JPH05238705A - Sulfuric acid composition - Google Patents
Sulfuric acid compositionInfo
- Publication number
- JPH05238705A JPH05238705A JP517392A JP517392A JPH05238705A JP H05238705 A JPH05238705 A JP H05238705A JP 517392 A JP517392 A JP 517392A JP 517392 A JP517392 A JP 517392A JP H05238705 A JPH05238705 A JP H05238705A
- Authority
- JP
- Japan
- Prior art keywords
- sulfuric acid
- acid composition
- surfactant
- composition
- group
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は硫酸組成物に係るもので
あり、特に半導体製造工程にて洗浄剤として使用される
硫酸組成物に関する。詳しくは、本発明は特定のフッ素
系界面活性剤を配合した硫酸組成物の改良に関するもの
である。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfuric acid composition, and more particularly to a sulfuric acid composition used as a cleaning agent in semiconductor manufacturing processes. More specifically, the present invention relates to improvement of a sulfuric acid composition containing a specific fluorosurfactant.
【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、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、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に
伴いパターンの微細化、凹凸の複雑化なども相まって洗
浄工程に要求されるパーティクルの除去もより厳しい要
求がなされてきている。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, the particles present on the wafer have a significant effect on the processing accuracy, and it is customary to remove the particles on the wafer by using a cleaning agent such as sulfuric acid in each process such as photolithography. is there. As the degree of integration of the integrated circuit is improved, finer patterns and more complicated concaves and convexes are accompanied by more stringent requirements for removing particles required in the cleaning process.
【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にて、または
他の物質と混合にて使用されている。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間内に浸透し難く、洗
浄が不十分になるなどの不都合があった。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）。しかし、
濡れ性を向上させるには表面張力も大切であるが、それ
以上に接触角を低下させることも重要である。上述の公
開特許に提案されている界面活性剤は表面張力を低下さ
せても必ずしも濡れ性向上の効果は十分とは言えない。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, the cleaning agent has a large contact angle with the wafer and poor wettability, so that the cleaning agent is difficult to permeate between fine patterns, resulting in insufficient cleaning. In order to solve these problems, a method of reducing the surface tension of sulfuric acid to improve the wettability by adding a specific surfactant has been proposed (JP-A-2-240285). But,
Surface tension is important to improve wettability, but it is also important to further reduce the contact angle. The surfactants proposed in the above-mentioned published patents are not necessarily sufficient in improving the wettability even if the surface tension is reduced.
【０００４】通常、硫酸は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、この系での濡れ
性が特に問題になる。また、この洗浄は１００〜１３０
℃の温度で実施されるので、高温下での濡れ性がより重
要となる。Usually, sulfuric acid is often mixed with hydrogen peroxide to be used for cleaning silicon wafers, and the wettability in this system becomes a particular problem. Also, this cleaning is 100 to 130.
Since it is carried out at a temperature of ° C, wettability at high temperatures becomes more important.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、前記
の背景に鑑み、既に提案されている界面活性剤を配合し
た硫酸組成物に比し、更にシリコンウエハに対する接触
角が小さく濡れ性の優れた硫酸組成物を提供することに
ある。In view of the above background, an object of the present invention is to provide a silicon wafer having a smaller contact angle and a higher wettability than a sulfuric acid composition containing a surfactant, which has already been proposed. An object is to provide an excellent sulfuric acid composition.
【０００６】[0006]
【課題を解決するための手段】このような問題点を解決
するために我々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出来
ることを見出し本発明を完成した。すなわち、本発明の
要旨は一般式（Ｉ）[Means for Solving the Problems] As a result of various studies to solve such problems, it was found that the above object can be achieved by using a specific fluorine-based surfactant. Completed the invention. That is, the gist of the present invention is the general formula (I)
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】（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、Ｒ3 、Ｒ4 は炭素数１〜４の低級アルキ
ル基または、ベンゼン環を１つもつアリール基もしくは
アラルキル基を表わし、ｍは１〜１０の整数を、ｎは１
〜５の整数を表わす。）で示されるフルオロアルキルス
ルフォンアミド化合物よりなるフッ素系界面活性剤を配
合することを特徴とする硫酸組成物に存する。(In the formula, R 1 is a fluoroalkyl group having 3 or more carbon atoms, R 2 is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms, and R 3 and R 4 are lower alkyl groups having 1 to 4 carbon atoms. Represents an alkyl group, an aryl group having one benzene ring or an aralkyl group, m is an integer of 1 to 10 and n is 1
Represents an integer of ~ 5. ) A sulfuric acid composition comprising a fluorosurfactant composed of a fluoroalkyl sulfonamide compound.
【０００９】以下本発明を詳細に説明する。上式中、Ｒ
1 のフルオロアルキル基としては、通常、炭素数３以
上、好ましくは炭素数５〜２０のアルキル基のフッ素置
換物が挙げられ、そのフッ素置換率は５０％以上、好ま
しくは８０％以上である。Ｒ2としては水素原子または
炭素数１〜４のアルキル基が挙げられる。Ｒ3 、Ｒ4 と
しては炭素数１〜４のアルキル基または、ベンゼン環を
１つ持つアリール基、もしくはアラルキル基が挙げられ
る。また、これらのアルキル基は直鎖でも分岐鎖でもよ
い。また、アリール基としては、例えば、低級アルキル
基、ハロゲン原子、ヒドロキシル基などで置換されても
よいフェニル基が挙げられ、アラルキル基としては、通
常、ベンジル基またはフェネチル基が挙げられる。ｍは
通常１〜１０、好ましくは１〜５の整数である。また、
ｎは通常１〜５、好ましくは１〜３の整数である。The present invention will be described in detail below. In the above formula, R
The fluoroalkyl group of 1 is usually a fluorine-substituted product of an alkyl group having 3 or more carbon atoms, preferably 5 to 20 carbon atoms, and the fluorine substitution rate is 50% or more, preferably 80% or more. Examples of R 2 include a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Examples of R 3 and R 4 include an alkyl group having 1 to 4 carbon atoms, an aryl group having one benzene ring, or an aralkyl group. Further, these alkyl groups may be linear or branched. Further, the aryl group includes, for example, a phenyl group which may be substituted with a lower alkyl group, a halogen atom, a hydroxyl group and the like, and the aralkyl group usually includes a benzyl group or a phenethyl group. m is usually an integer of 1 to 10, preferably 1 to 5. Also,
n is usually an integer of 1 to 5, preferably 1 to 3.
【００１０】本発明の硫酸組成物においては、上記一般
式に示されるフルオロアルキルスルフォンアミド化合物
を適当量添加し溶解させることを必須とするものであ
り、その添加量は、硫酸に対して０．００１〜０．１重
量％であり、より好ましい添加量は０．００５〜０．０
５重量％である。上記添加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。In the sulfuric acid composition of the present invention, it is essential that an appropriate amount of the fluoroalkyl sulfonamide compound represented by the above general formula is added and dissolved, and the addition amount is 0. 001 to 0.1% by weight, more preferably 0.005 to 0.0
It is 5% by weight. If the amount added is too small, the effect is not sufficient, and if the amount is too large, no further effect is obtained and it is meaningless.
【００１１】また、界面活性剤を配合する硫酸（水溶
液）は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６０重量％以上、好ましくは７０重量％以上の
ものが使用される。通常、硫酸組成物は過酸化水素と混
合され洗浄液とされるが、その場合の過酸化水素の混合
比率は硫酸に対して５〜３０重量％程度である。本発明
で用いられるフルオロアルキルスルフォンアミド化合物
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
果を発揮する。本発明の硫酸組成物は半導体製造工程で
の使用を目的とするものであるから、使用される硫酸、
界面活性剤等は高純度のものが使用される。Further, if the sulfuric acid (aqueous solution) containing the surfactant is too thin, the cleaning effect will not be sufficient, so 60% by weight or more, preferably 70% by weight or more is generally used. Usually, the sulfuric acid composition is mixed with hydrogen peroxide to form a cleaning liquid, and in this case, the mixing ratio of hydrogen peroxide is about 5 to 30% 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 performed 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. Since the sulfuric acid composition of the present invention is intended for use in the semiconductor manufacturing process, the sulfuric acid used,
A high-purity surfactant or the like is used.
【００１２】[0012]
【実施例】次に、具体例を挙げて本発明を更に詳しく説
明するが、本発明はその要旨を越えないかぎりは以下の
実施例により何ら制限を受けるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
【００１３】実施例−１〜４及び比較例−１〜２ ８９重量％硫酸に表１に示すフッ素系界面活性剤を０．
０１重量％添加した硫酸組成物の２２℃におけるベアシ
リコンに対する接触角を測定した。また、界面活性剤を
用いない硫酸、及び特開平２−２４０２８５記載の界面
活性剤を用いた硫酸組成物についても、同様に接触角を
測定した。なお、接触角の測定は以下に示す液滴法によ
った。Examples 1 to 4 and Comparative Examples 1 to 2 89% by weight of sulfuric acid was added with the fluorine-containing surfactants shown in Table 1 in an amount of 0.
The contact angle of bare sulfuric acid at 22 ° C. of the sulfuric acid composition added with 01 wt% was measured. In addition, the contact angle was similarly measured for sulfuric acid not using a surfactant and the sulfuric acid composition using a surfactant described in JP-A-2-240285. The contact angle was measured by the droplet method shown below.
【００１４】（接触角の測定法）シリコンウエハ上に測
定する液滴を作り、測角器のついた顕微鏡で読み取るも
ので、この際、接線の規定が難しいため液滴の頂点と液
滴と面との接点を結ぶ角度の２倍を接触角と見なした。
以下の例に於ても同じ。表１に使用した界面活性剤を、
表２に実験結果を示す。(Method of measuring contact angle) A droplet to be measured is formed on a silicon wafer and read by a microscope equipped with a goniometer. At this time, since it is difficult to define the tangent line, the apex of the droplet and the droplet are separated. Twice the angle connecting the contact points with the surface was considered the contact angle.
The same applies to the following examples. The surfactants used in Table 1 are
Table 2 shows the experimental results.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】実施例−５〜６及び比較例−３〜４ 実施例２〜３、比較例１〜２の硫酸組成物と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
成物について、実施例１と同様に２２℃におけるベアシ
リコンに対する接触角を測定した。結果を表３に示す。Examples-5 to 6 and Comparative Examples-3 to 4 The sulfuric acid compositions of Examples 2-3 and Comparative Examples 1-2 and 30% by weight.
The contact angle with respect to bare silicon at 22 ° C. was measured in the same manner as in Example 1 for the mixed composition in which hydrogen peroxide solution was mixed at a ratio of 4: 1 (volume ratio). The results are shown in Table 3.
【００１８】[0018]
【表３】 [Table 3]
【００１９】実施例−７〜８及び比較例−５ 実施例−５〜６、比較例４の混合組成物を１３０℃の温
度で２時間加熱処理したのち、これを冷却して、同様に
２２℃におけるベアシリコンに対する接触角を測定し
た。結果を表４に示す。Examples-7 to 8 and Comparative Example-5 The mixed compositions of Examples-5 to 6 and Comparative Example 4 were heat-treated at a temperature of 130 ° C. for 2 hours, cooled, and then cooled to 22 in the same manner. The contact angle to bare silicon at ° C was measured. The results are shown in Table 4.
【００２０】[0020]
【表４】 [Table 4]
【００２１】[0021]
【発明の効果】本発明の硫酸組成物は、シリコンウエハ
の洗浄剤とした場合、シリコンウエハに対する接触角が
小さく、濡れ性に優れ、その結果、良好な洗浄効果が発
揮される。また、表３、表４から判るように、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。INDUSTRIAL APPLICABILITY The sulfuric acid composition of the present invention, when used as a cleaning agent for silicon wafers, has a small contact angle with the silicon wafer and excellent wettability, and as a result, a good cleaning effect is exhibited. Further, as can be seen from Tables 3 and 4, the sulfuric acid composition of the present invention stably exists even in a high oxidizing atmosphere and at a high temperature, and therefore exhibits a good effect without deterioration even in an actual production line. be able to.
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、Ｒ3 、Ｒ4 は炭素数１〜４の低級アルキル基また
は、ベンゼン環を１つもつアリール基もしくはアラルキ
ル基を表わし、ｍは１〜１０の整数を、ｎは１〜５の整
数を表わす。）で示されるフルオロアルキルスルフォン
アミド化合物よりなるフッ素系界面活性剤を配合するこ
とを特徴とする硫酸組成物。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, R 3 and R 4 represent a lower alkyl group having 1 to 4 carbon atoms, an aryl group having one benzene ring or an aralkyl group, and m represents The integer of 1-10 and n represent the integer of 1-5. ) A sulfuric acid composition comprising a fluorosurfactant comprising a fluoroalkyl sulfonamide compound represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP517392A JPH05238705A (en) | 1992-01-14 | 1992-01-14 | Sulfuric acid composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP517392A JPH05238705A (en) | 1992-01-14 | 1992-01-14 | Sulfuric acid composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05238705A true JPH05238705A (en) | 1993-09-17 |
Family
ID=11603850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP517392A Pending JPH05238705A (en) | 1992-01-14 | 1992-01-14 | Sulfuric acid composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05238705A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106350296A (en) * | 2016-08-25 | 2017-01-25 | 大连奥首科技有限公司 | High-efficiency environment-friendly LED chip cleaning agent and application method |
-
1992
- 1992-01-14 JP JP517392A patent/JPH05238705A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN106350296A (en) * | 2016-08-25 | 2017-01-25 | 大连奥首科技有限公司 | High-efficiency environment-friendly LED chip cleaning agent and application method |
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