JPH09286999A - Cleaning agent for silicon wafer - Google Patents
Cleaning agent for silicon waferInfo
- Publication number
- JPH09286999A JPH09286999A JP12077696A JP12077696A JPH09286999A JP H09286999 A JPH09286999 A JP H09286999A JP 12077696 A JP12077696 A JP 12077696A JP 12077696 A JP12077696 A JP 12077696A JP H09286999 A JPH09286999 A JP H09286999A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid
- cleaning
- phosphonic acid
- silicon wafer
- 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
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- Photosensitive Polymer And Photoresist Processing (AREA)
- Detergent Compositions (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の技術分野】本発明は半導体装置の製造の際に
用いるシリコンウェハの洗浄用組成物に関する。さらに
詳しく言えば、本発明はフルオロアルキルスルホンアミ
ド化合物及びホスホン酸化合物を含有せしめたシリコン
ウェハ洗浄用組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for cleaning a silicon wafer used in manufacturing a semiconductor device. More specifically, the present invention relates to a silicon wafer cleaning composition containing a fluoroalkyl sulfonamide compound and a phosphonic acid compound.
【０００２】[0002]
【背景技術】従来、半導体装置の製造工程において、シ
リコンウェハの洗浄液として、特に微粒子、レジストア
ッシング後の残渣の除去などを目的にアンモニア水に他
の薬品を添加した水溶液が多く用いられている。半導体
装置の高集積化に伴い、パターンの微細化、複雑化を余
儀なくされているが、そのことは同時にシリコンウェハ
上の微粒子、金属不純物等をより厳しく制限することが
必要とされる。アンモニア水と過酸化水素水と水を混合
した洗浄液は半導体製造業界においてはＳＣ−１洗浄液
と呼ばれ微粒子の除去を目的として広く用いられてい
る。このＳＣ−１洗浄液は１９７０年にＲＣＡ社のW．K
ern等によって提唱され、四半世紀の長きに渡り使用さ
れてきたが、いくつかの問題点が指摘されている。2. Description of the Related Art Conventionally, in a semiconductor device manufacturing process, an aqueous solution prepared by adding other chemicals to ammonia water is often used as a cleaning liquid for a silicon wafer, particularly for the purpose of removing fine particles and residues after resist ashing. With the high integration of semiconductor devices, it is inevitable to make patterns finer and more complicated, but at the same time, it is necessary to more strictly limit fine particles, metal impurities, etc. on a silicon wafer. A cleaning liquid obtained by mixing ammonia water, hydrogen peroxide water and water is called SC-1 cleaning liquid in the semiconductor manufacturing industry and is widely used for the purpose of removing fine particles. This SC-1 cleaning solution was developed by W. K
Proposed by ern et al. and used for a long quarter of a century, some problems have been pointed out.
【０００３】それは、（１）パーティクル除去能力が技
術の進歩した現状においては不十分であること、（２）
シリコン基板に対してエッチング作用を持つため基板表
面を荒らすこと、（３）遷移金属を中心とした金属不純
物をシリコンウェハ表面に吸着させ易いこと、などであ
る。That is, (1) the particle removing ability is insufficient in the present state of technological progress, and (2)
Since it has an etching action on the silicon substrate, the surface of the substrate is roughened, and (3) metal impurities centering on a transition metal are easily adsorbed on the surface of the silicon wafer.
【０００４】上記（１）（２）の問題点の解決策とし
て、本発明者らは、ＳＣ−１洗浄液にパーフルオロアル
キルスルホンアミド型のフッ素系界面活性剤を添加した
低表面張力アンモニア水組成物を提案した（特開平５−
２５１４１６号公報参照）。しかし、この洗浄液は、添
加した界面活性剤の作用による発泡が半導体装置の製造
工程において、その使用範囲を制限する可能性がある。As a solution to the problems (1) and (2), the present inventors have prepared a low surface tension ammonia water composition obtained by adding a perfluoroalkylsulfonamide type fluorosurfactant to an SC-1 cleaning solution. Proposal of a product
(See Japanese Patent No. 251416). However, foaming due to the action of the added surfactant may limit the range of use of this cleaning liquid in the manufacturing process of semiconductor devices.
【０００５】そこで、本発明者らは上記洗浄液の発泡の
原因を追及したところ、洗浄液中の過酸化水素がアンモ
ニア等の作用により分解した酸素が気泡発生の原因とな
っており、さらに添加した界面活性剤が一方で気泡を安
定化せしめているためであることを突き止めた。したが
って、洗浄液中の過酸化水素の分解を抑制すれば発泡の
問題を解決することが可能であるという考えに至ったの
である。Then, the inventors of the present invention investigated the cause of the foaming of the cleaning liquid, and found that the oxygen decomposed by the hydrogen peroxide in the cleaning liquid by the action of ammonia or the like was the cause of the generation of bubbles, and the interface further added. It was discovered that the activator, on the one hand, was stabilizing the bubbles. Therefore, it came to the idea that it is possible to solve the problem of foaming by suppressing the decomposition of hydrogen peroxide in the cleaning liquid.
【０００６】本発明者らはこのような知見を基に鋭意研
究を重ねた結果、種々の化合物の中からホスホン酸系化
合物を併用することにより、洗浄液中の過酸化水素の分
解が抑制され、かつ前記ＳＣ−１洗浄液の上記（３）の
問題点を解決しうることを見いだした。すなわち、フロ
ロアルキルスルホンアミド型のフッ素系界面活性剤とホ
スホン酸化合物とを組み合わせて用いることにより、前
記ＳＣ−１洗浄液の有する（１）（２）（３）の問題点
と界面活性剤を用いることによる発泡の問題を一度に解
決することが可能となったのである。The present inventors have conducted extensive studies based on these findings, and as a result, by using a phosphonic acid compound from among various compounds in combination, decomposition of hydrogen peroxide in the cleaning liquid was suppressed, It was also found that the problem (3) of the SC-1 cleaning solution can be solved. That is, by using a fluoroalkylsulfonamide type fluorine-based surfactant in combination with a phosphonic acid compound, the problems (1), (2) and (3) of the SC-1 cleaning solution and the surfactant are used. It is now possible to solve the problem of foaming at once.
【０００７】[0007]
【発明の開示】本発明は、パーティクル除去能力に優
れ、シリコンウェハへの金属吸着を防止する性質を有
し、かつ低発泡性の洗浄用組成物に関するものであり、
特に、半導体装置の製造工程で使用される洗浄液として
好適な洗浄用組成物に関する。DISCLOSURE OF THE INVENTION The present invention relates to a cleaning composition having excellent ability to remove particles, having a property of preventing metal adsorption on a silicon wafer, and having a low foaming property,
In particular, the present invention relates to a cleaning composition suitable as a cleaning liquid used in the manufacturing process of semiconductor devices.
【０００８】すなわち、本発明は、下記一般式（Ｉ）で
表わされるフルオロアルキルスルホンアミド化合物より
なるフッ素系界面活性剤の少なくとも１種と、二つ以上
のホスホン酸基を持つ化合物及びアンモニアを含有せし
めたことを特徴とするシリコンウェハ洗浄用組成物を提
供するものである。That is, the present invention comprises at least one fluorosurfactant comprising a fluoroalkylsulfonamide compound represented by the following general formula (I), a compound having two or more phosphonic acid groups and ammonia. The present invention provides a composition for cleaning a silicon wafer, which is characterized by being soaked.
【０００９】[0009]
【化２】 （式中、Ｒ1はフルオロアルキル基を表わし、Ｒ2は水素
原子又は低級アルキル基を表わし、Ｘは−ＣＨ2ＣＯＯ
−又は−(ＣＨ2ＣＨ2Ｏ)n−を表わし、ｎは２〜１０の
整数を表わす）。Embedded image (In the formula, R 1 represents a fluoroalkyl group, R 2 represents a hydrogen atom or a lower alkyl group, and X represents —CH 2 COO.
- or - (CH 2 CH 2 O) n - represents, n represents an integer of 2 to 10).
【００１０】以下に本発明を詳細に説明する。本発明の
組成物において使用される一般式（Ｉ）で表わされるフ
ルオロアルキルスルホンアミド化合物は、フッ素系界面
活性剤として市販されている公知物質であり、容易に入
手可能なものである。特に、好適な化合物は一般式
（Ｉ）において、Ｒ1がＣ8Ｆ17、Ｒ2がＣ3Ｈ7、Ｘが−
(ＣＨ2ＣＨ2Ｏ)11−である化合物（化合物Ａという）、
およびＲ1がＣ8Ｆ17、Ｒ2がＣ3Ｈ7、Ｘが−ＣＨ2ＣＯＯ
−である化合物（化合物Ｂという）である。又、これら
の化合物にはその化学構造中に半導体装置の製造におい
て有害とされるナトリウム、カリウム、カルシウム等の
金属元素を含まないので何等悪影響を及ぼすことがな
い。Hereinafter, the present invention will be described in detail. The fluoroalkyl sulfonamide compound represented by the general formula (I) used in the composition of the present invention is a known substance commercially available as a fluorine-based surfactant and is easily available. Particularly preferable compounds are those represented by the general formula (I) in which R 1 is C 8 F 17 , R 2 is C 3 H 7 and X is-.
A compound which is (CH 2 CH 2 O) 11 − (referred to as compound A),
And R 1 is C 8 F 17 , R 2 is C 3 H 7 , and X is —CH 2 COO.
A compound that is − (referred to as compound B). In addition, since these compounds do not contain metal elements such as sodium, potassium and calcium, which are harmful in the manufacture of semiconductor devices, in their chemical structures, they have no adverse effect.
【００１１】これらのフルオロアルキルスルホン酸アミ
ド化合物は単独もしくは２種以上をアンモニア水に溶解
して用いられ、その添加量はアンモニア水に対して０.
００１〜０.３重量％であり、特に好ましくは０.００５
〜０.０２重量％である。上記添加量の下限値以下では
界面活性剤としての充分な効果は得られず、一方上限値
以上を添加してもそれ以上の効果は期待し得ない。These fluoroalkyl sulfonic acid amide compounds are used alone or as a mixture of two or more thereof dissolved in ammonia water, and the addition amount thereof is 0.
001 to 0.3% by weight, particularly preferably 0.005
~ 0.02% by weight. If the addition amount is less than the lower limit value, a sufficient effect as a surfactant cannot be obtained, while if the addition amount is more than the upper limit value, no further effect can be expected.
【００１２】本発明に使用されるホスホン酸化合物とし
ては、Ｎ,Ｎ,Ｎ′,Ｎ′−エチレンジアミンテトラ（メ
チレンホスホン酸）、１−ヒドロキシエチリデン−１,
１−ジホスホン酸、ニトリロトリス（メチレンホスホン
酸）、グリシン−Ｎ,Ｎ−ビスメチレンホスホン酸、フ
イチン酸、メチルジホスホン酸、エチリデンジホスホン
酸、エチレンジアミンビス（メチレンホスホン酸）、ジ
エチレントリアミンペンタ（メチレンホスホン酸）、ト
リエチレンテトラミンヘキサ（メチレンホスホン酸）、
プロピレンジアミンテトラ（メチレンホスホン酸）、ヘ
キサメチレンジアミンテトラ（メチレンホスホン酸）、
グリコールエーテルジアミンテトラ（メチレンホスホン
酸）、ヘキセンジアミンテトラキス（メチレンホスホン
酸）、トランス−１,２−シクロヘキサンジアミンテト
ラ（メチレンホスホン酸）、トリアミノトリエチルアミ
ンヘキサ（メチレンホスホン酸）、テトラエチレンペン
タミンヘプタ（メチレンホスホン酸）、エチルアミノビ
ス（メチレンホスホン酸）、ドデシルアミノビス（メチ
レンホスホン酸）、１−ヒドロキシプロピリデン−１,
１−ジホスホン酸、１−ヒドロキシブチリデン−１,１
−ジホスホン酸等が挙げられる。特に好ましくはＮ,Ｎ,
Ｎ′,Ｎ′−エチレンジアミンテトラ（メチレンホスホ
ン酸）、１−ヒドロキシエチリデン−１,１−ジホスホ
ン酸、ニトリロトリス（メチレンホスホン酸）、グリシ
ン−Ｎ,Ｎ−ビスメチレンホスホン酸等である。Examples of the phosphonic acid compound used in the present invention include N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethylidene-1,
1-diphosphonic acid, nitrilotris (methylenephosphonic acid), glycine-N, N-bismethylenephosphonic acid, phytic acid, methyldiphosphonic acid, ethylidenediphosphonic acid, ethylenediaminebis (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid) Acid), triethylenetetramine hexa (methylenephosphonic acid),
Propylenediaminetetra (methylenephosphonic acid), hexamethylenediaminetetra (methylenephosphonic acid),
Glycol ether diamine tetra (methylene phosphonic acid), hexene diamine tetrakis (methylene phosphonic acid), trans-1,2-cyclohexane diamine tetra (methylene phosphonic acid), triaminotriethylamine hexa (methylene phosphonic acid), tetraethylene pentamine hepta ( Methylenephosphonic acid), ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), 1-hydroxypropylidene-1,
1-diphosphonic acid, 1-hydroxybutylidene-1,1
-Diphosphonic acid etc. are mentioned. Particularly preferably N, N,
Examples thereof include N ', N'-ethylenediaminetetra (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), glycine-N, N-bismethylenephosphonic acid.
【００１３】ホスホン酸化合物も同様にアンモニア水に
溶解して用いられる。その添加量はアンモニア水に対し
て０.００００５〜０.０３重量％、特に好ましくは０.
０００５〜０.０１重量％である。The phosphonic acid compound is also used by dissolving it in aqueous ammonia. The amount added is 0.00005 to 0.03% by weight, and particularly preferably 0.05% by weight based on the ammonia water.
It is 0005 to 0.01% by weight.
【００１４】以下に本発明の実施例及び比較例を掲げ、
本発明をさらに詳細に説明するが、本発明はこれらの実
施例により制限されるものではない。The following are examples of the present invention and comparative examples.
The present invention will be described in more detail, but the present invention is not limited to these examples.
【００１５】〔発泡性試験〕 〔比較例１〕２９重量％アンモニア水５Ｋｇに化合物Ａ
および化合物Ｂをそれぞれ０.５ｇ溶解したアンモニア
水溶液と３０重量％濃度過酸化水素水及び水を１：１：
６の容量比で混合し洗浄液を調製した。この洗浄液の８
００mlを１リットルビーカーに入れ、これを５０℃に保
ったのち３０分後に発生した泡の高さを測定した。[Foamability Test] [Comparative Example 1] Compound A was added to 5 kg of 29% by weight aqueous ammonia.
And 0.5 g of compound B, respectively, and an aqueous ammonia solution, 30% by weight hydrogen peroxide solution and water 1: 1:
A washing solution was prepared by mixing the mixture in a volume ratio of 6. 8 of this cleaning solution
00 ml was placed in a 1 liter beaker and kept at 50 ° C., and after 30 minutes, the height of bubbles generated was measured.
【００１６】〔比較例２〕比較例１に記載の洗浄液の液
温を８０℃とし、同様に泡の高さを測定した。Comparative Example 2 The washing liquid described in Comparative Example 1 was heated to 80 ° C. and the height of bubbles was measured in the same manner.
【００１７】〔比較例３〕本比較例においては、化合物
Ａのみを０.５ｇ用いて比較例１に記載の処方に準じて
洗浄液を調製し、同様にこの洗浄液の８０℃、３０分後
に発生した泡の高さを測定した。[Comparative Example 3] In this comparative example, 0.5 g of Compound A alone was used to prepare a cleaning solution according to the formulation described in Comparative Example 1, and this cleaning solution was also generated at 80 ° C. for 30 minutes. The height of the foam formed was measured.
【００１８】〔実施例１〕２９重量％アンモニア水５Ｋ
ｇに化合物Ａおよび化合物Ｂをそれぞれ０.５ｇ、およ
びＮ,Ｎ,Ｎ′,Ｎ′−エチレンジアミンテトラ（メチレ
ンホスホン酸）を０.０２５ｇ溶解したアンモニア水溶
液と過酸化水素水及び水との比較例１の同容量比で調製
した洗浄液を比較例１と同様にして液温５０℃、３０分
後における泡の高さを測定した。[Example 1] 29% by weight aqueous ammonia 5K
Comparative Example of Aqueous Ammonia Solution in which 0.5 g of Compound A and 0.5 g of Compound B and 0.025 g of N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid) are dissolved in hydrogen peroxide and water. In the same manner as in Comparative Example 1, the cleaning liquid prepared at the same volume ratio of 1 was measured for the foam height after 30 minutes at a liquid temperature of 50 ° C.
【００１９】〔実施例２〕ホスホン酸化合物を、ニトリ
ロトリス（メチレンホスホン酸）０.５ｇに代えたほか
は実施例１と同様にして調製した洗浄液について、発生
した泡の高さを測定した。Example 2 With respect to the cleaning liquid prepared in the same manner as in Example 1 except that the phosphonic acid compound was changed to 0.5 g of nitrilotris (methylenephosphonic acid), the height of bubbles generated was measured.
【００２０】〔実施例３〕フルオロアルキルスルホンア
ミド化合物として化合物Ａのみを０.５ｇ用い、またホ
スホン酸化合物として、１−ヒドロキシエチリデン−
１,１−ジホスホン酸０.５ｇを用いたほかは実施例１と
同様にして調製した洗浄液について、発生した泡の高さ
を測定した。Example 3 0.5 g of Compound A alone was used as the fluoroalkyl sulfonamide compound, and 1-hydroxyethylidene- was used as the phosphonic acid compound.
The height of bubbles generated in the cleaning liquid prepared in the same manner as in Example 1 except that 0.5 g of 1,1-diphosphonic acid was used was measured.
【００２１】〔実施例４〕ホスホン酸化合物を、グリシ
ン−Ｎ,Ｎ−ビスメチレンホスホン酸０.５ｇとしたほか
は実施例１と同様にして調製した洗浄液について、発生
した泡の高さを測定した。Example 4 With respect to the cleaning liquid prepared in the same manner as in Example 1 except that the phosphonic acid compound was 0.5 g of glycine-N, N-bismethylenephosphonic acid, the height of bubbles generated was measured. did.
【００２２】〔実施例５〕フルオロアルキルスルホンア
ミド化合物として化合物Ａのみ０.５ｇを用い、またホ
スホン酸化合物として、Ｎ,Ｎ,Ｎ′,Ｎ′−エチレンジ
アミンテトラ（メチレンホスホン酸）を０.０２５ｇ用
いたほかは実施例１に準じて調製した洗浄液について、
液温８０℃、３０分後における発生した泡の高さを測定
した。EXAMPLE 5 Only 0.5 g of Compound A was used as the fluoroalkyl sulfonamide compound, and 0.025 g of N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid) was used as the phosphonic acid compound. For the cleaning liquid prepared in accordance with Example 1 except that it was used,
The height of bubbles generated after 30 minutes at a liquid temperature of 80 ° C. was measured.
【００２３】〔実施例６〕Ｎ,Ｎ,Ｎ′,Ｎ′−エチレン
ジアミンテトラ（メチレンホスホン酸）の使用量を０.
０５ｇとしたほかは、実施例１と同じ処方で調製した洗
浄液について、液温８０℃、３０分後に発生した泡の高
さを測定した。以上、比較例１〜３および実施例１〜６
の測定結果を表１に示す。Example 6 The amount of N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid) used was adjusted to 0.
With respect to the cleaning liquid prepared by the same formulation as in Example 1 except that the amount was 05 g, the height of bubbles generated after 30 minutes at a liquid temperature of 80 ° C. was measured. As described above, Comparative Examples 1 to 3 and Examples 1 to 6
The measurement results of are shown in Table 1.
【００２４】[0024]
【表１】 [Table 1]
【００２５】〔パーティクル除去能力試験〕 〔比較例４〕ベアシリコンウェハ（４インチφ）をポリ
スチレンラテックス（日本合成ゴム製ＳＴＡＤＥＸ、粒
径０.３０９μｍ）を分散させた希ふっ酸液に浸漬し
て、ポリスチレンラテックスをシリコンウェハ表面に付
着させた。このウェハを２９重量％アンモニア水と３０
重量％過酸化水素水及び水を容量比１：１：６で混合
し、５０℃に調整したＳＣ−１洗浄液で１０分間洗浄
し、ポリスチレンラテックスの除去を行った。洗浄後ウ
ェハを超純水で５分水洗し、スピンドライによって乾燥
した。その後、表面検査装置（Surfscan 4500）により
ウェハ表面に残留するパーティクルを測定した。[Particle Removal Capability Test] [Comparative Example 4] A bare silicon wafer (4 inches φ) was dipped in a dilute hydrofluoric acid solution in which polystyrene latex (STADEX made by Japan Synthetic Rubber, particle size 0.309 μm) was dispersed. , Polystyrene latex was attached to the surface of the silicon wafer. This wafer was treated with 29 wt% ammonia water and 30
A weight% hydrogen peroxide solution and water were mixed at a volume ratio of 1: 1: 6 and washed with an SC-1 cleaning solution adjusted to 50 ° C. for 10 minutes to remove the polystyrene latex. After cleaning, the wafer was rinsed with ultrapure water for 5 minutes and dried by spin drying. After that, the particles remaining on the wafer surface were measured by a surface inspection device (Surfscan 4500).
【００２６】〔比較例５〕比較例４において用いたＳＣ
−１液にかえて、２９重量％アンモニア水５ＫｇにＮ,
Ｎ,Ｎ′,Ｎ′−エチレンジアミンテトラ（メチレンホス
ホン酸）を０.０２５ｇ溶解した洗浄液を用いて比較例
４と同様の方法によりパーティクルを測定した。Comparative Example 5 SC used in Comparative Example 4
-1 liquid was replaced with 29 wt% ammonia water 5 Kg N,
Particles were measured in the same manner as in Comparative Example 4 using a cleaning solution in which 0.025 g of N, N ', N'-ethylenediaminetetra (methylenephosphonic acid) was dissolved.
【００２７】〔実施例７〕比較例４において用いたＳＣ
−１液にかえて、２９重量％アンモニア水５Ｋｇに化合
物Ａおよび化合物Ｂをそれぞれ０.５ｇ、およびＮ,Ｎ,
Ｎ′,Ｎ′−エチレンジアミンテトラ（メチレンホスホ
ン酸）を０.０２５ｇ溶解した洗浄液を用いて比較例４
と同様の方法によりパーティクルを測定した。以上比較
例４、５及び実施例７の試験の結果を表２に示す。Example 7 SC used in Comparative Example 4
-1 liquid, 0.5 g of Compound A and Compound B were added to 5 kg of 29% by weight ammonia water, and N, N,
Comparative Example 4 using a cleaning solution in which 0.025 g of N ', N'-ethylenediaminetetra (methylenephosphonic acid) was dissolved.
Particles were measured by the same method as in. Table 2 shows the results of the tests of Comparative Examples 4 and 5 and Example 7 described above.
【００２８】[0028]
【表２】 [Table 2]
【００２９】〔鉄の吸着防止能力試験〕 〔比較例６〕２９重量％アンモニア水と３０重量％過酸
化水素水及び水を容量比１：１：６で混合し、ＳＣ−１
洗浄液を調製した。調製したＳＣ−１液を１ｐｐｂの鉄
で汚染し、この汚染したＳＣ−１洗浄液に４インチφベ
アシリコンウェハを５０℃で１０分間浸漬した。ウェハ
を取り出し超純水で５分水洗しのち、スピンドライ法に
よって乾燥した。その後、ウェハ表面に吸着されている
鉄をふっ酸で回収し、回収された鉄を黒鉛炉原子吸光装
置を用いて定量し、ウェハ表面の鉄の吸着量を算出し
た。[Iron adsorption preventing ability test] [Comparative Example 6] 29% by weight aqueous ammonia, 30% by weight aqueous hydrogen peroxide and water were mixed at a volume ratio of 1: 1: 6 and SC-1.
A washing solution was prepared. The prepared SC-1 solution was contaminated with 1 ppb of iron, and a 4-inch φ bare silicon wafer was immersed in this contaminated SC-1 cleaning solution at 50 ° C. for 10 minutes. The wafer was taken out, washed with ultrapure water for 5 minutes, and then dried by a spin dry method. Then, the iron adsorbed on the wafer surface was recovered with hydrofluoric acid, and the recovered iron was quantified using a graphite furnace atomic absorption spectrometer, and the adsorption amount of iron on the wafer surface was calculated.
【００３０】〔実施例８〕２９重量％アンモニア水５Ｋ
ｇに化合物Ａおよび化合物Ｂをそれぞれ０.５ｇ、およ
びＮ,Ｎ,Ｎ′,Ｎ′−エチレンジアミンテトラ（メチレ
ンホスホン酸）を０.０２５ｇ溶解し洗浄液を調製し
た。この洗浄液を１ｐｐｂの鉄で汚染後、比較例６と同
様にしてシリコンウェハ表面への鉄の吸着量を定量し
た。比較例６および実施例８の試験の結果を表３に示
す。Example 8 29% by weight aqueous ammonia 5K
0.5 g of each of Compound A and Compound B and 0.025 g of N, N, N ', N'-ethylenediaminetetra (methylenephosphonic acid) were dissolved in g to prepare a washing solution. After the cleaning liquid was contaminated with 1 ppb iron, the amount of iron adsorbed on the surface of the silicon wafer was quantified in the same manner as in Comparative Example 6. The results of the tests of Comparative Example 6 and Example 8 are shown in Table 3.
【００３１】[0031]
【表３】 [Table 3]
【００３２】以上、本発明に係るシリコンウェハ洗浄用
組成物は、表１〜表３に示した試験の結果から明らかな
ように、発泡性、パーティクル除去能力および鉄の吸着
防止能力のいずれにおいても、従来のＳＣ−１液および
ＳＣ−１液に界面活性剤が添加された洗浄液に比べて格
段に優れた特性を有することが認められた。従って、本
発明に係る洗浄液は、半導体装置、特に高集積化半導体
装置の製造における洗浄液として利用し得るものであ
り、極めてその利用価値は高い。As is clear from the results of the tests shown in Tables 1 to 3, the composition for cleaning a silicon wafer according to the present invention has any of foamability, particle removing ability and iron adsorption preventing ability. It was found that the SC-1 solution had significantly better properties than the conventional SC-1 solution and the cleaning solution prepared by adding a surfactant to the SC-1 solution. Therefore, the cleaning liquid according to the present invention can be used as a cleaning liquid in the manufacture of semiconductor devices, particularly highly integrated semiconductor devices, and its utility value is extremely high.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ１１Ｄ 3:36 7:06） (72)発明者 森 清人 埼玉県草加市稲荷１−７−１ 関東化学株 式会社中央研究所内 (72)発明者 森川 文博 富山県婦負郡婦中町笹倉635 日産化学工 業株式会社富山工場内 (72)発明者 角田 誠 富山県婦負郡婦中町笹倉635 日産化学工 業株式会社富山工場内Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C11D 3:36 7:06) (72) Inventor Kiyoto Mori 1-7-1 Inari, Soka City, Saitama Kanto Kagaku Incorporated company Central Research Laboratory (72) Inventor Fumihiro Morikawa 635 Sasakura, Samurai-machi, Tozagi-gun, Toyama Prefecture Nissan Chemical Industry Co., Ltd.Toyama Plant (72) Inventor Makoto Kakuda 635 Sasakukura, Nakama-cho, Toyama Prefecture Nissan Chemical Industry Co., Ltd. Company Toyama Factory
Claims (5)
アルキルスルホンアミド化合物よりなるフッ素系界面活
性剤の少なくとも１種と、二つ以上のホスホン酸基を持
つ化合物及びアンモニアを含有せしめたことを特徴とす
るシリコンウェハ洗浄用組成物。 【化１】 （式中、Ｒ1はフルオロアルキル基を表わし、Ｒ2は水素
原子又は低級アルキル基を表わし、Ｘは−ＣＨ2ＣＯＯ
−又は−(ＣＨ2ＣＨ2Ｏ)n−を表わし、ｎは２〜１０の
整数を表わす）。1. A method comprising at least one fluorosurfactant comprising a fluoroalkylsulfonamide compound represented by the following general formula (I), a compound having two or more phosphonic acid groups and ammonia. A characteristic composition for cleaning a silicon wafer. Embedded image (In the formula, R 1 represents a fluoroalkyl group, R 2 represents a hydrogen atom or a lower alkyl group, and X represents —CH 2 COO.
- or - (CH 2 CH 2 O) n - represents, n represents an integer of 2 to 10).
化合物の含有量が０.００１〜０.３重量％である請求項
１に記載の洗浄用組成物。2. The cleaning composition according to claim 1, wherein the content of the fluoroalkylsulfonamide compound is 0.001 to 0.3% by weight.
００００５〜０.０３重量％である請求項１に記載の洗
浄用組成物。3. The content of the phosphonic acid compound is 0.
The cleaning composition according to claim 1, which is from 00005 to 0.03% by weight.
のである請求項１ないし請求項３に記載の洗浄用組成
物。4. The cleaning composition according to claim 1, wherein the composition is one to which hydrogen peroxide is added.
Ｎ′−エチレンジアミンテトラ（メチレンホスホン
酸）、ニトリロトリス（メチレンホスホン酸）、１−ヒ
ドロキシエチリデン−１,１−ジホスホン酸又はグリシ
ン−Ｎ,Ｎ−ビスメチレンホスホン酸である請求項１な
いし請求項４に記載の洗浄用組成物。5. The phosphonic acid compound is N, N, N ',
N'-ethylenediaminetetra (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), 1-hydroxyethylidene-1,1-diphosphonic acid or glycine-N, N-bismethylenephosphonic acid. The cleaning composition as described in 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12077696A JPH09286999A (en) | 1996-04-19 | 1996-04-19 | Cleaning agent for silicon wafer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12077696A JPH09286999A (en) | 1996-04-19 | 1996-04-19 | Cleaning agent for silicon wafer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09286999A true JPH09286999A (en) | 1997-11-04 |
Family
ID=14794728
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12077696A Pending JPH09286999A (en) | 1996-04-19 | 1996-04-19 | Cleaning agent for silicon wafer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09286999A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000030162A1 (en) * | 1998-11-12 | 2000-05-25 | Sharp Kabushiki Kaisha | Novel detergent and cleaning method using it |
| US6277749B1 (en) * | 1998-09-10 | 2001-08-21 | Hiatchi, Ltd. | Method of manufacturing a semiconductor integrated circuit device |
| US6277203B1 (en) | 1998-09-29 | 2001-08-21 | Lam Research Corporation | Method and apparatus for cleaning low K dielectric and metal wafer surfaces |
| JP2007526944A (en) * | 2004-03-03 | 2007-09-20 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| US8268186B2 (en) | 2009-10-15 | 2012-09-18 | E. I. Du Pont De Nemours And Company | Fluorinated amphoteric surfactants |
| JP2013119579A (en) * | 2011-12-06 | 2013-06-17 | Kanto Chem Co Inc | Cleaning liquid composition for electronic device |
-
1996
- 1996-04-19 JP JP12077696A patent/JPH09286999A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6277749B1 (en) * | 1998-09-10 | 2001-08-21 | Hiatchi, Ltd. | Method of manufacturing a semiconductor integrated circuit device |
| US6774047B2 (en) | 1998-09-10 | 2004-08-10 | Renesas Technology Corp. | Method of manufacturing a semiconductor integrated circuit device |
| US6794305B2 (en) | 1998-09-10 | 2004-09-21 | Renesas Technology Corp. | Method of manufacturing a semiconductor integrated circuit device |
| US6277203B1 (en) | 1998-09-29 | 2001-08-21 | Lam Research Corporation | Method and apparatus for cleaning low K dielectric and metal wafer surfaces |
| WO2000030162A1 (en) * | 1998-11-12 | 2000-05-25 | Sharp Kabushiki Kaisha | Novel detergent and cleaning method using it |
| JP2007526944A (en) * | 2004-03-03 | 2007-09-20 | スリーエム イノベイティブ プロパティズ カンパニー | Fluorinated sulfonamide surfactants for aqueous cleaning solutions |
| US8268186B2 (en) | 2009-10-15 | 2012-09-18 | E. I. Du Pont De Nemours And Company | Fluorinated amphoteric surfactants |
| JP2013119579A (en) * | 2011-12-06 | 2013-06-17 | Kanto Chem Co Inc | Cleaning liquid composition for electronic device |
| US9334470B2 (en) | 2011-12-06 | 2016-05-10 | Kanto Kagaku Kabushiki Kaisha | Cleaning liquid composition for electronic device |
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