of HF and HNO 3 are 0.05 to 0.5 mol / L and 1 to 10 mol / L, respectively, and the reaction time is 10 -1000 seconds and the reaction temperature is 5-45 ° C.
(6) A step of cleaning the silicon wafer and spin drying to obtain a surface texture structure of the crystalline silicon solar cell.
上記技術的手段において、前記工程（２）では、金属ナノ粒子層における金属ナノ粒子の濃度が０．０００１〜０．１ｍｏｌ／Ｌである。 In the above technical means, in the step (2), the concentration of the metal nanoparticles in the metal nanoparticle layer is 0.0001 to 0.1 mol / L.
上記技術的手段において、前記工程（２）では、浸漬時間が１０〜１０００秒であり、溶液温度が５〜８５℃である。 In the above technical means, in the step (2), the immersion time is 10 to 1000 seconds, and the solution temperature is 5 to 85 ° C.
上記技術的手段において、前記工程（３）では、腐食時間が３０〜３０００秒であり、反応温度が５〜４５℃である。 In the above technical means, in the step (3), the corrosion time is 30 to 3000 seconds, and the reaction temperature is 5 to 45 ° C.
本発明は上記製造方法により得られる結晶シリコン太陽電池の表面テクスチャ構造を保護することを更に請求する。 The present invention further claims to protect the surface texture structure of the crystalline silicon solar cell obtained by the above manufacturing method.
上記技術的手段において、前記結晶シリコン太陽電池は、多結晶シリコン太陽電池であり、その表面テクスチャ構造の反射率が１２％〜２０％である。 In the above technical means, the crystalline silicon solar cell is a polycrystalline silicon solar cell, and the reflectance of the surface texture structure is 12% to 20%.
上記技術的手段において、前記結晶シリコン太陽電池は、単結晶シリコン太陽電池であり、その表面テクスチャ構造の反射率が５％〜１５％である。 In the above technical means, the crystalline silicon solar cell is a single crystal silicon solar cell, and the reflectance of the surface texture structure is 5% to 15%.
テストした結果、本発明に係る多結晶シリコン太陽電池の表面テクスチャ構造は、サイズが１００〜５００ｎｍであり、表面反射率が１２〜２０％であり、中国特許出願公開第１０２６１０６９２号明細書に開示されているナノ−ミクロン複合テクスチャ構造に比べて、セルの変換効率が０．２〜０．５％程度向上することができ、予想できない効果を取得した。本発明に係るナノレベルの表面テクスチャ構造は、現在の生産ラインで多結晶シリコン太陽電池の製造プロセスに更に適し、表面反射率を低下させると同時に、その後の表面不動態化プロセスに悪影響を及ぼさない。 As a result of the test, the surface texture structure of the polycrystalline silicon solar cell according to the present invention has a size of 100 to 500 nm and a surface reflectance of 12 to 20%, which is disclosed in Chinese Patent Application No. 102610692. Compared with the nano-micron composite texture structure, the cell conversion efficiency can be improved by about 0.2 to 0.5%, and an unexpected effect was obtained. The nano-level surface texture structure according to the present invention is more suitable for the manufacturing process of polycrystalline silicon solar cells in the current production line and does not adversely affect the subsequent surface passivation process while reducing the surface reflectivity. .
本発明の原理では、従来のミクロンレベルの表面テクスチャ構造を形成した上で、先ず、シリコンウエハの表面に、均一に分布している金属ナノ粒子層をコーティングし、その後、表面に金属ナノ粒子が分布しているシリコンウエハを、酸化剤（Ｈ２Ｏ２又はＨＮＯ３又はＨ２ＣｒＯ４）がシリコンウエハを酸化する役割を果す第１化学エッチング液に浸漬し、同時にエッチング液中のフッ化水素酸は、シリコンウエハが酸化されて生成したＳｉＯ２をヘキサフルオロケイ酸とするように溶液へ輸送し、金属粒子の触媒作用下で、その近傍におけるシリコンウエハが迅速に反応し、反応速度の差異でシリコンウエハの表面に線状又は深孔状の微細構造を形成し、最後に、第２化学エッチング溶液でシリコンウエハの表面に対し修正エッチングを行い、即ちアルカリ溶液（ＮａＯＨ溶液、ＫＯＨ溶液、テトラメチルアンモニウムヒドロキシド溶液又は混合酸（ＨＦとＨＮＯ３））で、製造された線状又は深孔状の微細構造に対してエッチング修正を行う。アルカリ溶液は、主に上記線状又は深孔状の微細構造に対して異方性エッチングを行い、このような異方性エッチングは、元の線状又は深孔状の微細構造に沿って優先的に行い、そのエッチング結果として、元の線状又は深孔状の微細構造が角付きのナノピラミッド又はナノ円錐体又はナノピット状構造に修正され、混合酸（ＨＦとＨＮＯ３）は、主に上記線状又は深孔状の微細構造に対して等方性エッチングを行い、このような等方性エッチングは、元の線状又は深孔状の微細構造に沿って優先的に行い、そのエッチング結果として、元の線状又は深孔状の微細構造が孔径の大きくかつ深さの浅いナノ孔状構造に修正され、該修正エッチングを行うことで、優れた結晶性シリコン太陽電池のナノテクスチャを製造する。 In the principle of the present invention, after forming a conventional micron-level surface texture structure, the surface of the silicon wafer is first coated with a uniformly distributed metal nanoparticle layer, and then the metal nanoparticles are formed on the surface. The distributed silicon wafer is immersed in a first chemical etching solution in which an oxidizing agent (H 2 O 2 or HNO 3 or H 2 CrO 4 ) plays a role of oxidizing the silicon wafer, and at the same time, hydrogen fluoride in the etching solution. The acid is transported to the solution so that SiO 2 produced by oxidation of the silicon wafer becomes hexafluorosilicic acid, and the silicon wafer in the vicinity reacts rapidly under the catalytic action of the metal particles, and the difference in reaction rate. To form a linear or deep hole microstructure on the surface of the silicon wafer. Perform ring, i.e. an alkaline solution (NaOH solution, KOH solution, tetramethylammonium hydroxide solution or a mixed acid (HF and HNO 3)), the etching modifications to manufactured linear or deep hole-shaped fine structure Do. Alkaline solutions primarily perform anisotropic etching on the linear or deep pore microstructures, and such anisotropic etching takes precedence over the original linear or deep pore microstructures. As a result of the etching, the original linear or deep pore microstructure is modified into a horned nanopyramid or nanocone or nanopit structure, and the mixed acid (HF and HNO 3 ) is mainly Isotropic etching is performed on the linear or deep hole microstructure, and the isotropic etching is performed preferentially along the original linear or deep hole microstructure. As a result, the original linear or deep pore microstructure is modified to a nanopore structure having a large pore diameter and a shallow depth, and by performing the modified etching, a nanotexture of an excellent crystalline silicon solar cell can be obtained. To manufacture.
従来技術に比べて、上記技術的手段に係る本発明は下記利点を有する。 Compared with the prior art, the present invention according to the above technical means has the following advantages.
１．本発明は、新しい結晶シリコン太陽電池の表面テクスチャ構造の製造方法を開発した。即ち、従来のミクロンレベルの表面テクスチャ構造を形成した上で、第１化学エッチング液でシリコンウエハの表面を腐食し、ナノレベルの表面テクスチャ構造を形成し、洗浄後に更に第２化学エッチング液に浸漬して微細構造に対し修正エッチングを行い、結晶シリコン太陽電池に一層適したテクスチャ構造を得る。試験によれば、本発明に係る多結晶シリコン太陽電池の表面テクスチャ構造は、サイズが１００〜５００ｎｍであり、孔径が大きく深さが浅いナノ孔状又は角付きのナノピラミッド又は角付きのナノ円錐体又は角付きのナノピット状構造となりその表面反射率が１２〜２０％である。中国特許出願公開第１０２６１０６９２号明細書に開示されているナノ―ミクロン複合テクスチャ構造に比べて、セルの変換効率が０．２〜０．５％程度向上でき、予想できない効果を取得した。 1. The present invention has developed a method for producing a surface texture structure of a new crystalline silicon solar cell. That is, after forming a conventional micron-level surface texture structure, the surface of the silicon wafer is corroded with the first chemical etching solution to form a nano-level surface texture structure, which is further immersed in the second chemical etching solution after cleaning. Then, the fine structure is subjected to correction etching to obtain a texture structure more suitable for a crystalline silicon solar cell. According to the test, the surface texture structure of the polycrystalline silicon solar cell according to the present invention has a nanoporous or angular nanopyramid or angular nanocone having a size of 100 to 500 nm and a large pore diameter and a shallow depth. It becomes a body or a nanopit-like structure with corners, and its surface reflectance is 12 to 20%. Compared to the nano-micron composite texture structure disclosed in Chinese Patent Application No. 102610692, the cell conversion efficiency can be improved by about 0.2 to 0.5%, and an unexpected effect was obtained.
２．本発明に係る製造方法は、簡単で実施しやすく、従来の工業化生産プロセスとの互換性が良く、工業化生産に迅速に応用でき、普及や応用化に適する。 2. The manufacturing method according to the present invention is simple and easy to implement, has good compatibility with conventional industrialized production processes, can be quickly applied to industrialized production, and is suitable for popularization and application.
以下、実施例を参照して本発明を更に説明する。 Hereinafter, the present invention will be further described with reference to examples.
実施例１
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬して、２０℃の条件下で６０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬して、２０℃の条件下で３００ｓ反応させる工程と、
（３）前記工程（２）で処理されたコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを０．０５ｍｏｌ／ＬのＫＯＨ溶液に浸漬して、２０℃の条件下で３００ｓ反応させる工程と、
（６）前記工程（５）で処理されたシリコンウエハを洗浄して、スピン乾燥し、多結晶シリコン太陽電池の表面テクスチャ構造を得る工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Example 1
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 20 ° C. for 60 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, and the condition is set at 20 ° C. A step of reacting for 300 s,
(3) A step of putting the conwafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) A step of immersing the silicon wafer treated in the step (4) in a 0.05 mol / L KOH solution and reacting it at 20 ° C. for 300 s;
(6) manufacturing the surface texture structure of the polycrystalline silicon solar cell, including cleaning and spin drying the silicon wafer treated in the step (5) to obtain a surface texture structure of the polycrystalline silicon solar cell. Method.
本実施例で製造された多結晶シリコン太陽電池の表面テクスチャ構造は、寸法が１００〜２００ｎｍ（図１に示す）であり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が１３．４％である。 The surface texture structure of the polycrystalline silicon solar cell manufactured in this example has a size of 100 to 200 nm (shown in FIG. 1), and the average reflectance of the surface in the wavelength range of 400 to 1050 nm is 13.4. %.
比較例１
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成する工程と、
（２）洗浄して、スピン乾燥させ、多結晶シリコン太陽電池の表面テクスチャ構造を得る工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Comparative Example 1
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And a process of
(2) A method for producing a surface texture structure of a polycrystalline silicon solar cell, comprising: washing and spin drying to obtain a surface texture structure of the polycrystalline silicon solar cell.
実施例１に係る多結晶シリコンのテクスチャと比較例１に係る通常の酸テクスチャにより得られた多結晶シリコンのテクスチャの反射スペクトルの比較図は、図２に示す。 A comparison diagram of the reflection spectra of the texture of the polycrystalline silicon obtained by the texture of the polycrystalline silicon according to Example 1 and the ordinary acid texture according to Comparative Example 1 is shown in FIG.
実施例２
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬して、２０℃の条件下で６０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬して、２０℃の条件下で３００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを０．０２５ｍｏｌ／Ｌのテトラメチルアンモニウムヒドロキシド溶液（ＴＭＡＨ溶液）に浸漬して、２０℃の条件下で、３００ｓ反応させる工程と、
（６）前記工程（５）で処理されたシリコンウエハを脱イオン水で洗浄してスピン乾燥させる工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Example 2
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 20 ° C. for 60 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, and the condition is set at 20 ° C. A step of reacting for 300 s,
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) a step of immersing the silicon wafer treated in the step (4) in a 0.025 mol / L tetramethylammonium hydroxide solution (TMAH solution) and reacting it at 20 ° C. for 300 s;
(6) A method for producing a surface texture structure of a polycrystalline silicon solar cell, comprising: washing the silicon wafer treated in the step (5) with deionized water and spin-drying the silicon wafer.
本実施例で製造された多結晶シリコン太陽電池のテクスチャ微細構造は、寸法が１５０〜３００ｎｍ（図３に示す）であり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が１２．１％である。 The texture microstructure of the polycrystalline silicon solar cell produced in this example has a dimension of 150 to 300 nm (shown in FIG. 3), and an average reflectance of its surface in the wavelength range of 400 to 1050 nm is 12.1. %.
実施例２に係る多結晶シリコンのテクスチャと比較例１に係る通常の酸テクスチャにより得られた多結晶シリコンのテクスチャの反射スペクトルの比較図は、図４に示す。 A comparison diagram of the reflection spectra of the polycrystalline silicon texture according to Example 2 and the polycrystalline silicon texture obtained with the normal acid texture according to Comparative Example 1 is shown in FIG.
実施例３
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬して、２０℃の条件下で、６０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬し、２０℃の条件下で３００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを濃度が０．１ｍｏｌ／ＬであるＨＦと濃度が５ｍｏｌ／ＬであるＨＮＯ３の混合溶液に浸漬して、２０℃の条件下で、１５０ｓ反応させる工程と、
（６）前記工程（５）で処理されたシリコンウエハを脱イオン水で洗浄してスピン乾燥させる工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Example 3
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 20 ° C. for 60 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, A step of reacting for 300 s;
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) The silicon wafer processed in the step (4) is immersed in a mixed solution of HF having a concentration of 0.1 mol / L and HNO 3 having a concentration of 5 mol / L. A step of reacting for 150 s;
(6) A method for producing a surface texture structure of a polycrystalline silicon solar cell, comprising: washing the silicon wafer treated in the step (5) with deionized water and spin-drying the silicon wafer.
本実施例で製造された多結晶シリコン太陽電池のテクスチャの微細構造は、寸法が１５０〜３００ｎｍ（図５に示す）であり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が１０％である。 The microstructure of the texture of the polycrystalline silicon solar cell manufactured in this example has a dimension of 150 to 300 nm (shown in FIG. 5), and an average reflectance of the surface of 10% in the wavelength range of 400 to 1050 nm. It is.
実施例３に係る多結晶シリコンのテクスチャ面と比較例１に係る通常の酸テクスチャにより得られた多結晶シリコンのテクスチャの反射スペクトルの比較図は図６に示す。 A comparative diagram of the reflection spectrum of the texture of the polycrystalline silicon obtained by the texture surface of the polycrystalline silicon according to Example 3 and the ordinary acid texture according to Comparative Example 1 is shown in FIG.
実施例４
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬して、２０℃の条件下で１２０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬し、２０℃の条件下で、６００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを０．０２５ｍｏｌ／ＬのＴＭＡＨ溶液に浸漬して、２０℃の条件下で３００ｓ反応させる工程と、
（６）前記工程（５）で処理されたシリコンウエハを脱イオン水で洗浄してスピン乾燥させる工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Example 4
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 20 ° C. for 120 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, , Reacting for 600 s,
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) A step of immersing the silicon wafer treated in the step (4) in a 0.025 mol / L TMAH solution and reacting it at 20 ° C. for 300 s;
(6) A method for producing a surface texture structure of a polycrystalline silicon solar cell, comprising: washing the silicon wafer treated in the step (5) with deionized water and spin-drying the silicon wafer.
比較例２
多結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型多結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬して、２０℃の条件下で、６０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬し、２０℃の条件下で、３００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを洗浄して、スピン乾燥させ、多結晶シリコン太陽電池の表面テクスチャ構造を得る工程と、を含む多結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Comparative Example 2
A method of manufacturing a surface texture structure of a polycrystalline silicon solar cell,
(1) After removing and cleaning the damaged layer of the P-type polycrystalline silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 20 ° C. for 60 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, , Reacting for 300 s,
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) manufacturing the surface texture structure of the polycrystalline silicon solar cell, including: cleaning the silicon wafer processed in the step (4) and spin drying to obtain a surface texture structure of the polycrystalline silicon solar cell. Method.
実施例４では、ＮａＯＨ溶液で修正エッチングを行った多結晶シリコン太陽電池の表面テクスチャ構造は、寸法が１５０〜３００ｎｍ（図７、８に示す）であり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が１５．６％（図９に示す）である。 In Example 4, the surface texture structure of the polycrystalline silicon solar cell subjected to the correction etching with the NaOH solution has a dimension of 150 to 300 nm (shown in FIGS. 7 and 8), and the surface texture structure in the wavelength range of 400 to 1050 nm. The average reflectance is 15.6% (shown in FIG. 9).
比較例２では、修正エッチングを行わずに製造されたナノレベルの表面テクスチャ構造は、ナノ深孔状構造であり、孔径が５０ｎｍ程度（図１０、１１に示す）だけであり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が５．９％（図９に示す）である。前記「修正エッチングを行わない」とは、中国特許出願公開第１０２６１０６９２号明細書に記載の方法のように、製造されたナノ−ミクロン複合テクスチャ構造は、上記工程（５）の修正エッチングを行わないことを意味する。 In Comparative Example 2, the nano-level surface texture structure manufactured without performing the correction etching is a nano-deep hole-like structure, the pore diameter is only about 50 nm (shown in FIGS. 10 and 11), and 400 to 1050 nm. In the wavelength range, the average reflectance of the surface is 5.9% (shown in FIG. 9). The “does not perform the correction etching” means that the manufactured nano-micron composite texture structure does not perform the correction etching in the above step (5) as in the method described in Chinese Patent Application No. 102610692. Means that.
実施例５
単結晶シリコン太陽電池のナノテクスチャの製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型単結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬し、２０℃の条件下で、１２０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬し、２０℃の条件下で、６００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを０．０２５ｍｏｌ／ＬのＴＭＡＨ溶液に浸漬して、２０℃の条件下で、３００ｓ反応させる工程と、
（６）前記工程（５）で処理されたシリコンウエハを脱イオン水で洗浄してスピン乾燥させる工程と、を含む単結晶シリコン太陽電池のナノテクスチャの製造方法。
Example 5
A method for producing a nano-texture of a single crystal silicon solar cell,
(1) After removing the damaged layer of a P-type single crystal silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 120 ° C. for 120 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, , Reacting for 600 s,
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) a step of immersing the silicon wafer treated in the step (4) in a 0.025 mol / L TMAH solution and reacting it at 20 ° C. for 300 s;
(6) A method for producing a nano-texture of a single crystal silicon solar cell, comprising: a step of washing the silicon wafer treated in the step (5) with deionized water and spin drying.
比較例３
単結晶シリコン太陽電池の表面テクスチャ構造の製造方法であって、
（１）厚みが１８０±１０μｍであり、サイズが１５６ｍｍ×１５６ｍｍであるＰ型単結晶シリコンウエハの損傷層を除去して洗浄した後、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成し、その後、濃度が０．００８ｍｏｌ／ＬであるＡｇＮＯ３溶液に浸漬し、２０℃の条件下で、１２０ｓ反応させる工程と、
（２）前記工程（１）で処理されたシリコンウエハを濃度が３ｍｏｌ／ＬであるＨＦと濃度が０．１ｍｏｌ／ＬであるＨ２Ｏ２の混合溶液に浸漬し、２０℃の条件下で６００ｓ反応させる工程と、
（３）前記工程（２）で処理されたシリコンウエハを６９質量％の硝酸溶液に投入して、２０℃の洗浄温度下で３００ｓ洗浄する工程と、
（４）前記工程（３）で処理されたシリコンウエハを５質量％のフッ化水素酸溶液に投入して、２０℃の洗浄温度下で２００ｓ洗浄する工程と、
（５）前記工程（４）で処理されたシリコンウエハを洗浄して、スピン乾燥させ、前記単結晶シリコン太陽電池の表面テクスチャ構造を得る工程と、を含む単結晶シリコン太陽電池の表面テクスチャ構造の製造方法。
Comparative Example 3
A method for producing a surface texture structure of a single crystal silicon solar cell,
(1) After removing the damaged layer of a P-type single crystal silicon wafer having a thickness of 180 ± 10 μm and a size of 156 mm × 156 mm, it is corroded and textured to form a micron level surface texture structure. And then immersing in an AgNO 3 solution having a concentration of 0.008 mol / L and reacting at 120 ° C. for 120 s,
(2) The silicon wafer processed in the step (1) is immersed in a mixed solution of HF having a concentration of 3 mol / L and H 2 O 2 having a concentration of 0.1 mol / L, A step of reacting for 600 s;
(3) A step of putting the silicon wafer processed in the step (2) into a 69% by mass nitric acid solution and cleaning it at a cleaning temperature of 20 ° C. for 300 s;
(4) A step of putting the silicon wafer processed in the step (3) into a 5 mass% hydrofluoric acid solution and cleaning it for 200 s at a cleaning temperature of 20 ° C .;
(5) cleaning the silicon wafer processed in the step (4) and spin-drying to obtain a surface texture structure of the single crystal silicon solar cell. Production method.
実施例５では、ＮａＯＨ溶液で修正エッチングを行った単結晶シリコン太陽電池の表面テクスチャ構造は、寸法が１５０〜３００ｎｍ（図１２、１３に示す）であり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が６．４％（図１４に示す）である。 In Example 5, the surface texture structure of a single crystal silicon solar cell that has been subjected to correction etching with an NaOH solution has dimensions of 150 to 300 nm (shown in FIGS. 12 and 13), and the surface texture structure in the wavelength range of 400 to 1050 nm. The average reflectance is 6.4% (shown in FIG. 14).
比較例３では、修正エッチングを行わずに製造されたナノレベルの表面テクスチャ構造は、ナノ深孔状構造であり、孔径が５０ｎｍ程度（図１５、１６に示す）だけであり、４００〜１０５０ｎｍの波長範囲において、その表面の平均反射率が５．０％（図１４に示す）である。前記「修正エッチングを行わない」とは、中国特許出願公開第１０２６１０６９２号明細書に記載の方法のように、製造されたナノ−ミクロン複合テクスチャ構造は、上記工程（５）の修正エッチングを行わないことを意味する。 In Comparative Example 3, the nano-level surface texture structure manufactured without performing the correction etching is a nano-deep hole structure, and the pore diameter is only about 50 nm (shown in FIGS. 15 and 16), and 400 to 1050 nm. In the wavelength range, the average reflectance of the surface is 5.0% (shown in FIG. 14). The “does not perform the correction etching” means that the manufactured nano-micron composite texture structure does not perform the correction etching in the above step (5) as in the method described in Chinese Patent Application No. 102610692. Means that.
Claims (7)
（１）多結晶シリコンウエハを洗浄し、腐食してテクスチャリングし、ミクロンレベルの表面テクスチャ構造を形成する工程と、
（２）前記工程（１）で処理されたシリコンウエハを、金イオン、銀イオン及び銅イオンから選ばれるいずれか１種の金属イオンを含有する溶液に浸漬して、シリコンウエハの表面に金属ナノ粒子層をコーティングする工程と、
（３）ＨＦの濃度を１〜１５ｍｏｌ／Ｌとし、Ｈ２Ｏ２、ＨＮＯ３又はＨ２ＣｒＯ４の濃度を０．０５〜０．５ｍｏｌ／Ｌとし、ＨＦとＨ２Ｏ２の混合溶液、ＨＦとＨＮＯ３の混合溶液、ＨＦとＨ２ＣｒＯ４の混合溶液から選ばれるいずれか１種である第１化学エッチング液を使用して、前記工程（２）で処理されたシリコンウエハの表面を腐食し、ナノレベルの表面テクスチャ構造を形成する工程と、
（４）順に、洗浄時間を６０〜１２００秒とし、洗浄温度を５〜８５℃とする２７〜６９質量％の硝酸溶液である第１洗浄液と、
洗浄時間を６０〜６００秒とし、洗浄温度を５〜４５℃とする１〜１０質量％のフッ化水素酸溶液である第２洗浄液と、
脱イオン水とを使用して、前記工程（３）で処理されたシリコンウエハを洗浄して、金属粒子を除去する工程と、
（５）ＮａＯＨ溶液、ＫＯＨ溶液、テトラメチルアンモニウムヒドロキシド溶液、ＨＮＯ３とＨＦ酸の混合溶液から選ばれるいずれか１種であり、
ＮａＯＨ溶液である場合、その濃度を０．００１〜０．１ｍｏｌ／Ｌとし、反応時間を１０〜１０００秒とし、反応温度を５〜８５℃として、
ＫＯＨ溶液である場合、その濃度を０．００１〜０．１ｍｏｌ／Ｌとし、反応時間を１０〜１０００秒とし、反応温度を５〜８５℃として、
テトラメチルアンモニウムヒドロキシド溶液である場合、その濃度を０．００１〜０．１ｍｏｌ／Ｌとし、反応時間を１０〜１０００秒とし、反応温度を５〜８５℃として、
ＨＮＯ３とＨＦ酸の混合溶液である場合、ＨＦとＨＮＯ３の濃度をそれぞれ０．０５〜０．５ｍｏｌ／Ｌ、１〜１０ｍｏｌ／Ｌとし、反応時間を１０〜１０００秒とし、反応温度を５〜４５℃とする、
第２化学エッチング液に、前記工程（４）で処理されたシリコンウエハを浸漬して、微細構造に対し修正エッチングを行う工程と、
（６）前記工程（５）で処理されたシリコンウエハを洗浄して、スピン乾燥させ、結晶シリコン太陽電池の表面テクスチャ構造を得る工程と、を含むことを特徴とする結晶シリコン太陽電池の表面テクスチャ構造の製造方法。 A method for producing a surface texture structure of a crystalline silicon solar cell,
(1) cleaning, corroding and texturing the polycrystalline silicon wafer to form a micron level surface texture structure;
(2) The silicon wafer treated in the step (1) is immersed in a solution containing any one kind of metal ions selected from gold ions, silver ions, and copper ions, and metal nano particles are formed on the surface of the silicon wafer. Coating the particle layer;
(3) The concentration of HF is 1 to 15 mol / L, the concentration of H 2 O 2 , HNO 3 or H 2 CrO 4 is 0.05 to 0.5 mol / L, and a mixed solution of HF and H 2 O 2 , The surface of the silicon wafer treated in the step (2) is used by using a first chemical etching solution which is any one selected from a mixed solution of HF and HNO 3 and a mixed solution of HF and H 2 CrO 4. Corroding and forming a nano-level surface texture structure;
(4) In order, the 1st washing | cleaning liquid which is a 27-69 mass% nitric acid solution which makes washing | cleaning time 60-1200 second and makes washing | cleaning temperature 5-85 degreeC,
A second cleaning liquid that is a 1 to 10% by mass hydrofluoric acid solution with a cleaning time of 60 to 600 seconds and a cleaning temperature of 5 to 45 ° C .;
Cleaning the silicon wafer treated in the step (3) using deionized water to remove metal particles;
(5) It is any one selected from NaOH solution, KOH solution, tetramethylammonium hydroxide solution, mixed solution of HNO 3 and HF acid,
In the case of an NaOH solution, the concentration is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, the reaction temperature is 5 to 85 ° C.,
In the case of a KOH solution, the concentration is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, the reaction temperature is 5 to 85 ° C.,
In the case of a tetramethylammonium hydroxide solution, the concentration is 0.001 to 0.1 mol / L, the reaction time is 10 to 1000 seconds, the reaction temperature is 5 to 85 ° C.,
In the case of a mixed solution of HNO 3 and HF acid, the concentrations of HF and HNO 3 are 0.05 to 0.5 mol / L, 1 to 10 mol / L, the reaction time is 10 to 1000 seconds, and the reaction temperature is 5 ˜45 ° C.,
Immersing the silicon wafer processed in the step (4) in a second chemical etching solution and performing correction etching on the microstructure;
(6) cleaning the silicon wafer processed in the step (5), spin drying, and obtaining a surface texture structure of the crystalline silicon solar cell, the surface texture of the crystalline silicon solar cell, Structure manufacturing method.
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| JP2018526835A (en) * | 2015-07-09 | 2018-09-13 | ▲蘇▼州阿特斯▲陽▼光▲電▼力科技有限公司 | Method for manufacturing local back contact solar cell |
| KR101919487B1 (en) * | 2017-09-14 | 2018-11-19 | 한국과학기술연구원 | Method for texturing semiconductor substrate, semiconductor substrate manufactured by the method and solar cell comprising the same |
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| CN103219428B (en) | 2015-08-19 |
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