JPH05275406A - Sulfuric acid composition - Google Patents
Sulfuric acid compositionInfo
- Publication number
- JPH05275406A JPH05275406A JP4066313A JP6631392A JPH05275406A JP H05275406 A JPH05275406 A JP H05275406A JP 4066313 A JP4066313 A JP 4066313A JP 6631392 A JP6631392 A JP 6631392A JP H05275406 A JPH05275406 A JP H05275406A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- acid composition
- carbon atoms
- surface tension
- formula
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Semiconductor Memories (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は硫酸組成物に関し、特に
半導体製造工程において洗浄剤として使用されるのに適
した硫酸組成物に関する。FIELD OF THE INVENTION This invention relates to sulfuric acid compositions, and more particularly to sulfuric acid compositions suitable for use as cleaning agents in semiconductor manufacturing processes.
【０００２】[0002]
【従来の技術】集積回路に代表される微細加工技術は近
年益々その加工精度を向上させており、ダイナミックラ
ンダムアクセスメモリー（ＤＲＡＭ）を例にとれば、現
在では、サブミクロンの加工技術が大量生産レベルの技
術として確立されている。微細加工技術においては、ウ
エハ上に存在するパーティクルが加工精度に重大な影響
を与えるため、フォトリソグラフィー等の各工程では、
硫酸等の洗浄剤を用いてウエハ上のパーティクルを除去
して使用するのが通例である。上記集積・回路の集積度
が向上するのに伴い、パターンの微細化、凹凸の複雑化
などとも相まって洗浄工程に要求されるパーティクルの
除去性能もより厳しくなってきている。2. Description of the Related Art In recent years, microfabrication technology represented by integrated circuits has been increasingly improved in machining accuracy. Taking dynamic random access memory (DRAM) as an example, submicron processing technology is now mass-produced. Established as a level technology. In microfabrication technology, particles present on the wafer have a significant effect on the processing accuracy, so in each process such as photolithography,
It is customary to remove particles on the wafer using a cleaning agent such as sulfuric acid before use. As the degree of integration and the degree of integration of circuits are improved, the performance of removing particles required for the cleaning process is becoming more severe due to the miniaturization of patterns and the complication of irregularities.
【０００３】硫酸は、半導体製造工程において、シリコ
ン基板の洗浄、レジスト膜の除去などに単独で、または
他の物質と混合して使用されている。従来の高純度硫酸
を使用すると、ウエハに対する接触角が大きく濡れ性が
悪いために、洗浄剤が微細なパターン内に浸透し難く、
洗浄が不十分になるなどの不都合があった。硫酸は通
常、過酸化水素水と混合してシリコンウエハの洗浄に用
いることが多く、この系での表面張力が特に問題にな
る。また、この洗浄は１００〜１３０℃の温度で実施さ
れるので、高温下で表面張力がより重要となる。これら
の問題を解決するため、特定の界面活性剤を添加するこ
とにより硫酸の表面張力を低下させ濡れ性を向上させる
方法が提案されている。（特開平２−２４０２８５
号）。Sulfuric acid is used alone or in a mixture with other substances for cleaning a silicon substrate, removing a resist film, etc. in a semiconductor manufacturing process. When conventional high-purity sulfuric acid is used, since the contact angle to the wafer is large and the wettability is poor, it is difficult for the cleaning agent to penetrate into the fine pattern,
There were inconveniences such as insufficient cleaning. Sulfuric acid is usually mixed with hydrogen peroxide to be used for cleaning silicon wafers, and the surface tension in this system is a particular problem. Further, since this cleaning is carried out at a temperature of 100 to 130 ° C., the surface tension becomes more important at high temperatures. In order to solve these problems, a method of adding a specific surfactant to reduce the surface tension of sulfuric acid to improve the wettability has been proposed. (JP-A-2-240285
issue).
【０００４】[0004]
【発明が解決しようとする課題】しかし、これらのもの
を使用した場合、表面張力を一時的に低下させることは
できても、高温下では界面活性剤としての機能が失われ
て、徐々に表面張力が上昇し、濡れ性が低下してしま
う。一方、半導体製造工程では、これらの薬液の交換頻
度は数時間から数十時間に１回であり、その意味で、こ
れらの組成物には長時間の熱安定性が要求される。本発
明の目的は、前記の背景に鑑み、既に提案されている硫
酸組成物の特性を改良し、低表面張力にて濡れ性に優
れ、かつ長時間の熱安定性を持つ硫酸組成物を提供する
ことにある。However, when these substances are used, the surface tension can be temporarily reduced, but at a high temperature, the function as a surfactant is lost, and the surface is gradually reduced. Tension increases and wettability decreases. On the other hand, in the semiconductor manufacturing process, the frequency of exchanging these chemicals is once every several hours to several tens of hours, which means that these compositions are required to have long-term thermal stability. In view of the above background, the object of the present invention is to improve the properties of the sulfuric acid composition already proposed, to provide a sulfuric acid composition having low surface tension, excellent wettability, and long-term thermal stability. To do.
【０００５】[0005]
【課題を解決するための手段】このような問題点を解決
するために本発明者らは種々検討を重ねた結果、特定の
フッ素系界面活性剤を用いれば上記目的を達成すること
ができることを見出して本発明を完成した。即ち、本発
明の要旨は、硫酸に下記一般式（Ｉ）As a result of various studies conducted by the present inventors in order to solve such problems, it was found that the above object can be achieved by using a specific fluorine-containing surfactant. The present invention has been completed by finding out. That is, the gist of the present invention is to add sulfuric acid to the following general formula (I)
【化２】 （式中、Ｒ1は炭素数３以上のフルオロアルキル基を、
Ｒ2は水素原子または炭素数１〜４の低級アルキル基
を、ｎは３〜５の整数を、ＡはＨまたはＳＯ3Ｈを表
す。）で示されるフルオロアルキルスルホンアミド化合
物を含有させてなる硫酸組成物、に存する。[Chemical 2] (In the formula, R 1 is a fluoroalkyl group having 3 or more carbon atoms,
R 2 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, n represents an integer of 3 to 5, and A represents H or SO 3 H. ) The sulfuric acid composition containing the fluoroalkyl sulfonamide compound represented by the formula (1).
【０００６】以下、本発明を詳細に説明する。上記式
（Ｉ）中、Ｒ1のフルオロアルキル基としては、炭素数
３以上、好ましくは炭素数５〜２０、更に好ましくは炭
素数５〜１０のアルキル基のフッ素置換物が挙げられ
る。尚、アルキル基は、直鎖、分岐鎖のいずれでもよい
が、通常、直鎖アルキル基である。フルオロアルキル基
のフッ素置換率は通常、約５０％以上、好ましくは約８
０％以上である。Ｒ2としては、水素原子または炭素数
１〜４の直鎖または分岐鎖のアルキル基が挙げられる。
また、ｎは３〜５の整数、好ましくは３又は４である。
ｎが２以下では、表面張力低下能は優れているが安定性
に劣り、逆にｎが６以上では表面張力低下能が劣る。The present invention will be described in detail below. In the above formula (I), examples of the fluoroalkyl group represented by R 1 include fluorine-substituted alkyl groups having 3 or more carbon atoms, preferably 5 to 20 carbon atoms, and more preferably 5 to 10 carbon atoms. The alkyl group may be linear or branched, but is usually a linear alkyl group. The fluorine substitution rate of the fluoroalkyl group is usually about 50% or more, preferably about 8%.
It is 0% or more. Examples of R 2 include a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
In addition, n is an integer of 3 to 5, preferably 3 or 4.
When n is 2 or less, the surface tension lowering ability is excellent, but the stability is poor, and conversely, when n is 6 or more, the surface tension lowering ability is poor.
【０００７】本発明の硫酸組成物は、上記一般式（Ｉ）
で示されるフルオロアルキルスルホンアミド化合物が硫
酸に適当量混合、溶解されていることを必須とするもの
であるが、その含有量は、硫酸に対して通常０．００１
〜０．１重量％であり、より好ましい含有量は０．００
５〜０．０５重量％である。上記量より少なすぎると効
果が十分でなく、また多すぎてもそれ以上の効果が得ら
れず意味がない。The sulfuric acid composition of the present invention has the general formula (I) above.
It is essential that the fluoroalkyl sulfonamide compound represented by is mixed and dissolved in sulfuric acid in an appropriate amount, and the content thereof is usually 0.001 with respect to sulfuric acid.
To 0.1% by weight, more preferably 0.00
It is 5 to 0.05% by weight. If the amount is less than the above amount, the effect is not sufficient, and if the amount is too large, no further effect is obtained and it is meaningless.
【０００８】一方、上記式（Ｉ）で示される化合物を含
有させる硫酸は、通常水溶液として用いられるが、あま
り薄すぎると洗浄効果が十分でないため、一般的には６
０重量％以上、好ましくは７０重量％以上の濃度のもの
が使用される。尚、硫酸組成物は通常、過酸化水素と混
合されて洗浄液とされるが、その場合の過酸化水素の混
合比率は、硫酸に対して５〜２０重量％程度である。本
発明で用いれられるフルオロアルキルスルホンアミド化
合物は、このような強酸化性の雰囲気にても安定であ
る。また通常、洗浄は１００〜１３０℃の高温で行われ
るが、本発明の硫酸組成物はこのような高温下でも十分
にその効果を発揮し、なおかつ長時間の安定性にも優れ
ている。On the other hand, sulfuric acid containing the compound represented by the above formula (I) is usually used as an aqueous solution. However, if it is too thin, the cleaning effect is not sufficient, so that it is generally 6
A concentration of 0% by weight or more, preferably 70% by weight or more is used. The sulfuric acid composition is usually mixed with hydrogen peroxide to form a cleaning liquid. In this case, the mixing ratio of hydrogen peroxide is about 5 to 20% by weight with respect to sulfuric acid. The fluoroalkyl sulfonamide compound used in the present invention is stable even in such a strongly oxidizing atmosphere. Usually, washing is carried out at a high temperature of 100 to 130 ° C., but the sulfuric acid composition of the present invention sufficiently exhibits its effect even under such a high temperature, and is also excellent in long-term stability.
【０００９】[0009]
【実施例】次に、実施例により本発明の具体的態様を更
に詳しく説明するが、本発明はその要旨を越えないかぎ
り、以下の実施例により何ら制限を受けるものではな
い。 実施例１〜３及び比較例１〜３ ８９重量％硫酸に表−１に示す前記一般式（Ｉ）のフッ
素系界面活性剤を０．０１重量％添加した硫酸組成物及
び無添加の場合の２２℃における表面張力を測定した。
表面張力はウィルヘルミ法にて測定した。結果を表−２
に示す。EXAMPLES Next, specific examples of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Examples 1 to 3 and Comparative Examples 1 to 89 89% by weight of sulfuric acid composition containing 0.01% by weight of the fluorine-containing surfactant of the general formula (I) shown in Table 1 in sulfuric acid and the case of no addition The surface tension at 22 ° C. was measured.
The surface tension was measured by the Wilhelmi method. The results are shown in Table-2.
Shown in.
【００１０】[0010]
【表１】 [Table 1]
【００１１】[0011]
【表２】 [Table 2]
【００１２】実施例４〜５及び比較例４〜６ 実施例１、３及び比較例１〜３の各硫酸組成物と３０重
量％過酸化水素水とを４：１（容量比）にて混合した混
合組成物をそれぞれ１３０℃の温度で加熱保持し、４時
間後、及び８時間後にサンプリングし、これを冷却して
同様に２２℃における表面張力を測定した。結果を表−
３に示す。Examples 4 to 5 and Comparative Examples 4 to 6 The sulfuric acid compositions of Examples 1 and 3 and Comparative Examples 1 to 3 were mixed with 30% by weight aqueous hydrogen peroxide at 4: 1 (volume ratio). Each of the mixed compositions was heated and maintained at a temperature of 130 ° C., sampled after 4 hours and 8 hours, cooled, and the surface tension at 22 ° C. was measured in the same manner. Table of results
3 shows.
【００１３】[0013]
【表３】 [Table 3]
【００１４】[0014]
【発明の効果】本発明の硫酸組成物は、表面張力が低
く、濡れ性に優れ、その結果、シリコンウエハの洗浄剤
とした場合、良好な洗浄効果が発揮される。また、本発
明の硫酸組成物は高酸化性雰囲気下、高温下でも安定に
存在するので、実際の生産ラインにおいても変質するこ
となく良好な効果を発揮することができる。The sulfuric acid composition of the present invention has a low surface tension and is excellent in wettability. As a result, when used as a cleaning agent for silicon wafers, a good cleaning effect is exhibited. Further, since the sulfuric acid composition of the present invention stably exists even under high oxidizing atmosphere and high temperature, it is possible to exert a good effect without deterioration even in an actual production line.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１１Ｄ 7:34） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C11D 7:34)
Claims (1)
Ｒ2は水素原子または炭素数１〜４の低級アルキル基
を、ｎは３〜５の整数を、ＡはＨまたはＳＯ3Ｈを表
す。）で示されるフルオロアルキルスルホンアミド化合
物を含有させてなる硫酸組成物。1. Sulfuric acid has the following general formula (I): (In the formula, R 1 is a fluoroalkyl group having 3 or more carbon atoms,
R 2 represents a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, n represents an integer of 3 to 5, and A represents H or SO 3 H. ) A sulfuric acid composition containing a fluoroalkyl sulfonamide compound represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4066313A JPH05275406A (en) | 1992-03-24 | 1992-03-24 | Sulfuric acid composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4066313A JPH05275406A (en) | 1992-03-24 | 1992-03-24 | Sulfuric acid composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05275406A true JPH05275406A (en) | 1993-10-22 |
Family
ID=13312216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4066313A Pending JPH05275406A (en) | 1992-03-24 | 1992-03-24 | Sulfuric acid composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05275406A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005095567A1 (en) | 2004-03-03 | 2005-10-13 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| KR100655647B1 (en) * | 2005-07-04 | 2006-12-08 | 삼성전자주식회사 | Cleaning composition for a semiconductor substrate, method of preparing the cleaning composition, method of cleaning a semiconductor substrate and method of manufacturing a semiconductor device using the cleaning composition |
| US8258341B2 (en) | 2009-07-10 | 2012-09-04 | E.I. Du Pont De Nemours And Company | Polyfluorosulfonamido amine and intermediate |
| US8729138B2 (en) | 2010-03-25 | 2014-05-20 | E I Du Pont De Nemours And Company | Mixture of polyfluoroalkylsulfonamido alkyl amines |
| US8779196B2 (en) | 2010-03-25 | 2014-07-15 | E I Du Pont De Nemours And Company | Polyfluoroalkylsulfonamido alkyl halide intermediate |
| US9168408B2 (en) | 2010-03-25 | 2015-10-27 | The Chemours Company Fc, Llc | Surfactant composition from polyfluoroalkylsulfonamido alkyl amines |
| US11193059B2 (en) | 2016-12-13 | 2021-12-07 | Current Lighting Solutions, Llc | Processes for preparing color stable red-emitting phosphor particles having small particle size |
-
1992
- 1992-03-24 JP JP4066313A patent/JPH05275406A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005095567A1 (en) | 2004-03-03 | 2005-10-13 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| US7294610B2 (en) | 2004-03-03 | 2007-11-13 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| US7811978B2 (en) | 2004-03-03 | 2010-10-12 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| US7985723B2 (en) | 2004-03-03 | 2011-07-26 | 3M Innovative Properties Company | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| KR100655647B1 (en) * | 2005-07-04 | 2006-12-08 | 삼성전자주식회사 | Cleaning composition for a semiconductor substrate, method of preparing the cleaning composition, method of cleaning a semiconductor substrate and method of manufacturing a semiconductor device using the cleaning composition |
| US8258341B2 (en) | 2009-07-10 | 2012-09-04 | E.I. Du Pont De Nemours And Company | Polyfluorosulfonamido amine and intermediate |
| US8729138B2 (en) | 2010-03-25 | 2014-05-20 | E I Du Pont De Nemours And Company | Mixture of polyfluoroalkylsulfonamido alkyl amines |
| US8779196B2 (en) | 2010-03-25 | 2014-07-15 | E I Du Pont De Nemours And Company | Polyfluoroalkylsulfonamido alkyl halide intermediate |
| US9168408B2 (en) | 2010-03-25 | 2015-10-27 | The Chemours Company Fc, Llc | Surfactant composition from polyfluoroalkylsulfonamido alkyl amines |
| US11193059B2 (en) | 2016-12-13 | 2021-12-07 | Current Lighting Solutions, Llc | Processes for preparing color stable red-emitting phosphor particles having small particle size |
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