JP5021427B2 - Etching solution for texture formation - Google Patents
Etching solution for texture formation Download PDFInfo
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- JP5021427B2 JP5021427B2 JP2007294253A JP2007294253A JP5021427B2 JP 5021427 B2 JP5021427 B2 JP 5021427B2 JP 2007294253 A JP2007294253 A JP 2007294253A JP 2007294253 A JP2007294253 A JP 2007294253A JP 5021427 B2 JP5021427 B2 JP 5021427B2
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- etching
- hydrogen carbonate
- texture
- etching solution
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- 238000005530 etching Methods 0.000 title claims description 27
- 230000015572 biosynthetic process Effects 0.000 title claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 10
- 229910052710 silicon Inorganic materials 0.000 claims description 10
- 239000010703 silicon Substances 0.000 claims description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940086066 potassium hydrogencarbonate Drugs 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 229920002678 cellulose Polymers 0.000 description 3
- 235000010980 cellulose Nutrition 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 2
- AKEKKCGPLHMFCI-UHFFFAOYSA-L potassium sodium hydrogen carbonate Chemical compound [Na+].[K+].OC([O-])=O.OC([O-])=O AKEKKCGPLHMFCI-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- -1 1-methylvinyl alcohol Chemical compound 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
Classifications
-
- 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
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- Photovoltaic Devices (AREA)
- Weting (AREA)
Description
本発明は、例えば単結晶シリコン太陽電池や光センサー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。
The present invention can be used for, for example, a single crystal silicon solar cell or an optical sensor to form a texture that forms fine pyramidal uneven portions called texture on a single crystal silicon surface {plane orientation (100)}. The present invention relates to an etching solution used.
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.
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、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が添加されたエッチング液を８５℃に加熱し、この溶液中に４〜５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るものがある（例えば、特許文献１参照）。
また、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）が形成されるものもある（例えば、特許文献２参照）。
Conventionally, as this type of texture-forming etching solution, an alkaline medium composed of sodium hydroxide (NaOH) or potassium hydroxide (KOH) is used as one of lignin, celluloses, ketones, esters, and glycols. An etching solution to which plural kinds are added is heated to 85 ° C., and a silicon wafer is immersed in this solution for 4 to 5 minutes to perform wet etching, whereby a pyramidal uneven portion is formed on the surface of the silicon wafer. Yes (see, for example, Patent Document 1).
Also, pyramidal uneven portions (texture structure) are obtained by immersing a silicon wafer in an etching solution obtained by adding isopropyl alcohol (IPA) to sodium hydroxide or potassium hydroxide heated to 60 to 95 ° C. for 10 to 30 minutes. Is formed (see, for example, Patent Document 2).
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、特許文献１の場合、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が、これらの合成が困難で工業的に得難いという問題があった。
また特許文献２の場合、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を添加するが、イソプロピルアルコールは揮発性、引火性が高い物質であるため、大量使用には火災対策、防爆が必要で設備費用が高価になるという問題があった。
However, in such a conventional texture-forming etching solution, in the case of Patent Document 1, a base of sodium hydroxide or potassium hydroxide is selected from lignin, celluloses, ketones, esters, and glycols. However, there is a problem that these are difficult to synthesize and are difficult to obtain industrially.
In the case of Patent Document 2, isopropyl alcohol is added to sodium hydroxide or potassium hydroxide, but isopropyl alcohol is a highly volatile and flammable substance. There was a problem of becoming expensive.
本発明は、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。
さらに、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。
This onset Ming is intended to provide the etchant to reproduce easily and stably excellent fine pyramidal uneven portions uniformity.
Furthermore, it aims at providing the etching liquid which improves the reproducibility of a uniform and fine pyramid-shaped uneven | corrugated | grooved part.
前述した目的を達成するために、本発明は、アルカリ金属水酸化物溶液に炭酸水素ナトリウム又は炭酸水素カリウムが加えられたものをベースとし、これに添加剤としてポリビニルアルコールを含有したことを特徴とするものである。
また、本発明は、アルカリ金属水酸化物に炭酸水素ナトリウム又は炭酸水素カリウムを加えたものをベースとし、これに添加剤としてポリ−１−メチルビニルアルコールを含有したことを特徴とすることも可能である。
To achieve the above object, the present onset Ming, characterized in that the alkali metal hydroxide solution to a solution of potassium bicarbonate sodium or hydrogen carbonate was added based, containing polyvinyl alcohol as an additive thereto It is what.
Further, the present invention is a plus sodium hydrogen carbonate or potassium hydrogen carbonate to A alkali metal hydroxide as a base, also be characterized by, that contained poly-1-methylvinyl alcohol as an additive Is possible .
本発明は、アルカリ金属水酸化物溶液に炭酸水素ナトリウム又は炭酸水素カリウムが加えられたものをベースとして、ポリビニルアルコール又はポリ−１−メチルビニルアルコール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。
従って、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を提供することができる。
その結果、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従来のものに比べ、安定かつ安価な合成が可能であると共に、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を添加する従来のものに比べ、火災対策、防爆を必要とせず、その分だけ設備も簡素化できるから低コストで製造できる。
This onset Ming, as a base a solution of potassium bicarbonate sodium or hydrogen carbonate was added to the alkali metal hydroxide solution, by adding polyvinyl alcohol or poly-1-methylvinyl alcohol, uniform and fine on the silicon surface A stable pyramid-shaped uneven portion can be obtained.
Therefore, it is possible to provide an etching solution that easily and stably reproduces a fine pyramid-shaped uneven portion having excellent uniformity.
As a result, a stable and inexpensive synthesis can be achieved compared to the conventional one in which one or more of lignin, celluloses, ketones, esters and glycols are added to the base of sodium hydroxide or potassium hydroxide. In addition, it can be manufactured at low cost because it does not require fire countermeasures and explosion protection, and the equipment can be simplified correspondingly compared to the conventional one in which isopropyl alcohol is added to sodium hydroxide or potassium hydroxide.
さらに、本発明は、アルカリ金属水酸化物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。
従って、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を提供することができる。
Furthermore, the present invention is by the addition of sodium hydrogen carbonate or potassium hydrogen carbonate to A alkali metal hydroxide, to obtain a uniform and fine pyramid-shaped uneven portion further stably.
Therefore, it is possible to provide an etching solution that improves the reproducibility of the uniform and fine pyramidal uneven portions.
本発明のテクスチャー形成用エッチング液は、例えば水酸化ナトリウム（ＮａＯＨ）又は水酸化カリウム（ＫＯＨ）などのアルカリ金属水酸化物溶液をベースとし、これに添加剤として例えばポリビニルアルコール（ＰＶＡ）やポリ−１−メチルビニルアルコール（ＰＭＶＡ）などの脂肪族ポリアルコールを含有させることで得られ、このエッチング液に、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が形成されるものである。
更に必要に応じて、上記エッチング液のベースとして、アルカリ金属水酸化物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も可能である。
以下、本発明の一実施例を図面に基づいて説明する。
The texture-forming etching solution of the present invention is based on an alkali metal hydroxide solution such as sodium hydroxide (NaOH) or potassium hydroxide (KOH), for example, and an additive such as polyvinyl alcohol (PVA) or poly- It is obtained by containing an aliphatic polyalcohol such as 1-methylvinyl alcohol (PMVA), and a silicon substrate is immersed in this etching solution, and the silicon surface is subjected to alkali etching. Is formed.
Further, if necessary, sodium hydrogen carbonate or potassium hydrogen carbonate can be added to the alkali metal hydroxide as the base of the etching solution.
Hereinafter, an embodiment of the present invention will be described with reference to the drawings.
この実施例は、水酸化ナトリウムが４重量％と、炭酸水素ナトリウムが４重量％とを混合したベース液に対し、添加剤としてポリビニルアルコール（重合度５００）を０．０１重量％添加したものである。
エッチング条件としては、エッチング温度は８５℃、エッチング時間は１３分である。
In this example, 0.01% by weight of polyvinyl alcohol (polymerization degree 500) was added as an additive to a base solution in which 4% by weight of sodium hydroxide and 4% by weight of sodium bicarbonate were mixed. is there.
As etching conditions, the etching temperature is 85 ° C. and the etching time is 13 minutes.
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。
それにより、シリコン基板の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、この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ることが実験により解った。
The result can be seen in the electron micrograph shown in FIG.
As a result, uniform and fine pyramidal uneven portions were stably obtained on the surface of the silicon substrate, and it was experimentally found that the uniformity of the pyramid uneven portions and the reproducibility in etching were good.
更に、分光光度計の測定による反射率の分布を図２のグラフに示している。
それにより、反射率は波長８００ｎｍ付近で１４．４％の最小値が得られた。
Furthermore, the distribution of the reflectance measured by the spectrophotometer is shown in the graph of FIG.
As a result, the minimum reflectance of 14.4% was obtained near the wavelength of 800 nm.
また、水酸化ナトリウムに適量の炭酸水素ナトリウムを添加することで、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。 Further, it has been experimentally found that uniform and fine pyramidal irregularities can be obtained more stably by adding an appropriate amount of sodium hydrogen carbonate to sodium hydroxide.
尚、前示実施例では、エッチング液のベースが、水酸化ナトリウムに炭酸水素ナトリウムを混合したベース液にポリビニルアルコールを添加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のみにポリビニルアルコールやポリ−１−メチルビニルアルコール（ＰＭＶＡ）などの脂肪族ポリアルコールを添加したり、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。
In the previous example, the base of the etching solution was described only when polyvinyl alcohol was added to the base solution in which sodium bicarbonate was mixed with sodium hydrogen carbonate. However, the present invention is not limited to this. Add aliphatic polyalcohol such as polyvinyl alcohol and poly-1-methyl vinyl alcohol (PMVA) to the surface, use potassium hydroxide instead of sodium hydroxide, use potassium hydrogen carbonate instead of sodium hydrogen carbonate You may do it.
In this case, the same result as described above can be obtained.
Claims (2)
アルカリ金属水酸化物溶液に炭酸水素ナトリウム又は炭酸水素カリウムが加えられたものをベースとし、これに添加剤としてポリビニルアルコールを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。 By etching in a liquid, a texture forming etching liquid for forming a pyramidal uneven portion on the silicon surface,
An etching solution for texture formation, characterized in that a base obtained by adding sodium hydrogen carbonate or potassium hydrogen carbonate to an alkali metal hydroxide solution and containing polyvinyl alcohol as an additive thereto.
アルカリ金属水酸化物溶液に炭酸水素ナトリウム又は炭酸水素カリウムが加えられたものをベースとし、これに添加剤としてポリ−１−メチルビニルアルコールを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。 By etching in a liquid, a texture forming etching liquid for forming a pyramidal uneven portion on the silicon surface,
An etching solution for texture formation, characterized in that a base obtained by adding sodium hydrogen carbonate or potassium hydrogen carbonate to an alkali metal hydroxide solution and containing poly-1-methylvinyl alcohol as an additive thereto.
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| KR101079261B1 (en) * | 2009-09-29 | 2011-11-03 | 한국세라믹기술원 | A solar cell and method for the same |
| US20120295447A1 (en) | 2010-11-24 | 2012-11-22 | Air Products And Chemicals, Inc. | Compositions and Methods for Texturing of Silicon Wafers |
| JP6109713B2 (en) * | 2013-11-01 | 2017-04-05 | 日本酢ビ・ポバール株式会社 | Texture etching solution, additive solution for texture etching solution, texture forming substrate, method for producing texture forming substrate, and solar cell |
| JP2015088710A (en) * | 2013-11-01 | 2015-05-07 | 日本酢ビ・ポバール株式会社 | Etchant, liquid additive agent for etchant, uneven substrate and method for manufacturing uneven substrate, and solar battery |
| CN108242477B (en) * | 2016-12-27 | 2020-03-24 | 中国科学院上海高等研究院 | Micro-contact wet etching preparation method of seed crystal substrate for layer transfer monocrystalline silicon thin film |
| CN115000241A (en) * | 2022-05-27 | 2022-09-02 | 重庆臻宝实业有限公司 | Low-reflectivity monocrystalline silicon and texturing method thereof |
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| US5431777A (en) * | 1992-09-17 | 1995-07-11 | International Business Machines Corporation | Methods and compositions for the selective etching of silicon |
| DE19811878C2 (en) * | 1998-03-18 | 2002-09-19 | Siemens Solar Gmbh | Process and etching solution for wet chemical pyramidal texture etching of silicon surfaces |
| JP3719632B2 (en) * | 1998-12-17 | 2005-11-24 | 三菱電機株式会社 | Method for manufacturing silicon solar cell |
| JP3740138B2 (en) * | 2003-06-25 | 2006-02-01 | 直江津電子工業株式会社 | Etching solution for texture formation |
| JP2006093453A (en) * | 2004-09-24 | 2006-04-06 | Siltronic Japan Corp | Alkali etchant and alkali etching method |
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