JP2009123811A - Etchant for formation of texture - Google Patents
Etchant for formation of texture Download PDFInfo
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- JP2009123811A JP2009123811A JP2007294253A JP2007294253A JP2009123811A JP 2009123811 A JP2009123811 A JP 2009123811A JP 2007294253 A JP2007294253 A JP 2007294253A JP 2007294253 A JP2007294253 A JP 2007294253A JP 2009123811 A JP2009123811 A JP 2009123811A
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- 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
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Abstract
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.
本発明のうち第一の発明は、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。
第二の発明は、第一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。
The first invention of the present invention aims 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 first invention, the second invention aims to provide an etching solution that improves the reproducibility of a uniform and fine pyramidal uneven portion.
前述した目的を達成するために、本発明のうち第一の発明は、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脂肪族ポリアルコールを含有したことを特徴とするものである。
第二の発明は、第一の発明の構成に、前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た構成を加えたことを特徴とする。
In order to achieve the above-mentioned object, the first invention of the present invention is characterized in that an alkali metal hydroxide solution is used as a base and an aliphatic polyalcohol is added as an additive thereto.
The second invention is characterized in that a structure in which sodium hydrogen carbonate or potassium hydrogen carbonate is added to an alkali metal hydroxide is added to the structure of the first invention as the base of the etching solution.
本発明のうち第一の発明は、アルカリ金属水酸化物溶液をベースに脂肪族ポリ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。
According to the first aspect of the present invention, uniform and fine pyramidal uneven portions can be stably obtained on the silicon surface by adding an aliphatic polyalcohol based on an alkali metal hydroxide solution.
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.
第二の発明は、第一の発明の効果に加えて、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。
In the second invention, in addition to the effects of the first invention, a uniform and fine pyramidal uneven portion can be obtained more stably by adding sodium hydrogen carbonate or potassium hydrogen carbonate to the alkali metal hydroxide.
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。 Moreover, it has been experimentally found that uniform and fine pyramidal uneven portions 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をベースとし、これに添加剤として脂肪族ポリ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。 In the etching solution for texture formation that forms uneven portions on the silicon surface by etching in the solution,
An etching solution for texture formation, characterized by comprising an alkali metal hydroxide solution as a base and containing an aliphatic polyalcohol as an additive.
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| JP2007294253A JP5021427B2 (en) | 2007-11-13 | 2007-11-13 | Etching solution for texture formation |
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| JP2007294253A JP5021427B2 (en) | 2007-11-13 | 2007-11-13 | Etching solution for texture formation |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101079261B1 (en) * | 2009-09-29 | 2011-11-03 | 한국세라믹기술원 | A solar cell and method for the same |
| EP2458622A2 (en) | 2010-11-24 | 2012-05-30 | Air Products and Chemicals, Inc. | Compositions and methods for texturing of silicon wafers |
| 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 |
| WO2015064174A1 (en) * | 2013-11-01 | 2015-05-07 | 日本酢ビ・ポバール株式会社 | Texture-etching liquid, liquid additive for texture-etching liquid, textured substrate, method for manufacturing textured substrate, and solar cell |
| CN108242477A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院上海高等研究院 | Micro- contact wet etching preparation method of layer transfer monocrystalline silicon thin film Seed crystal substrate |
| 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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| JPH06188236A (en) * | 1992-09-17 | 1994-07-08 | Internatl Business Mach Corp <Ibm> | Selective etching of silicon and composition |
| JP2000001792A (en) * | 1998-03-18 | 2000-01-07 | Siemens Solar Gmbh | Method for wet-etching pyramidal structure on surface of silicon and etching solution |
| JP2000183378A (en) * | 1998-12-17 | 2000-06-30 | Mitsubishi Electric Corp | Manufacture of silicon solar battery |
| JP2005019605A (en) * | 2003-06-25 | 2005-01-20 | Naoetsu Electronics Co Ltd | Etchant for texture formation |
| JP2006093453A (en) * | 2004-09-24 | 2006-04-06 | Siltronic Japan Corp | Alkali etchant and alkali etching method |
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2007
- 2007-11-13 JP JP2007294253A patent/JP5021427B2/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06188236A (en) * | 1992-09-17 | 1994-07-08 | Internatl Business Mach Corp <Ibm> | Selective etching of silicon and composition |
| JP2000001792A (en) * | 1998-03-18 | 2000-01-07 | Siemens Solar Gmbh | Method for wet-etching pyramidal structure on surface of silicon and etching solution |
| JP2000183378A (en) * | 1998-12-17 | 2000-06-30 | Mitsubishi Electric Corp | Manufacture of silicon solar battery |
| JP2005019605A (en) * | 2003-06-25 | 2005-01-20 | Naoetsu Electronics Co Ltd | Etchant for texture formation |
| JP2006093453A (en) * | 2004-09-24 | 2006-04-06 | Siltronic Japan Corp | Alkali etchant and alkali etching method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101079261B1 (en) * | 2009-09-29 | 2011-11-03 | 한국세라믹기술원 | A solar cell and method for the same |
| EP2458622A2 (en) | 2010-11-24 | 2012-05-30 | Air Products and Chemicals, Inc. | Compositions and methods for texturing of silicon wafers |
| 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 |
| WO2015064174A1 (en) * | 2013-11-01 | 2015-05-07 | 日本酢ビ・ポバール株式会社 | Texture-etching liquid, liquid additive for texture-etching liquid, textured substrate, method for manufacturing textured substrate, and solar cell |
| CN108242477A (en) * | 2016-12-27 | 2018-07-03 | 中国科学院上海高等研究院 | Micro- contact wet etching preparation method of layer transfer monocrystalline silicon thin film Seed crystal substrate |
| 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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