JPH03268327A - Etching of silicon compound film - Google Patents
Etching of silicon compound filmInfo
- Publication number
- JPH03268327A JPH03268327A JP6600190A JP6600190A JPH03268327A JP H03268327 A JPH03268327 A JP H03268327A JP 6600190 A JP6600190 A JP 6600190A JP 6600190 A JP6600190 A JP 6600190A JP H03268327 A JPH03268327 A JP H03268327A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- phosphoric acid
- silicon compound
- compound film
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005530 etching Methods 0.000 title claims abstract description 28
- 150000003377 silicon compounds Chemical class 0.000 title claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 27
- -1 polyoxyethylene Polymers 0.000 claims abstract description 13
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 230000007423 decrease Effects 0.000 abstract 1
- 239000012466 permeate Substances 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 7
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 7
- 238000001039 wet etching Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- PZLGBVIKYPHZTH-UHFFFAOYSA-N ethene;2-nonylphenol Chemical compound C=C.CCCCCCCCCC1=CC=CC=C1O PZLGBVIKYPHZTH-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Landscapes
- Weting (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、シリコン化合物膜のエツチング方法に関し、
更に詳しくはリン酸系溶液を用いたウェットエツチング
方法に係るものである。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method of etching a silicon compound film,
More specifically, it relates to a wet etching method using a phosphoric acid solution.
「発明の概要り
本発明は、リン酸系溶液によりシリコン化合物膜をエツ
チングする方法において、
前記リン酸系溶液にポリオキシエチレンアルキルエーテ
ル系の非イオン性界面活性剤を添加したことにより、
シリコン化合物膜表面の表面張力を低下させて、エツチ
ングふれを低減させると共に、エツチング速度の向上を
図ったものである。``Summary of the Invention The present invention provides a method for etching a silicon compound film with a phosphoric acid solution, in which a polyoxyethylene alkyl ether-based nonionic surfactant is added to the phosphoric acid solution. This is intended to reduce the surface tension of the film surface, reduce etching runout, and improve the etching speed.
Ｃ従来の技術］
従来、窒化シリコン（Ｓｉ３Ｎ、）膜等のシリコン化合
物膜をウェットエツチングする場合、エツチング液とし
てリン酸（Ｈ，ＰＯ４）が用いられている。また、この
他のエツチング液として、リン酸に酢酸、硝酸等を加え
たものを用いたエツチング方法が知られている。このよ
うなエツチング液は、通常１５０〜１６０℃程度の高温
で用いられている。C. Prior Art] Conventionally, when wet etching a silicon compound film such as a silicon nitride (Si3N) film, phosphoric acid (H, PO4) has been used as an etching solution. Further, as another etching solution, an etching method using a solution prepared by adding acetic acid, nitric acid, etc. to phosphoric acid is known. Such an etching solution is normally used at a high temperature of about 150 to 160°C.
また、半導体表面の洗浄処理剤ではあるが、特開昭６３
−２７４１４９号公報記載の発明のように、第四級アン
モニウム水酸化物と非イオン性界面活性剤と過酸化水素
を含有するものが知られている。In addition, although it is a cleaning treatment agent for semiconductor surfaces, JP-A-63
An invention containing quaternary ammonium hydroxide, a nonionic surfactant, and hydrogen peroxide is known, as in the invention described in Japanese Patent No. 274149.
「発明が解決しようとする課題］
しかしながら、上記したようなエツチング液を用いたウ
ェットエツチングにおいては、リン酸系溶液の表面張力
が高いため、ウェハ表面に形成されている例えば窒化シ
リコン膜のエツチングを行った場合、窒化ノリコン膜表
面へのリン酸系溶液の浸透性が低くエッチレートか低下
し、又エツチングの不均一化が生じるなどの問題点を有
している。"Problems to be Solved by the Invention" However, in wet etching using the above-mentioned etching solution, the surface tension of the phosphoric acid solution is high, so it is difficult to etch the silicon nitride film formed on the wafer surface. If this is done, there are problems such as low permeability of the phosphoric acid solution to the surface of the nitride film, resulting in a lower etch rate and non-uniform etching.
また、例えば、微細なトレンチ構造を有するウェハのウ
ェットエツチングにおいては、上記したような表面張力
の高いリン酸系溶液では、トレンチ内部までの溶液の浸
透がさらに困難となるため、エツチング漏れの箇所が多
く発生する問題点がある。In addition, for example, in wet etching of a wafer with a fine trench structure, using a phosphoric acid solution with a high surface tension as described above, it becomes more difficult for the solution to penetrate into the trenches, making it difficult to avoid etching leakage points. There are many problems that occur.
本発明は、このような従来の問題点に着目して創案され
たものであって、表面張力が低く浸透性の優れたリン酸
系溶液を用いたシリコン化合物膜のエツチング方法を得
んとするものである。The present invention was devised by focusing on these conventional problems, and aims to provide a method for etching silicon compound films using a phosphoric acid solution that has low surface tension and excellent permeability. It is something.
［課題を解決するための手段］
そこで、本発明は、リン酸系溶液によりシリコン化合物
膜をエツチングする方法において、前記リン酸系溶液に
ポリオキシエチレンアルキルエーテル系の非イオン性界
面活性剤を添加したことを、その解決手段としている。[Means for Solving the Problems] Therefore, the present invention provides a method for etching a silicon compound film using a phosphoric acid solution, in which a polyoxyethylene alkyl ether-based nonionic surfactant is added to the phosphoric acid solution. This is what I did as a solution.
５作用５
ポリオキシエチレンアルキルエーテル系の非イオン性界
面活性剤は、リン酸系溶液の表面張力を下げる。また、
リン酸系溶液中の該非イオン性界面活性剤は、酸による
分解を受は経時変化を起こすことなく、また、１５０〜
１６０ ’Ｃ程度の熱に対しても安定である。さらに、
ポリオキシエチレンアルキルエーテル系の非イオン性界
面活性剤は、親水性であるため、例えばウェットエツチ
ング後の純水リンスにて容易に洗い流すことが可能であ
る。5 Effect 5 Polyoxyethylene alkyl ether-based nonionic surfactants lower the surface tension of phosphoric acid-based solutions. Also,
The nonionic surfactant in the phosphoric acid solution does not undergo decomposition by acid and does not change over time.
It is also stable against heat of about 160'C. moreover,
Since the polyoxyethylene alkyl ether type nonionic surfactant is hydrophilic, it can be easily washed away, for example, by rinsing with pure water after wet etching.
「実施例］
以下、本発明に係るノリコン化合物膜のエツチング方法
の詳細を実施例に基づいて説明する。``Example'' Hereinafter, details of the method for etching a Noricon compound film according to the present invention will be explained based on Examples.
本実施例は、リン酸溶液にポリオキソエチレンアルキル
エーテルを添加したエツチング液を用いて、窒化シリコ
ン膜（ｓｘ３Ｎ４）のウェットエツチングを行っている
。本実施例においては、エツチング液を１５０〜１６０
℃に設定している。In this embodiment, a silicon nitride film (sx3N4) is wet etched using an etching solution prepared by adding polyoxoethylene alkyl ether to a phosphoric acid solution. In this example, the etching solution was
It is set to ℃.
ポリオキシエチレンアルキルエーテルは、一般式
％式％）
Ｒ：ＣＩ２〜．Ｓの飽和及び不飽和アルキル基例エバ、
Ｃ、ｓＨ４、ＣｅＨ、−ｅ 、 Ｃ、ｚＨｚｓｃｏΣｎ
：２〜７０
で表わされるものであり、特に、上記ＲがＣ９ＨＩｌｌ
ＣＸであるポリオキンエチレンノニルフェノールエーテ
ル型の界面活性剤がよい。Polyoxyethylene alkyl ether has the general formula %) R: CI2~. Examples of saturated and unsaturated alkyl groups of S: Eva,
C, sH4, CeH, -e, C, zHzscoΣn
:2 to 70, and in particular, the above R is C9HIll
A polyoxine ethylene nonylphenol ether type surfactant such as CX is preferable.
本実施例においては、リン酸溶液にポリオキシエチレン
アルキルエーテルを添加したことにより、リン酸溶液の
表面張力を低下させる。In this example, the surface tension of the phosphoric acid solution is reduced by adding polyoxyethylene alkyl ether to the phosphoric acid solution.
また、エツチング液を１５０〜１６０°Ｃとした場合も
、ポリオキシエチレンアルキルエーテルは、安定であり
、酸による分解も生じなかった。Further, even when the etching solution was heated to 150 to 160°C, the polyoxyethylene alkyl ether was stable and did not decompose due to acid.
さらに、ポリオキンエチレンアルキルエーテルは、親水
性を有するため、ウェットエツチング後の純水リンスに
より容易に洗い流しが可能である。Furthermore, since polyoxine ethylene alkyl ether has hydrophilic properties, it can be easily washed away by rinsing with pure water after wet etching.
以上、実施例について説明したが、本発明は、この他各
種の変更が可能であり、例えば、上記実施例にあっては
、リン酸溶液にポリオキンエチレンアルキルエーテルを
加えたものを用いたが、リン酸溶液に酢酸や硝酸等を加
えた、他のリン酸系溶液に添加したものを用いても同様
な作用を得ることが出来る。Although the embodiments have been described above, the present invention can be modified in various ways. For example, in the above embodiments, a solution in which polyoxine ethylene alkyl ether was added to the phosphoric acid solution was used. Similar effects can be obtained by adding acetic acid, nitric acid, etc. to a phosphoric acid solution, or by adding other phosphoric acid solutions.
特に、リン酸に、酢酸又は硝酸を加えたエツチング液を
用いれば、アルミニウム膜やアルミ系合金膜のウェット
エツチングも可能である。In particular, if an etching solution containing phosphoric acid and acetic acid or nitric acid is used, wet etching of aluminum films and aluminum alloy films is also possible.
また、上記実施例においては、シリコン化合物膜として
窒化シリコン膜を適用したが、Ｓｉｎ！膜等を適用する
ことも可能である。Furthermore, in the above embodiment, a silicon nitride film was used as the silicon compound film, but Sin! It is also possible to apply a membrane or the like.
［発明の効果］
以りの説明から明らかなように、本発明に係るノリコン
化合物膜のエツチング方法によれば、非イオン性界面活
性剤（ポリオキシエチレンアルキルエーテル）を添加し
たことにより、リン酸系溶液の表面張力を低下させ、ウ
ェハ表面の微細構造部（例えばトレンヂ構造）の窒化シ
リコン＆ｊ（Ｓｉ３Ｎ、膜）のエツチングの均−性並び
にエツチング速度を向上させる効果がある。[Effect of the invention] As is clear from the explanation below, according to the method for etching a Noricon compound film according to the present invention, by adding a nonionic surfactant (polyoxyethylene alkyl ether), phosphoric acid This has the effect of lowering the surface tension of the system solution and improving the etching uniformity and etching rate of silicon nitride (Si3N, film) in the fine structure (for example, trend structure) on the wafer surface.
また、リン酸系溶液の低表面張力化に使用する界面活性
剤が非イオン性であるため、耐酸性、耐熱性に優れ、ま
た、不純物（特に金属）の混入の恐れもなく、さらに親
水性が高いため、流水リンスにて容易に洗い流すことが
できる効果がある。In addition, since the surfactant used to lower the surface tension of phosphoric acid solutions is nonionic, it has excellent acid resistance and heat resistance, and there is no fear of contamination with impurities (particularly metals), and it is also hydrophilic. Since it has a high oxidation rate, it has the effect of being easily washed away with running water.
Claims (1)
グする方法において、 前記リン酸系溶液にポリオキシエチレンアルキルエーテ
ル系の非イオン性界面活性剤を添加したことを特徴とす
るシリコン化合物膜のエッチング方法。(1) A method of etching a silicon compound film with a phosphoric acid solution, characterized in that a polyoxyethylene alkyl ether-based nonionic surfactant is added to the phosphoric acid solution. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6600190A JP2808799B2 (en) | 1990-03-16 | 1990-03-16 | Etching method of silicon nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6600190A JP2808799B2 (en) | 1990-03-16 | 1990-03-16 | Etching method of silicon nitride film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03268327A true JPH03268327A (en) | 1991-11-29 |
| JP2808799B2 JP2808799B2 (en) | 1998-10-08 |
Family
ID=13303277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6600190A Expired - Fee Related JP2808799B2 (en) | 1990-03-16 | 1990-03-16 | Etching method of silicon nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2808799B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10270542A (en) * | 1997-03-18 | 1998-10-09 | Lg Semicon Co Ltd | Method for separating semiconductor memory element |
| EP0871209A1 (en) * | 1995-11-15 | 1998-10-14 | Daikin Industries, Limited | Wafer-cleaning solution and process for the production thereof |
| WO2005091347A1 (en) * | 2004-03-19 | 2005-09-29 | Daikin Industries, Ltd. | SiN FILM SELECTIVE ETCHING SOLUTION AND ETCHING METHOD |
| JP2008311436A (en) * | 2007-06-14 | 2008-12-25 | Tosoh Corp | Composition for etching, and etching method |
| JP2009501436A (en) * | 2005-07-12 | 2009-01-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Composite media for etching and doping for silicon dioxide and basic silicon |
| JP2012018983A (en) * | 2010-07-06 | 2012-01-26 | Tosoh Corp | Etching liquid and etching method for silicon nitride |
| WO2012043830A1 (en) * | 2010-10-01 | 2012-04-05 | 和光純薬工業株式会社 | Etching agent and etching method |
-
1990
- 1990-03-16 JP JP6600190A patent/JP2808799B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0871209A1 (en) * | 1995-11-15 | 1998-10-14 | Daikin Industries, Limited | Wafer-cleaning solution and process for the production thereof |
| EP0871209A4 (en) * | 1995-11-15 | 2006-02-08 | Daikin Ind Ltd | Wafer-cleaning solution and process for the production thereof |
| JPH10270542A (en) * | 1997-03-18 | 1998-10-09 | Lg Semicon Co Ltd | Method for separating semiconductor memory element |
| WO2005091347A1 (en) * | 2004-03-19 | 2005-09-29 | Daikin Industries, Ltd. | SiN FILM SELECTIVE ETCHING SOLUTION AND ETCHING METHOD |
| JP2009501436A (en) * | 2005-07-12 | 2009-01-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフトング | Composite media for etching and doping for silicon dioxide and basic silicon |
| JP2008311436A (en) * | 2007-06-14 | 2008-12-25 | Tosoh Corp | Composition for etching, and etching method |
| JP2012018983A (en) * | 2010-07-06 | 2012-01-26 | Tosoh Corp | Etching liquid and etching method for silicon nitride |
| WO2012043830A1 (en) * | 2010-10-01 | 2012-04-05 | 和光純薬工業株式会社 | Etching agent and etching method |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2808799B2 (en) | 1998-10-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |