JP2008007471A - Raw material for metal organic chemical vapor deposition (mocvd) method and method for producing silicon-containing film using the raw material - Google Patents
Raw material for metal organic chemical vapor deposition (mocvd) method and method for producing silicon-containing film using the raw material Download PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 43
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 title claims description 9
- 239000002184 metal Substances 0.000 title claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 title claims description 6
- 238000000034 method Methods 0.000 title abstract description 25
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 26
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 18
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 abstract description 33
- 239000010408 film Substances 0.000 description 90
- 230000015572 biosynthetic process Effects 0.000 description 61
- 150000003961 organosilicon compounds Chemical class 0.000 description 40
- 239000010409 thin film Substances 0.000 description 33
- 239000000758 substrate Substances 0.000 description 23
- 238000005160 1H NMR spectroscopy Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910004129 HfSiO Inorganic materials 0.000 description 14
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 7
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000005049 silicon tetrachloride Substances 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 150000002363 hafnium compounds Chemical class 0.000 description 4
- 150000002429 hydrazines Chemical group 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- PFJOTFSIBVZGPK-UHFFFAOYSA-N 1-ethyl-2-methylhydrazine Chemical compound CCNNC PFJOTFSIBVZGPK-UHFFFAOYSA-N 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- YCBOYOYVDOUXLH-UHFFFAOYSA-N 1,2-Diethylhydrazine Chemical compound CCNNCC YCBOYOYVDOUXLH-UHFFFAOYSA-N 0.000 description 2
- WHOYVSQXYWBSLY-UHFFFAOYSA-N 1-ethyl-2-propan-2-ylhydrazine Chemical compound CCNNC(C)C WHOYVSQXYWBSLY-UHFFFAOYSA-N 0.000 description 2
- ANLRYZKIYUPHRY-UHFFFAOYSA-N 1-methyl-2-propan-2-ylhydrazine Chemical compound CNNC(C)C ANLRYZKIYUPHRY-UHFFFAOYSA-N 0.000 description 2
- PRRZZGITWYAIGP-UHFFFAOYSA-N 1-tert-butyl-2-ethylhydrazine Chemical compound CCNNC(C)(C)C PRRZZGITWYAIGP-UHFFFAOYSA-N 0.000 description 2
- RLAAGLYHVAPVRG-UHFFFAOYSA-N 1-tert-butyl-2-methylhydrazine Chemical compound CNNC(C)(C)C RLAAGLYHVAPVRG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 150000001343 alkyl silanes Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002738 metalloids Chemical group 0.000 description 2
- HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- VBCSQFQVDXIOJL-UHFFFAOYSA-N diethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VBCSQFQVDXIOJL-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Formation Of Insulating Films (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本発明は、有機金属化学気相成長法（Metal Organic Chemical Vapor Deposition、以下、ＭＯＣＶＤ法という。）にてＳｉＮ薄膜やＨｆＳｉＯ薄膜等のシリコン含有膜を作製するための原料として好適なＭＯＣＶＤ法用原料及び該原料を用いたシリコン含有膜の製造方法に関するものである。 The present invention is a MOCVD method material suitable as a material for producing a silicon-containing film such as a SiN thin film or a HfSiO thin film by metal organic chemical vapor deposition (hereinafter referred to as MOCVD method). And a method for producing a silicon-containing film using the raw material.
ウェーハのパッシベーション膜には、ＳｉＮ系絶縁膜が広く用いられている。ＳｉＮ系絶縁膜を成膜する方法としては、基板上に形成されたＡｌ配線等の低融点材料層にダメージを与えないように、プラズマＣＶＤ法によって低温での成膜が行われている。ここでの原料ガスとしては、シラン／アンモニア混合ガス、シラン／窒素混合ガス等が用いられている。
しかしプラズマＣＶＤ法により形成されるＳｉＮ系絶縁膜の段差被覆性は、半導体装置の微細化や多層配線化に伴う基板の表面段差の増大に対応できず、ボイドが形成されたり、クラックが発生し易くなっていた。
A SiN insulating film is widely used as a wafer passivation film. As a method of forming a SiN-based insulating film, film formation is performed at a low temperature by a plasma CVD method so as not to damage a low melting point material layer such as an Al wiring formed on the substrate. As the source gas here, a silane / ammonia mixed gas, a silane / nitrogen mixed gas, or the like is used.
However, the step coverage of the SiN insulating film formed by the plasma CVD method cannot cope with the increase in the level difference of the substrate surface due to the miniaturization of semiconductor devices and the multilayer wiring, resulting in the formation of voids and cracks. It was easy.
そこで段差被覆性に優れたＳｉＮ系絶縁膜を成膜する方法として、原料ガスに有機シリコン化合物を用いてＣＶＤ法を行うことが検討及び開発されている。[(ＣＨ3)2Ｎ]4Ｓｉ等のＳｉ原子とＮ原子との結合（Ｓｉ−Ｎ結合）を有する化合物を原料ガスとして成膜を行うと、Ｓｉ−Ｎ結合の存在により効率のよいＳｉＮ系絶縁膜の成膜が可能となる。また成膜時に有機シリコン化合物から炭化水素基が切断されることでＳｉ−Ｎ結合を存続した中間生成物が高分子化されやすく、流動性が高くなるために、段差被覆性に優れたＳｉＮ系絶縁膜が成膜できると考えられている。 Therefore, as a method for forming a SiN-based insulating film having excellent step coverage, it has been studied and developed to perform a CVD method using an organic silicon compound as a source gas. When film formation is performed using a compound having a bond of Si atom and N atom (Si—N bond) such as [(CH 3 ) 2 N] 4 Si as a source gas, SiN is more efficient due to the presence of the Si—N bond. A system insulating film can be formed. Moreover, since the hydrocarbon group is cleaved from the organic silicon compound during film formation, the intermediate product in which the Si—N bond is maintained is easily polymerized, and the fluidity is increased. It is considered that an insulating film can be formed.
一方、高誘電体ゲート絶縁膜としてシリコン酸化膜が使用されているが、近年ＬＳＩの高集積化に伴って、シリコン酸化膜の薄膜化が進んでいる。膜厚が１００ｎｍ以下の薄さとなった薄膜にはトンネル電流が流れて絶縁効果が低下してしまうため、シリコン酸化膜でのこれ以上の薄膜化は限界となっている。
そのためシリコン酸化膜に代わるゲート絶縁膜が要望されており、候補としてＨｆＳｉＯ等が注目されている。これら薄膜の製造方法としては、スパッタリング、イオンプレーティング、塗布熱分解、ゾルゲル等のＭＯＤが挙げられるが、組成制御性、段差被覆性に優れること、半導体製造プロセスとの整合性等からＭＯＣＶＤ法が最適な薄膜製造プロセスとして検討されている。
On the other hand, a silicon oxide film is used as the high dielectric gate insulating film. However, in recent years, with the high integration of LSI, the silicon oxide film is becoming thinner. Since a tunnel current flows through a thin film having a thickness of 100 nm or less and the insulation effect is lowered, further reduction in the thickness of the silicon oxide film is limited.
Therefore, there is a demand for a gate insulating film that replaces the silicon oxide film, and HfSiO and the like are attracting attention as candidates. Examples of the method for producing these thin films include MOD such as sputtering, ion plating, coating pyrolysis, and sol-gel. However, the MOCVD method is used because of its excellent composition controllability, step coverage, and consistency with the semiconductor manufacturing process. It has been studied as an optimal thin film manufacturing process.
そこで本出願人は、ＭＯＣＶＤ法によりＳｉＮ薄膜やＨｆＳｉＯ薄膜を成膜するための原料として、一般式Ｍ［(Ｒi)2Ｎ］(n-s)(Ｒii)sで示される金属原子と窒素原子との結合又は半金属原子と窒素原子との結合を有する有機金属化合物において、化合物中に含まれる塩素の含有量が２００ｐｐｍ以下、かつ水の含有量が３０ｐｐｍ以下である有機金属化合物を開示した（例えば、特許文献１参照。）。上記一般式のＭは金属原子又は半金属原子であって、金属原子がＨｆ、Ｚｒ、Ｔａ、Ｔｉ、Ｃｅ、Ａｌ、Ｖ、Ｌａ、Ｎｂ又はＮｉであり、半金属原子がＳｉであり、Ｒiはメチル基又はエチル基であり、Ｒiiはエチル基であり、ｎはＭの価数であり、ｓは０〜ｎ−１の整数である。上記特許文献１では上記一般式で示される化合物中の塩素と水の含有量をそれぞれ規定することにより、塩素と水とがそれぞれ上記範囲以上含有した場合に形成される架橋した化合物の発生を抑制するため、この有機金属化合物を用いて成膜すると気化安定性を向上することができる。
しかしながら、上記特許文献１の一般式に示される有機金属化合物は、塩素と水の含有量を規定することで気化安定性は向上できたが、４００℃のような低温条件での成膜では、十分な成膜速度が得られているとは言えず、低温条件での成膜で高い成膜速度を有するＭＯＣＶＤ法用原料が求められていた。 However, the organometallic compound represented by the general formula of Patent Document 1 has improved vaporization stability by defining the contents of chlorine and water, but in film formation under a low temperature condition such as 400 ° C., It cannot be said that a sufficient film formation rate has been obtained, and there has been a demand for a raw material for MOCVD that has a high film formation rate in film formation under low temperature conditions.
本発明の目的は、上記文献１に記載された原料に比べて、４００℃のような低温条件での成膜でも高い成膜速度が得られ、安定した成膜が可能であり、かつ段差被覆性に優れるＭＯＣＶＤ法用原料及び該原料を用いたシリコン含有膜の製造方法を提供することにある。 The object of the present invention is to achieve a high film formation rate even in film formation under a low temperature condition such as 400 ° C., stable film formation, and step coverage as compared with the raw material described in Document 1 above. An object of the present invention is to provide a raw material for MOCVD method having excellent properties and a method for producing a silicon-containing film using the raw material.
請求項１に係る発明は、次の式（１）で示される有機シリコン化合物を用いたことを特徴とするＭＯＣＶＤ法用原料である。 The invention according to claim 1 is a raw material for an MOCVD method characterized by using an organic silicon compound represented by the following formula (1).
但し、式中のＲ1はメチル基又はエチル基であり、Ｒ2は水素、メチル基又はエチル基であり、Ｒ3は水素又はメチル基であり、Ｒ4は炭素数１〜４の直鎖又は分岐状アルキル基である。 However, R 1 in the formula is a methyl or ethyl group, R 2 is hydrogen, methyl or ethyl group, R 3 is hydrogen or methyl, R 4 is a straight chain of 1 to 4 carbon atoms Or it is a branched alkyl group.
請求項１に係る発明では、上記（１）で示される有機シリコン化合物をＭＯＣＶＤ法用原料として用いることで、４００℃のような低温条件での成膜でも、高い成膜速度が得られる。また、安定した成膜が可能であり、かつ段差被覆性に富んだ薄膜を形成することができる。 In the invention according to claim 1, by using the organic silicon compound shown in (1) as a raw material for the MOCVD method, a high film formation rate can be obtained even in a film formation under a low temperature condition such as 400 ° C. In addition, a stable film can be formed, and a thin film rich in step coverage can be formed.
請求項２に係る発明は、請求項１記載のＭＯＣＶＤ法用原料を用いてＭＯＣＶＤ法によりシリコン含有膜を製造する方法である。 The invention according to claim 2 is a method of manufacturing a silicon-containing film by MOCVD using the raw material for MOCVD according to claim 1.
本発明のＭＯＣＶＤ法用原料及び該原料を用いたシリコン含有膜の製造方法は、アルキルシランにヒドラジン誘導体が結合した構造を有する上記式（１）で示される有機シリコン化合物をＭＯＣＶＤ法用原料として用いた場合に、４００℃のような低温条件での成膜でも高い成膜速度が得られるので低温での成膜に優れ、安定した成膜が可能であり、かつ段差被覆性に富んだ薄膜を形成することができる。 The raw material for MOCVD method and the method for producing a silicon-containing film using the raw material of the present invention use an organic silicon compound represented by the above formula (1) having a structure in which a hydrazine derivative is bonded to alkylsilane as a raw material for MOCVD method. In this case, a high film formation rate can be obtained even at a low temperature condition such as 400 ° C., so that a thin film that is excellent in low temperature film formation, stable film formation and rich in step coverage can be obtained. Can be formed.
次に本発明を実施するための最良の形態を説明する。
本発明のＭＯＣＶＤ法用原料は、次の式（１）で示される有機シリコン化合物を用いたことを特徴とする。
Next, the best mode for carrying out the present invention will be described.
The raw material for MOCVD method of the present invention is characterized by using an organic silicon compound represented by the following formula (1).
但し、式中のＲ1はメチル基又はエチル基であり、Ｒ2は水素、メチル基又はエチル基であり、Ｒ3は水素又はメチル基であり、Ｒ4は炭素数１〜４の直鎖又は分岐状アルキル基である。 However, R 1 in the formula is a methyl or ethyl group, R 2 is hydrogen, methyl or ethyl group, R 3 is hydrogen or methyl, R 4 is a straight chain of 1 to 4 carbon atoms Or it is a branched alkyl group.
アルキルシランにヒドラジン誘導体が結合した構造を有する上記式（１）で示される有機シリコン化合物は、室温で液体状態であって、ＭＯＣＶＤ法用原料として用いた場合に、４００℃のような低温条件での成膜でも高い成膜速度が得られるので低温での成膜に優れ、安定した成膜が可能であり、かつ段差被覆性に富んだ薄膜を形成することができる。 The organosilicon compound represented by the above formula (1) having a structure in which a hydrazine derivative is bonded to an alkylsilane is in a liquid state at room temperature and is used at a low temperature condition such as 400 ° C. when used as a raw material for MOCVD. Since a high film formation rate can be obtained even in this film formation, it is excellent in film formation at a low temperature, a stable film formation is possible, and a thin film rich in step coverage can be formed.
上記式（１）で示される有機シリコン化合物が低温成膜が可能であるのは、シリコン原子に結合した水素原子と、窒素原子に結合した水素原子が、成膜基板上で接近し、シリコン原子に結合した水素原子が、７０ｅＶの熱エネルギーによって、容易に切断され、分子のエネルギーが偏在化するので、窒素原子側の水素ラジカルが放出されて、基板へのシリコン−窒素の接近を促進する効果があるためである。 The organic silicon compound represented by the above formula (1) can be formed at a low temperature because the hydrogen atom bonded to the silicon atom and the hydrogen atom bonded to the nitrogen atom approach each other on the film formation substrate. Since the hydrogen atom bonded to is easily cleaved by the thermal energy of 70 eV and the molecular energy is unevenly distributed, the hydrogen radical on the nitrogen atom side is released, and the effect of promoting the approach of silicon-nitrogen to the substrate Because there is.
本発明のＭＯＣＶＤ法用原料に用いる上記式（１）のＲ1がメチル基、Ｒ2がメチル基、Ｒ3が水素及びＲ4がメチル基を示す有機シリコン化合物の合成方法について説明する。
先ず、四塩化珪素１モル等量に対してｎ−メチルリチウムが３モル等量の割合となるように、四塩化珪素を−４０℃に保ちながらｎ−メチルリチウムのエーテル溶液をゆっくりと滴下する。滴下後は０℃に保ちながら約２４時間攪拌することにより、四塩化珪素とｎ−メチルリチウムとを反応させる。この反応後は反応液の液温を室温にまで戻す。次に、反応液に無水モノメチルヒドラジン１モル等量を−８０℃の冷却下で、１分間に０．８〜１ｃｃの割合となるように約５時間かけて滴下する。この間１，２−ジメチルヒドラジン（ＣＨ3ＮＨＮＨＣＨ3）についても反応液に１，２−ジメチルヒドラジン１モル等量を−８０℃の冷却下で、１分間に０．８〜１ｃｃの割合となるように約５時間かけて滴下する。滴下後は、反応液を３０℃で約２６６Ｐａ（２ｔｏｒｒ）にまで減圧して溶媒を除去することにより、目的物であるモノメチルヒドラジドジメチルシランを約０．４モル得ることができる。
A method for synthesizing an organosilicon compound in which R 1 of the above formula (1) used in the MOCVD method of the present invention is a methyl group, R 2 is a methyl group, R 3 is hydrogen, and R 4 is a methyl group will be described.
First, an ether solution of n-methyllithium is slowly added dropwise while maintaining silicon tetrachloride at -40 ° C. so that 3 mol equivalent of n-methyllithium is equivalent to 1 mol equivalent of silicon tetrachloride. . After dropping, silicon tetrachloride and n-methyllithium are reacted by stirring for about 24 hours while maintaining at 0 ° C. After this reaction, the temperature of the reaction solution is returned to room temperature. Next, 1 mol equivalent of anhydrous monomethylhydrazine is added dropwise to the reaction solution over about 5 hours at a rate of 0.8 to 1 cc per minute under cooling at −80 ° C. During this time, 1,2-dimethylhydrazine (CH 3 NHNHCH 3 ) was also added to the reaction solution at a rate of 0.8 to 1 cc per minute with 1 mol equivalent of 1,2-dimethylhydrazine under cooling at −80 ° C. In about 5 hours. After the dropwise addition, the reaction solution is decompressed to about 266 Pa (2 torr) at 30 ° C. to remove the solvent, whereby about 0.4 mol of monomethylhydrazide dimethylsilane as the target product can be obtained.
なお、上記使用した１，２−ジメチルヒドラジンの代わりに、所望の官能基に対応する直鎖又は分岐状アルキル基を有するヒドラジン誘導体を使用すること、並びに必要によってヒドラジン誘導体とともにＮａＢＨ4を少量加えることによって、目的とする式（１）のＲ1〜Ｒ4を変化させた有機シリコン化合物が得られる。 Instead of the 1,2-dimethylhydrazine used above, use a hydrazine derivative having a linear or branched alkyl group corresponding to the desired functional group, and if necessary, add a small amount of NaBH 4 together with the hydrazine derivative. Thus, an organic silicon compound in which R 1 to R 4 of the target formula (1) are changed is obtained.
本発明のＭＯＣＶＤ法用原料を用いてＭＯＣＶＤ法によりシリコン含有膜を製造することで、低温での成膜に優れ、安定した成膜が可能であり、かつ段差被覆性に富んだ薄膜を形成することができる。製造するシリコン含有膜としてはＳｉＮ薄膜やＨｆＳｉＯ薄膜等が挙げられる。ＳｉＮ薄膜は配線保護膜のようなパッシベーション膜として使用され、ＨｆＳｉＯ薄膜はゲート絶縁膜として使用される。 By producing a silicon-containing film by the MOCVD method using the raw material for the MOCVD method of the present invention, a thin film excellent in low-temperature film formation, stable film formation, and rich in step coverage can be formed. be able to. Examples of the silicon-containing film to be manufactured include a SiN thin film and a HfSiO thin film. The SiN thin film is used as a passivation film such as a wiring protective film, and the HfSiO thin film is used as a gate insulating film.
なお、本発明のＭＯＣＶＤ法用原料は、室温で液体状態の有機シリコン化合物を用いているので、このままＭＯＣＶＤに用いることができる以外に、この原料を有機溶媒に１２〜１５重量％溶液となるように溶解して溶液を調製し、この溶液をＭＯＣＶＤ法用原料として使用しても良い。 In addition, since the raw material for MOCVD method of the present invention uses an organic silicon compound in a liquid state at room temperature, in addition to being able to be used for MOCVD as it is, this raw material is made into a 12 to 15% by weight solution in an organic solvent. It is also possible to prepare a solution by dissolving it in the solution and use this solution as a raw material for MOCVD.
次に本発明の実施例を比較例とともに詳しく説明する。
＜実施例１＞
先ず、四塩化珪素１モル等量に対してｎ−メチルリチウムが３モル等量の割合となるように、四塩化珪素を−４０℃に保ちながらｎ−メチルリチウムのエーテル溶液をゆっくりと滴下した。滴下後は０℃に保ちながら約２４時間攪拌することにより、四塩化珪素とｎ−メチルリチウムとを反応させた。反応後は反応液の液温を室温にまで戻した。次に、反応液に無水モノメチルヒドラジン１モル等量を−８０℃の冷却下で、１分間に０．８〜１ｃｃの割合となるように約５時間かけて滴下した。この間１，２−ジメチルヒドラジンについても反応液に１，２−ジメチルヒドラジン１モル等量を−８０℃の冷却下で、１分間に０．８〜１ｃｃの割合となるように約５時間かけて滴下した。滴下後は、反応液を３０℃で約２６６Ｐａ（２ｔｏｒｒ）にまで減圧して溶媒を除去することにより、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がメチル基、Ｒ2がメチル基、Ｒ3が水素及びＲ4がメチル基を示す有機シリコン化合物であることが同定された。
Next, examples of the present invention will be described in detail together with comparative examples.
<Example 1>
First, an ether solution of n-methyllithium was slowly added dropwise while maintaining the silicon tetrachloride at -40 ° C. so that the molar ratio of n-methyllithium was 3 mol equivalent to 1 mol equivalent of silicon tetrachloride. . After dripping, silicon tetrachloride and n-methyllithium were reacted by stirring for about 24 hours while maintaining at 0 ° C. After the reaction, the temperature of the reaction solution was returned to room temperature. Next, 1 mol equivalent of anhydrous monomethylhydrazine was added dropwise to the reaction solution over about 5 hours at a rate of 0.8 to 1 cc per minute under cooling at −80 ° C. During this time, 1,2-dimethylhydrazine was also added to the reaction solution in an amount of 1 mol equivalent of 1,2-dimethylhydrazine over about 5 hours so that the rate was 0.8 to 1 cc per minute under cooling at -80 ° C. It was dripped. After the dropwise addition, the reaction solution was decompressed to about 266 Pa (2 torr) at 30 ° C. to remove the solvent, thereby obtaining a desired organosilicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) represents a methyl group, R 2 represents a methyl group, R 3 represents hydrogen, and R 4 represents a methyl group. Was identified.
＜実施例２＞
１，２−ジメチルヒドラジンを１−メチル−２−エチルヒドラジン（ＣＨ3ＮＨＮＨＣ2Ｈ5）に変更し、この１−メチル−２−エチルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がメチル基、Ｒ2が水素、Ｒ3がメチル基及びＲ4がエチル基を示す有機シリコン化合物であることが同定された。
<Example 2>
The same as Example 1 except that 1,2-dimethylhydrazine was changed to 1-methyl-2-ethylhydrazine (CH 3 NHNHC 2 H 5 ) and a small amount of NaBH 4 was added together with this 1-methyl-2-ethylhydrazine. Synthesis was performed to obtain a desired organosilicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) is a methyl group, R 2 is hydrogen, R 3 is a methyl group, and R 4 is an ethyl group. Was identified.
＜実施例３＞
１，２−ジメチルヒドラジンを１−メチル−２−イソプロピルヒドラジン（ＣＨ3ＮＨＮＨ(ｉ-Ｃ3Ｈ7)）に変更し、この１−メチル−２−イソプロピルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がメチル基、Ｒ2がエチル基、Ｒ3が水素及びＲ4がイソプロピル基を示す有機シリコン化合物であることが同定された。
<Example 3>
Except that 1,2-dimethylhydrazine was changed to 1-methyl-2-isopropylhydrazine (CH 3 NHNH (i-C 3 H 7 )) and a small amount of NaBH 4 was added together with 1-methyl-2-isopropylhydrazine. Synthesis was performed in the same manner as in Example 1 to obtain a desired organic silicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) is a methyl group, R 2 is an ethyl group, R 3 is hydrogen, and R 4 is an isopropyl group. Was identified.
＜実施例４＞
１，２−ジメチルヒドラジンを１−メチル−２−ターシャリーブチルヒドラジン（ＣＨ3ＮＨＮＨ(ｔ-Ｃ4Ｈ9)）に変更し、この１−メチル−２−ターシャリーブチルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がメチル基、Ｒ2が水素、Ｒ3が水素及びＲ4がターシャリーブチル基を示す有機シリコン化合物であることが同定された。
<Example 4>
1,2-dimethylhydrazine was changed to 1-methyl-2-tertiary butyl hydrazine (CH 3 NHNH (t—C 4 H 9 )), and a small amount of NaBH 4 was added together with the 1-methyl-2-tertiary butyl hydrazine. Synthesis was performed in the same manner as in Example 1 except that a desired organosilicon compound was obtained.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) represents a methyl group, R 2 represents hydrogen, R 3 represents hydrogen, and R 4 represents a tertiary butyl group. It was identified.
＜実施例５＞
１，２−ジメチルヒドラジンを１−エチル−２−メチルヒドラジン（Ｃ2Ｈ5ＮＨＮＨＣＨ3）に変更した以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がエチル基、Ｒ2がメチル基、Ｒ3が水素及びＲ4がメチル基を示す有機シリコン化合物であることが同定された。
<Example 5>
Synthesis was performed in the same manner as in Example 1 except that 1,2-dimethylhydrazine was changed to 1-ethyl-2-methylhydrazine (C 2 H 5 NHNHCH 3 ) to obtain a desired organic silicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) represents an ethyl group, R 2 represents a methyl group, R 3 represents hydrogen, and R 4 represents a methyl group. Was identified.
＜実施例６＞
１，２−ジメチルヒドラジンを１，２−ジエチルヒドラジン（Ｃ2Ｈ5ＮＨＮＨＣ2Ｈ5）に変更し、この１，２−ジエチルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がエチル基、Ｒ2が水素、Ｒ3がメチル基及びＲ4がエチル基を示す有機シリコン化合物であることが同定された。
<Example 6>
Except that 1,2-dimethylhydrazine was changed to 1,2-diethylhydrazine (C 2 H 5 NHNHC 2 H 5 ) and a small amount of NaBH 4 was added together with this 1,2-diethylhydrazine, the same as in Example 1. Synthesis was performed to obtain a desired organosilicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) is an ethyl group, R 2 is hydrogen, R 3 is a methyl group, and R 4 is an ethyl group. Was identified.
＜実施例７＞
１，２−ジメチルヒドラジンを１−エチル−２−イソプロピルヒドラジン（Ｃ2Ｈ5ＮＨＮＨ(ｉ-Ｃ3Ｈ7)）に変更し、この１−エチル−２−イソプロピルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がエチル基、Ｒ2がエチル基、Ｒ3が水素及びＲ4がイソプロピル基を示す有機シリコン化合物であることが同定された。
<Example 7>
1,2-Dimethylhydrazine was changed to 1-ethyl-2-isopropylhydrazine (C 2 H 5 NHNH (i-C 3 H 7 )), and a small amount of NaBH 4 was added together with the 1-ethyl-2-isopropylhydrazine. Except that, synthesis was performed in the same manner as in Example 1 to obtain a desired organosilicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) is an ethyl group, R 2 is an ethyl group, R 3 is hydrogen, and R 4 is an isopropyl group. Was identified.
＜実施例８＞
１，２−ジメチルヒドラジンを１−エチル−２−ターシャリーブチルヒドラジン（Ｃ2Ｈ5ＮＨＮＨ(ｔ-Ｃ4Ｈ9)）に変更し、この１−エチル−２−ターシャリーブチルヒドラジンとともにＮａＢＨ4を少量加えた以外は実施例１と同様にして合成を行い、所望の有機シリコン化合物を得た。
得られた有機シリコン化合物について1Ｈ-ＮＭＲにより同定を行った。1Ｈ-ＮＭＲの結果を次の表１に示す。表１の結果から、得られた有機シリコン化合物は、上記式（１）のＲ1がエチル基、Ｒ2が水素、Ｒ3が水素及びＲ4がターシャリーブチル基を示す有機シリコン化合物であることが同定された。
<Example 8>
1,2-dimethylhydrazine was changed to 1-ethyl-2-tertiary butyl hydrazine (C 2 H 5 NHNH (t—C 4 H 9 )) and NaBH 4 together with the 1-ethyl-2-tertiary butyl hydrazine. Synthesis was performed in the same manner as in Example 1 except that a small amount of was added to obtain a desired organosilicon compound.
The obtained organosilicon compound was identified by 1 H-NMR. The results of 1 H-NMR are shown in Table 1 below. From the results of Table 1, the obtained organosilicon compound is an organosilicon compound in which R 1 in the above formula (1) represents an ethyl group, R 2 represents hydrogen, R 3 represents hydrogen, and R 4 represents a tertiary butyl group. It was identified.
＜比較例１＞
従来よりＳｉＮ膜形成材料として使用されているヘキサクロロジシランを用意した。
<Comparative Example 1>
Hexachlorodisilane, which has been conventionally used as a SiN film forming material, was prepared.
＜比較試験１＞
実施例１〜８で得られた有機シリコン化合物と比較例１で用意した有機シリコン化合物をそれぞれＭＯＣＶＤ法用原料として、以下の条件でＳｉＮ薄膜を成膜し、成膜したＳｉＮ薄膜における成膜時間当たりの膜厚試験、表面粗さ及び段差被覆性試験を行った。
先ず、基板として基板表面にＳｉＯ2膜（厚さ５０００Å）を形成したシリコン基板を４枚ずつ用意し、この基板をＭＯＣＶＤ装置の成膜室に設置した。また、有機シリコン化合物をＭＯＣＶＤ法用原料として原料容器に貯留した。次いで、成膜室内の基板温度を４００℃、気化室内の気化温度を１５０℃、成膜室内の圧力を約１．３３ｋＰａ（１０ｔｏｒｒ）にそれぞれ設定した。反応ガスとしてはＮＨ3ガスを用い、成膜室内に供給される反応ガス流量が１０００ｃｃｍとなるように制御した。次に、キャリアガスを原料容器内に供給して原料容器に貯留した有機シリコン化合物を０．５ｇ／ｍｉｎの割合で気化器に供給して気化させ、気化器で気化した有機シリコン化合物とＮＨ3ガスとを成膜室に送り込み、成膜室内の基板上にＳｉＮを堆積させた。成膜時間が５分、１０分、２０分及び３０分となったときに基板をそれぞれ１枚ずつ成膜室より取出した。
<Comparison test 1>
Using the organosilicon compounds obtained in Examples 1 to 8 and the organosilicon compound prepared in Comparative Example 1 as raw materials for the MOCVD method, a SiN thin film was formed under the following conditions, and the deposition time in the formed SiN thin film Film thickness test, surface roughness and step coverage test were performed.
First, four silicon substrates each having a SiO 2 film (thickness 5000 mm) formed on the substrate surface were prepared as substrates, and these substrates were placed in a film formation chamber of an MOCVD apparatus. Moreover, the organic silicon compound was stored in the raw material container as a raw material for the MOCVD method. Next, the substrate temperature in the film formation chamber was set to 400 ° C., the vaporization temperature in the vaporization chamber was set to 150 ° C., and the pressure in the film formation chamber was set to about 1.33 kPa (10 torr). NH 3 gas was used as the reaction gas, and the flow rate of the reaction gas supplied into the film formation chamber was controlled to 1000 ccm. Next, the organic silicon compound stored in the raw material container by supplying the carrier gas into the raw material container is supplied to the vaporizer at a rate of 0.5 g / min to vaporize, and the organic silicon compound vaporized by the vaporizer and NH 3 Gas was fed into the film formation chamber, and SiN was deposited on the substrate in the film formation chamber. When the film formation time was 5 minutes, 10 minutes, 20 minutes, and 30 minutes, one substrate was taken out from the film formation chamber.
（１）成膜時間あたりの膜厚試験
成膜を終えて成膜室より取出した基板上の薄膜を走査型電子顕微鏡（scanning electron microscope；以下、ＳＥＭという。）により測定した断面ＳＥＭ像から膜厚を測定した。
(1) Film thickness test per film formation time Films from cross-sectional SEM images obtained by measuring a thin film on a substrate taken out of the film formation chamber after film formation with a scanning electron microscope (hereinafter referred to as SEM) The thickness was measured.
（２）段差被覆性試験
成膜時間が１０分で成膜室より取出した基板上の薄膜を原子間力顕微鏡（atomic force microscope、ＡＦＭ）により測定し、薄膜表面のＲａ（average roughness）を測定した。
(2) Step coverage test The thin film on the substrate taken out from the film formation chamber in 10 minutes is measured with an atomic force microscope (AFM), and the Ra (average roughness) of the thin film surface is measured. did.
（３）段差被覆性試験
成膜時間が１０分で成膜室より取出した基板上の薄膜をＳＥＭにより測定した断面ＳＥＭ像から段差被覆性を測定した。
(3) Step coverage test The step coverage was measured from a cross-sectional SEM image obtained by measuring the thin film on the substrate taken out from the deposition chamber in 10 minutes with the SEM.
実施例１〜８及び比較例１のＭＯＣＶＤ法用原料を用いたＳｉＮ薄膜における各試験結果を表２に示す。 Table 2 shows the test results of the SiN thin films using the MOCVD raw materials of Examples 1 to 8 and Comparative Example 1.
表２より明らかなように、従来より知られている比較例１で用意した有機シリコン化合物を用いて得られたＳｉＮ薄膜は、低い成膜速度であり、ＡＦＭによる表面粗さＲａが大きく、成膜の安定性が悪いことが判った。また段差被覆性も非常に悪い結果となっていた。以上の評価試験より比較例１で用意した有機シリコン化合物は４００℃のような低温での成膜には適していないことが判った。これに対して実施例１〜８で得られた有機シリコン化合物を用いて得られたＳｉＮ薄膜は、比較例１で用意した有機シリコン化合物を用いた場合に比べて非常に成膜速度が高く、ＡＦＭによる表面粗さＲａも小さく、成膜安定性が高い結果が得られた。また、段差被覆性も０．８〜１．０と、基板の平坦部分と同様に溝の奥まで均一に成膜されていることが判った。このような成膜特性を有する本発明の有機シリコン化合物を用いたＭＯＣＶＤ法用原料は、低温条件でのＳｉＮ薄膜等のシリコン含有薄膜の製造に好適であることが判る。 As is clear from Table 2, the SiN thin film obtained using the conventionally known organosilicon compound prepared in Comparative Example 1 has a low film formation rate, a large surface roughness Ra by AFM, and a high growth rate. It was found that the stability of the membrane was poor. Also, the step coverage was very bad. From the above evaluation test, it was found that the organosilicon compound prepared in Comparative Example 1 was not suitable for film formation at a low temperature such as 400 ° C. On the other hand, the SiN thin film obtained using the organic silicon compound obtained in Examples 1 to 8 has a very high film formation rate as compared with the case where the organic silicon compound prepared in Comparative Example 1 is used. The surface roughness Ra by AFM was also small, and the film formation stability was high. In addition, it was found that the step coverage was 0.8 to 1.0, and the film was uniformly formed to the depth of the groove as in the flat portion of the substrate. It can be seen that the raw material for MOCVD method using the organosilicon compound of the present invention having such film formation characteristics is suitable for the production of silicon-containing thin films such as SiN thin films under low temperature conditions.
＜比較例２＞
従来よりＨｆＳｉＯ膜形成材料として使用されているテトラキスジメチルアミノシランを用意した。
＜比較例３＞
従来よりＨｆＳｉＯ膜形成材料として使用されているシランを用意した。
<Comparative example 2>
Tetrakisdimethylaminosilane, which has been conventionally used as a HfSiO film forming material, was prepared.
<Comparative Example 3>
Silane which has been conventionally used as a HfSiO film forming material was prepared.
＜比較試験２＞
実施例１〜８で得られた有機シリコン化合物と比較例２〜３で用意した有機シリコン化合物をそれぞれＭＯＣＶＤ法用原料として、以下の条件でＨｆＳｉＯ薄膜を成膜し、前述した比較試験１と同様にして成膜したＨｆＳｉＯ薄膜における成膜時間当たりの膜厚試験、表面粗さ及び段差被覆性試験を行った。
先ず、基板として基板表面にＳｉＯ2膜（厚さ５０００Å）を形成したシリコン基板を４枚ずつ用意し、この基板をＭＯＣＶＤ装置の成膜室に設置した。また、有機シリコン化合物をＭＯＣＶＤ法用原料として第１原料容器に貯留した。同様に有機ハフニウム化合物をＭＯＣＶＤ法用原料として第２原料容器に貯留した。有機ハフニウム化合物としては、テトラキスジエチルアミノハフニウム（以下、ＴＤＥＡＨという。）又はテトラキスエチルメチルアミノハフニウム（以下、ＴＥＭＡＨという。）を使用した。次いで、成膜室内の基板温度を４００℃、気化室内の気化温度を１５０℃、成膜室内の圧力を約１．３３ｋＰａ（１０ｔｏｒｒ）にそれぞれ設定した。反応ガスとしてはＯ2ガスを用い、成膜室内に供給される反応ガス流量が１０００ｃｃｍとなるように制御した。次に、キャリアガスを第１原料容器内に供給して第１原料容器に貯留した有機シリコン化合物を０．５ｇ／ｍｉｎの割合で気化器に供給して気化させた。同様に、キャリアガスを第２原料容器内に供給して第２原料容器に貯留した有機ハフニウム化合物を０．１ｃｃｍの割合で気化器に供給して気化させた。気化器で気化した有機シリコン化合物及び有機ハフニウム化合物とＯ2ガスとを成膜室に送り込み、成膜室内の基板上にＨｆＳｉＯを堆積させた。成膜時間が５分、１０分、２０分及び３０分となったときに基板をそれぞれ１枚ずつ成膜室より取出した。
<Comparison test 2>
Using the organic silicon compounds obtained in Examples 1 to 8 and the organic silicon compounds prepared in Comparative Examples 2 to 3 as raw materials for the MOCVD method, HfSiO thin films were formed under the following conditions, and the same as Comparative Test 1 described above. The film thickness test per film formation time, the surface roughness and the step coverage test were performed on the HfSiO thin film formed as described above.
First, four silicon substrates each having a SiO 2 film (thickness 5000 mm) formed on the substrate surface were prepared as substrates, and these substrates were placed in a film formation chamber of an MOCVD apparatus. Further, the organic silicon compound was stored in the first raw material container as a raw material for the MOCVD method. Similarly, the organic hafnium compound was stored in the second raw material container as a raw material for the MOCVD method. Tetrakisdiethylaminohafnium (hereinafter referred to as TDEAH) or tetrakisethylmethylaminohafnium (hereinafter referred to as TEMAH) was used as the organic hafnium compound. Next, the substrate temperature in the film formation chamber was set to 400 ° C., the vaporization temperature in the vaporization chamber was set to 150 ° C., and the pressure in the film formation chamber was set to about 1.33 kPa (10 torr). O 2 gas was used as the reaction gas, and the flow rate of the reaction gas supplied into the film formation chamber was controlled to be 1000 ccm. Next, the carrier gas was supplied into the first raw material container, and the organosilicon compound stored in the first raw material container was supplied to the vaporizer at a rate of 0.5 g / min and vaporized. Similarly, the carrier gas was supplied into the second raw material container, and the organic hafnium compound stored in the second raw material container was supplied to the vaporizer at a rate of 0.1 ccm and vaporized. The organic silicon compound and organic hafnium compound vaporized by the vaporizer and O 2 gas were sent into the film formation chamber, and HfSiO was deposited on the substrate in the film formation chamber. When the film formation time was 5 minutes, 10 minutes, 20 minutes, and 30 minutes, one substrate was taken out from the film formation chamber.
実施例１〜８及び比較例２〜３のＭＯＣＶＤ法用原料を用いたＨｆＳｉＯ薄膜における各試験結果を表３に示す。 Table 3 shows the test results of the HfSiO thin films using the raw materials for MOCVD in Examples 1 to 8 and Comparative Examples 2 to 3.
表３より明らかなように、従来より知られている比較例２，３で用意した有機シリコン化合物を用いて得られたＨｆＳｉＯ薄膜は、低い成膜速度であり、ＡＦＭによる表面粗さＲａが大きく、成膜の安定性が悪いことが判った。また段差被覆性も非常に悪い結果となっていた。以上の評価試験より比較例２，３で用意した有機シリコン化合物は４００℃のような低温での成膜には適していないことが判った。これに対して実施例１〜８で得られた有機シリコン化合物を用いて得られたＨｆＳｉＯ薄膜は、比較例２，３で用意した有機シリコン化合物を用いた場合に比べて非常に成膜速度が高く、ＡＦＭによる表面粗さＲａも小さく、成膜安定性が高い結果が得られた。また、段差被覆性も０．８〜１．０と、基板の平坦部分と同様に溝の奥まで均一に成膜されていることが判った。このような成膜特性を有する本発明の有機シリコン化合物を用いたＭＯＣＶＤ法用原料は、低温条件でのＨｆＳｉＯ薄膜等のシリコン含有薄膜の製造に好適であることが判る。
As is apparent from Table 3, the HfSiO thin film obtained by using the organic silicon compounds prepared in Comparative Examples 2 and 3 that have been conventionally known has a low film formation rate and a large surface roughness Ra by AFM. It was found that the stability of film formation was poor. Also, the step coverage was very bad. From the above evaluation tests, it was found that the organosilicon compounds prepared in Comparative Examples 2 and 3 were not suitable for film formation at a low temperature such as 400 ° C. On the other hand, the HfSiO thin film obtained by using the organic silicon compounds obtained in Examples 1 to 8 has a very high film forming speed as compared with the case of using the organic silicon compounds prepared in Comparative Examples 2 and 3. The result was high, the surface roughness Ra by AFM was small, and the film formation stability was high. In addition, it was found that the step coverage was 0.8 to 1.0, and the film was uniformly formed to the depth of the groove as in the flat portion of the substrate. It can be seen that the raw material for MOCVD using the organosilicon compound of the present invention having such film formation characteristics is suitable for the production of silicon-containing thin films such as HfSiO thin films under low temperature conditions.
Claims (2)
A method for producing a silicon-containing film by metal organic chemical vapor deposition using the metal organic chemical vapor deposition raw material according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158927A (en) * | 2007-11-08 | 2009-07-16 | Air Products & Chemicals Inc | Preparation of metal-containing film via ald or cvd processes |
| WO2011155353A1 (en) * | 2010-06-10 | 2011-12-15 | 東ソー株式会社 | Hydrosilane derivative, method for producing same, and method for producing silicon-containing thin film |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009158927A (en) * | 2007-11-08 | 2009-07-16 | Air Products & Chemicals Inc | Preparation of metal-containing film via ald or cvd processes |
| WO2011155353A1 (en) * | 2010-06-10 | 2011-12-15 | 東ソー株式会社 | Hydrosilane derivative, method for producing same, and method for producing silicon-containing thin film |
| JP2012126704A (en) * | 2010-06-10 | 2012-07-05 | Tosoh Corp | Hydrosilane derivative, method for producing the same, and method for producing silicon-containing thin film |
| CN103124734A (en) * | 2010-06-10 | 2013-05-29 | 东曹株式会社 | Hydrosilane derivative, method for producing same, and method for producing silicon-containing thin film |
| US9120825B2 (en) | 2010-06-10 | 2015-09-01 | Tosoh Corporation | Hydrosilane derivative, method for producing same, and method for producing silicon-containing thin film |
| KR101768259B1 (en) | 2010-06-10 | 2017-08-14 | 토소가부시키가이샤 | Hydrosilane derivative, method for producing same, and method for producing silicon-containing thin film |
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