JPH09213704A - Manufacture of semiconductor device - Google Patents
Manufacture of semiconductor deviceInfo
- Publication number
- JPH09213704A JPH09213704A JP1896596A JP1896596A JPH09213704A JP H09213704 A JPH09213704 A JP H09213704A JP 1896596 A JP1896596 A JP 1896596A JP 1896596 A JP1896596 A JP 1896596A JP H09213704 A JPH09213704 A JP H09213704A
- Authority
- JP
- Japan
- Prior art keywords
- film
- conductive film
- photoresist
- mask
- semiconductor device
- 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
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- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Cleaning Or Drying Semiconductors (AREA)
- Drying Of Semiconductors (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体ウエハー上
に金属導電膜を形成する半導体集積回路の製造工程にお
いて、フォトレジストをフッ素系化合物を含有する剥離
液を用いて剥離した後の洗浄方法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 method after a photoresist is stripped using a stripping solution containing a fluorine compound in a manufacturing process of a semiconductor integrated circuit for forming a metal conductive film on a semiconductor wafer. It is a thing.
【０００２】[0002]
【従来の技術】半導体集積回路は、半導体ウエハーにス
パッタリング、ＣＶＤ等の方法により金属配線材料の導
電膜を形成する。次いで導電膜上にフォトレジストを塗
布し、露光、現像によるフォトリソプロセスによりパタ
ーンを形成し、さらに該フォトレジストをマスクとし、
反応性ガスを使用し、非マスク領域の導電膜のドライエ
ッチングを行い、アッシングにより、マスク領域の残存
するレジストを除去し、微細配線回路を形成する。2. Description of the Related Art In a semiconductor integrated circuit, a conductive film of a metal wiring material is formed on a semiconductor wafer by a method such as sputtering or CVD. Next, a photoresist is applied on the conductive film, a pattern is formed by a photolithography process by exposure and development, and the photoresist is used as a mask.
The conductive film in the non-mask area is dry-etched using a reactive gas, and the resist remaining in the mask area is removed by ashing to form a fine wiring circuit.
【０００３】この導電膜のドライエッチングを行うにあ
たり、ドライエッチングの際に反応性ガスとレジストの
反応物である保護堆積膜が形成する。この保護堆積膜が
残存すると断線や配線異常の原因となり種々のトラブル
を引き起こす。従って保護堆積膜の完全な除去が望まれ
ており、従来、酸性や塩基性の有機系剥離液が一般的に
使用されているが、これらの剥離液は使用する際に剥離
温度が高温であったり、引火点を有するために危険性が
高く、更には微細配線加工に使用される金属の導電膜を
腐食する等の欠点を有していることから、近年寸法精度
が厳しい超微細配線加工には適していない。When performing dry etching of this conductive film, a protective deposited film which is a reaction product of a reactive gas and a resist is formed during the dry etching. If this protective deposited film remains, it may cause disconnection or abnormal wiring, causing various troubles. Therefore, complete removal of the protective deposited film is desired, and conventionally, acidic and basic organic strippers are generally used, but these strippers have high stripping temperatures when used. In addition, it has a high risk of having a flash point and has the drawback of corroding the conductive film of the metal used for fine wiring processing. Is not suitable.
【０００４】また該剥離液は剥離後にリンス液として大
量のアルコール等の有機溶剤を使用するために危険であ
り、また工程も複雑である。近年安全で且つ簡便な剥離
方法として、エチレングルコール等の有機溶媒にフッ素
系化合物を溶解した剥離液、或いはフッ素系化合物に有
機系の防食剤を添加した水溶液である剥離液（特開平７
−２０１７９４号）等が使用されている。これらのフッ
素系剥離液は剥離温度が常温で可能であり、またリンス
液が超純水や純水を使用できる等の利点を有している。Further, the stripping solution is dangerous because a large amount of organic solvent such as alcohol is used as a rinsing solution after stripping, and the process is complicated. In recent years, as a safe and simple stripping method, a stripping solution prepared by dissolving a fluorine-based compound in an organic solvent such as ethylene glycol, or an aqueous solution obtained by adding an organic anticorrosive to a fluorine-based compound (Japanese Patent Laid-Open No. H07-78307).
-201794) and the like are used. These fluorine-based stripping solutions have the advantages that they can be stripped at room temperature and that the rinse solution can use ultrapure water or pure water.
【０００５】しかしながら、これらのフッ素系剥離液を
使用しても金属表面上に発生する微少なクレーター状あ
るいはピット状の腐食は回避することはできない。この
ような腐食は酸性や塩基性の有機系剥離液あるいはフッ
素系剥離液についても何等解決策が見い出せておらず、
金属配線材料に対する腐食現象が全く起こらないリンス
液を含めた安全で且つ簡便な剥離方法が望まれている。However, even if these fluorine-based stripping solutions are used, the slight crater-like or pit-like corrosion that occurs on the metal surface cannot be avoided. For such corrosion, no solution has been found for acidic or basic organic stripper or fluorine stripper,
There is a demand for a safe and simple peeling method that includes a rinse liquid that does not cause any corrosion phenomenon to metal wiring materials.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、半導
体装置の製造方法においてドライエッチング後に形成さ
れる保護堆積膜を容易に除去でき、金属配線材料の導電
膜を全く腐食せず、安全で且つ簡便に剥離、洗浄するこ
とにより、高精度の回路配線を製造する方法を提供する
ことである。SUMMARY OF THE INVENTION An object of the present invention is to easily remove a protective deposited film formed after dry etching in a method of manufacturing a semiconductor device, to prevent corrosion of a conductive film of a metal wiring material at all, and to keep it safe. Further, it is to provide a method for manufacturing highly accurate circuit wiring by simply peeling and washing.
【０００７】[0007]
【課題を解決するための手段】本発明者等は上記の如き
課題を解決すべく鋭意検討を行った結果、金属導電膜上
のフォトレジストによるマスク形成を行った後、ドライ
エッチングにより、配線構造を形成する際、導電膜及び
フォトレジストの側壁部に発生する保護堆積膜（レジス
ト残渣物、側壁保護膜とも言う）をフッ素系化合物を含
有する剥離液で剥離後、過酸化物を含有する超純水ある
いは純水であるリンス液で洗浄することにより、金属導
電膜等の配線材料を全く腐食することなく、またアルコ
ール等の危険性の高い有機溶剤を使用せずに、簡便に剥
離できることを見い出し、本発明に到達した。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, after forming a mask with a photoresist on a metal conductive film, dry etching is performed to form a wiring structure. When forming a film, a protective deposited film (also referred to as a resist residue or a sidewall protective film) generated on the side wall of the conductive film and the photoresist is stripped with a stripping solution containing a fluorine-based compound, and then a superoxide containing a peroxide is contained. By cleaning with pure water or a rinse solution that is pure water, it is possible to peel easily without corroding the wiring material such as the metal conductive film, and without using a highly dangerous organic solvent such as alcohol. Found and arrived at the present invention.
【０００８】即ち本発明は、半導体ウエハー上に、形成
した金属導電膜上のフォトレジストを塗布し、フォトリ
ソプロセスによるマスク形成後、非マスク領域をドライ
エッチングし、配線構造を形成する際、導電膜およびフ
ォトレジストの側壁部に発生する保護堆積膜を、フッ系
素化合物を含有する剥離液で剥離後、過酸化物を含有す
る水で洗浄することを特徴とする半導体装置製造方法で
ある。That is, according to the present invention, when a photoresist on a formed metal conductive film is applied on a semiconductor wafer and a mask is formed by a photolithography process, a non-mask region is dry-etched to form a wiring structure. And a protective deposited film generated on the side wall of the photoresist is stripped with a stripping solution containing a fluorine-containing compound, and then washed with water containing a peroxide.
【０００９】[0009]
【発明の実施の形態】本発明において半導体ウエハー上
に形成する金属導電膜は、特に制限されないが、アルミ
ニウムおよびアルミニウム合金、チタン、タングステン
合金などが好適に用いられる。このような導電膜上にフ
ォトレジストを塗布し、フォトリソプロセスによるマス
ク形成後、非マスク領域をドライエッチングおよびアッ
シングにより配線構造を形成する際、導電膜およびフォ
トレジストの側壁部に反応性ガスとレジストの反応物で
ある保護堆積膜が発生する。BEST MODE FOR CARRYING OUT THE INVENTION The metal conductive film formed on a semiconductor wafer in the present invention is not particularly limited, but aluminum and aluminum alloys, titanium, tungsten alloys and the like are preferably used. When a photoresist is applied on such a conductive film and a wiring structure is formed by dry etching and ashing on a non-masked area after forming a mask by a photolithography process, a reactive gas and a resist are formed on the sidewalls of the conductive film and the photoresist. A protective deposited film, which is a reaction product of, is generated.
【００１０】本発明ににおいてこの保護堆積膜を除去す
るために使用される剥離液に、フッ酸、フッ化アンモニ
ウム、フッ化水素アンモニウム等のフッ素系化合物を含
有する剥離液であれば、何等限定されるものではなく、
防食剤、あるいは、有機溶剤等を添加した水溶液、非水
溶液を問わず、フッ素系化合物を含有する剥離液であれ
ば、すべてに適用できる。The stripping solution used for removing the protective deposited film in the present invention is not limited as long as it is a stripping solution containing a fluorine-based compound such as hydrofluoric acid, ammonium fluoride, ammonium hydrogen fluoride or the like. Not what is done,
It can be applied to any stripping solution containing a fluorine compound, whether it is an anticorrosive agent, an aqueous solution containing an organic solvent, or a non-aqueous solution.
【００１１】本発明に使用される剥離液は、フッ酸、フ
ッ化アンモニウム、フッ化水素アンモニウム等のフッ素
系化合物を含有する剥離液であれば、何等限定されるも
のではなく、防食剤、あるいは、有機溶剤等を添加した
水溶液、非水溶液を問わず、フッ素系化合物を含有する
剥離液であれば全てに適用される。The stripping solution used in the present invention is not particularly limited as long as it is a stripping solution containing a fluorine compound such as hydrofluoric acid, ammonium fluoride and ammonium hydrogen fluoride. It is applicable to any stripping solution containing a fluorine-based compound, regardless of whether it is an aqueous solution added with an organic solvent or a non-aqueous solution.
【００１２】本発明に使用される過酸化物としては、
過酸化水素、過酸化ベンゾイル、過酸化−ジ−ｔ−ブ
チル等の過酸化ジアルキル類、クミルヒドロペルオキ
シド等のヒドロペルオキシド類、過酢酸、過安息香
酸、過トルイル酸等の過酸等があげられる。これらの中
では過酸化水素が最も好適である。これらの過酸化物の
濃度は、リンス液中の０．１〜３０％の範囲で使用さ
れ、好ましくは０．５〜２０％である。リンス液中の過
酸化物濃度が０．１重量％以下では、アルミニウム系導
電膜等の金属膜に対する防蝕効果が認められず、３０重
量％以上では何等、防蝕効果は向上せず、経済的にも得
策ではない。The peroxide used in the present invention includes:
Examples include hydrogen peroxide, benzoyl peroxide, dialkyl peroxides such as peroxydi-t-butyl, hydroperoxides such as cumyl hydroperoxide, peracids such as peracetic acid, perbenzoic acid, and pertoluic acid. To be Of these, hydrogen peroxide is most suitable. The concentration of these peroxides is used in the range of 0.1 to 30% in the rinse liquid, preferably 0.5 to 20%. When the peroxide concentration in the rinse liquid is 0.1% by weight or less, the anticorrosion effect on the metal film such as the aluminum-based conductive film is not recognized, and when it is 30% by weight or more, the anticorrosion effect is not improved at all. Is not a good idea.
【００１３】本発明において過酸化物を含有する水から
なるリンス液の使用温度は室温で充分であるが、必要に
応じて適宜加熱あるいは超音波を併用することができ
る。また該リンス液を使用する処理方法としては、浸漬
法が一般的であるが、その他、例えばスプレーによる法
を用いても良い。In the present invention, the rinsing liquid consisting of water containing a peroxide may be used at room temperature, but heating or ultrasonic waves may be appropriately used as necessary. A dipping method is generally used as a treatment method using the rinse liquid, but other methods such as a spray method may be used.
【００１４】[0014]
【実施例】以下、実施例により本発明を更に具体的に説
明する。但し本発明は、これらの実施例により制限され
るものではない。なお各実施例および比較例におけるＳ
ＥＭ観察による評価の表示は次の通りである。 （剥離性）◎：完全に除去された。 △：一部残さ物が認められた。 ×：大部分が残存していた。 （除去性）◎：腐食はまったく認められなかった。 ○：わずかにクレーター状あるいはピット状の腐食が認
められた。 △：クレーター状あるいはピット状の一部腐食が認めら
れた。 ×：アルミニウム配線体に全面に荒れが認められ、さら
にＡｌ−Ｓｉ−Ｃｕ層の後退が認められた。The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by these examples. Note that S in each example and comparative example
The display of evaluation by EM observation is as follows. (Peelability) A: Completely removed. Δ: Some residue was observed. X: Most of them remained. (Removability) A: No corrosion was observed at all. ◯: A slight crater-like or pit-like corrosion was observed. Δ: Some crater-like or pit-like corrosion was observed. X: Roughness was observed on the entire surface of the aluminum wiring body, and further receding of the Al-Si-Cu layer was observed.
【００１５】実施例１〜４、比較例１〜４ 図１はフォトレジスト膜４をマスクとしてドライエッチ
ングを行い、アルミニウム配線体（Ａｌ−Ｓｉ−Ｃｕ
層）３を形成した半導体装置の断面を示す。図１におい
て半導体基板１は絶縁膜である酸化膜（ＳｉＯ2 ）２に
被覆されており、またドライエッチング時に側壁保護膜
５が形成されている。図２は、図１の半導体装置を酸素
プラズマを用いてレジストアッシンングを行い、レジス
ト膜を除去した半導体装置の断面図を示す。図２におい
ては側壁保護膜５は酸素系プラズマでは除去されず、側
壁保護膜５の上側は、アルミニウム配線体（Ａｌ−Ｓｉ
−Ｃｕ層）３の中心に対して、開くように変形されてい
るだけである。図２のレジストアッシングを行った後の
半導体装置を、表１に示す組成の剥離剤に所定時間浸漬
後、過酸化物を含む超純水をリンス液とし洗浄を行った
後、水洗し、乾燥後、電子顕微鏡（ＳＥＭ）で観察を行
った。側壁保護膜５の剥離性とアルミニウム配線体（Ａ
ｌ−Ｓｉ−Ｃｕ層）３の表面の腐食状態について評価を
行った結果を表１に示す。Examples 1 to 4 and Comparative Examples 1 to 4 In FIG. 1, dry etching was performed using the photoresist film 4 as a mask to obtain an aluminum wiring body (Al-Si-Cu).
The cross section of the semiconductor device which formed layer 3 is shown. In FIG. 1, a semiconductor substrate 1 is covered with an oxide film (SiO 2 ) 2 which is an insulating film, and a side wall protective film 5 is formed during dry etching. FIG. 2 shows a cross-sectional view of the semiconductor device in which the semiconductor device of FIG. 1 is resist-ashed using oxygen plasma to remove the resist film. In FIG. 2, the side wall protective film 5 is not removed by oxygen-based plasma, and the upper side of the side wall protective film 5 is an aluminum wiring body (Al-Si).
It is only deformed so as to open with respect to the center of the (Cu layer) 3. The semiconductor device after the resist ashing of FIG. 2 was immersed in a stripper having the composition shown in Table 1 for a predetermined time, washed with ultrapure water containing peroxide as a rinse liquid, washed with water, and then dried. Then, it was observed with an electron microscope (SEM). The peelability of the side wall protective film 5 and the aluminum wiring body (A
Table 1 shows the results of evaluation of the corrosion state of the surface of the (1-Si-Cu layer) 3.
【００１６】[0016]
【発明の効果】実施例から明らかなように各種の塩基性
剥離液で完全に剥離された側壁保護膜に対して、本発明
の方法により過酸化物を含む水で洗浄を行えばアルミニ
ウム配線体に対して腐食性が全く認められない。本発明
の方法ではアルコール等の危険性の高い有機溶剤を使用
しないので安全であるので、工業的に極めて容易に完全
な洗浄を行うことができ、高精度の回路配線を工業的に
有利に製造することができる。As is apparent from the examples, if the side wall protective film completely stripped with various basic stripping solutions is washed with water containing peroxide by the method of the present invention, an aluminum wiring body is obtained. No corrosiveness is observed. Since the method of the present invention is safe because it does not use a highly dangerous organic solvent such as alcohol, it can be completely washed industrially very easily, and a highly accurate circuit wiring can be produced industrially advantageously. can do.
【００１７】[0017]
【表１】 [Table 1]
【図１】フォトレジスト膜をマスクとしドライエッチン
グを行い、アルミニウム配線体（Ａｌ−Ｓｉ−Ｃｕ層）
を形成した半導体装置の断面を示す。FIG. 1 is an aluminum wiring body (Al-Si-Cu layer) which is dry-etched using a photoresist film as a mask.
3 is a cross-sectional view of a semiconductor device on which is formed.
【図２】図１の半導体装置を酸素プラズマを用いてレジ
ストアッシンングを行い、フォトレジスト膜を除去した
半導体装置の断面図を示す。FIG. 2 is a sectional view of the semiconductor device in which the photoresist film is removed by subjecting the semiconductor device of FIG. 1 to resist assembling using oxygen plasma.
１ 半導体基板 ２ 酸化膜（ＳｉＯ2 ） ３ アルミニウム配線体（Ａｌ−Ｓｉ−Ｃｕ層） ４ フォトレジスト膜 ５ 側壁保護膜（フォトレジスト残渣物）1 Semiconductor Substrate 2 Oxide Film (SiO 2 ) 3 Aluminum Wiring Body (Al-Si-Cu Layer) 4 Photoresist Film 5 Sidewall Protection Film (Photoresist Residue)
───────────────────────────────────────────────────── フロントページの続き (72)発明者 青山 哲男 新潟県新潟市太夫浜字新割182番地 三菱 瓦斯化学株式会社新潟研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Tetsuo Aoyama 182 Shinwari, Tayuhama, Niigata City, Niigata Prefecture Mitsubishi Gas Chemical Co., Ltd. Niigata Research Center
Claims (1)
上のフォトレジストを塗布し、フォトリソプロセスによ
るマスク形成後、非マスク領域をドライエッチングし、
配線構造を形成する際、導電膜およびフォトレジストの
側壁部に発生する保護堆積膜を、フッ系素化合物を含有
する剥離液で剥離後、過酸化物を含有する水で洗浄する
ことを特徴とする半導体装置製造方法。1. A semiconductor wafer is coated with a photoresist on the formed metal conductive film, a mask is formed by a photolithography process, and then a non-mask region is dry-etched.
When the wiring structure is formed, the protective deposited film generated on the sidewalls of the conductive film and the photoresist is stripped with a stripping solution containing a fluorine-based compound, and then washed with water containing a peroxide. Semiconductor device manufacturing method.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1896596A JPH09213704A (en) | 1996-02-05 | 1996-02-05 | Manufacture of semiconductor device |
| US08/781,774 US5911836A (en) | 1996-02-05 | 1997-01-09 | Method of producing semiconductor device and rinse for cleaning semiconductor device |
| KR1019970001509A KR100446590B1 (en) | 1996-02-05 | 1997-01-20 | Method of manufacturing semiconductor device and semiconductor device cleaning liquid |
| DE69703052T DE69703052T2 (en) | 1996-02-05 | 1997-01-21 | Method of manufacturing a semiconductor device and use of a detergent for semiconductor cleaning |
| EP97100935A EP0788143B1 (en) | 1996-02-05 | 1997-01-21 | Method of producing semiconductor device and use of a rinse for cleaning semiconductor device |
| TW086100669A TW324832B (en) | 1996-02-05 | 1997-01-22 | Method for producing semiconductor |
| SG1997000242A SG60039A1 (en) | 1996-02-05 | 1997-02-03 | Method of producing semiconductor device and rinse for cleaning semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1896596A JPH09213704A (en) | 1996-02-05 | 1996-02-05 | Manufacture of semiconductor device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09213704A true JPH09213704A (en) | 1997-08-15 |
Family
ID=11986376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1896596A Pending JPH09213704A (en) | 1996-02-05 | 1996-02-05 | Manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09213704A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6638899B1 (en) | 1999-09-10 | 2003-10-28 | Tokyo Ohka Kogyo Co., Ltd. | Photoresist stripping solution and a method of stripping photoresists with the same |
| JP2005317699A (en) * | 2004-04-28 | 2005-11-10 | Semiconductor Energy Lab Co Ltd | Semiconductor device manufacturing method |
| CN112310121A (en) * | 2020-10-22 | 2021-02-02 | Tcl华星光电技术有限公司 | Array substrate, preparation method thereof and display panel |
-
1996
- 1996-02-05 JP JP1896596A patent/JPH09213704A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6638899B1 (en) | 1999-09-10 | 2003-10-28 | Tokyo Ohka Kogyo Co., Ltd. | Photoresist stripping solution and a method of stripping photoresists with the same |
| JP2005317699A (en) * | 2004-04-28 | 2005-11-10 | Semiconductor Energy Lab Co Ltd | Semiconductor device manufacturing method |
| JP4519512B2 (en) * | 2004-04-28 | 2010-08-04 | 株式会社半導体エネルギー研究所 | Manufacturing method and removal method of semiconductor device |
| CN112310121A (en) * | 2020-10-22 | 2021-02-02 | Tcl华星光电技术有限公司 | Array substrate, preparation method thereof and display panel |
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