JPH01129972A - Formation of silicon oxynitride film - Google Patents
Formation of silicon oxynitride filmInfo
- Publication number
- JPH01129972A JPH01129972A JP28889787A JP28889787A JPH01129972A JP H01129972 A JPH01129972 A JP H01129972A JP 28889787 A JP28889787 A JP 28889787A JP 28889787 A JP28889787 A JP 28889787A JP H01129972 A JPH01129972 A JP H01129972A
- Authority
- JP
- Japan
- Prior art keywords
- base material
- silicon
- oxide film
- silicon nitride
- nitride oxide
- 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052710 silicon Inorganic materials 0.000 title abstract description 9
- 239000010703 silicon Substances 0.000 title abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 239000000463 material Substances 0.000 claims abstract description 20
- 230000005855 radiation Effects 0.000 claims abstract description 4
- 230000005284 excitation Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 23
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 21
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000012159 carrier gas Substances 0.000 abstract description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BPFJPVNVBGKWFG-UHFFFAOYSA-N 1-diaminosilyloxybutane Chemical group C(CCC)O[SiH](N)N BPFJPVNVBGKWFG-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（発明の目的）
産業上の利用分野
本発明は、電子素子等を製造するに当って、基材の表面
を被覆するためのシリコン窒化酸化膜を形成する方法に
関する。DETAILED DESCRIPTION OF THE INVENTION (Object of the Invention) Industrial Field of Use The present invention relates to a method for forming a silicon nitride oxide film for covering the surface of a base material in manufacturing electronic devices and the like.
従来の技術
シリコン窒化酸化膜は、耐蝕性や絶縁性並びに基材との
親和性が優れているところから、電子素子製造時の絶縁
膜や保護膜あるいはマスク材料等に利用される。BACKGROUND OF THE INVENTION Silicon nitride oxide films are used as insulating films, protective films, mask materials, etc. in the manufacture of electronic devices because of their excellent corrosion resistance, insulation properties, and compatibility with base materials.
シリコン基材上にシリコン窒化酸化膜を形成するには、
高温下で水を含んだアンモニアガスと接触させる方法等
があるが、シリコン基材以外の基材には使用できない欠
点がある。したがって、基材の材質に制約されることが
ない化学気相成長法（ＣＶＤ法）が提案されている。
゛かかるＣＶＤ法の一つとして、シランと
アンモニアと水の混合ガスを８００’ＣＬＸ上の温度で
基材と接触させ、基材の表面にシリコン窒化酸化膜を形
成する方法があるが、この方法は三つの成分ガスの混合
比の制御が難かしく、膜組成が一定となりにくい欠点が
ある。 ゛また、上記のシラン
に換えて、ジクロロシランを用いる方法があるが、この
方法は塩化アンモニウムのダストが生成し基材が汚染さ
れ易い欠点がある。To form a silicon nitride oxide film on a silicon substrate,
There are methods such as contacting with ammonia gas containing water at high temperatures, but these methods have the drawback that they cannot be used with base materials other than silicon base materials. Therefore, a chemical vapor deposition method (CVD method) that is not limited by the material of the base material has been proposed.
One such CVD method is a method in which a mixed gas of silane, ammonia, and water is brought into contact with the substrate at a temperature above 800'CLX to form a silicon nitride oxide film on the surface of the substrate. However, it is difficult to control the mixing ratio of the three component gases, making it difficult to maintain a constant film composition. Furthermore, there is a method of using dichlorosilane instead of the above-mentioned silane, but this method has the disadvantage that ammonium chloride dust is generated and the substrate is likely to be contaminated.
また、シランと水を含むアンモニアの低圧混合ガス中で
高周波放電等を利用してプラズマを生成させ、基材表面
にシリコン窒化酸化膜を形成する方法がある。この方法
は高温に耐えない基材に対しても適用できる利点がある
が、形成された膜に応力が残留し易くクラックの発生な
どの欠陥を生じ易いほか、不必要な元素特に水素などが
膜中に残留し易く、この水素が基材中に移動して基材の
性質を変化させ、製造された素子の特性を損なう原因と
なる欠点がある。Another method is to generate plasma using high frequency discharge or the like in a low-pressure mixed gas of ammonia containing silane and water to form a silicon nitride oxide film on the surface of the substrate. This method has the advantage of being applicable to substrates that cannot withstand high temperatures; however, stress tends to remain in the formed film and defects such as cracks are likely to occur, and unnecessary elements, especially hydrogen, may There is a disadvantage that hydrogen tends to remain in the substrate, and this hydrogen migrates into the substrate, changing the properties of the substrate and impairing the characteristics of the manufactured device.
さらにまた、シランと窒素と酸化窒素の混合ガスを紫外
線照射した基材の表面に接触させ、基材表面にシリコン
窒化酸化膜を形成する方法がある。Furthermore, there is a method in which a mixed gas of silane, nitrogen, and nitrogen oxide is brought into contact with the surface of a base material irradiated with ultraviolet rays to form a silicon nitride oxide film on the surface of the base material.
この方法は高温の必要がなく、また、欠陥の少ない窒化
酸化膜が得られる利点があるが、膜組成が一定になりに
くく、膜の性能の再現性に欠ける欠点がある。This method does not require high temperatures and has the advantage of producing a nitrided oxide film with few defects, but has the disadvantage that the film composition is difficult to maintain constant and the film performance lacks reproducibility.
以上のようなＣＶＤ法では、使用する原料ガスの自然発
火や爆発の危険性が常につきまとう欠点がある。The CVD method described above has the drawback that there is always a risk of spontaneous combustion or explosion of the raw material gas used.
決しようとする５ 、
本発明は、組成が均一で性能のすぐれたシリコン窒化酸
化膜を再現性よく形成し、かつ、製造工程中自然発火や
爆発を起さない安全な方法を提供しようとするものであ
る。5. The present invention aims to provide a safe method for forming a silicon nitride oxide film with uniform composition and excellent performance with good reproducibility, and that does not cause spontaneous combustion or explosion during the manufacturing process. It is something.
（発明の構成）
間 １、を ′するための手
本発明は、高エネルギー状態下においた基材の表面に、
酸素−ケイ素−窒素結合を有する化合物を含む気体を接
触させることにより目的を達成することができる。(Structure of the Invention) The present invention provides a method for reducing the time 1.
The objective can be achieved by contacting a gas containing a compound having an oxygen-silicon-nitrogen bond.
本発明において用いられる酸素−ケイ素−窒素結合を有
する化合物としては、アミノアルコキシシラン化合物も
しくはアミノイミノアルコキシシラン化合物である。The compound having an oxygen-silicon-nitrogen bond used in the present invention is an aminoalkoxysilane compound or an aminoiminoalkoxysilane compound.
かかる化合物の例としては、化学式が 。An example of such a compound is the chemical formula:
（ｔ−Ｃ４Ｈ９０）２Ｓｉ （Ｎｌ２）２で表わされる
ジターシャリブトキシジアミノシラン、化学式が５
［（ｔ−Ｃ４Ｈ９０）２３１ＮＨ２１２ＮＨで表わされ
るビスジターシャリブトキシアミノシランイミド等のア
ミノアルコキシシラン類やアミノアルコキシシランイミ
ド類があげられる。 。(t-C4H90)2Si(Nl2)2 Aminoalkoxysilanes and aminoalkoxysilanimides such as bisditertoxybutoxyaminosilane, whose chemical formula is 5 [(t-C4H90)231NH212NH can be given. .
本発明においては、基材を高エネルギー状態下におくが
、これは例えばシリコンウェハーを熱板の上にのせて加
熱する方法とか、紫外線のような放射線の照射あるいは
プラズマ励起を使用する方法とか、あるいは加熱とこれ
らの方法を併用する方法によって達成される。In the present invention, the substrate is placed under high energy conditions, such as by placing a silicon wafer on a hot plate and heating it, by irradiating it with radiation such as ultraviolet rays, or by using plasma excitation. Alternatively, it can be achieved by a method that uses heating in combination with these methods.
本発明においてシリコン窒化酸化膜の原料となるアミノ
アルコキシシラン化合物またはアミノイミノアルコキシ
シラン化合物はガス状で基材と接゛触させるが、その際
、キャリアガスとしては経済性や安全性の点から不活性
ガスであるアルゴンまたは窒素ガスが好ましい。In the present invention, the aminoalkoxysilane compound or aminoiminoalkoxysilane compound that is the raw material for the silicon nitride oxide film is brought into contact with the base material in a gaseous state, but at that time, it is not necessary to use it as a carrier gas from the economical and safety points of view. The active gases argon or nitrogen gas are preferred.
また、これらの原料に少量のアンモニアガスを共存させ
ることによって、窒素含量の高いシリコン窒化酸化膜を
得ることもできる。Furthermore, by coexisting a small amount of ammonia gas with these raw materials, a silicon nitride oxide film with a high nitrogen content can be obtained.
また、同様に少量の酸素ガスを共存させることによって
、酸素含量の高いシリコン窒化酸化膜を得ることができ
る。 ゛ ・シリコン窒化酸化膜を形
成させる基材は、膜形成時における高エネルギー状態で
変質を起さない基材であればどのような基材でも使用で
きる。Similarly, by coexisting a small amount of oxygen gas, a silicon nitride oxide film with a high oxygen content can be obtained.゛ - Any base material can be used as the base material for forming the silicon nitride oxide film as long as it does not undergo deterioration in the high energy state during film formation.
宜塵五１
外気と隔離した反応室中にシリコンウェハーをのせる熱
板を設け、との反応室の一端から原料ガスを導入し、他
端から排出できる装置を構成した。Yijin 51 A hot plate on which a silicon wafer is placed was provided in a reaction chamber isolated from the outside air, and a device was constructed in which raw material gas could be introduced from one end of the reaction chamber and discharged from the other end.
反応室内を窒素で置換したのち、排出口より油回転真空
ポンプで排出した。After the inside of the reaction chamber was replaced with nitrogen, it was exhausted from the exhaust port using an oil rotary vacuum pump.
シリコンウェハーをのせた熱板の温度を５５０℃に保ち
、来れに７７℃に保ったビスジターシャリブトキシアミ
ノシランイミド（以下ＢＤＢＡＳＩという）の中にキャ
リヤーとして窒素ガスを０、４１／ｍｉｎの速度で送入
しＢＤＢＡＳＩガスを反応室の一端から導入し接触させ
た。この時、反応室に送入したＢＤＢＡＳＩの濃度は約
０．２８９看であり、反応室内圧は約８０Ｔｏｒｒであ
った。The temperature of the hot plate on which the silicon wafer was placed was maintained at 550°C, and nitrogen gas was fed as a carrier at a rate of 0.41/min into bisditary butoxyaminosilanimide (hereinafter referred to as BDBASI), which was kept at 77°C. BDBASI gas was introduced from one end of the reaction chamber and brought into contact with the reactor. At this time, the concentration of BDBASI fed into the reaction chamber was about 0.289 mn, and the pressure in the reaction chamber was about 80 Torr.
形成された膜の厚さは、５分間当り約３００人であり、
赤外吸収スペクトルの解析結果、ケイ素の窒化酸化膜で
あることがわかった。The thickness of the film formed is about 300 per 5 minutes,
Analysis of the infrared absorption spectrum revealed that it was a silicon nitride oxide film.
釆鳳烈λ
実施例１と全く同様な装置内に同様にシリコンウェハー
を置き、原料としてジターシャリブトキシジアミノシラ
ン（以下ＤＢＤＡＳという）を用いて、実施例１と同様
な操作を行った。この時、反応室に送入されたＤＢＤＡ
Ｓの濃度は約０．２９０／Ｉであった。A silicon wafer was similarly placed in the same apparatus as in Example 1, and the same operations as in Example 1 were performed using ditertiary butoxydiaminosilane (hereinafter referred to as DBDAS) as a raw material. At this time, the DBDA introduced into the reaction chamber
The concentration of S was approximately 0.290/I.
形成された膜の厚さは、５分間当り約３００人であり、
赤外吸収スペクトルの解析結果、ケイ素の窒化酸化膜で
あることがね力じた。The thickness of the film formed is about 300 per 5 minutes,
Analysis of the infrared absorption spectrum revealed that it was a silicon nitride oxide film.
（発明の効果）
本発明によれば、酸素−ケイ素−窒素結合を有する化合
物を用いるＣＶＤ法によって、基材の表面にシリコン窒
化酸化膜を再現性よく形成することができ、その膜は均
質で歪みの少ない非晶質のすぐれた膜である特徴がある
。(Effects of the Invention) According to the present invention, a silicon nitride oxide film can be formed on the surface of a base material with good reproducibility by a CVD method using a compound having an oxygen-silicon-nitrogen bond, and the film is homogeneous. It is characterized by an excellent amorphous film with little distortion.
本法によって製造されたシリコン窒化酸化膜は製造され
る電子素子の特性に悪影響を与えることなく、充分な素
子への保護力を備えた均一な膜であり、電子素子の性能
の安定化にすぐれた効果がある。The silicon nitride oxide film produced by this method is a uniform film that has sufficient protection for the electronic devices without adversely affecting the characteristics of the electronic devices being manufactured, and is excellent in stabilizing the performance of electronic devices. It has a positive effect.
また、本法で使用される原料ガスは自然発火や爆発の危
険性が全くない利点がある。Furthermore, the raw material gas used in this method has the advantage of having no risk of spontaneous combustion or explosion.
Claims (6)
−ケイ素−窒素結合を有する化合物を含む気体を接触さ
せ、素材表面にシリコン窒化酸化膜を形成する方法。(1) A method in which a gas containing a compound having an oxygen-silicon-nitrogen bond is brought into contact with the surface of a base material under a high energy condition to form a silicon nitride oxide film on the surface of the material.
ズマ励起の少なくともその一方を用いて生成されたもの
である、特許請求の範囲第１項記載のシリコン窒化酸化
膜の形成方法。(2) The method for forming a silicon nitride oxide film according to claim 1, wherein the high energy state is generated using at least one of radiation irradiation and plasma excitation.
載のシリコン窒化酸化膜の形成方法。(3) The method for forming a silicon nitride oxide film according to claim 2, wherein the radiation is ultraviolet rays.
ものである、特許請求の範囲第１項記載のシリコン窒化
酸化膜の形成方法。(4) The method for forming a silicon nitride oxide film according to claim 1, wherein the high energy state is at a temperature of 900° C. or lower.
したものである、特許請求の範囲第２項または第３項記
載のシリコン窒化酸化膜の形成方法。(5) The method for forming a silicon nitride oxide film according to claim 2 or 3, wherein the high energy state is used in combination with a temperature of 700° C. or lower.
ノアルコキシシラン化合物もしくはアミノイミノアルコ
キシシラン化合物である、特許請求の範囲第１項記載の
シリコン窒化酸化膜の形成方法。(6) The method for forming a silicon nitride oxide film according to claim 1, wherein the compound having an oxygen-silicon-nitrogen bond is an aminoalkoxysilane compound or an aminoiminoalkoxysilane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288897A JP2585029B2 (en) | 1987-11-16 | 1987-11-16 | Method of forming silicon oxynitride film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62288897A JP2585029B2 (en) | 1987-11-16 | 1987-11-16 | Method of forming silicon oxynitride film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01129972A true JPH01129972A (en) | 1989-05-23 |
| JP2585029B2 JP2585029B2 (en) | 1997-02-26 |
Family
ID=17736199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62288897A Expired - Fee Related JP2585029B2 (en) | 1987-11-16 | 1987-11-16 | Method of forming silicon oxynitride film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2585029B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004186210A (en) * | 2002-11-29 | 2004-07-02 | Applied Materials Inc | Method for forming silicon compound film comprising nitrogen |
| WO2018182305A1 (en) * | 2017-03-29 | 2018-10-04 | Dnf Co., Ltd. | Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition |
| WO2018182318A1 (en) * | 2017-03-29 | 2018-10-04 | Dnf Co., Ltd. | Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same |
| US11358974B2 (en) | 2017-03-29 | 2022-06-14 | Dnf Co., Ltd. | Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition |
-
1987
- 1987-11-16 JP JP62288897A patent/JP2585029B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004186210A (en) * | 2002-11-29 | 2004-07-02 | Applied Materials Inc | Method for forming silicon compound film comprising nitrogen |
| WO2018182305A1 (en) * | 2017-03-29 | 2018-10-04 | Dnf Co., Ltd. | Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition |
| WO2018182318A1 (en) * | 2017-03-29 | 2018-10-04 | Dnf Co., Ltd. | Composition for depositing silicon-containing thin film and method for manufacturing silicon-containing thin film using the same |
| US11358974B2 (en) | 2017-03-29 | 2022-06-14 | Dnf Co., Ltd. | Silylamine compound, composition for depositing silicon-containing thin film containing the same, and method for manufacturing silicon-containing thin film using the composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2585029B2 (en) | 1997-02-26 |
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