JP2977150B2 - Method for manufacturing silicon dioxide insulating film - Google Patents
Method for manufacturing silicon dioxide insulating filmInfo
- Publication number
- JP2977150B2 JP2977150B2 JP7071860A JP7186095A JP2977150B2 JP 2977150 B2 JP2977150 B2 JP 2977150B2 JP 7071860 A JP7071860 A JP 7071860A JP 7186095 A JP7186095 A JP 7186095A JP 2977150 B2 JP2977150 B2 JP 2977150B2
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- Japan
- Prior art keywords
- insulating film
- sio
- gas
- target
- substrate
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】この発明は、太陽電池、トランジ
スタ等の半導体素子に用いられる二酸化シリコン（Ｓｉ
Ｏ2 ）絶縁膜の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicon dioxide (Si) used for semiconductor devices such as solar cells and transistors.
O 2 ) A method for producing an insulating film.
【０００２】[0002]
【従来の技術】従来、ＳｉＯ2 絶縁膜は、シリコン（Ｓ
ｉ）を高温状態に保ったまま酸化性のガスを流すことに
より酸化させる熱酸化法、酸化シリコン（ＳｉＯ2 ）を
ターゲッ トに用いたスパッタ法、ＳｉＨ4 ＋Ｏ2 等を
原料ガスとした熱ＣＶＤ法、ＴＥＯＳ（Tetra-Ethyl-Or
tho-Silicate）を原料に用いたプラズマＣＶＤ法等の方
法により形成されていた。 2. Description of the Related Art Conventionally, an SiO 2 insulating film has been made of silicon (S).
thermal oxidation method in which i) is oxidized by flowing an oxidizing gas while maintaining a high temperature state, sputtering method using silicon oxide (SiO 2 ) as a target, thermal CVD using SiH 4 + O 2 or the like as a source gas Method, TEOS (Tetra-Ethyl-Or
tho-Silicate) as a raw material by a method such as a plasma CVD method.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上述し
た熱酸化法及び熱ＣＶＤ法は、１０００℃程度の高温を
必要とするため加熱装置を必要とし、製造プロセスが複
雑になるという問題があった。また、ＳｉＯ2 絶縁膜を
形成中に半導体素子に不純物の拡散や化学変化といった
悪影響を引き起こす恐れがあった。However, the above-described thermal oxidation method and thermal CVD method require a high temperature of about 1000 ° C., and thus require a heating device, and have a problem that the manufacturing process becomes complicated. In addition, during formation of the SiO 2 insulating film, there is a possibility that an adverse effect such as diffusion of impurities or chemical change may be caused in the semiconductor element.
【０００４】ＳｉＯ2 をターゲットとしたスパッタの場
合には、ターゲットから基板に向かっ てＳｉＯ2 が一
方向に飛来するためにステップカバレージ（Step cover
age）が悪く、凹凸形状を持った基板の部分によってＳ
ｉＯ2 絶縁膜の膜厚が大きく異なるという問題点があっ
た。また、同様の理由により、従来の方法では膜厚１ｎ
ｍ以下の単分子レベルの超薄膜ＳｉＯ2 絶縁膜を均一に
形成することが困難であった。[0004] In the case of sputtering using SiO 2 as a target, step coverage (Step cover) is required because SiO 2 flies in one direction from the target toward the substrate.
age) is poor, and S
There is a problem that the thickness of the iO 2 insulating film is greatly different. For the same reason, the conventional method has a film thickness of 1n.
It has been difficult to uniformly form an ultra-thin SiO 2 insulating film having a molecular weight of less than m.
【０００５】この発明は、上述した従来の問題点を解消
するためになされたものにして、高温を必要とせずに簡
単なプロセスでステップカバレージの良好なＳｉＯ2 絶
縁膜の製造方法を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and provides a method of manufacturing an SiO 2 insulating film having good step coverage by a simple process without requiring a high temperature. With the goal.
【０００６】[0006]
【課題を解決するための手段】この発明は、スパッタ法
を用いて基板上にＳｉＯ2 絶縁膜を形成するＳｉＯ2絶
縁膜の製造方法であって、プラズマ生成用ガスとして炭
酸ガスまたは希ガスと炭酸ガス（ＣＯ2 ）の混合ガスを
用いてＳｉターゲットをスパッタすることを特徴とす
る。SUMMARY OF THE INVENTION The present invention provides a method for producing a SiO 2 insulating film to form the SiO 2 insulating film on a substrate using a sputtering method, a carbon dioxide gas or a rare gas as the plasma generation gas It is characterized in that a Si target is sputtered using a mixed gas of carbon dioxide (CO 2 ).
【０００７】上記混合ガスはＣＯ2 を１％以上含むよう
に希ガスとＣＯ2 とを混合すると良い。[0007] The mixed gas may be mixed with the CO 2 noble gases to include CO 2 than 1%.
【０００８】また、Ｓｉターゲット中の酸素量を原子数
で３０％以下にすると良い。It is preferable that the amount of oxygen in the Si target is 30% or less in terms of the number of atoms.
【０００８】[0008]
【作用】この発明は、スパッタにより、Ｓｉターゲット
からＳｉ原子やＳｉ原子の集合体が放出される。これら
が希ガスとＣＯ2 の混合ガスまたはＣＯ2 ガスのプラズ
マと反応することにより、Ｓｉ がＣＯ2 中のＯと結合
し、ＳｉＯ2 絶縁膜が形成される。According to the present invention, Si atoms or aggregates of Si atoms are released from a Si target by sputtering. When these react with a mixed gas of rare gas and CO 2 or a plasma of CO 2 gas, Si is combined with O in CO 2 to form an SiO 2 insulating film.
【０００９】その際混合ガスにＣＯ2 が１％以上含まれ
ると、ＳｉとＯの組成比が１対２のＳｉＯ2 絶縁膜が形
成される。[0009] At this time CO 2 mixed gas is contained more than 1%, the composition ratio of Si and O is 1: 2 of the SiO 2 insulating film is formed.
【００１０】そして、Ｓｉ−Ｏ結合はプラズマ中ででき
るため、高温は必要としない。更に、ターゲットから基
板に向かってＳｉは一方向に飛来するが、これが種々の
方向の速度を持ったプラズマ中のＣＯ2 （又はＣＯ2 が
プラズマ中で分解した励起種）と反応することによりＳ
ｉＯ2 絶縁膜が形成されるので、ステップカバレージが
ＳｉＯ2 をターゲットとしてＡｒガスを用いた従来のス
パッタ法と比べて大幅に改善される。また、ＣＯ2 （又
はＣＯ2 がプラズマ中で分解した励起種）と反応したＳ
ｉのみがＳｉＯ2 絶縁膜の成膜に寄与するため、成膜は
モノレイヤ（monolayer）に近い単位で起こり、１ｎｍ
以下の超薄膜の形成が従来よりも容易に行える。[0010] Since the Si-O bond is formed in the plasma, a high temperature is not required. Further, Si flies in one direction from the target toward the substrate, and this reacts with CO 2 (or an excited species in which CO 2 is decomposed in the plasma) in the plasma having velocities in various directions to cause S to fly.
Since the iO 2 insulating film is formed, the step coverage is greatly improved as compared with the conventional sputtering method using SiO 2 as a target and using Ar gas. In addition, S reacts with CO 2 (or an excited species in which CO 2 is decomposed in plasma).
Since only i contributes to the formation of the SiO 2 insulating film, the film formation occurs in a unit close to a monolayer and is 1 nm.
The following ultra-thin films can be formed more easily than before.
【００１１】[0011]
【実施例】以下、この発明の実施例につき図面を参照し
て説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１２】図１は、この発明が適用される高周波スパ
ッタ装置の概略図である。FIG. 1 is a schematic diagram of a high frequency sputtering apparatus to which the present invention is applied.
【００１３】図１において、１はＳｉターゲット、２は
プラズマ生成用ガスでこの実施例では、希ガスとしての
ＡｒとＣＯ2 との混合ガス、３は金属や絶縁体等からな
る基板、４は基板加熱機構を内蔵したアース電極、５は
マグネトロン放電用磁石を内蔵した高周波電極、６はＳ
ＵＳ製の真空チャンバ、７は真空排気口である。In FIG. 1, reference numeral 1 denotes a Si target, 2 denotes a plasma generating gas, and in this embodiment, a mixed gas of Ar and CO 2 as a rare gas, 3 denotes a substrate made of a metal or an insulator, and 4 denotes a substrate. Earth electrode with built-in substrate heating mechanism, 5 high-frequency electrode with built-in magnetron discharge magnet, 6 S
The US vacuum chamber 7 is a vacuum exhaust port.
【００１４】この図１に示す装置を用いて、高周波マグ
ネトロンスパッタにより表１に示すスパッタ条件で基板
３にシリコンの酸化膜を形成した。Using the apparatus shown in FIG. 1, a silicon oxide film was formed on the substrate 3 by high frequency magnetron sputtering under the sputtering conditions shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】そして、ＡｒとＣＯ2 との混合ガスとの混
合比を変化、すなわち、それぞれのガスの流量比を変え
て基板３上にシリコンの酸化膜を形成した。混合ガスの
混合比（流量比）とシリコンの酸化膜の組成を調べた結
果を表２に示す。Then, a silicon oxide film was formed on the substrate 3 by changing the mixing ratio of the mixed gas of Ar and CO 2 , that is, changing the flow ratio of each gas. Table 2 shows the results obtained by examining the mixing ratio (flow rate ratio) of the mixed gas and the composition of the silicon oxide film.
【００１７】[0017]
【表２】 [Table 2]
【００１８】表２より、Ａｒ：ＣＯ2 の混合比が１：
０．０１から０：１の間、すなわちＣＯ2 ガスを１％以
上含むガスを用いると、ＳｉとＯの比が１対２のＳｉＯ
2 絶縁膜を形成するのに適していることが分かる。According to Table 2, the mixing ratio of Ar: CO 2 is 1:
When a gas containing 0.01 to 0: 1, that is, a gas containing 1% or more of CO 2 gas, is used, the ratio of Si to O is 1: 2.
2 It can be seen that it is suitable for forming an insulating film.
【００１９】なお、炭素（Ｃ）は赤外吸収法では観測さ
れず、原子数で１％又はそれ以下と思われる。Ｃ量が少
ない理由は明らかではないが、Ｓｉ−Ｏ結合エネルギー
（３６９ｋＪ／ｍｏｌ）がＳｉ−Ｃ結合エネルギー（２
９０ｋＪ／ｍｏｌ）よりも大きいこと、およびＳｉＯ2
は固体であるがＣＯ、ＣＯ2 は通常気体であるので成長
表面から離脱しやすいこと等より、Ｃは膜中に取り込ま
れにくいと考えられる。Incidentally, carbon (C) is not observed by the infrared absorption method, and is considered to be 1% or less in terms of the number of atoms. It is not clear why the C content is small, but the Si—O bond energy (369 kJ / mol) is lower than the Si—C bond energy (2 kJ / mol).
90 kJ / mol) and SiO 2
Is a solid, but it is considered that C is hardly taken into the film because CO and CO 2 are usually gases and thus easily separated from the growth surface.
【００２０】この実施例において、ＣＯ2 ：Ａｒ＝１：
１の条件で、形成時間の調整により、アルミニウム基板
上に１ｎｍ以下の任意の膜厚のＳｉＯ2 絶縁膜を形成で
きた。従来の熱ＣＶＤ法および熱酸化法では、１０００
℃程度の高温を必要とするため、ＳｉＯ2 とアルミニウ
ムの合金層が形成され、１ｎｍ以下のＳｉＯ2 絶縁膜は
形成できなかった。また、従来のＳｉＯ2 をターゲット
に用いたスパッタ法では、大きさ数ｎｍのＳｉＯ2 のク
ラスターも基板に飛来するため、やはり膜厚１ｎｍ以下
の均一なＳｉ酸化膜は形成できなかった。In this embodiment, CO 2 : Ar = 1:
Under condition 1, the SiO 2 insulating film having an arbitrary thickness of 1 nm or less was formed on the aluminum substrate by adjusting the formation time. In the conventional thermal CVD method and thermal oxidation method, 1000
Since a high temperature of about ° C. was required, an alloy layer of SiO 2 and aluminum was formed, and a SiO 2 insulating film of 1 nm or less could not be formed. In the conventional sputtering method using SiO 2 as a target, a cluster of SiO 2 having a size of several nm also flies to the substrate, so that a uniform Si oxide film having a thickness of 1 nm or less could not be formed.
【００２１】なお、この実施例でプラズマ生成用ガスに
窒素ガス（Ｎ2 ）を加えることにより、酸化窒化シリコ
ンを形成することもできた。In this embodiment, silicon oxynitride could be formed by adding nitrogen gas (N 2 ) to the plasma generation gas.
【００２２】図２は、この発明が適用される４極スパッ
タ装置の概略図である。FIG. 2 is a schematic diagram of a quadrupole sputtering apparatus to which the present invention is applied.
【００２３】図２において、１はＳｉターゲット、１２
はプラズマ生成用ガスでこの実施例では、ＡｒとＣＯ2
との混合ガス、１３は表面に凹凸が形成されたシリコン
（Ｓｉ）基板、１４はアース電極、１５は高周波電極、
１６はプラズマ生成用陽極、１７はプラズマ生成用陰
極、１８は石英製の真空チャンバ、１９はプラズマ閉じ
込め用の電磁石、２０は真空排気口である。In FIG. 2, 1 is a Si target, 12
Is a gas for plasma generation, and in this embodiment, Ar and CO 2
13 is a silicon (Si) substrate having irregularities on its surface, 14 is a ground electrode, 15 is a high-frequency electrode,
Reference numeral 16 denotes an anode for plasma generation, 17 denotes a cathode for plasma generation, 18 denotes a vacuum chamber made of quartz, 19 denotes an electromagnet for confining plasma, and 20 denotes a vacuum exhaust port.
【００２４】この図２に示す装置を用いて、表３に示す
スパッタ条件で基板１３にＳｉＯ2絶縁膜を形成した。Using the apparatus shown in FIG. 2, a SiO 2 insulating film was formed on the substrate 13 under the sputtering conditions shown in Table 3.
【００２５】[0025]
【表３】 [Table 3]
【００２６】図３は、Ｓｉターゲット中の酸素量をそれ
ぞれ変化させて、表３に示す条件でＳｉＯ2 絶縁膜を形
成し、凹凸の表面を有する基板１３上に形成されたＳｉ
Ｏ2絶縁膜３２の断面をＳＥＭで観察した結果を示す模
式図である。同図（ａ）はＳｉターゲット中の酸素量が
原子数で０％、（ｂ）は３０％、（ｃ）は５０％であ
る。FIG. 3 shows that an SiO 2 insulating film was formed under the conditions shown in Table 3 by changing the amount of oxygen in the Si target, and that the Si film was formed on a substrate 13 having an uneven surface.
FIG. 4 is a schematic diagram showing a result of observing a cross section of the O 2 insulating film 32 with an SEM. FIG. 3A shows that the amount of oxygen in the Si target is 0% in atomic number, FIG. 3B shows 30%, and FIG. 3C shows 50%.
【００２８】この図３に示すように、Ｓｉターゲット中
の酸素量によってＳｉＯ2 絶縁膜３２の膜厚に差があっ
た。すなわち、Ｓｉターゲット中の酸素量が多いほど、
基板３１上のＳｉＯ2 絶縁膜３２の膜厚むらが大きくな
った。酸素量が３０％以下であれば、膜厚むらは小さか
った。As shown in FIG. 3, the thickness of the SiO 2 insulating film 32 varied depending on the amount of oxygen in the Si target. That is, as the amount of oxygen in the Si target increases,
The thickness unevenness of the SiO 2 insulating film 32 on the substrate 31 was increased. When the oxygen content was 30% or less, the film thickness unevenness was small.
【００２７】尚、以上の実施例では希ガスとしてＡｒを
用いたが、これに限るものではなく、Ｈｅ，Ｎｅ，Ｋ
ｒ，Ｘｅといった他の希ガスを用いることもできる。In the above embodiment, Ar is used as the rare gas. However, the present invention is not limited to this. He, Ne, K
Other rare gases such as r and Xe can also be used.
【００２８】[0028]
【発明の効果】以上説明したように、この発明は、スパ
ッタ法を用いてＳｉＯ2 絶縁膜を形成する際に、炭酸ガ
スまたは希ガスとＣＯ2 の混合ガスを用いてＳｉターゲ
ットをスパッタすることにより、従来の熱酸化法や熱Ｃ
ＶＤ法で問題であった高温プロセスの必要がなく、簡単
なプロセスで形成することができる。As described above, according to the present invention, when an SiO 2 insulating film is formed by a sputtering method, a Si target is sputtered using a carbon dioxide gas or a mixed gas of a rare gas and CO 2. The conventional thermal oxidation method and thermal C
There is no need for a high-temperature process, which is a problem in the VD method, and it can be formed by a simple process.
【００２９】また、従来のＳｉＯ2 をターゲットとした
スパッタ法で問題であったステップカバレージの悪さ、
すなわち凹凸基板における膜厚むらの問題なく、均一な
ＳｉＯ2 絶縁膜を形成することができる。In addition, poor step coverage, which is a problem in the conventional sputtering method using SiO 2 as a target,
That is, a uniform SiO 2 insulating film can be formed without a problem of unevenness in the thickness of the uneven substrate.
【００３０】さらに、ＣＯ2 （又はＣＯ2 がプラズマ中
で分解した励起種）と反応したＳｉのみがＳｉＯ2 絶縁
膜の成膜に寄与するため、成膜はモノレイヤに近い単位
で起こり、従来形成できなかった膜厚１ｎｍ以下の超薄
膜ＳｉＯ2 絶縁膜を形成することができる。Furthermore, since only Si that has reacted with CO 2 (or an excited species in which CO 2 is decomposed in plasma) contributes to the formation of the SiO 2 insulating film, the film formation occurs in a unit close to a monolayer. An ultra-thin SiO 2 insulating film having a thickness of 1 nm or less, which could not be formed, can be formed.
【図１】この発明が適用される高周波スパッタ装置の概
略図である。FIG. 1 is a schematic diagram of a high frequency sputtering apparatus to which the present invention is applied.
【図２】この発明が適用される４極スパッタ装置の概略
図である。FIG. 2 is a schematic view of a quadrupole sputtering apparatus to which the present invention is applied.
【図３】表面が凹凸の形状を持ったシリコン基板上に形
成したＳｉＯ2 絶縁膜の断面をＳＥＭで観察した模式図
である。FIG. 3 is a schematic view of a cross section of an SiO 2 insulating film formed on a silicon substrate having an uneven surface, observed by SEM.
１ Ｓｉターゲット ２、１２ プラズマ生成用ガス ３、１３ 基板 ４、１４ アース電極 ５、１５ 高周波電極 ６ 真空チャンバ ７ 真空排気口 １６ プラズマ生成用陽極 １７ プラズマ生成用陰極 １８ 真空チャンバ １９ 電磁石 ２０ 真空排気口 DESCRIPTION OF SYMBOLS 1 Si target 2,12 Plasma generation gas 3,13 Substrate 4,14 Ground electrode 5,15 High frequency electrode 6 Vacuum chamber 7 Vacuum exhaust port 16 Plasma generation anode 17 Plasma generation cathode 18 Vacuum chamber 19 Electromagnet 20 Vacuum exhaust port
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C23C 14/00 - 14/58 H01L 21/312 - 21/32 ＩＮＳＰＥＣ（ＤＩＡＬＯＧ) ＪＩＣＳＴファイル（ＪＯＩＳ)────────────────────────────────────────────────── ─── Continued on the front page (58) Fields surveyed (Int. Cl. 6 , DB name) C23C 14/00-14/58 H01L 21/312-21/32 INSPEC (DIALOG) JICST file (JOIS)
Claims (3)
コン絶縁膜を形成する二酸化シリコン絶縁膜の製造方法
であって、プラズマ生成用ガスとして炭酸ガス（Ｃ
Ｏ2）または希ガスと炭酸ガスの混合ガスを用いてシリ
コンターゲットをスパッタすることを特徴とする二酸化
シリコン絶縁膜の製造方法。1. A method for manufacturing a silicon dioxide insulating film, comprising forming a silicon dioxide insulating film on a substrate by a sputtering method, wherein a carbon dioxide gas (C
A method for manufacturing a silicon dioxide insulating film, comprising sputtering a silicon target using O 2 ) or a mixed gas of a rare gas and a carbon dioxide gas.
とを特徴とする請求項１に記載の二酸化シリコン絶縁膜
の製造方法。2. The method according to claim 1, wherein the mixed gas contains 1% or more of CO 2 .
で３０％以下であることを特徴とする請求項１または２
に記載の二酸化シリコン絶縁膜の製造方法。3. The silicon target according to claim 1, wherein the amount of oxygen in the silicon target is 30% or less in terms of the number of atoms.
3. The method for producing a silicon dioxide insulating film according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7071860A JP2977150B2 (en) | 1995-03-29 | 1995-03-29 | Method for manufacturing silicon dioxide insulating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7071860A JP2977150B2 (en) | 1995-03-29 | 1995-03-29 | Method for manufacturing silicon dioxide insulating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08269706A JPH08269706A (en) | 1996-10-15 |
| JP2977150B2 true JP2977150B2 (en) | 1999-11-10 |
Family
ID=13472707
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7071860A Expired - Fee Related JP2977150B2 (en) | 1995-03-29 | 1995-03-29 | Method for manufacturing silicon dioxide insulating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2977150B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6002109B2 (en) * | 2013-10-24 | 2016-10-05 | 住友電気工業株式会社 | Method for manufacturing group III nitride semiconductor device |
-
1995
- 1995-03-29 JP JP7071860A patent/JP2977150B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH08269706A (en) | 1996-10-15 |
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