JPH0298932A - Manufacture of silicon oxide film - Google Patents
Manufacture of silicon oxide filmInfo
- Publication number
- JPH0298932A JPH0298932A JP25255188A JP25255188A JPH0298932A JP H0298932 A JPH0298932 A JP H0298932A JP 25255188 A JP25255188 A JP 25255188A JP 25255188 A JP25255188 A JP 25255188A JP H0298932 A JPH0298932 A JP H0298932A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- silicon oxide
- oxide film
- silicon
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000007789 gas Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 16
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 abstract description 13
- 235000013842 nitrous oxide Nutrition 0.000 abstract description 9
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 56
- 150000004706 metal oxides Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- -1 but instead of this Chemical compound 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、酸化シリコン膜の製造方法に関する。詳しく
は、有機シランと酸素ガスまたは非金属酸化物ガスとを
用いたプラズマＣＶＤ法にである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a silicon oxide film. Specifically, it is a plasma CVD method using organic silane and oxygen gas or nonmetal oxide gas.
［従来の技術］
従来における、薄膜トランジスタのゲート絶縁膜やパッ
ジベージロン膜などに用いられている酸化シリコン膜は
、シラン系ガスと非金属酸化物ガスを用いて、いわゆる
ＣＶＤ法で形成する方法が実施されている。例えば、減
圧容器中にグロー放電領域を形成し、同容器中にモノシ
ランガスと笑気ガス（−酸化二窒素ガス）との混合ガス
を導入し、基板上に酸化シリコン膜を成膜させる。[Prior Art] Conventionally, the silicon oxide film used for the gate insulating film and the padding film of thin film transistors is formed by the so-called CVD method using silane-based gas and non-metallic oxide gas. ing. For example, a glow discharge region is formed in a reduced pressure container, a mixed gas of monosilane gas and laughing gas (-dinitrogen oxide gas) is introduced into the container, and a silicon oxide film is formed on the substrate.
［発明が解決しようとする課題］
上記のような薄膜トランジスタのゲート絶な膜やパッジ
ベージロン膜等に用いられるこの種の酸化シリコン膜に
要求される特性は、■絶縁耐圧が高く、■分極等のヒス
テリシス特性が小さく、■電荷の蓄積が少ない、■屈折
率が小さいこと等である。[Problems to be Solved by the Invention] The characteristics required of this type of silicon oxide film used for the gate isolation film and padded film of thin film transistors as described above are: 1) high dielectric strength voltage, and 2) low hysteresis such as polarization. It has small characteristics such as (1) low charge accumulation, and (2) low refractive index.
しかしながら、有機シランと非金属酸化物ガスを用いる
従来のプラズマＣＶＤ法で成膜された酸化シリコン膜は
、薄膜トランジスタのゲート絶縁膜等に用いるに必要な
特性を満足することができなかった。これは、酸化シリ
コン膜の反応成長中に生成するハイドロカーボン基やヒ
ドロキシル基が、同酸化シリコン膜中に残留することが
その主な原因である。However, the silicon oxide film formed by the conventional plasma CVD method using organic silane and non-metal oxide gas has not been able to satisfy the characteristics necessary for use as a gate insulating film of a thin film transistor. The main reason for this is that hydrocarbon groups and hydroxyl groups generated during the reaction growth of the silicon oxide film remain in the silicon oxide film.
すなわち、酸化シリコン膜中にハイドロカーボン基が残
存すると、酸化シリコン膜の屈折率が高くなる。また、
酸化シリコン膜にヒドロキシル基が残存すると、同酸化
シリコン膜中の絶縁耐圧が低く、分極等のヒステリ特性
が大きく、電荷の蓄積が大きくなる等の問題を生じる。That is, when hydrocarbon groups remain in the silicon oxide film, the refractive index of the silicon oxide film increases. Also,
When hydroxyl groups remain in the silicon oxide film, problems arise such as the silicon oxide film has a low dielectric breakdown voltage, large hysterical characteristics such as polarization, and large charge accumulation.
本発明の目的は、前記従来の問題点に鑑み、これを解決
することができる該酸化シリコン膜の製造方法を提供す
ることにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a silicon oxide film that can solve the above-mentioned conventional problems.
〔課題を解決するための手段］
すなわち、前記本発明の目的を達成するため採用された
第一の手段の要旨は、減圧容器中にグロー放電領域を形
成し、同容器中に有機シランと酸素ガスまたは非金属酸
化物ガスを導入して基板上に酸化シリコン膜を形成する
方法においで、前記減圧容器に導入される有機シランと
酸素ガスまたは非金属酸化物ガスとの混合ガスの珪素原
子に対する酸素原子の成分比を１００以上とする酸化シ
リコン膜の製造方法である。[Means for Solving the Problems] That is, the gist of the first means adopted to achieve the object of the present invention is to form a glow discharge region in a reduced pressure container, and place organic silane and oxygen in the container. In the method of forming a silicon oxide film on a substrate by introducing a gas or a non-metal oxide gas, the mixed gas of organic silane and oxygen gas or non-metal oxide gas introduced into the reduced pressure container has an effect on silicon atoms. This is a method for manufacturing a silicon oxide film in which the component ratio of oxygen atoms is 100 or more.
また、第二の手段の要旨は、前記酸化シリコン腰の製造
方法において、基板の温度を３３０℃以上に加熱する方
法である。Moreover, the gist of the second means is a method of heating the substrate to a temperature of 330° C. or higher in the method for manufacturing the silicon oxide base.
〔作 用］
第１図は、減圧容器内に導入する混合ガスの酸素原子／
珪素原子の組成比と、成膜された酸化シリコン膜に残存
するハイドロカーボン基の８１−〇基に対する比（α５
ｒ−ｃｓ３／α１ｔ−ａ）との関係、及び同組成比と、
成膜された酸化シリコン膜の屈折率の関係の一例を示す
グラフである。本発明は、このグラフに示された事実を
着目することにより、なされたものである。[Function] Figure 1 shows the oxygen atoms/
The composition ratio of silicon atoms and the ratio of hydrocarbon groups remaining in the formed silicon oxide film to 81-0 groups (α5
r-cs3/α1t-a) and the same composition ratio,
3 is a graph showing an example of the relationship between the refractive index of a deposited silicon oxide film. The present invention was made by paying attention to the fact shown in this graph.
すなわち、有機シランと酸素ガスまたは非金属酸化物ガ
スを用いてＣＶＤ法によって酸化シリコン膜を形成する
場合、上記混合ガスに含まれる珪素原子に対する酸素原
子の成分比を変化させると、第１図に実線で示すように
、成膜された酸化シリコン膜に残存するハイドロカーボ
ン基と５ｉ−０基との組成比が変化する。このグラフか
ら明かな通り、上記混合ガスの珪素原子に対する酸素原
子の成分比が、１００に満たない場合、成膜された酸化
シリコン膜中にハイドロカーボン基が残留し、その５ｉ
−０基に対する比は、上記酸素原子の比が毘くなるに従
って急激に減少する。そして、上記組成比が１００に達
しそれ以上になると、酸化シリコン膜中に残存するハイ
ドロカーボン基は膜中に残存しなくなる。That is, when forming a silicon oxide film by the CVD method using organic silane and oxygen gas or non-metal oxide gas, if the component ratio of oxygen atoms to silicon atoms contained in the mixed gas is changed, the result shown in FIG. As shown by the solid line, the composition ratio of hydrocarbon groups remaining in the formed silicon oxide film and 5i-0 groups changes. As is clear from this graph, when the ratio of oxygen atoms to silicon atoms in the mixed gas is less than 100, hydrocarbon groups remain in the formed silicon oxide film, and the 5i
The ratio to -0 groups sharply decreases as the ratio of oxygen atoms increases. When the composition ratio reaches or exceeds 100, the hydrocarbon groups remaining in the silicon oxide film no longer remain in the film.
さらに、酸化シリコン膜中にハイドロカーボン基が残存
する範囲、すなわち、上記混合ガスの珪素原子に対する
酸素原子の成分比が１００に満たない範囲において、成
膜された酸化シリコン膜の屈折率は、第１図において点
線で示すように、酸素／珪素の組成比が増大するｊこ従
って低減し、上記混合ガスの珪素原子に対する酸素原子
の成分比が１００に達すると、屈折率が約１．４６とな
り、それ以上では同じ屈折率で一定に推移する。従って
、本発明の第一の手段のように、上記混合ガスに含まれ
る珪素原子に対する酸素原子の成分比を１００以上に保
持することによって、成膜された酸化シリコン膜中のハ
イドロカーボン基を減少させ、その屈折率を最も低い値
に維持できる。Furthermore, in a range where hydrocarbon groups remain in the silicon oxide film, that is, in a range where the component ratio of oxygen atoms to silicon atoms in the mixed gas is less than 100, the refractive index of the silicon oxide film formed is As shown by the dotted line in Figure 1, when the oxygen/silicon composition ratio increases and decreases, and the ratio of oxygen atoms to silicon atoms in the mixed gas reaches 100, the refractive index becomes approximately 1.46. , above which the refractive index remains constant. Therefore, as in the first means of the present invention, by maintaining the component ratio of oxygen atoms to silicon atoms contained in the mixed gas at 100 or more, the hydrocarbon groups in the formed silicon oxide film are reduced. and maintain its refractive index at the lowest value.
次に、第２図は、育槻シランと酸素ガスまたは非金属酸
化物ガスを用（１でＣＶＤ法によって酸化シリコン膜を
形成する場合に、基板温度と成膜された酸化シリコン膜
中の酸化シリコン膜に残存するヒドロキシル基の５ｉ−
０基に対する比（αｏ−ｓ／α５ｌ−０） との関係
を実線で、基板温度と酸化シリコン膜の界面準位１（Ｎ
ｒｂ）との関係を点線で、基板温度と酸化シリコン膜の
ヒステリシスとの関係を一点鎖線で、基板温度と酸化シ
リコン膜の耐圧との関係を二点鎖線で各々示しである。Next, Figure 2 shows the relationship between the substrate temperature and the oxidation in the formed silicon oxide film when forming a silicon oxide film by the CVD method in step 1 using Ikutsuki silane and oxygen gas or non-metal oxide gas. 5i- of the hydroxyl group remaining in the silicon film
The solid line shows the relationship between the ratio of 0 groups (αos/α5l-0) and the relationship between the substrate temperature and the interface state 1 (N
rb) is shown by a dotted line, the relationship between the substrate temperature and the hysteresis of the silicon oxide film is shown by a one-dot chain line, and the relationship between the substrate temperature and the breakdown voltage of the silicon oxide film is shown by a two-dot chain line.
なお、基板温度は／にの単位で示しである。Note that the substrate temperature is expressed in units of /.
第２図に示すように該基板温度が３３０℃（１／Ｔ＝１
．６Ｅ！Ｘｌ０−りに満たない範囲において、成膜され
た酸化シリコン膜中に残存するヒドロキシル基は、温度
上昇に伴って漸次減少し、基板温度が３３０℃以上でヒ
ドロキシル基が残存しなくなる。また、酸化シリコンｒ
ＩＡの界面準位ｆｆ１ｌｂ）やヒステリシス量も、基板
温度が３３０℃に満たない場合は、高い値から基板温度
の上昇に伴って急激に低下し、基板温度が３３０℃以上
では低い値が底値的に推移する。As shown in Figure 2, the substrate temperature is 330°C (1/T=1
．． 6E! In the range below Xl0-, the hydroxyl groups remaining in the formed silicon oxide film gradually decrease as the temperature rises, and when the substrate temperature is 330° C. or higher, no hydroxyl groups remain. In addition, silicon oxide r
When the substrate temperature is less than 330°C, the IA interface state ff1lb) and the amount of hysteresis rapidly decrease from a high value as the substrate temperature rises, and when the substrate temperature is 330°C or higher, the lower value becomes the bottom value. Transition to .
これと共に、酸化シリコン膜の耐圧性も、基板温度が３
３０℃以下では、耐圧が急激に高くなり、基板温度３３
０℃で耐圧が３Ｘ１０’ｖ／ｃｍに達し、飽和する。本
発明はこの事実に着目し、酸化シリコン膜の成膜に際し
ての基板温度を３３０℃以上とすることを提案したもの
である。Along with this, the pressure resistance of the silicon oxide film also increases when the substrate temperature is 3.
Below 30℃, the withstand voltage increases rapidly and the substrate temperature increases to 33℃.
At 0°C, the withstand voltage reaches 3 x 10'v/cm and is saturated. The present invention focuses on this fact and proposes setting the substrate temperature at 330° C. or higher when forming a silicon oxide film.
［実 施 例］
次ぎに、第３図を参照しながら、本発明の実施例を詳細
に説明する。[Example] Next, an example of the present invention will be described in detail with reference to FIG.
（実施例１）
シリコン基板１を存機洗浄し、１％弗化水素酸にて表面
の酸化膜を除去し、純水で水洗した後、窒素ブローによ
り水分を除き、第３図に示すプラズマＣＶＤ装置内の基
板ホルダー２に固定した。排気装置４により、減圧容器
１内を減圧すると共に、基板ｌを基板ヒーター６により
湿度３５０℃に加熱した。上記減圧容器１内に笑気ガス
導入系５ｂから４５０ｓｅｃｍの流量で笑気ガスを、モ
ノメチルシランガス導入系５ａから１．５ｓｅｃｍの流
量でモノメチルシランを各々供給し、これらをガス混合
器５Ｃにて混合した後、減圧容器ｌ内に導入した。これ
により調整された減圧容器ｌ内の混合ガスの酸素原子／
珪素原子の組成比は３００である。なお、このとき同容
器ｌ内の圧力はＩ Ｔｏｒｒとした。(Example 1) The silicon substrate 1 was cleaned in a vacuum, the oxide film on the surface was removed with 1% hydrofluoric acid, and the oxide film on the surface was removed. After washing with pure water, moisture was removed by nitrogen blowing, and the plasma shown in FIG. It was fixed to the substrate holder 2 in the CVD apparatus. The pressure inside the vacuum container 1 was reduced by the exhaust device 4, and the substrate 1 was heated to a humidity of 350° C. by the substrate heater 6. Laughing gas is supplied into the vacuum container 1 at a flow rate of 450 seconds from the laughing gas introduction system 5b, and monomethylsilane is supplied at a flow rate of 1.5 seconds from the monomethylsilane gas introduction system 5a, and these are mixed in the gas mixer 5C. After that, it was introduced into a vacuum container 1. Oxygen atoms of the mixed gas in the reduced pressure vessel l adjusted by this /
The composition ratio of silicon atoms is 300. At this time, the pressure inside the container 1 was set to I Torr.
ＲＦｊｉＩ源３により、２００ ｍｍφ、２５ｍｍ間隔
の平行平板電極に１３．５６ＭＨｚのＲＦ電力を進行波
と反射波の差が１５Ｗとなる様に印加し、グロー放電を
起こし、シリコン基板ｌの上にプラズマＣＶＤ法による
酸化シリコン膜を形成した。そして、その酸化シリコン
膜の膜厚が１０００オングストロームになった時点で上
記ＲＦ電源３からの電力の給電を停止し、減圧容器１を
真空に維持したまま、基板１の温度を室温まで冷却した
後、同基板ｌを減圧容器１から取り出した。Using the RFjiI source 3, 13.56 MHz RF power was applied to parallel plate electrodes of 200 mmφ and 25 mm intervals so that the difference between the traveling wave and the reflected wave was 15 W, causing a glow discharge and generating plasma on the silicon substrate l. A silicon oxide film was formed using the CVD method. Then, when the thickness of the silicon oxide film reaches 1000 angstroms, the power supply from the RF power source 3 is stopped, and the temperature of the substrate 1 is cooled to room temperature while maintaining the reduced pressure vessel 1 in a vacuum. , the same substrate 1 was taken out from the vacuum container 1.
こうして得られた酸化シリコン膜の赤外吸収を測定し、
膜中に含まれるハイドロカーボーン基の残存量を、５ｉ
−０基量との比として算出したところ０であった。また
、エリプソ膜厚計ζごより屈折率を測定したところ、１
．４６であった。The infrared absorption of the silicon oxide film thus obtained was measured,
The remaining amount of hydrocarbon groups contained in the membrane is 5i
It was calculated as a ratio to the amount of -0 groups, and it was found to be 0. In addition, when the refractive index was measured using an ellipso film thickness meter ζ, it was found that 1
．． It was 46.
また比較のため、モノメチルシランガスの流量を１．５
ｓｅｃｍと一定に維持しながら、笑気ガスの流量を０〜
６００ｓｃｃｍの間で変化させて、減圧容器１内の混合
ガスの酸素原子／珪素原子の組成比を０〜４００の範囲
で変化させ、同様の方法でシリコン基板１の上に各々酸
化シリコン膜を成膜した。こうして得られた酸化シリコ
ン薄膜中に含まれるハイドロカーポーン基の残存量と屈
折率を求めた。For comparison, the flow rate of monomethylsilane gas was set to 1.5.
While maintaining the laughing gas flow rate at a constant value of sec.
600 sccm, the composition ratio of oxygen atoms/silicon atoms of the mixed gas in the reduced pressure vessel 1 was varied in the range of 0 to 400, and a silicon oxide film was formed on the silicon substrate 1 in the same manner. It was filmed. The remaining amount of hydrocarbon groups contained in the silicon oxide thin film thus obtained and the refractive index were determined.
この結果を、上記混合ガスの酸素原子／珪素原子の組成
比との関係で示したのが第１図である。すなわち第１図
では、酸化シリコン膜中に含まれるハイドロカーボン基
量と５ｉ−０基ｍとの比及び屈折率を縦軸にとり、モノ
メチルシランと笑気ガスの混合ガスに含まれる珪素原子
に対する酸素原子の組成比を横軸にとって示しである。FIG. 1 shows this result in relation to the oxygen atom/silicon atom composition ratio of the mixed gas. In other words, in FIG. 1, the ratio of the amount of hydrocarbon groups contained in the silicon oxide film to the 5i-0 group m and the refractive index are plotted on the vertical axis, and the ratio of oxygen to silicon atoms contained in the mixed gas of monomethylsilane and laughing gas is plotted on the vertical axis. The horizontal axis represents the atomic composition ratio.
既に述べた通り、上記混合ガスの珪素原子に対する酸素
原子の成分比を１００以上とすることにより、酸化シリ
コン膜に残存するハイドロカーボン基をほぼＯとするこ
とができ、同腹の屈折率を約１．４６の最も低い値に維
持できる。As already mentioned, by setting the ratio of oxygen atoms to silicon atoms in the mixed gas to 100 or more, the hydrocarbon groups remaining in the silicon oxide film can be made almost O, and the refractive index of the same gradient can be reduced to about 1. It can be maintained at the lowest value of .46.
（実施例２）
上記実施例１と同様にして得られた酸化シリコン膜の赤
外吸収を測定して、膜中に含まれるヒドロキシル基Ｍを
、５ｉ−０基量との比として算出した。また、真空蒸着
法により、膜厚５００オングストロームのＮｉＨからな
るドツト電極を形成して、ＭＯ８構造を構成し、基板と
該ドツト電極間の耐圧を測定した。更に、このＭＯ８構
造を用いて、界面準位量とＣ■特性のヒステリシスの大
きさを測定したところ、耐圧は１．０Ｘ１０’Ｖ／ｃｍ
、界面準位３１（Ｎｆｂ）は、３．５ＸｉＯ１１ヒステ
リシスｍはＯであった。(Example 2) The infrared absorption of a silicon oxide film obtained in the same manner as in Example 1 was measured, and the hydroxyl group M contained in the film was calculated as a ratio to the amount of 5i-0 groups. Furthermore, dot electrodes made of NiH with a thickness of 500 angstroms were formed by vacuum evaporation to form an MO8 structure, and the breakdown voltage between the substrate and the dot electrodes was measured. Furthermore, using this MO8 structure, we measured the amount of interface states and the magnitude of the hysteresis of the C characteristic, and found that the breakdown voltage was 1.0 x 10'V/cm.
, the interface level 31 (Nfb) was 3.5XiO11 hysteresis m was O.
また比較のため、基板温度を２００℃〜４００℃に変化
させて、同様の方法でシリコン基板１の上に各々酸化シ
リコン膜を成膜した。そして、上記と同様の方法で、膜
中に含まれるヒドロキシル基量と５ｉ−０基置との比、
間膜の耐圧、界面準位量及びＣＶ特性のヒステリシスを
各々測定した。For comparison, silicon oxide films were each formed on the silicon substrate 1 in the same manner while changing the substrate temperature from 200° C. to 400° C. Then, in the same manner as above, the ratio of the amount of hydroxyl groups contained in the film to the 5i-0 group,
The breakdown voltage of the interlayer, the amount of interface states, and the hysteresis of CV characteristics were measured.
この結果を第２図に示す。同図は耐圧、界面準位ＬＣＶ
特性のヒステリシスを縦軸にとり、基板温度をＩ／Ｔ
（／Ｋ）により横軸にとって示しである。既に述べた通
り、基板温度を３３０℃以上（１／Ｔ＝１．６６ｘｌＯ
−２）とすることにより、酸化シリコン膜に残存するヒ
ドロキシル基量をほぼＯとすることができ、間膜の耐圧
を高く、界面準位量とＣＶ特性を小さくすることができ
る。The results are shown in FIG. The figure shows breakdown voltage and interface level LCV.
The vertical axis is the hysteresis of the characteristics, and the board temperature is the I/T
(/K) indicates the horizontal axis. As already mentioned, the substrate temperature should be set to 330℃ or higher (1/T=1.66xlO
-2), the amount of hydroxyl groups remaining in the silicon oxide film can be approximately O, the withstand voltage of the interlayer can be increased, and the amount of interface states and CV characteristics can be reduced.
なお、上記各実施例に示された原料、条件等は一例であ
って、これらを様々に変えて実施することも可能である
。その主なものを以下に挙げる。It should be noted that the raw materials, conditions, etc. shown in each of the above-mentioned Examples are merely examples, and it is also possible to carry out the experiments with various changes. The main ones are listed below.
（ａ）上記実施例では、有機シランとしてモノメチルシ
ランを用いているが、これに代えてジメチルシラン、ト
リメチルシラン、テトラメチルシラン、及び前記の有機
シランのメチル基が他のアルキル基である有機シランを
用いても同等の結果が得られる。但し、有機シランが気
体でない場合は、該有機シランを気体にする方法、もし
くは霧状にして非金属酸化物ガスと混合する必要がある
。(a) In the above examples, monomethylsilane is used as the organic silane, but instead of this, dimethylsilane, trimethylsilane, tetramethylsilane, and organic silanes in which the methyl group of the organic silane is another alkyl group can be used. Equivalent results can be obtained using . However, if the organic silane is not a gas, it is necessary to convert the organic silane into a gas or form it into a mist and mix it with the non-metal oxide gas.
（ｂ）上記実施例では、非金属酸化物ガスとして笑気ガ
スを用いているが、これに代えて酸素等のＯｔガス、水
蒸気等のＨＯエガス、二酸化炭素などの００８ガス等を
用いても同等の結果が得られる。(b) In the above example, laughing gas is used as the non-metal oxide gas, but instead of this, Ot gas such as oxygen, HO gas such as water vapor, 008 gas such as carbon dioxide, etc. may be used. Equivalent results are obtained.
（ｃ）上記実施例では、平行平板型プラズマＣＶＤ装置
により実施されているが、これに代えて、グロー放電に
より非金属酸化物ガスと有機シランを分解することの出
来る他の形式のＣＶＤ装置を用いても同等な結果が得ら
れる。(c) In the above embodiment, a parallel plate type plasma CVD apparatus is used, but instead of this, another type of CVD apparatus capable of decomposing non-metal oxide gas and organic silane by glow discharge may be used. Equivalent results can be obtained by using
（ｄ）成膜圧力、ＲＦ電力３１、ＲＦ周波数、非金属酸
化物ガスと有機シランの全流量、電極面頂及び電極間隔
などの成膜条件も、グロー放電により非金屈酸化物ガス
と有機シランを分解することの出来る条件であれば、そ
れを適宜変えることは、本発明の作用、効果を失うもの
ではない。(d) Film-forming conditions such as film-forming pressure, RF power 31, RF frequency, total flow rates of non-metallic oxide gas and organic silane, electrode surface top and electrode spacing are also controlled by glow discharge. As long as the conditions are such that the silane can be decomposed, changing the conditions as appropriate will not impair the function and effect of the present invention.
〔発明の効果コ
以上説明した通り、本発明によれば、絶縁耐圧が高く、
分極等のヒステリシス特性が小さく、電荷の蓄積が小さ
い酸化シリコン膜が得られる。[Effects of the Invention] As explained above, according to the present invention, the dielectric strength is high;
A silicon oxide film with low hysteresis characteristics such as polarization and low charge accumulation can be obtained.
従って、薄膜トランジスタのゲート絶縁膜やバッジベー
ジジン膜などに用いるのに必要な諸特性を備えた酸化シ
リコン膜が、有機シランと酸素ガスまたは非金属酸化物
ガスとを用いたプラズマＣＶＤ法により製造が可能とな
る。Therefore, silicon oxide films with various properties necessary for use as gate insulating films and badge-base films of thin film transistors can be manufactured by the plasma CVD method using organic silane and oxygen gas or non-metal oxide gas. It becomes possible.
第１図は、膜中に含まれるハイドロカボーン基ｍと屈折
率の有機シランと非金属酸化物ガスの混合ガスに含まれ
る珪素原子に対する酸素原子の組成比に対するグラフで
ある。
第２図は、耐圧、界面準位３１、ＣＶ特性のヒステリシ
スの大きさの基板温度に対するグラフである。
第３図は、本発明の実施例に用いたプラズマＣＶＤ装置
を示す概念図である。
図中で１は減圧容器、２は基板ホルダー ３はＲＦ電源
、４は排気装［，５ａはモノメチルシランガス導入系、
５ｂは笑気ガス導入系、５Ｃはガス混合器、６は基板ヒ
ーターを示す。
特許出願人 工 業 技 術 院 長
間 上 太陽誘電株式会社
同 上 信越化学工業株式会社
第１図
Ｏ
０／Ｓｉ組成比
第２図
基板温度１／Ｔ（／Ｋ）FIG. 1 is a graph of the hydrocarbon group m contained in the film and the composition ratio of oxygen atoms to silicon atoms contained in a mixed gas of organic silane and nonmetal oxide gas having a refractive index. FIG. 2 is a graph of the breakdown voltage, the interface level 31, and the magnitude of hysteresis of the CV characteristic versus the substrate temperature. FIG. 3 is a conceptual diagram showing a plasma CVD apparatus used in an example of the present invention. In the figure, 1 is a vacuum container, 2 is a substrate holder, 3 is an RF power source, 4 is an exhaust system [, 5a is a monomethylsilane gas introduction system,
5b is a laughing gas introduction system, 5C is a gas mixer, and 6 is a substrate heater. Patent Applicant: Institute of Industrial Technology, Nagama, Taiyo Yuden Co., Ltd., Shin-Etsu Chemical Co., Ltd. Figure 1 O0/Si composition ratio Figure 2 Substrate temperature 1/T (/K)
Claims (2)
に有機シランと酸素ガスまたは非金属酸化物ガスを導入
して基板上に酸化シリコン膜を形成する方法において、
前記減圧容器に導入される有機シランと酸素ガスまたは
非金属酸化物ガスとの混合ガスの珪素原子に対する酸素
原子の成分比を１００以上とすることを特徴とする酸化
シリコン膜の製造方法。(1) In a method of forming a glow discharge region in a reduced pressure container and introducing organic silane and oxygen gas or nonmetal oxide gas into the container to form a silicon oxide film on a substrate,
A method for producing a silicon oxide film, characterized in that the mixed gas of organic silane and oxygen gas or nonmetal oxide gas introduced into the vacuum container has a component ratio of oxygen atoms to silicon atoms of 100 or more.
を３３０℃以上に加熱することを特徴とする酸化シリコ
ン膜の製造方法。(2) The method for manufacturing a silicon oxide film according to claim 1, characterized in that the temperature of the substrate is heated to 330° C. or higher.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252551A JP2660297B2 (en) | 1988-10-05 | 1988-10-05 | Method for manufacturing silicon oxide film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63252551A JP2660297B2 (en) | 1988-10-05 | 1988-10-05 | Method for manufacturing silicon oxide film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0298932A true JPH0298932A (en) | 1990-04-11 |
| JP2660297B2 JP2660297B2 (en) | 1997-10-08 |
Family
ID=17238946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63252551A Expired - Lifetime JP2660297B2 (en) | 1988-10-05 | 1988-10-05 | Method for manufacturing silicon oxide film |
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| Country | Link |
|---|---|
| JP (1) | JP2660297B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06240459A (en) * | 1993-02-16 | 1994-08-30 | G T C:Kk | Formation of silicon oxide thin film |
| JP2002026004A (en) * | 2000-06-30 | 2002-01-25 | Hynix Semiconductor Inc | Method of forming insulating film for semiconductor device |
| US7465679B1 (en) | 1993-02-19 | 2008-12-16 | Semiconductor Energy Laboratory Co., Ltd. | Insulating film and method of producing semiconductor device |
| JP2010028130A (en) * | 1998-05-29 | 2010-02-04 | Dow Corning Corp | Method for producing hydrogenated silicon oxycarbide film having low dielectric constant |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6450429A (en) * | 1987-08-20 | 1989-02-27 | Semiconductor Energy Lab | Formation of insulating film |
-
1988
- 1988-10-05 JP JP63252551A patent/JP2660297B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6450429A (en) * | 1987-08-20 | 1989-02-27 | Semiconductor Energy Lab | Formation of insulating film |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06240459A (en) * | 1993-02-16 | 1994-08-30 | G T C:Kk | Formation of silicon oxide thin film |
| US7465679B1 (en) | 1993-02-19 | 2008-12-16 | Semiconductor Energy Laboratory Co., Ltd. | Insulating film and method of producing semiconductor device |
| JP2010028130A (en) * | 1998-05-29 | 2010-02-04 | Dow Corning Corp | Method for producing hydrogenated silicon oxycarbide film having low dielectric constant |
| JP2002026004A (en) * | 2000-06-30 | 2002-01-25 | Hynix Semiconductor Inc | Method of forming insulating film for semiconductor device |
| JP4616492B2 (en) * | 2000-06-30 | 2011-01-19 | 株式会社ハイニックスセミコンダクター | Method for forming insulating film of semiconductor element |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2660297B2 (en) | 1997-10-08 |
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