JP2005019605A - Etchant for texture formation - Google Patents
Etchant for texture formation Download PDFInfo
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- JP2005019605A JP2005019605A JP2003181129A JP2003181129A JP2005019605A JP 2005019605 A JP2005019605 A JP 2005019605A JP 2003181129 A JP2003181129 A JP 2003181129A JP 2003181129 A JP2003181129 A JP 2003181129A JP 2005019605 A JP2005019605 A JP 2005019605A
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- etching solution
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- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 229920005610 lignin Polymers 0.000 claims abstract description 19
- 229920002678 cellulose Polymers 0.000 claims abstract description 17
- 235000010980 cellulose Nutrition 0.000 claims abstract description 17
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 150000002334 glycols Chemical class 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims description 71
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 47
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 44
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 22
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 22
- 239000000654 additive Substances 0.000 claims description 17
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 9
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 9
- 239000011736 potassium bicarbonate Substances 0.000 claims description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 9
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000000635 electron micrograph Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 229920002301 cellulose acetate Polymers 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000000996 additive effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002310 reflectometry Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
-
- 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
- Y02E10/547—Monocrystalline silicon PV cells
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Photovoltaic Devices (AREA)
- Weting (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、例えば単結晶シリコン太陽電池などに使用するために、単結晶シリコン表面｛面方位（１００）｝にテクスチャー（ｔｅｘｔｕｒｅ）と呼ばれる微細なピラミッド状凹凸部を形成するテクスチャー形成に用いられるエッチング液に関する。
詳しくは、液中でエッチングすることによりシリコン表面にピラミッド状凹凸部（テクスチャー）を形成するテクスチャー形成用エッチング液に関する。
【０００２】
【従来の技術】
従来、この種のテクスチャー形成用エッチング液として、水酸化ナトリウム（ＮａＯＨ）又は水酸化カリウム（ＫＯＨ）からなるアルカリ性媒体にエチレングリコールが添加されたエッチング液を６０〜８０℃に加熱し、この溶液中に５〜２０分間シリコンウエハを浸漬してウエットエッチングすることにより、シリコンウエハの表面にピラミッド状凹凸部が形成され、エッチング液が消費した分は必要な媒体の添加により補償するものがある（例えば、特許文献１参照）。
また、炭酸ナトリウム（Ｎａ２ＣＯ３）をベースとして、水酸化ナトリウムや炭酸水素ナトリウム（ＮａＨＣＯ３）が添加されたエッチング液を８０℃〜１００℃に加熱し、これに３０分を目安として単結晶シリコンウエハを浸漬してウエットエッチングすることにより、単結晶シリコンウエハの表面に低反射率で結晶シリコン太陽電池に適したピラミッド状凹凸部が形成され、更にエッチング液の交換をせずに連続的に処理を行う場合は、処理する際に蒸発する量の水もしくはエッチング液を補充している。またその従来方法として、６０〜９５℃に加温した水酸化ナトリウム又は水酸化カリウムにイソプロピルアルコール（ＩＰＡ）を添加したエッチング液にシリコンウエハを１０〜３０分間浸漬させることにより、ピラミッド状凹凸部（テクスチャー構造）を形成するためのエッチング液も例示されている（例えば、特許文献２参照）。
【０００３】
【特許文献１】
特開２０００−１７９２号公報（第２〜４頁）
【特許文献２】
特開２０００−１８３３７８号公報（第２〜３頁）
【０００４】
【発明が解決しようとする課題】
しかし乍ら、このような従来のテクスチャー形成用エッチング液では、それらの明細書に記載された所定の条件下で実際に再現実験を行ったところ、その条件設定が厳しくて確かに再現はされるものの、優れたピラミッド状凹凸部を容易に安定して再現することは難しく再現性に劣り、しかもエッチング時間は少なくとも２０〜３０分程度必要で生産性も劣るという問題がある。
更に、後工程のパターニングでは、微細で均一なピラミッド状凹凸部が形成されることが理想的であるが、このような均一で微細なピラミッド状凹凸部は得られないという問題がある。
また、イソプロピルアルコールやエチレングリコールを添加した場合には、廃液にアルカリとアルコールが混在するため、廃液処理のコストが高くて、そのために設備が必要となると共に、廃液処理が確実に行えないと環境に悪影響を与える可能性もある。
また更に、イソプロピルアルコールを添加した場合には、プロセスコストが高く、しかも沸点より高温で使用するために危険であると共に消費した分だけ、随時補充が必要になってコストアップになるという問題もある。
【０００５】
本発明のうち請求項１記載の発明は、均一性に優れた微細なピラミッド状凹凸部を容易に安定して再現するエッチング液の提供を目的としたものである。
請求項２記載の発明は、請求項１に記載の発明の目的に加えて、均一で微細なピラミッド状凹凸部の再現性を向上させるエッチング液の提供を目的としたものである。
請求項３記載の発明は、請求項２に記載の発明の目的に加えて、結晶シリコン太陽電池に適したピラミッド状凹凸部を安全な生産環境下で容易に大量生産可能なエッチング液の提供を目的としたものである。
【０００６】
【課題を解決するための手段】
上記課題を解決するために本発明が講じた手段は、以下の通りである。
請求項１では、水酸化ナトリウム又は水酸化カリウムをベースとし、これに添加剤として、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種含有したエッチング液を提供する。
請求項２では、請求項１記載の構成に加えて、エッチング液のベースとして、水酸化ナトリウム又は水酸化カリウムに炭酸水素ナトリウム又は炭酸水素カリウムを加えたエッチング液を提供する。
請求項３では、請求項２記載の構成に加えて、エッチング液の許容濃度範囲が、水酸化ナトリウム又は水酸化カリウムの濃度範囲を０．５〜１２重量％とし、炭酸水素ナトリウム又は炭酸水素カリウムの濃度範囲を０．５〜１８重量％とし、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種からなる添加剤の濃度範囲を各１重量％以下としたエッチング液を提供する。
【０００７】
【作用】
上記エッチング液を採用することにより以下の作用を生じる。
請求項１では、水酸化ナトリウム又は水酸化カリウムのベースに、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種を添加することにより、シリコン表面に均一で微細なピラミッド状凹凸部を安定して得られることが実験により解った。
請求項２では、請求項１記載の発明の作用に加えて、水酸化ナトリウム又は水酸化カリウムに炭酸水素ナトリウム又は炭酸水素カリウムを加えることにより、均一で微細なピラミッド状凹凸部を更に安定して得られることが実験により解った。
請求項３では、請求項１または２記載の発明の作用に加えて、水酸化ナトリウム又は水酸化カリウムの濃度範囲を０．５〜１２重量％とし、炭酸水素ナトリウム又は炭酸水素カリウムの濃度範囲を０．５〜１８重量％とし、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種からなる添加剤の濃度範囲を各１重量％以下とすることにより、２分以内のエッチング時間でも良好なピラミッド状凹凸部を得られると共に、エッチング時間を設定すれば、６０℃以下でも良好なピラミッド状凹凸部及び低反射率を得られることが実験により解った。
【０００８】
【発明の実施の形態】
以下、本発明の各実施例について説明する。
下記の表１に示す実施例１〜５のエッチング液に、シリコン基板を浸漬してシリコン表面のアルカリエッチングすることにより、均一で微細なピラミッド状凹凸部を形成した。
【０００９】
【表１】
【００１０】
【実施例１】
実施例１のエッチング液は、水酸化ナトリウム（ＮａＯＨ）が４重量％と、炭酸水素ナトリウム（ＮａＨＣＯ３）が６重量％とを混合したベース液に対し、添加剤としてリグニンを１重量％以下添加したものである。
【００１１】
その結果は、図１に示した電子顕微鏡写真で見ることができる。
リグニンの添加により、ピラミッド状凹凸部が非常に小さくなる傾向がある。凹凸高さは１μｍ以下である。
【００１２】
【実施例２】
実施例２のエッチング液は、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に、添加剤としてセルロース類（酢酸セルロース）を各１重量％以下ずつ添加したものである。
【００１３】
その結果は、図２に示した電子顕微鏡写真で見ることができる。
セルロース類（酢酸セルロース）の添加により、ピラミッド状凹凸部のピラミッド形状が顕著に現れる。
【００１４】
【実施例３】
実施例３のエッチング液は、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に、添加剤してリグニンと例えばアセトン、メチルエチルケトン、シクロヘキサン、ジアセトンアルコールなどのケトン類を合計で１重量％以下添加したものである。
【００１５】
その結果は、図３に示した電子顕微鏡写真で見ることができる。
リグニンとケトン類の添加により、微細で鮮明なピラミッド状凹凸部が現れる。
【００１６】
【実施例４】
実施例４のエッチング液は、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に、添加剤としてリグニンとケトン類とセルロース類（酢酸セルロース）を各１重量％以下ずつ添加したものである。
【００１７】
その結果は、図４に示した電子顕微鏡写真で見ることができる。
リグニンとセルロース類（酢酸セルロース）とケトン類の添加により、反射率が１０．１％で最小値が得られた。
更にピラミッド状凹凸部の均一性、エッチングにおける再現安定性が良好であった。凹凸高さは３〜５μｍである。
【００１８】
【実施例５】
実施例５のエッチング液は、水酸化ナトリウム４重量％だけのベース液に、添加剤としてリグニンとケトン類とセルロース類（酢酸セルロース）を各１重量％以下ずつ添加したものである。
【００１９】
その結果は、図５に示した電子顕微鏡写真で見ることができる。
水酸化ナトリウム単体にリグニンとセルロース類（酢酸セルロース）とケトン類を添加することにより、良好なピラミッド状凹凸部が形成されるが、水酸化ナトリウム単体だけのエッチング液では良好なピラミッド状凹凸部が形成されない。
【００２０】
なお、上記添加剤は、実施例１〜５に例示したリグニン、セルロース類（酢酸セルロース）、ケトン類に限定されず、これらに代えるか又は加えて例えば例、蟻酸メチル、酢酸メチル、酢酸エチル、乳酸エチルなどのエステル類や例えばメチルグリコール、エチレングリコールなどのグリコール類を添加しても良い。
このようなエステル類やグリコール類を、上述したように水酸化ナトリウムのみ又はそれに炭酸水素ナトリウムが混合されたベースに添加しても、リグニン、セルロース類（酢酸セルロース）、ケトン類と同様な結果が得られることが実験により解った。
【００２１】
次に、上記エッチング液の許容濃度範囲について説明する。
下記の表２には、各添加剤を添加した場合の水酸化ナトリウムと炭酸水素ナトリウムの各濃度と反射率及びピラミッド状凹凸部の形成範囲を示している。
【００２２】
【表２】
その結果は、添加剤がエッチング液中に存在する場合、水酸化ナトリウムと炭酸水素ナトリウムの重量濃度比率を１：１〜１：１．５にバランス調整することにより、広範囲でピラミッド状凹凸部が形成されると共に低反射率を得ることができる。
例えば、水酸化ナトリウムの濃度２〜８％に対して、炭酸水素ナトリウム濃度比を合わせて１：１〜１：１．５に混合した場合の反射率は１０．１〜１０．３％である。
【００２４】
その次に、上記エッチング液によるエッチング時間について説明する。
下記の表３には、エッチング時間と反射率の関係を示している。
なお、共通のエッチング条件として、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に上記添加剤の中から一種か又は複数種を各１重量％以下添加したエッチング液によりウエットエッチングしている。
【００２５】
【表３】
その結果、良好である均一で微細なピラミッド状凹凸部をエッチング時間が２分でも形成され、２〜３０分のエッチング時間で反射率は１０．２〜１０．９％である。
【００２７】
そして、上記エッチング液によるエッチング温度について説明する。
下記の表４には、エッチング温度とエッチング時間における反射率の関係を示している。
なお、共通のエッチング条件として、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に上記添加剤の中から一種か又は複数種を各１重量％以下添加したエッチング液によりウエットエッチングしている。
【００２８】
【表４】
その結果、良好である均一で微細なピラミッド状凹凸部及び反射率を得るには、低温側ではそれに見合うエッチング時間を設定することにより、均一で微細なピラミッド状凹凸部及び反射率が得られ、例えば温度６０℃においてエッチング時間を３０分とすることにより、反射率１１．１％で均一で微細なピラミッド状凹凸部が形成される。
【００３０】
最後に、分光光度計の測定による反射率の分布の比較について説明する。
代表例と比較例の各反射率の分布の比較を図６のグラフに示している。
【００３１】
代表例としては、水酸化ナトリウム４重量％と炭酸水素ナトリウム６重量％の混合液に上記添加剤の中から一種か又は複数種を各１重量％以下添加したエッチング液によりエッチング温度８５℃、エッチング時間４分でウエットエッチングしたものを使用している。
これに対する比較例としては、水酸化カリウム（ＫＯＨ）にイソプロピルアルコール（ＩＰＡ）を添加した従来条件のものを使用している。
【００３２】
その結果、上記代表例における反射率は、４００〜１１００ｎｍの平均値で、１０．１％、最小値で８．２％が得られた。
しかし、従来条件の比較例は、平均反射率が１２．６％であった。
【００３３】
尚、前示実施例では、エッチング液のベースが、水酸化ナトリウムのみ又はそれに炭酸水素ナトリウムを混合した場合のみを説明したが、これに限定されず、上記水酸化ナトリウムに代えて水酸化カリウムを使用したり、炭酸水素ナトリウムに代えて炭酸水素カリウムを使用しても良い。
この場合も、上述したものと同様な結果が得られる。
【００３４】
【発明の効果】
以上説明したように、本発明のうち請求項１記載の発明は、水酸化ナトリウム又は水酸化カリウムのベースに、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種を添加することにより、シリコン表面に均一で微細なピラミッド状凹凸部を安定して得られるので、均一性に優れた微細なピラミッド状凹凸部を容易に安定して再現できる。
従って、水酸化ナトリウム又は水酸化カリウムにエチレングリコールやイソプロピルアルコールが添加されたエッチング液や炭酸ナトリウムに水酸化ナトリウムや炭酸水素ナトリウムが添加されたエッチング液を使用する従来のものに比べ、原材料や廃液コストを低減化できるだけでなく設備も簡素化できるから低コストで製造できると共に環境への負荷低減も図れる。
【００３５】
請求項２の発明は、請求項１の発明の効果に加えて、水酸化ナトリウム又は水酸化カリウムに炭酸水素ナトリウム又は炭酸水素カリウムを加えることにより、均一で微細なピラミッド状凹凸部を更に安定して得られるので、均一で微細なピラミッド状凹凸部の再現性を向上させることができる。
【００３６】
請求項３の発明は、請求項２の発明の効果に加えて、水酸化ナトリウム又は水酸化カリウムの濃度範囲を０．５〜１２重量％とし、炭酸水素ナトリウム又は炭酸水素カリウムの濃度範囲を０．５〜１８重量％とし、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種からなる添加剤の濃度範囲を各１重量％以下とすることにより、２分以内のエッチング時間でも良好なピラミッド状凹凸部を得られると共に、エッチング時間を設定すれば、６０℃以下でも良好なピラミッド状凹凸部及び低反射率を得られるので、単結晶シリコン太陽電池に適したピラミッド状凹凸部を安全な生産環境下で容易に大量生産できる。
【図面の簡単な説明】
【図１】本発明の実施例１のエッチング液を用いて形成したピラミッド状凹凸部の一例の電子顕微鏡写真である。
【図２】本発明の実施例２のエッチング液を用いて形成したピラミッド状凹凸部の一例の電子顕微鏡写真である。
【図３】本発明の実施例３のエッチング液を用いて形成したピラミッド状凹凸部の一例の電子顕微鏡写真である。
【図４】本発明の実施例４のエッチング液を用いて形成したピラミッド状凹凸部の一例の電子顕微鏡写真である。
【図５】本発明の実施例５のエッチング液を用いて形成したピラミッド状凹凸部の一例の電子顕微鏡写真である。
【図６】反射率の分布の比較を示すグラフである。[0001]
BACKGROUND OF THE INVENTION
The present invention is used for, for example, a single crystal silicon solar cell, and is used for forming a texture that forms a fine pyramidal uneven portion called texture on a single crystal silicon surface {plane orientation (100)}. Regarding liquids.
More specifically, the present invention relates to a texture-forming etching solution that forms pyramidal uneven portions (texture) on a silicon surface by etching in the solution.
[0002]
[Prior art]
Conventionally, as this kind of texture forming etching solution, an etching solution in which ethylene glycol is added to an alkaline medium composed of sodium hydroxide (NaOH) or potassium hydroxide (KOH) is heated to 60 to 80 ° C. The silicon wafer is dipped in wet etching for 5 to 20 minutes to form a pyramidal uneven portion on the surface of the silicon wafer, and the amount of the etching solution consumed can be compensated for by adding a necessary medium (for example, , See Patent Document 1).
In addition, an etching solution to which sodium hydroxide or sodium hydrogen carbonate (NaHCO 3 ) is added based on sodium carbonate (Na 2 CO 3 ) is heated to 80 ° C. to 100 ° C., and a single crystal is taken as a guide for 30 minutes. By dipping the silicon wafer and performing wet etching, a pyramidal uneven portion suitable for a crystalline silicon solar cell is formed on the surface of the single crystal silicon wafer with low reflectivity, and continuously without changing the etching solution. When processing is performed, water or an etching solution is replenished in an amount that evaporates during processing. Further, as a conventional method, pyramidal uneven portions (by immersing a silicon wafer for 10 to 30 minutes in an etching solution obtained by adding isopropyl alcohol (IPA) to sodium hydroxide or potassium hydroxide heated to 60 to 95 ° C. An etching solution for forming a (texture structure) is also exemplified (see, for example, Patent Document 2).
[0003]
[Patent Document 1]
JP 2000-1792 A (pages 2 to 4)
[Patent Document 2]
JP 2000-183378 A (pages 2 to 3)
[0004]
[Problems to be solved by the invention]
However, in such a conventional texture forming etching solution, when a reproduction experiment was actually performed under the predetermined conditions described in those specifications, the condition setting was severe and it was certainly reproduced. However, it is difficult to easily and stably reproduce an excellent pyramidal concavo-convex portion, and the reproducibility is inferior. Further, the etching time is required to be at least about 20 to 30 minutes, and the productivity is also inferior.
Furthermore, in the subsequent patterning, it is ideal that a fine and uniform pyramidal uneven portion is formed, but there is a problem that such a uniform and fine pyramid uneven portion cannot be obtained.
In addition, when isopropyl alcohol or ethylene glycol is added, alkali and alcohol coexist in the waste liquid, so the cost of waste liquid treatment is high, and equipment is required for this, and it is not possible to reliably perform waste liquid treatment. May adversely affect
Furthermore, when isopropyl alcohol is added, there is a problem in that the process cost is high, and it is dangerous to use at a temperature higher than the boiling point. .
[0005]
An object of the present invention is to provide an etching solution that easily and stably reproduces a fine pyramidal uneven portion having excellent uniformity.
In addition to the object of the invention described in claim 1, an object of the invention described in claim 2 is to provide an etching solution that improves the reproducibility of uniform and fine pyramidal uneven portions.
In addition to the object of the invention described in claim 3, the invention described in claim 3 provides an etching solution capable of easily mass-producing pyramidal irregularities suitable for crystalline silicon solar cells in a safe production environment. It is intended.
[0006]
[Means for Solving the Problems]
Means taken by the present invention to solve the above problems are as follows.
In claim 1, an etching solution containing sodium hydroxide or potassium hydroxide as a base and containing one or more of lignin, celluloses, ketones, esters, and glycols as an additive is provided. .
In addition to the structure of Claim 1, in Claim 2, the etching liquid which added sodium hydrogencarbonate or potassium hydrogencarbonate to sodium hydroxide or potassium hydroxide is provided as a base of etching liquid.
In claim 3, in addition to the structure of claim 2, the allowable concentration range of the etching solution is that the concentration range of sodium hydroxide or potassium hydroxide is 0.5 to 12% by weight, and sodium bicarbonate or potassium bicarbonate. Etching with a concentration range of 0.5 to 18% by weight and a concentration range of one or more additives selected from lignin, celluloses, ketones, esters, and glycols at 1% by weight or less. Provide liquid.
[0007]
[Action]
Employing the etching solution produces the following effects.
In claim 1, by adding one or more of lignin, celluloses, ketones, esters, and glycols to a base of sodium hydroxide or potassium hydroxide, the surface of silicon is uniform and fine. Experiments have shown that pyramidal irregularities can be obtained stably.
In Claim 2, in addition to the effect | action of invention of Claim 1, by adding sodium hydrogencarbonate or potassium hydrogencarbonate to sodium hydroxide or potassium hydroxide, a uniform and fine pyramid-shaped uneven part is further stabilized. Experiments have shown that it can be obtained.
In claim 3, in addition to the action of the invention of claim 1 or 2, the concentration range of sodium hydroxide or potassium hydroxide is 0.5 to 12% by weight, and the concentration range of sodium bicarbonate or potassium bicarbonate is 0.5% to 18% by weight, and the concentration range of one or more additives from lignin, celluloses, ketones, esters and glycols is 1% by weight or less for 2 minutes. It has been experimentally found that a good pyramidal uneven portion can be obtained even within the etching time, and that a good pyramid uneven portion and low reflectance can be obtained even at 60 ° C. or lower by setting the etching time.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the present invention will be described below.
The silicon substrate was immersed in the etching solutions of Examples 1 to 5 shown in Table 1 below, and the silicon surface was subjected to alkali etching, thereby forming uniform and fine pyramidal uneven portions.
[0009]
[Table 1]
[0010]
[Example 1]
In the etching solution of Example 1, 1% by weight or less of lignin was added as an additive to a base solution in which 4% by weight of sodium hydroxide (NaOH) and 6% by weight of sodium bicarbonate (NaHCO 3 ) were mixed. It is a thing.
[0011]
The result can be seen in the electron micrograph shown in FIG.
By adding lignin, the pyramidal irregularities tend to be very small. The height of the unevenness is 1 μm or less.
[0012]
[Example 2]
In the etching solution of Example 2, cellulose (cellulose acetate) is added in an amount of 1% by weight or less as an additive to a mixed solution of 4% by weight of sodium hydroxide and 6% by weight of sodium bicarbonate.
[0013]
The result can be seen in the electron micrograph shown in FIG.
By adding celluloses (cellulose acetate), the pyramid shape of the pyramidal irregularities appears remarkably.
[0014]
[Example 3]
The etching solution of Example 3 is a mixture of 4% by weight of sodium hydroxide and 6% by weight of sodium bicarbonate, and lignin and ketones such as acetone, methyl ethyl ketone, cyclohexane, diacetone alcohol, etc. as additives are added in total. It is added by weight% or less.
[0015]
The result can be seen in the electron micrograph shown in FIG.
By adding lignin and ketones, fine and clear pyramidal irregularities appear.
[0016]
[Example 4]
The etching solution of Example 4 was obtained by adding lignin, ketones, and celluloses (cellulose acetate) as additives in an amount of 1% by weight or less to a mixed solution of 4% by weight of sodium hydroxide and 6% by weight of sodium bicarbonate. It is.
[0017]
The result can be seen in the electron micrograph shown in FIG.
By adding lignin, celluloses (cellulose acetate) and ketones, the reflectance was 10.1% and the minimum value was obtained.
Furthermore, the uniformity of the pyramidal irregularities and the reproducibility in etching were good. The uneven height is 3 to 5 μm.
[0018]
[Example 5]
In the etching solution of Example 5, 1% by weight or less of lignin, ketones, and celluloses (cellulose acetate) were added to the base solution containing only 4% by weight of sodium hydroxide as additives.
[0019]
The result can be seen in the electron micrograph shown in FIG.
By adding lignin, cellulose (cellulose acetate) and ketones to sodium hydroxide alone, a good pyramidal irregularity is formed, but an etching solution containing only sodium hydroxide has a good pyramidal irregularity. Not formed.
[0020]
The above additives are not limited to the lignin, celluloses (cellulose acetate) and ketones exemplified in Examples 1 to 5, but instead of or in addition to these, for example, methyl formate, methyl acetate, ethyl acetate, Esters such as ethyl lactate and glycols such as methyl glycol and ethylene glycol may be added.
Even if such esters and glycols are added to a base in which sodium hydroxide alone or sodium bicarbonate is mixed as described above, the same results as lignin, celluloses (cellulose acetate), and ketones are obtained. Experiments have shown that it can be obtained.
[0021]
Next, the allowable concentration range of the etching solution will be described.
Table 2 below shows the concentrations and reflectivities of sodium hydroxide and sodium bicarbonate and the range of formation of the pyramidal irregularities when each additive is added.
[0022]
[Table 2]
As a result, when the additive is present in the etching solution, the weight concentration ratio of sodium hydroxide and sodium bicarbonate is balanced to 1: 1 to 1: 1.5, so that the pyramid-shaped uneven portion is formed over a wide range. As a result, a low reflectance can be obtained.
For example, with respect to the sodium hydroxide concentration of 2 to 8%, the reflectance when the sodium hydrogen carbonate concentration ratio is mixed and mixed at 1: 1 to 1: 1.5 is 10.1 to 10.3%. .
[0024]
Next, the etching time using the etching solution will be described.
Table 3 below shows the relationship between etching time and reflectance.
In addition, as a common etching condition, wet etching is performed with an etching solution in which one or more of the above additives are added to a mixed solution of 4% by weight of sodium hydroxide and 6% by weight of sodium hydrogen carbonate. ing.
[0025]
[Table 3]
As a result, good uniform fine pyramidal uneven portions are formed even with an etching time of 2 minutes, and the reflectance is 10.2 to 10.9% with an etching time of 2 to 30 minutes.
[0027]
And the etching temperature by the said etching liquid is demonstrated.
Table 4 below shows the relationship between the etching temperature and the reflectance at the etching time.
In addition, as a common etching condition, wet etching is performed with an etching solution in which one or more of the above additives are added to a mixed solution of 4% by weight of sodium hydroxide and 6% by weight of sodium hydrogen carbonate. ing.
[0028]
[Table 4]
As a result, in order to obtain a good uniform and fine pyramid uneven portion and reflectance, by setting an etching time commensurate with it on the low temperature side, a uniform and fine pyramid uneven portion and reflectance can be obtained, For example, by setting the etching time to 30 minutes at a temperature of 60 ° C., a uniform and fine pyramidal uneven portion with a reflectance of 11.1% is formed.
[0030]
Finally, a comparison of reflectance distributions by measurement with a spectrophotometer will be described.
A comparison of the reflectance distributions of the representative example and the comparative example is shown in the graph of FIG.
[0031]
As a typical example, an etching temperature of 85 ° C. is etched with an etching solution in which one or more of the above-mentioned additives are added to a mixed solution of 4% by weight of sodium hydroxide and 6% by weight of sodium hydrogencarbonate. What was wet-etched in 4 minutes is used.
As a comparative example for this, a conventional one in which isopropyl alcohol (IPA) is added to potassium hydroxide (KOH) is used.
[0032]
As a result, the reflectance in the above representative example was 10.1% with an average value of 400 to 1100 nm, and 8.2% with a minimum value.
However, the comparative example of the conventional condition has an average reflectance of 12.6%.
[0033]
In the previous examples, the base of the etching solution was described only when sodium hydroxide alone or a mixture of sodium bicarbonate was mixed therewith. However, the present invention is not limited to this, and potassium hydroxide is used instead of sodium hydroxide. It may be used, or potassium bicarbonate may be used instead of sodium bicarbonate.
In this case, the same result as described above can be obtained.
[0034]
【The invention's effect】
As described above, the invention according to claim 1 of the present invention is based on sodium hydroxide or potassium hydroxide, and one or more of lignin, celluloses, ketones, esters, and glycols. Since a uniform and fine pyramidal uneven portion is stably obtained on the silicon surface, the fine pyramid uneven portion having excellent uniformity can be easily and stably reproduced.
Therefore, compared to conventional products that use an etching solution in which ethylene glycol or isopropyl alcohol is added to sodium hydroxide or potassium hydroxide, or an etching solution in which sodium hydroxide or sodium bicarbonate is added to sodium carbonate, raw materials and waste liquids are used. Not only can the cost be reduced, but also the equipment can be simplified, so that it can be manufactured at a low cost and the load on the environment can be reduced.
[0035]
In addition to the effect of the invention of claim 1, the invention of claim 2 further stabilizes the uniform and fine pyramidal irregularities by adding sodium hydrogen carbonate or potassium hydrogen carbonate to sodium hydroxide or potassium hydroxide. Therefore, the reproducibility of the uniform and fine pyramidal uneven portions can be improved.
[0036]
In the invention of claim 3, in addition to the effect of the invention of claim 2, the concentration range of sodium hydroxide or potassium hydroxide is 0.5 to 12% by weight, and the concentration range of sodium bicarbonate or potassium bicarbonate is 0. Within 5 minutes by setting the concentration range of one or more additives of lignin, celluloses, ketones, esters and glycols to 1% by weight or less. Pyramids suitable for single crystal silicon solar cells can be obtained even when the etching time is set, and by setting the etching time, good pyramidal irregularities and low reflectivity can be obtained even at 60 ° C. or lower. Can be easily mass-produced in a safe production environment.
[Brief description of the drawings]
FIG. 1 is an electron micrograph of an example of a pyramidal concavo-convex portion formed using the etching solution of Example 1 of the present invention.
FIG. 2 is an electron micrograph of an example of a pyramidal concavo-convex portion formed using the etching solution of Example 2 of the present invention.
FIG. 3 is an electron micrograph of an example of a pyramidal uneven portion formed using the etching solution of Example 3 of the present invention.
FIG. 4 is an electron micrograph of an example of a pyramidal concavo-convex portion formed using the etching solution of Example 4 of the present invention.
FIG. 5 is an electron micrograph of an example of a pyramidal concavo-convex portion formed using the etching solution of Example 5 of the present invention.
FIG. 6 is a graph showing comparison of reflectance distributions.
Claims (3)
水酸化ナトリウム又は水酸化カリウムをベースとし、これに添加剤として、リグニン、セルロース類、ケトン類、エステル類、グリコール類の中から一種か又は複数種含有したことを特徴とするテクスチャー形成用エッチング液。In the etching solution for texture formation that forms pyramidal irregularities on the silicon surface by etching in the solution,
Etching solution for texture formation characterized by containing one or more of lignin, celluloses, ketones, esters and glycols as additives based on sodium hydroxide or potassium hydroxide. .
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| JP2003181129A JP3740138B2 (en) | 2003-06-25 | 2003-06-25 | Etching solution for texture formation |
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| JP2003181129A JP3740138B2 (en) | 2003-06-25 | 2003-06-25 | Etching solution for texture formation |
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| JP2009123811A (en) * | 2007-11-13 | 2009-06-04 | Niigata Univ | Etchant for formation of texture |
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2003
- 2003-06-25 JP JP2003181129A patent/JP3740138B2/en not_active Expired - Lifetime
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