JPS62185878A - Method for growing metal in vapor phase - Google Patents
Method for growing metal in vapor phaseInfo
- Publication number
- JPS62185878A JPS62185878A JP2820186A JP2820186A JPS62185878A JP S62185878 A JPS62185878 A JP S62185878A JP 2820186 A JP2820186 A JP 2820186A JP 2820186 A JP2820186 A JP 2820186A JP S62185878 A JPS62185878 A JP S62185878A
- Authority
- JP
- Japan
- Prior art keywords
- growth
- metal
- substrate
- vapor phase
- hydrogen
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 26
- 239000002184 metal Substances 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims description 8
- 239000012808 vapor phase Substances 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001947 vapour-phase growth Methods 0.000 claims description 4
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 abstract description 2
- 150000002902 organometallic compounds Chemical class 0.000 abstract 3
- RFONJRMUUALMBA-UHFFFAOYSA-N 2-methanidylpropane Chemical compound CC(C)[CH2-] RFONJRMUUALMBA-UHFFFAOYSA-N 0.000 abstract 2
- 239000007858 starting material Substances 0.000 abstract 2
- 150000002739 metals Chemical class 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- BLJHFCVPKWOHJX-UHFFFAOYSA-N ethylgallium Chemical compound CC[Ga] BLJHFCVPKWOHJX-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔概要〕
有機金属に水素を混合することにより、金属の成長速度
を大きくして被覆性に冨んだ金属の気相成長（ＣＶＤ）
法を提起し、複雑構造のデバイスの配線法として応用す
る。[Detailed Description of the Invention] [Summary] Vapor phase growth (CVD) of metals with increased coating properties by increasing the growth rate of metals by mixing hydrogen with organic metals.
We propose a new method and apply it as a wiring method for devices with complex structures.
本発明は成長速度の大きい金属の気相成長法に関する。 The present invention relates to a metal vapor phase growth method with a high growth rate.
ＣＶＤ法は半導体デバイスの製造プロセスに広く用いら
れ、導電膜、半導体膜として多結晶珪素等、絶縁膜、耐
食刻膜、耐酸化膜として窒化珪素、二酸化珪素等、配線
膜としてアルミニウム（Ａｔ）、タングステン（−）、
モリブデン（ＭＯ）、チタン（Ｔｉ）等金属の成膜に使
用される。The CVD method is widely used in the manufacturing process of semiconductor devices, and uses polycrystalline silicon, etc. as conductive films and semiconductor films, silicon nitride, silicon dioxide, etc. as insulating films, anti-etching films, and oxidation-resistant films, and aluminum (At), etc. as wiring films. Tungsten (-),
It is used to form films of metals such as molybdenum (MO) and titanium (Ti).
金属のＣＶＤ法は有機金属の熱分解によるが、成長温度
を低温化するために成長速度を上げる必要があるが、そ
れには限界がある。The CVD method for metals relies on thermal decomposition of organic metals, and although it is necessary to increase the growth rate in order to lower the growth temperature, there are limits to this.
一方、近年デバイスの複雑、微細にともない、プロセス
上深い段差被覆が必要になり、そのために成長速度の増
大が望まれる。On the other hand, in recent years, as devices have become more complex and finer, deep step coverage has become necessary in the process, and therefore an increase in the growth rate is desired.
以下本発明においては、半導体デバイスの配線層として
最も広く使用されているアル起ニウムを例にとり説明す
る。In the following, the present invention will be explained using aluminum, which is most widely used as a wiring layer of semiconductor devices, as an example.
従来のアルミニウムのＣＶＤ法は、有機金属としてしＴ
ｉｎ＾（トリイソブチルアルミニウム） 、ＴＭＡ（ト
リメチルアルミニウム）、ＴＥＡ（トリエチルアルミニ
ウム）をヘリウム（Ｈｅ）、アルゴン（Ａｒ）等でバブ
リングして被成長基板上に導き、約３００℃で熱分解し
て、この基板上に成長する。The conventional CVD method for aluminum uses T as an organic metal.
in^ (triisobutylaluminum), TMA (trimethylaluminum), and TEA (triethylaluminum) are bubbled with helium (He), argon (Ar), etc., introduced onto the growth substrate, and thermally decomposed at about 300°C. grow on this substrate.
この場合、成長速度は約５００人／分と遅く、原料ガス
の蒸気圧が低いため、これ以上に成長速度を上げること
は困難である。In this case, the growth rate is as slow as about 500 people/min, and because the vapor pressure of the raw material gas is low, it is difficult to increase the growth rate any further.
従来の金属のＣＶＤ法は成長速度が低く、複雑な構造の
デバイスの配線には不充分であった。Conventional metal CVD methods have low growth rates and are inadequate for wiring devices with complex structures.
上記問題点の解決は、原料ガスとしての有機金属と水素
とを混合して被成長基板上に導入し、発熱反応をともな
う、該有機金属の熱分解により金属を該被成長基板上に
析出する本発明による金属の気相成長方法により達成さ
れる。The solution to the above problem is to mix organic metal and hydrogen as raw material gases, introduce the mixture onto the growth substrate, and deposit the metal onto the growth substrate through thermal decomposition of the organic metal accompanied by an exothermic reaction. This is achieved by the method of vapor phase growth of metals according to the present invention.
例えば、有機金属としてＴＩＢＡ （Ａｔ（ｉ−ＣＪｑ
）３．１−Ｃ４１１ｇはイソブチル基〕を用いた場合に
ついて説明する。For example, TIBA (At(i-CJq
)3.1-C411g is an isobutyl group] will be explained.
従来例による反応は、
八１（ｉ−ＣＪｑ）３ →Ａｌ ＋ （３／２）１１
□＋３Ｃｆｈ ＝Ｃ（Ｃ１１３）ｚ。The reaction according to the conventional example is 81(i-CJq)3 →Al + (3/2)11
□+3Cfh =C(C113)z.
となるが、本発明による反応は、
Ａｔ（ｉ−ＣＪｑ）３＋ｎＨ２−ＡＩ＋ｍ１ｌｚ＋３Ｃ
ＩＩｚＣＨ（ＣＩ＋）ｇ ＋（ここにｎ＞ｍ ）。However, the reaction according to the present invention is At(i-CJq)3+nH2-AI+m1lz+3C
IIzCH(CI+)g+ (where n>m).
となる。becomes.
ここで有機金属に水素混合の効果は、つぎの通り考えら
れる。Here, the effect of mixing hydrogen with the organic metal can be considered as follows.
（１） 濃度平衡の観点よりの考察
上２式の右辺の不飽和炭化水素（イソブチレン３ＧＨｚ
＝Ｃ（ＣＨ３）ｚ ）より、飽和炭化水素〔イソブタン
３ＣＨｓＣＨ（ＣＨ３）ｚ ）の方が蒸気圧が高く、従
−２て基板上の反応界面では蒸気圧の高い方が拡散しや
すいため濃度が下がる。そのために本発明の反応は右辺
の方向に進行する。(1) Considering from the viewpoint of concentration equilibrium, the unsaturated hydrocarbon (isobutylene 3 GHz
The vapor pressure of saturated hydrocarbon [isobutane3CHsCH(CH3)z ) is higher than that of =C(CH3)z ), and therefore, at the reaction interface on the substrate, the higher the vapor pressure, the easier it is to diffuse, so the concentration is lower. Go down. Therefore, the reaction of the present invention proceeds in the direction on the right side.
（２） 温度平衡の観点よりの考察
上記の反応はいずれも発熱反応で、発熱により反応は左
辺の方向に進もうとするが、本発明の場合は熱伝導率の
大きい水素により反応によって生じた熱を除去すること
により、反応を右辺の方向に継続させることができる。(2) Consideration from the viewpoint of temperature equilibrium All of the above reactions are exothermic reactions, and the reaction tends to proceed in the direction on the left side due to heat generation, but in the case of the present invention, hydrogen with high thermal conductivity causes the reaction to occur. Removal of heat allows the reaction to continue in the right direction.
参考のために、１１□等の熱伝導率
（ｃａｌ／ｓｅｃ ｃｍ”（”Ｃ／ｃｏ＋））をつぎに
示す。For reference, the thermal conductivity (cal/sec cm"("C/co+)) of 11 □ etc. is shown below.
Ｈ２Ｎｚ ｆｌｅ Ａｒ
４７１．１１ ６５．７１ ３７６．０？ ４５．４
６ Ｘｌ０−’以上の作用により、成長速度の増大が期
待できる。H2Nz fle Ar 471.11 65.71 376.0? 45.4
An increase in the growth rate can be expected due to the effect of 6 Xl0-' or more.
第１図は本発明を実施するＣＶＤ装置の側断面図である
。FIG. 1 is a side sectional view of a CVD apparatus implementing the present invention.
図において、１は反応容器で、排気口２より通常の排気
系により排気される。In the figure, 1 is a reaction vessel, which is exhausted from an exhaust port 2 by a normal exhaust system.
３はガス混合容器兼シャワーで、４より原料ガスが、５
より水素が導入される。3 is a gas mixing container/shower, raw material gas is supplied from 4, and 5 is a shower.
More hydrogen is introduced.
反応容器１内のステージ６上には被成長基板７が載せら
れ、ヒータ８で加熱される。A growth substrate 7 is placed on a stage 6 inside the reaction vessel 1 and heated by a heater 8 .
有機金ＪｉＴＩＢＡをヘリウムでバブリングしては１１
０３ＣＣ，水素は０〜１１００５ｃｃ導入して、圧力１
〜５Ｔｏｒｒ、３００℃で成長した。11 Bubbling organic gold JiTIBA with helium
03CC, 0~11005cc of hydrogen was introduced and the pressure was 1
Growth was at ~5 Torr and 300°C.
第２図は本発明による成長速度と水素流量の関係を示す
図である。・
図示されるように、水素導入により成長速度が３〜４倍
に増加することが分かる。FIG. 2 is a diagram showing the relationship between growth rate and hydrogen flow rate according to the present invention. - As shown in the figure, it can be seen that the growth rate increases by 3 to 4 times by introducing hydrogen.
実施例においては、アルミニウム成長の場合の有機金属
としてＴＩＢＡを用いたが、これの代わりにＴＭＡ 、
ＴＥＡを用いた場合も本発明の効果は同様である。In the examples, TIBA was used as the organometallic in the case of aluminum growth, but TMA, TMA,
Even when TEA is used, the effects of the present invention are similar.
また、アルミニウム以外のを機金属、トリメチルガリウ
ムＴＭＧ、）リエチルガリウムＴＥＧ、トリプロピルガ
リウムＴＰＧ等ガリウムの有機金属、その他モリブテン
、インジウム等の有機金属を用いた成長に対しても、本
発明の要旨は変わらない。The gist of the present invention also applies to growth using organic metals other than aluminum, organic metals of gallium such as trimethyl gallium TMG, ethyl gallium TEG, and tripropyl gallium TPG, and other organic metals such as molybdenum and indium. remains unchanged.
以上説明したように本発明によれば、従来の金属のＣＶ
Ｏ法に比し成長速度が大きく、複雑な構造のデバイスの
配線に応用できる。As explained above, according to the present invention, the conventional metal CV
It has a faster growth rate than the O method and can be applied to wiring of devices with complex structures.
第１図は本発明を実施するＣＶＤ装置の側断面図、第２
図は本発明による成長速度と水素流量の関係を示す図で
ある。
図において、
１は反応容器、
２は排気口、
３はガス混合容器兼シャワー、
４は原料ガス導入口、
５は水素導入口、
６はステージ、
７は被成長基板、
凹FIG. 1 is a side sectional view of a CVD apparatus implementing the present invention, and FIG.
The figure is a diagram showing the relationship between growth rate and hydrogen flow rate according to the present invention. In the figure, 1 is a reaction vessel, 2 is an exhaust port, 3 is a gas mixing container/shower, 4 is a raw material gas inlet, 5 is a hydrogen inlet, 6 is a stage, 7 is a growth substrate, concave
Claims (1)
板上に導入し、 発熱反応をともなう、該有機金属の熱分解により金属を
該被成長基板上に析出する ことを特徴とする金属の気相成長方法。[Claims] Mixing an organic metal as a raw material gas and hydrogen and introducing the mixture onto a growth substrate, and depositing a metal on the growth substrate by thermal decomposition of the organic metal accompanied by an exothermic reaction. A metal vapor phase growth method characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2820186A JPS62185878A (en) | 1986-02-12 | 1986-02-12 | Method for growing metal in vapor phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2820186A JPS62185878A (en) | 1986-02-12 | 1986-02-12 | Method for growing metal in vapor phase |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62185878A true JPS62185878A (en) | 1987-08-14 |
Family
ID=12242054
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2820186A Pending JPS62185878A (en) | 1986-02-12 | 1986-02-12 | Method for growing metal in vapor phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62185878A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5074970A (en) * | 1973-11-02 | 1975-06-19 | ||
| JPS61136681A (en) * | 1984-12-04 | 1986-06-24 | Nec Corp | Thermal cvd method |
| JPS6220870A (en) * | 1985-07-18 | 1987-01-29 | Fujitsu Ltd | Chemical vapor phase growing method for aluminum layer |
-
1986
- 1986-02-12 JP JP2820186A patent/JPS62185878A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5074970A (en) * | 1973-11-02 | 1975-06-19 | ||
| JPS61136681A (en) * | 1984-12-04 | 1986-06-24 | Nec Corp | Thermal cvd method |
| JPS6220870A (en) * | 1985-07-18 | 1987-01-29 | Fujitsu Ltd | Chemical vapor phase growing method for aluminum layer |
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