JPH09148292A - Ashing step cleaning agent - Google Patents
Ashing step cleaning agentInfo
- Publication number
- JPH09148292A JPH09148292A JP33124295A JP33124295A JPH09148292A JP H09148292 A JPH09148292 A JP H09148292A JP 33124295 A JP33124295 A JP 33124295A JP 33124295 A JP33124295 A JP 33124295A JP H09148292 A JPH09148292 A JP H09148292A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning agent
- aluminum
- wiring
- protective film
- aqueous 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
Landscapes
- Drying Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Weting (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアッシング工程洗浄
剤に関するものであり、更に詳しくは半導体集積回路装
置製造において、アルミニウム及びアルミニウム合金の
配線形成工程におけるエッチング後のアッシング工程に
おける主としてＡｌＦ3 からなる側壁保護膜除去におい
て、この側壁保護膜除去中にアルミニウム及びアルミニ
ウム合金の配線の腐食なしに側壁保護膜を除去すること
が可能である洗浄剤に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent for an ashing process, and more specifically, in manufacturing a semiconductor integrated circuit device, a sidewall mainly made of AlF 3 in an ashing process after etching in a wiring forming process of aluminum and an aluminum alloy. The present invention relates to a cleaning agent capable of removing a side wall protective film without corroding aluminum and aluminum alloy wiring during the removal of the side wall protective film.
【０００２】[0002]
【従来の技術】半導体集積回路装置製造において、それ
を構成する回路素子や配線はｇ線、ｉ線などの光を使用
してフォトマスクのパターンを半導体ウェハーに転写す
るリソグラフィ技術によって作製される。半導体集積回
路の高集積化が進むにつれ、配線では配線幅の微細化、
配線膜厚の薄膜化、配線長の増加や多層化が進められて
いる。2. Description of the Related Art In the manufacture of a semiconductor integrated circuit device, circuit elements and wirings constituting the device are manufactured by a lithography technique in which a photomask pattern is transferred onto a semiconductor wafer by using light such as g-line and i-line. As the degree of integration of semiconductor integrated circuits has advanced, wiring has become finer in wiring width,
The wiring thickness is being reduced, the wiring length is increasing, and the number of layers is increasing.
【０００３】このため、配線材料としては積層アルミニ
ウム配線が用いられ、一般にＴｉＮ／Ａｌ−Ｓｉ−Ｃｕ
／ＴｉＮまたはＴｉＷ／Ａｌ−Ｓｉ−Ｃｕ／ＴｉＷが用
いられることが知られている。これらアルミニウム系配
線の作製には、反応性イオンエッチング（ＲＩＥ）など
のエッチングが用いられ、それにはフッ素系ガスや塩素
系ガスが使用されている。さらに、エッチング後、配線
パターンを形成していたレジストを酸素プラズマ等のド
ライアッシングにより除去することを行っていた。Therefore, a laminated aluminum wiring is used as the wiring material, and generally TiN / Al-Si-Cu is used.
It is known that / TiN or TiW / Al-Si-Cu / TiW is used. Etching such as reactive ion etching (RIE) is used for manufacturing these aluminum-based wirings, and fluorine-based gas or chlorine-based gas is used for the etching. Further, after etching, the resist on which the wiring pattern has been formed is removed by dry ashing such as oxygen plasma.
【０００４】この一連のエッチング、ドライアッシング
によりアルミニウム系配線の側壁に保護膜が生じ、この
側壁保護膜はドライアッシングでは除去されずに残って
しまっている。この側壁保護膜は主としてＡｌＦ3 から
なり、また塩化水素や有機ハロゲン化物も含まれてい
る。これらが残存すると、アッシング工程中やアッシン
グ工程後からアルミニウム系配線の腐食の発生に至るこ
ととなる。従って、この側壁保護膜を除去する必要があ
り、そのためにエッチングを経てアッシング工程でドラ
イアッシング後にウェット洗浄を設けて除去している。By this series of etching and dry ashing, a protective film is formed on the side wall of the aluminum wiring, and this side wall protective film remains without being removed by the dry ashing. This side wall protective film is mainly made of AlF 3 and also contains hydrogen chloride and an organic halide. If they remain, corrosion of the aluminum wiring will occur during or after the ashing step. Therefore, it is necessary to remove the side wall protective film, and for that purpose, it is removed by performing wet etching after dry ashing in the ashing process through etching.
【０００５】[0005]
【発明が解決しようとする課題】従来、アッシング工程
でドライアッシング後のウェット洗浄に使用されている
トリメチル（２−ヒドロキシエチル）アンモニウムヒド
ロキシド水溶液やテトラメチルアンモニウムヒドロキシ
ド水溶液などの有機塩基水溶液は、側壁保護膜を除去で
きるものの、処理中にアルミニウムの腐食を起こしてし
まうという問題がある。本発明の目的は、それらに代わ
り、主としてＡｌＦ3 からなる前記側壁保護膜除去にお
いて、この側壁保護膜除去中にアルミニウム及びアルミ
ニウム合金の配線の腐食なしに除去することを可能とす
る洗浄剤を提供することである。Conventionally, an organic base aqueous solution such as an aqueous solution of trimethyl (2-hydroxyethyl) ammonium hydroxide or an aqueous solution of tetramethylammonium hydroxide, which is conventionally used for wet cleaning after dry ashing in the ashing process, Although the side wall protection film can be removed, there is a problem that aluminum is corroded during the processing. An object of the present invention is to provide, instead of them, a cleaning agent capable of removing the side wall protective film mainly composed of AlF 3 without corroding aluminum and aluminum alloy wiring during the side wall protective film removal. It is to be.
【０００６】[0006]
【課題を解決するための手段】本発明者は前記目的を達
成するために鋭意研究を重ねた結果、トリメチル（２−
ヒドロキシエチル）アンモニウムヒドロキシド水溶液や
テトラメチルアンモニウムヒドロキシド水溶液などのア
ルミニウム系配線の腐食の発生を引き起こす有機塩基水
溶液でなく、特定の有機アルカノールアミンを必須成分
として含有する水溶液を使用すると、側壁保護膜の主成
分であるＡｌＦ3 を除去するために優れた効果を示し、
且つ、アルミニウム系配線の腐食を抑制できることを見
出し、本発明を完成するに至った。The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, trimethyl (2-
When an aqueous solution containing a specific organic alkanolamine as an essential component is used instead of an aqueous solution of an organic base such as an aqueous solution of (hydroxyethyl) ammonium hydroxide or an aqueous solution of tetramethylammonium hydroxide that causes corrosion of aluminum-based wiring, a sidewall protective film is formed. Has an excellent effect in removing AlF 3 which is the main component of
Moreover, they have found that corrosion of aluminum-based wiring can be suppressed, and have completed the present invention.
【０００７】すなわち、本発明の請求項１の発明は、下
記一般式（１）That is, the invention of claim 1 of the present invention is represented by the following general formula (1):
【０００８】[0008]
【化２】 Ｒ1 ＮＨn-2 −（ＣＨＲ2 ＣＨＲ3 −ＯＨ）n （１）Embedded image R 1 NH n-2 — (CHR 2 CHR 3 —OH) n (1)
【０００９】（式中のＲ1 は水素、メチル基であり、Ｒ
2 、Ｒ3 は少なくとも一方が水素、他方がメチル基であ
る。ｎは１〜２）で表される有機アルカノールアミン類
を必須成分として含有する水溶液からなることを特徴と
するアッシング工程洗浄剤を提供するものである。(Wherein R 1 is hydrogen or a methyl group,
At least one of R 2 and R 3 is hydrogen and the other is a methyl group. n is an aqueous solution containing an organic alkanolamine represented by 1 to 2) as an essential component, and an ashing step detergent.
【００１０】本発明の請求項２の発明は、請求項１記載
のアッシング工程洗浄剤において、有機アルカノールア
ミン類の濃度が４０重量％以上の水溶液からなることを
特徴とする。以下、本発明を詳細に説明する。The invention according to claim 2 of the present invention is characterized in that, in the ashing step cleaner according to claim 1, it comprises an aqueous solution having a concentration of organic alkanolamines of 40% by weight or more. Hereinafter, the present invention will be described in detail.
【００１１】[0011]
【発明の実施の形態】本発明の洗浄剤は、水溶液中に前
記一般式（１）で表される特定の有機アルカノールアミ
ン類を含有することが必須である。BEST MODE FOR CARRYING OUT THE INVENTION It is essential that the detergent of the present invention contains a specific organic alkanolamine represented by the general formula (1) in an aqueous solution.
【００１２】本発明の洗浄剤に用いられる前記一般式
（１）で表される特定の有機アルカノールアミンの具体
例としては、例えば、モノイソプロパノールアミン、ジ
イソプロパノールアミン、Ｎ−メチルエタノールアミ
ン、Ｎ−メチルジエタノールアミン、Ｎ−メチルイソプ
ロパノールアミン、Ｎ−メチルジイソプロパノールアミ
ンなどが挙げられる。これらは単独で用いてもよく、２
種以上組み合わせて用いてもよい。Specific examples of the specific organic alkanolamine represented by the above general formula (1) used in the detergent of the present invention include, for example, monoisopropanolamine, diisopropanolamine, N-methylethanolamine and N-. Methyldiethanolamine, N-methylisopropanolamine, N-methyldiisopropanolamine and the like can be mentioned. These may be used alone,
It may be used in combination of more than one kind.
【００１３】本発明の洗浄剤に含有される特定の有機ア
ルカノールアミンの濃度は、使用されるアルミニウム配
線の種類や様々な条件のエッチング及びドライアッシン
グの工程により生じた側壁保護膜の状態に応じて定めら
れる。室温処理において、前記有機アルカノールアミン
の濃度が４０重量％以上の水溶液からなるアッシング工
程洗浄剤は、アルミニウム系配線の腐食を抑制し、主と
してＡＬＦ3 からなる側壁保護膜を除去するのに適して
いる。The concentration of the specific organic alkanolamine contained in the cleaning agent of the present invention depends on the type of aluminum wiring used and the state of the side wall protective film formed by the etching and dry ashing process under various conditions. Determined. In the room temperature treatment, the ashing step cleaning agent composed of an aqueous solution having an organic alkanolamine concentration of 40% by weight or more is suitable for suppressing the corrosion of the aluminum wiring and removing the side wall protective film mainly composed of ALF 3 . .
【００１４】本発明のアッシング工程とは、アルミニウ
ム及びアルミニウム合金の配線形成工程において実施す
る微細パターン加工のフォトリソグラフィの最後に行う
用済みのマスクパターンレジストを除去する処理工程で
ある。このレジストを除去する方法は一般に酸素プラズ
マ等を用いたドライ剥離と、特定の溶液や溶剤を用いた
ウェット剥離とがある。本発明におけるアッシング工程
とは、酸素プラズマなどを用いたドライ剥離を行った後
に洗浄剤で処理をする一連の除去洗浄工程を言う。The ashing step of the present invention is a processing step of removing the used mask pattern resist at the end of the photolithography of the fine pattern processing performed in the wiring forming step of aluminum and aluminum alloy. Methods for removing this resist are generally dry stripping using oxygen plasma or the like and wet stripping using a specific solution or solvent. The ashing step in the present invention refers to a series of removal cleaning steps in which a dry cleaning using oxygen plasma or the like is performed and then a treatment with a cleaning agent is performed.
【００１５】本発明の洗浄剤は必要であるならば洗浄性
やアルミニウムに対する耐腐食性を損なわない範囲で他
の有機薬品、界面活性剤、キレート剤、着色剤、酸化防
止剤、紫外線吸収剤、潤滑剤、その他の添加剤を含んで
もよい。If necessary, the cleaning agent of the present invention may contain other organic chemicals, surfactants, chelating agents, colorants, antioxidants, ultraviolet absorbers, etc. within the range of not impairing the cleaning property and the corrosion resistance to aluminum. A lubricant and other additives may be included.
【００１６】本発明の洗浄剤が適用される側壁保護膜
は、アルミニウム系配線を作製する際反応性イオンエッ
チング（ＲＩＥ）などのエッチングや、その後配線パタ
ーンを形成していたレジストをドライアッシングにより
除去するなどの一連のエッチング、ドライアッシングの
工程によりアルミニウム系配線の側壁に生じるものであ
り、主としてＡｌＦ3 からなるが、塩化水素や有機ハロ
ゲン化物も含まれるものであり、特に限定されるもので
はない。The side wall protective film to which the cleaning agent of the present invention is applied is removed by etching such as reactive ion etching (RIE) when manufacturing an aluminum-based wiring or by dry ashing the resist on which the wiring pattern is formed. It is generated on the side wall of the aluminum-based wiring by a series of etching and dry ashing steps, such as etching, and is mainly made of AlF 3 , but it also contains hydrogen chloride and organic halides and is not particularly limited. .
【００１７】本発明の洗浄剤を用いた洗浄方法は、アル
ミニウム系配線を作製した基板と本発明の洗浄剤が接し
て洗浄処理が行えれば特に制限されるものではなく、必
要に応じて加熱、超音波等を併用しても差し支えない。The cleaning method using the cleaning agent of the present invention is not particularly limited as long as the substrate on which the aluminum-based wiring is manufactured and the cleaning agent of the present invention can be brought into contact with each other to perform the cleaning treatment, and heating is performed as necessary. , Ultrasonic waves may be used together.
【００１８】[0018]
【実施例】以下、実施例に基づいて本発明を具体的に説
明するが、本発明はこれらに限定されるものではない。EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited thereto.
【００１９】（実施例１〜５）側壁保護膜の主成分であ
るＡｌＦ3 を所定量（約０．２ｇ）はかりとり、表１に
示す洗浄剤水溶液に添加して、７０℃で１時間溶解後、
濾紙（Ｎｏ．５Ｃ、桐山濾紙）を用いて濾過操作をし、
未溶解ＡｌＦ3 を分離した濾紙をアルミカップにいれて
１２０℃、１時間乾燥を行い、未溶解ＡｌＦ3 の重量を
測定し、それよりＡｌＦ3 溶解率を求めた。また、表１
に示す洗浄剤水溶液にアルミ箔（巾５０ｍｍ×長さ２０
ｍｍ）を約半分常温で１０分浸漬してアルミニウム表面
の気泡発生状態及び変色状態を観察し、アルミニウムに
対する腐食性を試験した。これらの結果を表１に示し
た。(Examples 1 to 5) A predetermined amount (about 0.2 g) of AlF 3 which is the main component of the side wall protective film was weighed and added to the detergent aqueous solution shown in Table 1 and dissolved at 70 ° C. for 1 hour. rear,
Perform a filtering operation using filter paper (No. 5C, Kiriyama filter paper),
The filter paper from which the undissolved AlF 3 had been separated was placed in an aluminum cup and dried at 120 ° C. for 1 hour, the weight of the undissolved AlF 3 was measured, and the dissolution rate of AlF 3 was determined therefrom. Table 1
Aluminum solution (width 50 mm x length 20
(mm) was immersed for about 10 minutes at room temperature to observe the state of bubbles and discoloration on the surface of aluminum, and the corrosiveness to aluminum was tested. The results are shown in Table 1.
【００２０】（比較例１）１０重量％２−ヒドロキシ−
Ｎ，Ｎ，Ｎ−トリメチルエタンアミンヒドロオキサイド
水溶液を使用した以外は実施例１〜５と同様に試験を行
った。この結果を表１に示した。Comparative Example 1 10 wt% 2-hydroxy-
The test was performed in the same manner as in Examples 1 to 5 except that an aqueous solution of N, N, N-trimethylethanamine hydroxide was used. The results are shown in Table 1.
【００２１】（比較例２）１０重量％トリメチル（２−
ヒドロキシエチル）アンモニウムヒドロキシド水溶液を
使用した以外は実施例１〜５と同様に試験を行った。こ
の結果を表１に示した。(Comparative Example 2) 10 wt% trimethyl (2-
The test was performed in the same manner as in Examples 1 to 5 except that an aqueous solution of (hydroxyethyl) ammonium hydroxide was used. The results are shown in Table 1.
【００２２】（比較例３）６０重量％Ｎ，Ｎ−ジエチル
−１，３−ジアミノプロパン水溶液を使用した以外は実
施例１〜５と同様に試験を行った。この結果を表１に示
した。(Comparative Example 3) A test was conducted in the same manner as in Examples 1 to 5 except that a 60% by weight N, N-diethyl-1,3-diaminopropane aqueous solution was used. The results are shown in Table 1.
【００２３】[0023]
【表１】 [Table 1]
【００２４】表１から、実施例１〜５においてはＡｌＦ
3 溶解率およびアルミニウム腐食性ともに優れているの
に対して、比較例１〜３の場合はいずれもアルミニウム
腐食性が劣ることが判る。From Table 1, in Examples 1 to 5, AlF
3 While the dissolution rate and the aluminum corrosiveness are excellent, it can be seen that the aluminum corrosiveness is inferior in each of Comparative Examples 1 to 3.
【００２５】[0025]
【発明の効果】本発明のアッシング工程洗浄剤を使用す
ることにより、アルミニウム及びアルミニウム合金の配
線形成工程におけるエッチング及びアッシング後の側壁
保護膜除去において、アルミニウム及びアルミニウム合
金の配線の腐食なしに側壁保護膜を除去できる。EFFECTS OF THE INVENTION By using the cleaning agent of the ashing process of the present invention, the sidewall protection film after etching and ashing in the wiring forming process of aluminum and aluminum alloy is removed without corrosion of the aluminum and aluminum alloy wiring. The film can be removed.
Claims (2)
なくとも一方が水素、他方がメチル基である。ｎは１〜
２）で表される有機アルカノールアミン類を必須成分と
して含有する水溶液からなることを特徴とするアッシン
グ工程洗浄剤。1. A compound represented by the following general formula (1): embedded image R 1 NH n-2 — (CHR 2 CHR 3 —OH) n (1) (wherein R 1 is hydrogen or a methyl group, and R 2 , R 3 has at least one hydrogen atom and the other methyl group, and n is 1 to 1.
An ashing step cleaning agent comprising an aqueous solution containing an organic alkanolamine represented by 2) as an essential component.
重量％以上の水溶液からなることを特徴とする請求項１
記載のアッシング工程洗浄剤。2. The concentration of organic alkanolamines is 40.
2. An aqueous solution containing at least 1% by weight.
The ashing step cleaning agent described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33124295A JP3527934B2 (en) | 1995-11-28 | 1995-11-28 | Ashing process cleaning agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33124295A JP3527934B2 (en) | 1995-11-28 | 1995-11-28 | Ashing process cleaning agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09148292A true JPH09148292A (en) | 1997-06-06 |
| JP3527934B2 JP3527934B2 (en) | 2004-05-17 |
Family
ID=18241494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33124295A Expired - Fee Related JP3527934B2 (en) | 1995-11-28 | 1995-11-28 | Ashing process cleaning agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3527934B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7658803B2 (en) | 2005-12-06 | 2010-02-09 | Samsung Electronics Co., Ltd. | Manufacturing and cleansing of thin film transistor panels |
-
1995
- 1995-11-28 JP JP33124295A patent/JP3527934B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7658803B2 (en) | 2005-12-06 | 2010-02-09 | Samsung Electronics Co., Ltd. | Manufacturing and cleansing of thin film transistor panels |
| US8389454B2 (en) | 2005-12-06 | 2013-03-05 | Samsung Display Co., Ltd. | Manufacturing and cleansing of thin film transistor panels |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3527934B2 (en) | 2004-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4147320B2 (en) | Non-corrosive cleaning composition for removing plasma etching residues | |
| TWI264068B (en) | Detergent composition | |
| CN1784487B (en) | Non-aqueous, non-corrosive microelectronic cleaning compositions | |
| US7671001B2 (en) | Alkaline, post plasma etch/ash residue removers and photoresist stripping compositions containing metal-halide corrosion inhibitors | |
| US6191086B1 (en) | Cleaning composition and method for removing residues | |
| JP2527268B2 (en) | Release agent composition for resist | |
| JP4817579B2 (en) | Defect reduction method | |
| TW580516B (en) | Non-corrosive cleaning composition and method for removing photoresist and/or plasma etching residues | |
| JPWO2017208767A1 (en) | Processing solution, substrate cleaning method and resist removal method | |
| WO2003091376A1 (en) | Oxalic acid as a cleaning product for aluminium, copper and dielectric surfaces | |
| JP2002523546A (en) | Non-corrosive stripping and cleaning compositions | |
| JP2001249465A (en) | Residue cleaning liquid | |
| TW200400255A (en) | Cleaning composition | |
| US6245155B1 (en) | Method for removing photoresist and plasma etch residues | |
| WO2010037263A1 (en) | Rinse solution for removing resist | |
| JP2001022096A (en) | Positive type resist remover | |
| JP3527934B2 (en) | Ashing process cleaning agent | |
| JP4692799B2 (en) | Resist stripping composition | |
| JP2001033988A (en) | Rinsing solution for photolithography, and treatment of substrate using same | |
| JPH0627684A (en) | Rinse for lithography and production of semiconductor device using the same | |
| KR20010042461A (en) | Method for removing photoresist and plasma etch residues | |
| JP3865947B2 (en) | Photoresist ash residue cleaning agent | |
| JPH0667439A (en) | Treating liquid for semiconductor surface | |
| KR100583110B1 (en) | Cleaning Solution for Photoresist and Method for Forming Pattern Using the same | |
| JP2003142443A (en) | Washing method of substrate and rinse liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20040106 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20040129 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100305 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130305 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140305 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |