JP2000031132A - Diluting and mixing method for buffered hydrofluoric acid - Google Patents
Diluting and mixing method for buffered hydrofluoric acidInfo
- Publication number
- JP2000031132A JP2000031132A JP10198442A JP19844298A JP2000031132A JP 2000031132 A JP2000031132 A JP 2000031132A JP 10198442 A JP10198442 A JP 10198442A JP 19844298 A JP19844298 A JP 19844298A JP 2000031132 A JP2000031132 A JP 2000031132A
- Authority
- JP
- Japan
- Prior art keywords
- hydrofluoric acid
- buffered hydrofluoric
- etching rate
- diluting
- weight
- 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.)
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- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、バッファードフッ
酸の希釈混合方法、希釈混合されたバッファードフッ
酸、基板の処理方法、該方法で処理された基板及び希釈
混合装置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for diluting and mixing buffered hydrofluoric acid, a method for treating buffered hydrofluoric acid diluted and mixed, a substrate, a substrate processed by the method, and a diluting / mixing apparatus.
【０００２】[0002]
【従来の技術及びその課題】従来、バッファードフッ酸
はＨＦ（５０重量％）とＮＨ4Ｆ（４０重量％）を所望
のエッチングレートになるように適当な割合で混合して
調製されていた。数多くの異なるエッチングレートを有
するバッファードフッ酸が必要とされる半導体製造用途
では、多数のエッチングレート（例えば８０〜１５０ｎ
ｍ／ｍｉｎのものが１種類；１０〜５０ｎｍ／ｍｉｎの
ものが１〜２種類；０．１〜０．５ｎｍ／ｍｉｎのもの
が１種類）を有するバッファードフッ酸を調製する必要
があり、煩雑であった。2. Description of the Related Art Conventionally, buffered hydrofluoric acid has been prepared by mixing HF (50% by weight) and NH 4 F (40% by weight) in an appropriate ratio so as to obtain a desired etching rate. . In semiconductor manufacturing applications where buffered hydrofluoric acid having many different etching rates is required, many etching rates (eg, 80-150 n) are used.
buffered hydrofluoric acid having one m / min; one or two at 10-50 nm / min; and one at 0.1-0.5 nm / min). It was complicated.
【０００３】また、フッ化水素とフッ化アンモニウムを
含む廃液が多量に発生する問題があった。Further, there is a problem that a large amount of waste liquid containing hydrogen fluoride and ammonium fluoride is generated.
【０００４】本発明は、所望のエッチングレートを有す
るバッファードフッ酸を容易に製造できる方法を提供
し、該希釈バッファードフッ酸を用いて基板をエッチン
グないし洗浄する方法、エッチングないし洗浄処理され
た基板、およびバッファードフッ酸の希釈装置に関す
る。The present invention provides a method for easily producing a buffered hydrofluoric acid having a desired etching rate, a method for etching or cleaning a substrate using the diluted buffered hydrofluoric acid, and a method for etching or cleaning a substrate. The present invention relates to a substrate and an apparatus for diluting buffered hydrofluoric acid.
【０００５】[0005]
【課題を解決するための手段】本発明は、以下の項１〜
項７に関する。Means for Solving the Problems The present invention provides the following items 1 to
Regarding item 7.
【０００６】項１． フッ化水素とフッ化アンモニウム
を含む水溶液であって、フッ化水素が２．５重量％程度
以上の高エッチングレート・バッファードフッ酸を水で
希釈して、所定のエッチングレートのバッファードフッ
酸を得ることを特徴とするバッファードフッ酸の希釈混
合方法。Item 1. An aqueous solution containing hydrogen fluoride and ammonium fluoride, wherein buffered hydrofluoric acid having a high etching rate of about 2.5% by weight or more is diluted with water to obtain a buffered hydrofluoric acid having a predetermined etching rate. And a method for diluting and mixing buffered hydrofluoric acid.
【０００７】項２． 希釈後のバッファードフッ酸が、
０．００００１〜５重量％程度の界面活性剤を含むよう
に、界面活性剤を添加する工程をさらに含む項１に記載
の方法。Item 2. Buffered hydrofluoric acid after dilution
Item 1. The method according to Item 1, further comprising a step of adding a surfactant so as to contain about 0.00001 to 5% by weight of the surfactant.
【０００８】項３． 高エッチングレート・バッファー
ドフッ酸中のフッ化水素濃度が ２．５〜１５重量％程
度、バッファードフッ酸のｐＨが３以上である項１また
は２に記載の方法。Item 3. Item 3. The method according to Item 1 or 2, wherein the hydrogen fluoride concentration in the high etching rate buffered hydrofluoric acid is about 2.5 to 15% by weight, and the pH of the buffered hydrofluoric acid is 3 or more.
【０００９】項４． 項１の方法により得られたバッフ
ァードフッ酸。Item 4. Item 4. A buffered hydrofluoric acid obtained by the method according to Item 1.
【００１０】項５． 項２または３に記載のバッファー
ドフッ酸で基板を処理することを特徴とする基板の処理
方法。Item 5. Item 4. A method for treating a substrate, comprising treating the substrate with the buffered hydrofluoric acid according to Item 2 or 3.
【００１１】項６． 項４に記載の方法で得られた基
板。Item 6. Item 6. A substrate obtained by the method according to item 4.
【００１２】項７． フッ化水素が２．５重量％程度以
上の高エッチングレート・バッファードフッ酸の供給手
段、水供給手段、高エッチングレート・バッファードフ
ッ酸及び水が供給される複数の混合用容器を備えたバッ
ファードフッ酸の希釈混合装置。Item 7. A high etching rate buffered hydrofluoric acid supply means containing hydrogen fluoride of about 2.5% by weight or more; a water supply means; a plurality of mixing vessels to which the high etching rate buffered hydrofluoric acid and water are supplied; Buffered hydrofluoric acid dilution mixer.
【００１３】[0013]
【発明の実施の形態】本発明において、希釈工程に供さ
れる高エッチングレート・バッファードフッ酸のフッ化
水素酸の濃度は、２．５重量％程度以上、通常３〜１５
重量％程度、好ましくは６〜１５重量％程度である。DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, the concentration of hydrofluoric acid in a high etching rate buffered hydrofluoric acid to be subjected to a dilution step is about 2.5% by weight or more, usually 3 to 15%.
%, Preferably about 6 to 15% by weight.
【００１４】高エッチングレート・バッファードフッ酸
のｐＨは通常３以上、好ましくは３．５以上である。The pH of the high etching rate buffered hydrofluoric acid is usually 3 or more, preferably 3.5 or more.
【００１５】希釈前後のｐＨの変動は、１．０程度以
内、好ましくは０．９程度以内、より好ましくは０．８
程度以内、さらに好ましくは０．７程度以内、最も好ま
しくは０．６程度以内である。The fluctuation of pH before and after dilution is within about 1.0, preferably within about 0.9, more preferably within 0.8.
Within about, more preferably within about 0.7, and most preferably within about 0.6.
【００１６】高エッチングレート・バッファードフッ酸
のエッチングレートは、４０ｎｍ／ｍｉｎ以上、好まし
くは８０ｎｍ／ｍｉｎ、より好ましくは１００ｎｍ／ｍ
ｉｎ以上である。The etching rate of the high etching rate buffered hydrofluoric acid is 40 nm / min or more, preferably 80 nm / min, more preferably 100 nm / m.
in or more.
【００１７】希釈後のバッファードフッ酸のエッチング
レートは、０．１〜１００ｎｍ／ｍｉｎ程度である。The etching rate of the buffered hydrofluoric acid after dilution is about 0.1 to 100 nm / min.
【００１８】界面活性剤の配合量は、０．００００１〜
５重量％程度、好ましくは０．００１〜０．１重量％程
度である。界面活性剤としては、カチオン界面活性剤
（１級アミン塩、２級アミン塩、３級アミン塩、４級ア
ンモニウム塩、アルキルピリジニウム塩など）、アニオ
ン界面活性剤（カルボン酸、スルホン酸、スルホン酸の
アルカリ金属塩、硫酸モノエステルのアルカリ金属塩な
ど）、ノニオン界面活性剤（ポリオキシエチレンアルキ
ルエーテル、ポリオキシエチレンアルキルフェノラー
ト、ショ糖脂肪酸エステル、脂肪族アルコール、モノグ
リセリドなど）のいずれを用いてもよい。本発明の方法
に従い、バッファードフッ酸を希釈した場合、界面活性
剤濃度も希釈されることになるので、界面活性剤は必要
に応じて所定の濃度になるように添加される。The amount of the surfactant is 0.00001 to
It is about 5% by weight, preferably about 0.001 to 0.1% by weight. Examples of the surfactant include cationic surfactants (primary amine salt, secondary amine salt, tertiary amine salt, quaternary ammonium salt, alkylpyridinium salt, etc.) and anionic surfactants (carboxylic acid, sulfonic acid, sulfonic acid) Nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl phenolate, sucrose fatty acid ester, aliphatic alcohol, monoglyceride, etc.) Is also good. When the buffered hydrofluoric acid is diluted according to the method of the present invention, the surfactant concentration is also diluted. Therefore, the surfactant is added to a predetermined concentration as necessary.
【００１９】基板としては、シリコン単結晶ウェハ、液
晶のガラス基板、ガリウム−砒素ウェハなどのウェハが
挙げられる。Examples of the substrate include a silicon single crystal wafer, a liquid crystal glass substrate, and a gallium-arsenic wafer.
【００２０】本発明の基板の処理方法は、エッチング処
理及び洗浄処理を包含する。The substrate processing method of the present invention includes an etching process and a cleaning process.
【００２１】エッチング処理は、レジストパターンを有
する基板をバッファードフッ酸に浸し、１５〜４０℃程
度の温度で０．５〜１０分間程度処理することにより行
うことができる。バッファードフッ酸のエッチングレー
トは通常０．１〜１５０ｎｍ／ｍｉｎ程度である。The etching process can be performed by immersing a substrate having a resist pattern in buffered hydrofluoric acid and treating at a temperature of about 15 to 40 ° C. for about 0.5 to 10 minutes. The etching rate of buffered hydrofluoric acid is usually about 0.1 to 150 nm / min.
【００２２】洗浄処理は、例えば微細加工されたウェ
ハ、半導体素子などの基板を１５〜４０℃程度の温度で
０．５〜１０分間程度処理することにより行うことがで
きる。バッファードフッ酸のエッチングレートは通常
０．１〜１５０ｎｍ／ｍｉｎ程度である。The cleaning process can be performed, for example, by treating a substrate such as a microfabricated wafer or a semiconductor device at a temperature of about 15 to 40 ° C. for about 0.5 to 10 minutes. The etching rate of buffered hydrofluoric acid is usually about 0.1 to 150 nm / min.
【００２３】本発明の希釈混合装置は、高エッチングレ
ート・バッファードフッ酸の貯蔵タンク（１）、水の貯
蔵タンク（２）、バッファードフッ酸の供給手段
（３）、水の供給手段（４）及び希釈混合槽（５）を備
えてなる。該装置は、バッファードフッ酸簡易な装置で
任意のエッチングレートのバッファードフッ酸が得られ
る。The dilution / mixing apparatus of the present invention comprises a high etching rate buffered hydrofluoric acid storage tank (1), a water storage tank (2), a buffered hydrofluoric acid supply means (3), and a water supply means ( 4) and a dilution mixing tank (5). This apparatus can obtain buffered hydrofluoric acid at an arbitrary etching rate with a simple apparatus of buffered hydrofluoric acid.
【００２４】なお、該希釈装置には、界面活性剤供給手
段をさらに設けてもよい。あるいは、希釈水に界面活性
剤を添加してもよい。The diluting device may be further provided with a surfactant supplying means. Alternatively, a surfactant may be added to the dilution water.
【００２５】[0025]
【発明の効果】本発明によれば、任意のエッチングレー
トのバッファードフッ酸を容易に得ることができる。According to the present invention, buffered hydrofluoric acid having an arbitrary etching rate can be easily obtained.
【００２６】[0026]
【実施例】以下、本発明を実施例および比較例を用いて
より詳細に説明する。The present invention will be described below in more detail with reference to examples and comparative examples.
【００２７】実施例１ ５０％ＨＦと４０％ＮＨ4Ｆを適宜混合して得られた、
表１に示す組成の３種の高エッチングレート・バッファ
ードフッ酸（ＢＨＦ１５、ＢＨＦ１７、ＢＨＦ１１５）
を調製し、水を用いて各々２倍、４倍、８倍希釈を行
い、各種エッチングレートを有する希釈バッファードフ
ッ酸を得た。Example 1 A mixture obtained by appropriately mixing 50% HF and 40% NH 4 F was obtained.
Three types of high etching rate buffered hydrofluoric acid (BHF15, BHF17, BHF115) having the compositions shown in Table 1
Was prepared, and diluted 2-, 4-, and 8-fold with water, respectively, to obtain diluted buffered hydrofluoric acid having various etching rates.
【００２８】エッチレートは、Rudolf Trsearch 社 Aut
o EL-III エリプリメータを用いてエッチング前後の膜
厚を測定することで行った。ｐＨは比色式ｐＨ試験紙(P
EHANON, Macherey-Nagel社製）を用いて測定した。The etch rate is calculated by Rudolf Trsearch Aut.
o The measurement was performed by measuring the film thickness before and after etching using an EL-III ellipsometer. The pH is measured using a colorimetric pH test paper (P
EHANON, manufactured by Macherey-Nagel).
【００２９】バッファードフッ酸のエッチレートは、Ｈ
Ｆ−ＮＨ4Ｆ組成の薬液を２５℃で熱酸化ＳｉＯ2膜をエ
ッチングし、エッチング処理前の膜厚とエッチング処理
後の膜厚の差をエッチング時間で割って算出したもので
ある。The etch rate of buffered hydrofluoric acid is H
This is obtained by etching a thermally oxidized SiO 2 film at 25 ° C. using a chemical solution having an F—NH 4 F composition, and dividing the difference between the film thickness before the etching process and the film thickness after the etching process by the etching time.
【００３０】また、Ｎ含量は、試料中のＮＨ4Ｆ濃度を
測定し、Ｎ含量として算出した。The N content was calculated as the N content by measuring the NH 4 F concentration in the sample.
【００３１】結果を表１、表２に示す。また、ＨＦ及び
ＮＨ4Ｆの濃度とエッチングレートの関係、ＨＦ及びＮ
Ｈ4Ｆの濃度とｐＨの関係を各々図１及び図２に示す。The results are shown in Tables 1 and 2. Also, the relationship between the concentration of HF and NH 4 F and the etching rate, HF and N
The relationship between the concentration of H 4 F and the pH is shown in FIGS. 1 and 2, respectively.
【００３２】図２から明らかなように、ＮＨ4Ｆ濃度が
５重量％以上の場合には、１０〜１５０ｎｍ／ｍｉｎの
広い範囲で５０％ＨＦと４０％ＮＨ4Ｆを混合して所定
のエッチングレートの溶液を得るよりも、高エッチレー
トのバッファードフッ酸を希釈した方が、ＨＦ濃度を低
くすることができ、廃液処理の面でも好ましい。As is apparent from FIG. 2, when the NH 4 F concentration is 5% by weight or more, 50% HF and 40% NH 4 F are mixed in a wide range of 10 to 150 nm / min to perform a predetermined etching. It is preferable to dilute the buffered hydrofluoric acid with a high etch rate, rather than to obtain a solution with a high etch rate, since the HF concentration can be reduced and the waste liquid treatment is also preferred.
【００３３】また、図３に示すように、エッチングレー
トの変動に伴うｐＨの変動は、希釈したときの方が小さ
い。従って、エッチングないし洗浄処理をより狭い範囲
のｐＨ条件下に行うことができる。Further, as shown in FIG. 3, the fluctuation of the pH accompanying the fluctuation of the etching rate is smaller when diluted. Therefore, the etching or cleaning treatment can be performed under a narrower range of pH conditions.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【図１】本発明の希釈装置を示す概略図である。FIG. 1 is a schematic diagram showing a dilution device of the present invention.
【図２】ＨＦ及びＮＨ4Ｆの濃度とエッチングレートの
関係を示す図である。FIG. 2 is a diagram showing the relationship between the concentration of HF and NH 4 F and the etching rate.
【図３】ＨＦ及びＮＨ4Ｆの濃度とｐＨの関係を示す図
である。FIG. 3 is a diagram showing the relationship between the concentration of HF and NH 4 F and the pH.
１ バッファードフッ酸の貯蔵タンク；２ 水の貯蔵タ
ンク；３ バッファードフッ酸の供給手段；４ 水の供
給手段；５ 希釈混合槽DESCRIPTION OF SYMBOLS 1 Storage tank of buffered hydrofluoric acid; 2 Storage tank of water; 3 Supply means of buffered hydrofluoric acid; 4 Supply means of water; 5 Dilution mixing tank
Claims (7)
溶液であって、フッ化水素が２．５重量％程度以上の高
エッチングレート・バッファードフッ酸を水で希釈し
て、所定のエッチングレートのバッファードフッ酸を得
ることを特徴とするバッファードフッ酸の希釈混合方
法。An aqueous solution containing hydrogen fluoride and ammonium fluoride, wherein a high etching rate of about 2.5% by weight or more of hydrogen fluoride and buffered hydrofluoric acid are diluted with water to obtain a predetermined etching rate. A method for diluting and mixing buffered hydrofluoric acid, comprising obtaining buffered hydrofluoric acid.
００１〜５重量％程度の界面活性剤を含むように、界面
活性剤を添加する工程をさらに含む請求項１に記載の方
法。2. The buffered hydrofluoric acid after dilution is 0.00
The method according to claim 1, further comprising the step of adding a surfactant so as to contain about 001 to 5% by weight of the surfactant.
中のフッ化水素濃度が２．５〜１５重量％程度、バッフ
ァードフッ酸のｐＨが３以上である請求項１または２に
記載の方法。3. The method according to claim 1, wherein the hydrogen fluoride concentration in the high etching rate buffered hydrofluoric acid is about 2.5 to 15% by weight, and the pH of the buffered hydrofluoric acid is 3 or more.
ドフッ酸。4. A buffered hydrofluoric acid obtained by the method according to claim 1.
ッ酸で基板を処理することを特徴とする基板の処理方
法。5. A method for treating a substrate, comprising treating the substrate with the buffered hydrofluoric acid according to claim 2 or 3.
ッチングレート・バッファードフッ酸の供給手段、水供
給手段、高エッチングレート・バッファードフッ酸及び
水が供給される複数の混合用容器を備えたバッファード
フッ酸の希釈混合装置。7. A high etching rate buffered hydrofluoric acid supply means containing hydrogen fluoride of about 2.5% by weight or more, a water supply means, a plurality of mixtures supplied with a high etching rate buffered hydrofluoric acid and water. Hydrofluoric acid diluting / mixing device equipped with a container for use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10198442A JP2000031132A (en) | 1998-07-14 | 1998-07-14 | Diluting and mixing method for buffered hydrofluoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10198442A JP2000031132A (en) | 1998-07-14 | 1998-07-14 | Diluting and mixing method for buffered hydrofluoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000031132A true JP2000031132A (en) | 2000-01-28 |
Family
ID=16391166
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10198442A Pending JP2000031132A (en) | 1998-07-14 | 1998-07-14 | Diluting and mixing method for buffered hydrofluoric acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000031132A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005120373A (en) * | 2003-10-17 | 2005-05-12 | Samsung Electronics Co Ltd | Etching composition having high etching ratio, method for producing the same, method for etching oxidized film by using the same, and method for producing semiconductor device |
| JP2012191071A (en) * | 2011-03-11 | 2012-10-04 | Sony Corp | Semiconductor manufacturing device, manufacturing method of semiconductor device, and manufacturing method of electronic equipment |
| US9005464B2 (en) | 2011-06-27 | 2015-04-14 | International Business Machines Corporation | Tool for manufacturing semiconductor structures and method of use |
| US9514952B2 (en) | 2014-09-08 | 2016-12-06 | Kabushiki Kaisha Toshiba | Method of manufacturing semiconductor device and semiconductor manufacturing apparatus |
-
1998
- 1998-07-14 JP JP10198442A patent/JP2000031132A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005120373A (en) * | 2003-10-17 | 2005-05-12 | Samsung Electronics Co Ltd | Etching composition having high etching ratio, method for producing the same, method for etching oxidized film by using the same, and method for producing semiconductor device |
| JP2012191071A (en) * | 2011-03-11 | 2012-10-04 | Sony Corp | Semiconductor manufacturing device, manufacturing method of semiconductor device, and manufacturing method of electronic equipment |
| US9005464B2 (en) | 2011-06-27 | 2015-04-14 | International Business Machines Corporation | Tool for manufacturing semiconductor structures and method of use |
| US9514952B2 (en) | 2014-09-08 | 2016-12-06 | Kabushiki Kaisha Toshiba | Method of manufacturing semiconductor device and semiconductor manufacturing apparatus |
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