JPH07206410A - Formation of silicon nitride film - Google Patents
Formation of silicon nitride filmInfo
- Publication number
- JPH07206410A JPH07206410A JP314994A JP314994A JPH07206410A JP H07206410 A JPH07206410 A JP H07206410A JP 314994 A JP314994 A JP 314994A JP 314994 A JP314994 A JP 314994A JP H07206410 A JPH07206410 A JP H07206410A
- Authority
- JP
- Japan
- Prior art keywords
- silicon nitride
- nitride film
- film
- coating
- substrate
- 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
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、半導体装置の製造工程
で利用されるシリコン窒化膜の形成方法に関し、特に塗
布方式によりシリコン窒化膜を形成する方法に係わる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a silicon nitride film used in a semiconductor device manufacturing process, and more particularly to a method for forming a silicon nitride film by a coating method.
【０００２】[0002]
【従来の技術】半導体装置の製造工程においては、半導
体基板上の各種の膜をマスクをに用いてエッチングを行
うことが行われている。前記エッチングマスクの一つと
して耐プラズマ性の優れたシリコン窒化膜が知られてい
る。かかるシリコン窒化膜は、その下地層を選択的にエ
ッチングすることから膜質が安定していることが要望さ
れる。2. Description of the Related Art In the process of manufacturing a semiconductor device, various films on a semiconductor substrate are used as a mask for etching. A silicon nitride film having excellent plasma resistance is known as one of the etching masks. The silicon nitride film is required to have stable film quality because the underlying layer is selectively etched.
【０００３】ところで、前記シリコン窒化膜は従来より
塗布方式により形成する方法が知られている。この方法
は、半導体基板上にペルヒドロ系ポリシラザン溶液を塗
布した後、大気雰囲気中で焼成してシリコン窒化膜を形
成するものである。前記焼成において、前記ペルヒドロ
系ポリシラザン溶液中の−ＳｉＨ2 −ＮＨ−が下記化１
に示すように脱水素反応を起こして高分子化し、シリコ
ン窒化膜が形成される。By the way, a method of forming the silicon nitride film by a coating method has been conventionally known. In this method, a perhydro-based polysilazane solution is applied on a semiconductor substrate and then baked in an air atmosphere to form a silicon nitride film. In the calcination, —SiH 2 —NH— in the perhydro-polysilazane solution was converted to the following chemical formula 1.
As shown in (3), a dehydrogenation reaction is caused to polymerize and a silicon nitride film is formed.
【０００４】[0004]
【化１】 [Chemical 1]
【０００５】前記焼成工程は、その温度が高い程、前記
化１で生成された高分子物質の縮重合が進んで安定した
膜質のシリコン窒化膜が得られる。そのため、前記焼成
は５００℃以上の高温で行う必要がある。In the firing step, the higher the temperature is, the more the condensation polymerization of the polymer substance produced in the above chemical formula 1 proceeds, and the stable silicon nitride film is obtained. Therefore, the firing needs to be performed at a high temperature of 500 ° C. or higher.
【０００６】上述したように塗布、焼成によりシリコン
窒化膜を形成するには安定した膜質を得るために５００
℃以上の温度で焼成するすることが必要である。しかし
ながら、半導体装置の製造工程においてはその特性上、
熱処理温度を２００〜３００℃までしか上げられない工
程がある。前記ペルヒドロ系ポリシラザン溶液の塗布後
に２００〜３００℃で焼成すると、形成されたシリコン
窒化膜の膜質が著しく損なわれる。その結果、得られた
シリコン窒化膜を用いてその下地をドライエッチングす
ると、前記シリコン窒化膜にクラックが発生するためマ
スクとして使用することができなくなる。このようなク
ラックの発生機構を下記化２の反応から説明される。As described above, in order to obtain a stable film quality, a silicon nitride film is formed by coating and baking.
It is necessary to fire at a temperature of ℃ or more. However, in the manufacturing process of the semiconductor device, due to its characteristics,
There is a process in which the heat treatment temperature can be raised only to 200 to 300 ° C. When the perhydro-polysilazane solution is applied and baked at 200 to 300 ° C., the quality of the formed silicon nitride film is significantly impaired. As a result, if the underlying layer is dry-etched using the obtained silicon nitride film, cracks occur in the silicon nitride film, making it impossible to use it as a mask. The mechanism of generation of such cracks will be explained from the reaction of the following chemical formula 2.
【０００７】[0007]
【化２】 [Chemical 2]
【０００８】すなわち、膜質が粗悪なシリコン窒化膜は
その膜中の−ＮＨが存在するため、空気中に放置する
と、−ＮＨが空気中の水分と反応し、ＮＨ3 となって外
部に放出され、酸素（Ｏ）が膜中に取り込まれる。酸素
が膜中に取り込まれると、膜に歪みを生じるため、前記
ドライエッチング工程等においてクラックが発生する。
これは、低温焼成であるために前述した化１に示す脱水
素反応が十分に行われず、膜中に多量の水素が−ＮＨと
して残留したためである。事実、ペルヒドロ系ポリシラ
ザン溶液の塗布膜の焼成温度と得られたシリコン窒化膜
のＩＲスペクトルの関係を示す図１により５００℃以上
の焼成温度により得られたシリコン窒化膜には水素が存
在しないことがわかる。That is, since -NH is present in a silicon nitride film having a poor film quality, when left in the air, -NH reacts with moisture in the air to be released as NH 3 to the outside. , Oxygen (O) is taken into the film. When oxygen is taken into the film, the film is distorted, and thus cracks are generated in the dry etching process or the like.
This is because the dehydrogenation reaction shown in Chemical formula 1 above was not sufficiently performed due to the low temperature firing, and a large amount of hydrogen remained as —NH in the film. In fact, according to FIG. 1, which shows the relationship between the baking temperature of the coating film of the perhydropolysilazane solution and the IR spectrum of the obtained silicon nitride film, it can be seen that hydrogen is not present in the silicon nitride film obtained at a baking temperature of 500 ° C. or higher. Recognize.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、膜質
が安定したシリコン窒化膜を低温焼成により形成するこ
とが可能な方法を提供しようとするものである。An object of the present invention is to provide a method capable of forming a silicon nitride film having a stable film quality by low temperature firing.
【００１０】[0010]
【課題を解決するための手段】本発明に係わるシリコン
窒化膜の形成方法は、基板上にペルヒドロ系ポリシラザ
ン溶液を塗布した後、ＵＶ照射を行いながら焼成するこ
とを特徴とするものである。A method for forming a silicon nitride film according to the present invention is characterized in that a perhydro-based polysilazane solution is applied onto a substrate and then baked while being irradiated with UV.
【００１１】本発明に係わる別のシリコン窒化膜の形成
方法は、基板上にペルヒドロ系ポリシラザン溶液を塗布
した後、オゾンを含む雰囲気中でＵＶ照射を行いながら
焼成することを特徴とするものである。Another method for forming a silicon nitride film according to the present invention is characterized in that a perhydro-based polysilazane solution is applied on a substrate and then baked in an atmosphere containing ozone while performing UV irradiation. .
【００１２】前記焼成は、５００℃未満、特に２００〜
３００℃の低温で行なわれる。前記焼成は、大気雰囲気
でも、減圧下で行ってもよい。ただし、減圧下で焼成を
行うと、前記化１に示す脱水素を反応を促進して膜の変
質を防止できるという利点を有する。The firing is performed at a temperature of less than 500 ° C., especially 200 to
It is performed at a low temperature of 300 ° C. The firing may be performed in the air atmosphere or under reduced pressure. However, firing under reduced pressure has an advantage that the dehydrogenation shown in Chemical formula 1 above can be promoted to prevent the deterioration of the film.
【００１３】[0013]
【作用】本発明に係わるシリコン窒化膜の形成方法によ
れば、基板上にペルヒドロ系ポリシラザン溶液を塗布し
た後、ＵＶ照射を行いながら焼成することによって、前
記焼成温度が２００℃程度と低温であっても前記化１に
示す脱水素反応、縮重合反応が促進されるために、水素
の残留に起因する−ＮＨ量が低減されたシリコン窒化膜
を形成することができる。このような−ＮＨ量が低減さ
れたシリコン窒化膜は空気中に放置しても、−ＮＨの存
在によるＮＨ3 の外部放出、歪みの原因となる酸素
（Ｏ）の膜中への取り込みを抑制できるため、ドライエ
ッチング工程等においてクラックが発生するのを防止す
ることができる。According to the method for forming a silicon nitride film according to the present invention, the baking temperature is as low as about 200 ° C. by applying the perhydro-based polysilazane solution on the substrate and then baking while applying UV irradiation. However, since the dehydrogenation reaction and polycondensation reaction shown in Chemical Formula 1 are promoted, it is possible to form a silicon nitride film in which the amount of —NH resulting from the residual hydrogen is reduced. Even if the silicon nitride film with the reduced amount of —NH is left in the air, it suppresses the release of NH 3 due to the presence of —NH and the uptake of oxygen (O) into the film, which causes distortion. Therefore, it is possible to prevent cracks from being generated in the dry etching process or the like.
【００１４】また、本発明に係わる別のシリコン窒化膜
の形成方法によれば、基板上にペルヒドロ系ポリシラザ
ン溶液を塗布した後、オゾンを含む雰囲気中でＵＶ照射
を行いながら焼成することによって、前記焼成温度が２
００℃程度と低温であっても前記化１に示す脱水素反
応、縮重合反応を促進できると共に、−ＮＨがオゾン中
の活性な酸素で置換されたシリコン窒化膜を形成でき
る。このようなシリコン窒化膜は、−ＮＨの存在に起因
する空気中での変化、つまり歪みの発生を回避できるた
め、ドライエッチング工程等においてクラックが発生す
るのを防止することができる。Further, according to another method for forming a silicon nitride film according to the present invention, after coating a perhydro-based polysilazane solution on a substrate, baking is performed while irradiating with UV in an atmosphere containing ozone. Firing temperature is 2
Even at a low temperature of about 00 ° C., the dehydrogenation reaction and polycondensation reaction shown in Chemical formula 1 above can be promoted, and a silicon nitride film in which —NH is replaced by active oxygen in ozone can be formed. Since such a silicon nitride film can avoid a change in air, that is, a strain due to the presence of —NH, a crack can be prevented from occurring in a dry etching process or the like.
【００１５】[0015]
【実施例】以下、本発明の実施例を詳細に説明する。 実施例１ まず、シリコン基板上にペルヒドロ系ポリシラザン溶液
を０．１μｍの厚さ塗布した。つづいて、この塗布膜を
大気雰囲気中、ＵＶ照射を行いながら２００℃で焼成し
た。この焼成工程において、前記ＵＶ照射により前記塗
布膜中のペルヒドロ系ポリシラザンは前記化１に示す脱
水素反応、縮重合反応が促進され、水素の残留に起因す
る−ＮＨ量が低減されたシリコン窒化膜が形成された。EXAMPLES Examples of the present invention will be described in detail below. Example 1 First, a perhydro-based polysilazane solution was applied on a silicon substrate to a thickness of 0.1 μm. Subsequently, this coating film was baked at 200 ° C. in the atmosphere while UV irradiation was being performed. In the baking step, the UV irradiation accelerates the dehydrogenation reaction and the condensation polymerization reaction of the perhydro-based polysilazane in the coating film, and the silicon nitride film in which the amount of --NH resulting from the residual hydrogen is reduced. Was formed.
【００１６】次いで、前記シリコン窒化膜上にリソグラ
フィ技術によりレジストパターンを形成し、前記レジス
トパターンをマスクとして前記窒化膜を選択的にエッチ
ング除去してシリコン窒化膜パターンを形成した。その
後、前記シリコン窒化膜パターンをマスクとして前記シ
リコン基板をＣＦ4 系プラズマ中でドライエッチングを
行った。このドライエッチング工程において、前記シリ
コン窒化膜パターンはクラックが全く発生せず、良好な
エッチングマスクとして使用することができた。Next, a resist pattern was formed on the silicon nitride film by a lithographic technique, and the nitride film was selectively removed by etching using the resist pattern as a mask to form a silicon nitride film pattern. Then, the silicon substrate was dry-etched in CF 4 plasma using the silicon nitride film pattern as a mask. In this dry etching step, the silicon nitride film pattern had no cracks and could be used as a good etching mask.
【００１７】実施例２ まず、シリコン基板上にペルヒドロ系ポリシラザン溶液
を０．１μｍの厚さ塗布した。つづいて、この塗布膜を
オゾンを含む雰囲気中でＵＶ照射を行いながら２００℃
で焼成した。この焼成工程において、前記ＵＶ照射によ
り前記塗布膜中のペルヒドロ系ポリシラザンは前記化１
に示す脱水素反応、縮重合反応が促進され、同時に−Ｎ
Ｈがオゾン中の活性な酸素で置換されたシリコン窒化膜
が形成された。Example 2 First, a perhydro-based polysilazane solution was applied on a silicon substrate to a thickness of 0.1 μm. Subsequently, this coating film is irradiated with UV in an atmosphere containing ozone at 200 ° C.
It was baked in. In this baking step, the perhydro-based polysilazane in the coating film is converted to the chemical formula 1 by the UV irradiation.
The dehydrogenation reaction and polycondensation reaction shown in are promoted, and at the same time -N
A silicon nitride film was formed in which H was replaced by active oxygen in ozone.
【００１８】次いで、前記シリコン窒化膜上にリソグラ
フィ技術によりレジストパターンを形成し、前記レジス
トパターンをマスクとして前記窒化膜を選択的にエッチ
ング除去してシリコン窒化膜パターンを形成した。その
後、前記シリコン窒化膜パターンをマスクとして前記シ
リコン基板をＣＦ4 系プラズマ中でドライエッチングを
行った。このドライエッチング工程において、前記シリ
コン窒化膜パターンはクラック発生が皆無であり、良好
なエッチングマスクとして使用することができた。Next, a resist pattern was formed on the silicon nitride film by a lithographic technique, and the nitride film was selectively removed by etching using the resist pattern as a mask to form a silicon nitride film pattern. Then, the silicon substrate was dry-etched in CF 4 plasma using the silicon nitride film pattern as a mask. In this dry etching step, the silicon nitride film pattern had no cracks and could be used as a good etching mask.
【００１９】[0019]
【発明の効果】以上詳述したように、本発明によれば膜
質が安定したシリコン窒化膜を低温焼成により形成で
き、ひいては半導体装置の製造工程におけるエッチング
マスクとして有効に利用できる等顕著な効果を奏する。As described in detail above, according to the present invention, it is possible to form a silicon nitride film having stable film quality by low temperature firing, and to effectively use it as an etching mask in a semiconductor device manufacturing process. Play.
【図１】ペルヒドロ系ポリシラザン溶液の塗布膜の焼成
温度と得られたシリコン窒化膜のＩＲスペクトルの関係
を示す特性図。FIG. 1 is a characteristic diagram showing a relationship between a firing temperature of a coating film of a perhydro-polysilazane solution and an IR spectrum of the obtained silicon nitride film.
Claims (2)
を塗布した後、ＵＶ照射を行いながら焼成することを特
徴とするシリコン窒化膜の形成方法。1. A method for forming a silicon nitride film, which comprises applying a perhydro-based polysilazane solution on a substrate and baking the solution while irradiating with UV.
を塗布した後、オゾンを含む雰囲気中でＵＶ照射を行い
ながら焼成することを特徴とするシリコン窒化膜の形成
方法。2. A method for forming a silicon nitride film, which comprises applying a perhydro-polysilazane solution on a substrate and baking the solution while irradiating UV in an atmosphere containing ozone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP314994A JPH07206410A (en) | 1994-01-17 | 1994-01-17 | Formation of silicon nitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP314994A JPH07206410A (en) | 1994-01-17 | 1994-01-17 | Formation of silicon nitride film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07206410A true JPH07206410A (en) | 1995-08-08 |
Family
ID=11549301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP314994A Pending JPH07206410A (en) | 1994-01-17 | 1994-01-17 | Formation of silicon nitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07206410A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0947722A (en) * | 1995-08-11 | 1997-02-18 | Tokyo Ohka Kogyo Co Ltd | Formation of silica based coating film |
| JP2000100699A (en) * | 1998-09-22 | 2000-04-07 | Toshiba Corp | Pattern formation method |
| JP2005116706A (en) * | 2003-10-06 | 2005-04-28 | Tokyo Electron Ltd | Method and equipment for heat treatment |
| JP2006269899A (en) * | 2005-03-25 | 2006-10-05 | Toshiba Corp | Method of manufacturing semiconductor apparatus |
| WO2011158119A2 (en) | 2010-06-17 | 2011-12-22 | Ａｚエレクトロニックマテリアルズ株式会社 | Formation method for silicon oxynitride film, and substrate having silicon oxynitride film manufactured using same |
| US8084372B2 (en) | 2007-08-24 | 2011-12-27 | Tokyo Electron Limited | Substrate processing method and computer storage medium |
| JP2014528857A (en) * | 2011-09-26 | 2014-10-30 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Multi-layer structure providing improved gas impermeability |
| WO2019049735A1 (en) * | 2017-09-11 | 2019-03-14 | 東京エレクトロン株式会社 | Method for forming insulating film, apparatus for processing substrate, and system for processing substrate |
| WO2022106436A1 (en) | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Method of manufacturing silicon nitrogeneous film |
-
1994
- 1994-01-17 JP JP314994A patent/JPH07206410A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0947722A (en) * | 1995-08-11 | 1997-02-18 | Tokyo Ohka Kogyo Co Ltd | Formation of silica based coating film |
| JP2000100699A (en) * | 1998-09-22 | 2000-04-07 | Toshiba Corp | Pattern formation method |
| JP2005116706A (en) * | 2003-10-06 | 2005-04-28 | Tokyo Electron Ltd | Method and equipment for heat treatment |
| JP2006269899A (en) * | 2005-03-25 | 2006-10-05 | Toshiba Corp | Method of manufacturing semiconductor apparatus |
| US8084372B2 (en) | 2007-08-24 | 2011-12-27 | Tokyo Electron Limited | Substrate processing method and computer storage medium |
| US9029071B2 (en) | 2010-06-17 | 2015-05-12 | Merck Patent Gmbh | Silicon oxynitride film formation method and substrate equipped with silicon oxynitride film formed thereby |
| WO2011158119A2 (en) | 2010-06-17 | 2011-12-22 | Ａｚエレクトロニックマテリアルズ株式会社 | Formation method for silicon oxynitride film, and substrate having silicon oxynitride film manufactured using same |
| JP2014528857A (en) * | 2011-09-26 | 2014-10-30 | コミッサリア ア レネルジー アトミーク エ オ ゼネルジ ザルタナテイヴ | Multi-layer structure providing improved gas impermeability |
| US9771654B2 (en) | 2011-09-26 | 2017-09-26 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Multilayer structure offering improved impermeability to gases |
| WO2019049735A1 (en) * | 2017-09-11 | 2019-03-14 | 東京エレクトロン株式会社 | Method for forming insulating film, apparatus for processing substrate, and system for processing substrate |
| JPWO2019049735A1 (en) * | 2017-09-11 | 2020-10-01 | 東京エレクトロン株式会社 | Insulating film film formation method, substrate processing equipment and substrate processing system |
| WO2022106436A1 (en) | 2020-11-20 | 2022-05-27 | Merck Patent Gmbh | Method of manufacturing silicon nitrogeneous film |
| KR20230097214A (en) | 2020-11-20 | 2023-06-30 | 메르크 파텐트 게엠베하 | Manufacturing method of silicon nitrogen film |
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