JP2005294421A - 成膜方法および成膜装置、ならびにゲート絶縁膜の形成方法 - Google Patents
成膜方法および成膜装置、ならびにゲート絶縁膜の形成方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 56
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract description 53
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 24
- 229910052914 metal silicate Inorganic materials 0.000 claims abstract description 22
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 46
- 239000002994 raw material Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 27
- 150000004703 alkoxides Chemical class 0.000 claims description 27
- 229910052990 silicon hydride Inorganic materials 0.000 claims description 25
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical group [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 239000010703 silicon Substances 0.000 claims description 12
- 230000008016 vaporization Effects 0.000 claims description 10
- 239000004065 semiconductor Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 4
- WZVIPWQGBBCHJP-UHFFFAOYSA-N hafnium(4+);2-methylpropan-2-olate Chemical compound [Hf+4].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] WZVIPWQGBBCHJP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 132
- 239000007789 gas Substances 0.000 description 50
- 230000003746 surface roughness Effects 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 229910008045 Si-Si Inorganic materials 0.000 description 5
- 229910006411 Si—Si Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- -1 siloxane compound Chemical class 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 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
- 238000005516 engineering process Methods 0.000 description 2
- DFIPXJGORSQQQD-UHFFFAOYSA-N hafnium;tetrahydrate Chemical compound O.O.O.O.[Hf] DFIPXJGORSQQQD-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 229910004129 HfSiO Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- HRDRRWUDXWRQTB-UHFFFAOYSA-N hafnium(4+);propan-2-olate Chemical compound [Hf+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] HRDRRWUDXWRQTB-UHFFFAOYSA-N 0.000 description 1
- OAKMTVGBLXXWPZ-UHFFFAOYSA-J hafnium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Hf+4] OAKMTVGBLXXWPZ-UHFFFAOYSA-J 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 150000002978 peroxides Chemical group 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C23C16/46—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for heating the substrate
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
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- H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
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- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
Abstract
【解決手段】シャワーヘッド10を介してチャンバー1内にHTBとSi2H6ガスを導入し、CVDによりハフニウムシリケート膜を成膜するに際し、サセプタ2に埋設したヒーター5により成膜温度を、HTBが水酸化ハフニウムとイソブチレンに分解する温度以上で、かつSi2H6ガスの自己分解温度以下、好ましくは350〜450℃に設定してハフニウムシリケート膜を成膜する。
【選択図】図1
Description
図1は本発明に係る成膜方法の一実施形態を実施するための成膜装置を示す断面図である。この成膜装置100は、気密に構成された略円筒状のチャンバー1を有しており、その中には被処理体であるSi基板(ウエハ)Wを水平に支持するためのサセプタ2がその中央下部に設けられた円筒状の支持部材3により支持された状態で配置されている。このサセプタ2はAlN等のセラミックスからなっている。また、サセプタ2にはヒーター5が埋め込まれており、このヒーター5にはヒーター電源6が接続されている。一方、サセプタ2の上面近傍には熱電対7が設けられており、熱電対7の信号はコントローラ8に伝送されるようになっている。そして、コントローラ8は熱電対7の信号に応じてヒーター電源6に指令を送信し、ヒーター5の加熱を制御してSiウエハWを所定の温度に制御するようになっている。
図2はHTBの熱分解特性を示す赤外吸収スペクトル図である。この図に示すように、成膜温度が低い場合には、ターシャリブチル基(t−C4H9)が多く発生する。t−C4H9は炭素分が多く、揮発しにくいため、これが多いと膜中の炭素不純物となって特性に悪影響を与えるものと考えられる。これに対し、成膜温度が上昇するに従って、t−C4H9が徐々に低下し、イソブチレンが増加する。これは、以下の(2)式に示す反応により、HTBが水酸化ハフニウムとイソブチレンに分解したためと考えられる。
図7の(a)〜(c)は、基板温度を360℃、495℃、542℃とし、Si2H6ガスの流量を40mL/minとしてハフニウムシリケート膜を成膜した場合のXPSスペクトル(検出角度15度)を示す図である。なお、膜厚は上記それぞれの温度条件で、10.1nm、8.3nm、8.4nmである。この図に示すように、495℃では100eV付近にSi−Si結合に対応するピークが認められ、542℃ではそのピークが顕著なものとなっているが、360℃ではこのようなピークは見られない。このことから、495℃以上で膜中にSi−Si結合が生じていることが確認された。
2…サセプタ
5…ヒーター
6…ヒーター電源
7…熱電対
8…コントローラ
10…シャワーヘッド
30…ガス供給系
31…HTBタンク
35…気化ユニット
43…Si2H6ガス供給源
100…成膜装置
W…Siウエハ
Claims (25)
- 金属アルコキシド原料とシリコン水素化物原料とを用いて、CVDにより基板上に金属シリケート膜を成膜する成膜方法であって、
成膜の際の基板温度を、前記金属アルコキシド原料が金属水酸化物と所定の中間体に分解する温度以上で、かつ前記シリコン水素化物の自己分解温度以下に設定して金属シリケート膜を成膜することを特徴とする成膜方法。 - 前記金属アルコキシドはターシャリブトキシル基を配位子とすることを特徴とする請求項1に記載の成膜方法。
- 前記中間体はイソブチレンであることを特徴とする請求項2に記載の成膜方法。
- 前記金属アルコキシドはハフニウムテトラターシャリブトキサイド(HTB)であることを特徴とする請求項2または請求項3に記載の成膜方法。
- 前記成膜の際の基板温度は350℃以上であることを特徴とする請求項4に記載の成膜方法。
- 前記シリコン水素化物がジシラン(Si2H6)であることを特徴とする請求項1から請求項5のいずれか1項に記載の成膜方法。
- 前記成膜の際の基板温度は450℃以下であることを特徴とする請求項6に記載の成膜方法。
- ハフニウムテトラターシャリブトキサイド(HTB)とジシラン(Si2H6)とを用いて、CVDにより基板上にハフニウムシリケート膜を成膜する成膜方法であって、成膜の際の基板温度を350〜450℃にしたことを特徴とする成膜方法。
- 成膜の際に、枚様式成膜装置を用いることを特徴とする請求項1から請求項8のいずれか1項に記載の成膜方法。
- 金属アルコキシド原料とシリコン水素化物原料とを用いて、CVDにより基板上に金属シリケート膜を成膜する成膜装置であって、
基板が収容される処理容器と、
金属アルコキシド原料を気化する手段を有し、気化された金属アルコキシド原料とシリコン水素化物原料を前記処理容器まで独立に供給する原料供給系と、
前記気化された金属アルコキシド原料と前記シリコン水素化物原料を前記処理容器内に導入するシャワーヘッドと、
前記基板の温度を、前記金属アルコキシド原料が金属水酸化物と所定の中間体に分解する温度以上で、かつ前記シリコン水素化物の自己分解温度以下に制御する温度制御手段と
を具備することを特徴とする成膜装置。 - 前記金属アルコキシドはターシャリブトキシル基を配位子とすることを特徴とする請求項10に記載の成膜装置。
- 前記中間体はイソブチレンであることを特徴とする請求項11に記載の成膜装置。
- 前記金属アルコキシドはハフニウムテトラターシャリブトキサイド(HTB)であることを特徴とする請求項11または請求項12に記載の成膜装置。
- 前記温度制御手段は、成膜の際の基板温度を350℃以上に制御することを特徴とする請求項13に記載の成膜装置。
- 前記シリコン水素化物がジシラン(Si2H6)であることを特徴とする請求項10から請求項14のいずれか1項に記載の成膜装置。
- 前記温度制御手段は、成膜の際の基板温度を450℃以下に制御することを特徴とする請求項15に記載の成膜装置。
- 前記シャワーヘッドは、前記金属アルコキシド原料と前記シリコン水素化物とをそれぞれ独立に前記処理容器内に導入することを特徴とする請求項10から請求項16のいずれか1項に記載の成膜装置。
- 前記シャワーヘッドの温度を制御するシャワーヘッド温度制御手段をさらに具備することを特徴とする請求項10から請求項17のいずれか1項に記載の成膜装置。
- 前記シャワーヘッド温度制御手段は、前記シャワーヘッドを前記金属アルコキシド原料および前記シリコン水素化物の自己分解温度以下に制御することを特徴とする請求項18に記載の成膜装置。
- ハフニウムテトラターシャリブトキサイド(HTB)とジシラン(Si2H6)とを用いて、CVDにより基板上にハフニウムシリケート膜を成膜する成膜装置であって、
基板が収容される処理容器と、
ハフニウムテトラターシャリブトキサイド(HTB)を気化する手段を有し、気化されたハフニウムテトラターシャリブトキサイド(HTB)とジシラン(Si2H6)を前記処理容器まで独立に供給する原料供給系と、
前記気化されたハフニウムテトラターシャリブトキサイド(HTB)とジシラン(Si2H6)を前記処理容器内に導入するシャワーヘッドと、
前記基板の温度を、350〜450℃の範囲に制御する温度制御手段と
を具備することを特徴とする成膜装置。 - 前記シャワーヘッドは、前記ハフニウムテトラターシャリブトキサイド(HTB)と前記ジシラン(Si2H6)とをそれぞれ独立に前記処理容器内に導入することを特徴とする請求項20に記載の成膜装置。
- 前記シャワーヘッドの温度を制御するシャワーヘッド温度制御手段をさらに具備することを特徴とする請求項20または請求項21に記載の成膜装置。
- 前記シャワーヘッド温度制御手段は、前記シャワーヘッドを前記ハフニウムテトラターシャリブトキサイド(HTB)および前記ジシラン(Si2H6)の自己分解温度以下に制御することを特徴とする請求項22に記載の成膜装置。
- シリコン基板上にゲート絶縁膜を形成しその上にゲート電極を形成してなる半導体装置のゲート絶縁膜の形成方法であって、
シリコン基板上に、シリコン酸化膜または窒素を含有するシリコン酸化膜をベース絶縁膜として形成する第1工程と、
前記ベース絶縁膜上に金属シリケートからなる高誘電体膜を形成する第2工程とを含み、
前記第2工程を、請求項1から請求項9のいずれかの成膜方法を用いて実行することを特徴とするゲート絶縁膜の形成方法。 - 前記ベース絶縁膜は、紫外線で励起された酸素ラジカルによってシリコン基板を酸化することにより形成することを特徴とする請求項24に記載のゲート絶縁膜の形成方法。
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KR100731164B1 (ko) * | 2005-05-19 | 2007-06-20 | 주식회사 피에조닉스 | 샤워헤드를 구비한 화학기상 증착 방법 및 장치 |
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