JP2019102807A - 保護膜形成方法 - Google Patents
保護膜形成方法 Download PDFInfo
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- JP2019102807A JP2019102807A JP2018215571A JP2018215571A JP2019102807A JP 2019102807 A JP2019102807 A JP 2019102807A JP 2018215571 A JP2018215571 A JP 2018215571A JP 2018215571 A JP2018215571 A JP 2018215571A JP 2019102807 A JP2019102807 A JP 2019102807A
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- protective film
- gas
- etching
- forming
- organic
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- 230000001681 protective effect Effects 0.000 title claims abstract description 176
- 238000000034 method Methods 0.000 title claims abstract description 141
- 238000005530 etching Methods 0.000 claims abstract description 104
- 230000008569 process Effects 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 238000012545 processing Methods 0.000 claims description 46
- 230000015572 biosynthetic process Effects 0.000 claims description 42
- 230000001590 oxidative effect Effects 0.000 claims description 30
- 229910052752 metalloid Inorganic materials 0.000 claims description 23
- 150000002738 metalloids Chemical class 0.000 claims description 22
- 230000003647 oxidation Effects 0.000 claims description 22
- 238000007254 oxidation reaction Methods 0.000 claims description 22
- 125000002524 organometallic group Chemical group 0.000 claims description 17
- PXSHDOMYSLTUTJ-UHFFFAOYSA-N [Ti]N Chemical compound [Ti]N PXSHDOMYSLTUTJ-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 10
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- -1 metalloid metal oxide Chemical class 0.000 claims description 2
- 238000005137 deposition process Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 260
- 235000012431 wafers Nutrition 0.000 description 58
- 238000000926 separation method Methods 0.000 description 44
- 239000012495 reaction gas Substances 0.000 description 43
- 239000012159 carrier gas Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000002093 peripheral effect Effects 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical class O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 238000000231 atomic layer deposition Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001459 lithography Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002052 molecular layer Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000005672 electromagnetic field Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H01L21/02104—Forming layers
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- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- 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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- H01L21/02208—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02214—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—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 the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
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- B05D1/62—Plasma-deposition of organic layers
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- C23C16/50—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 using electric discharges
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/02112—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
- H01L21/02123—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
- H01L21/02164—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 being a silicon oxide, e.g. SiO2
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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Abstract
Description
前記平坦領域の表面上に有機金属又は有機半金属の酸化膜を上方成長させる上方成長工程と、
前記有機金属又は有機半金属の酸化膜の側面をエッチングし、横方向に成長した前記有機金属又は有機半金属の酸化膜を除去するエッチング工程と、を有する。
まず、本発明の実施形態に係る保護膜形成方法を実施するのに好適な成膜装置について説明する。本発明の実施形態に係る保護膜形成方法は、基板に供給するガスの種類を高速で切り替えることができれば、種々の成膜装置で実施可能であり、成膜装置の形態は問わない。ここでは、そのような基板に供給するガスの種類を高速に切り替える成膜処理が可能な成膜装置の一例について説明する。
<第1の実施形態>
次に、本発明の第1の実施形態による保護膜形成方法について上述の成膜装置を用いて行う場合を例に挙げて説明する。本実施形態に係る保護膜形成方法は、ウエハWの表面に形成されたトレンチ等の複数の窪み形状の間の平坦面上に保護膜を堆積させ、上方に成長させる上方成長工程と、上方成長工程において、横方向にも成長してしまった余分な保護膜の側面をエッチングにより除去するエッチング工程とを有する。
図13は、第1の実施形態に係る保護膜形成方法において、エッチングが強くなり過ぎてしまった場合の保護膜62を示した図である。多くの場合は、第1の実施形態に係る保護膜形成方法で上方にのみ成長した保護膜62を形成することができるが、トレンチTのアスペクト比を含めた形状、保護膜62の種類、要求される膜厚、エッチングガスの種類等の条件により、エッチングが強過ぎ、保護膜62がトレンチTの上端付近で局所的に大きく削れる場合が稀にある。エッチングの際、エッチングガスがトレンチTの底面で反射して逆流し、トレンチTの上端付近におけるエッチングガスの滞留割合が増加するためと考えられる。
次に、本発明を実施した実施例について説明する。
2 回転テーブル
7 ヒータユニット
11 天板
12 容器本体
15 搬送口
24 凹部
31〜33 反応ガスノズル
41、42 分離ガスノズル
60 犠牲膜
62 保護膜
80 プラズマ発生器
130〜132 ガス供給源
P1〜P3 処理領域
W ウエハ
T トレンチ
Claims (16)
- 基板の表面に複数の窪み形状が形成され、隣接する該複数の窪み形状間の平坦領域の表面上に保護膜を形成する保護膜形成方法であって、
前記平坦領域の表面上に有機金属又は有機半金属の酸化膜を上方成長させる上方成長工程と、
前記有機金属又は有機半金属の酸化膜の側面をエッチングし、横方向に成長した前記有機金属又は有機半金属の酸化膜を除去するエッチング工程と、を有する保護膜形成方法。 - 前記上方成長工程の前に、前記エッチング工程における犠牲膜を前記基板の表面にコンフォーマルに形成する犠牲膜形成工程を更に有する請求項1に記載の保護膜形成方法。
- 前記犠牲膜形成工程、前記上方成長工程及び前記エッチング工程を繰り返し、前記有機金属又は有機半金属の酸化膜を所定の厚さまで上方成長させる請求項2に記載の保護膜形成方法。
- 前記犠牲膜は、前記平坦領域上の前記有機金属又は有機半金属の酸化膜と同一種類の酸化膜である請求項3に記載の保護膜形成方法。
- 前記犠牲膜形成工程及び前記上方成長工程は、前記基板の表面に前記有機金属又は有機半金属を含有する原料ガスを吸着させる原料ガス吸着工程と、前記基板の表面に吸着した原料ガスを酸化ガスにより酸化して前記有機金属又は有機半金属の酸化膜を堆積させる酸化工程とを繰り返す酸化膜堆積工程を有する請求項4に記載の保護膜形成方法。
- 前記酸化ガスは、加熱又はプラズマにより活性化されたH2O、H2O2、O2又はO3である請求項5に記載の保護膜形成方法。
- 前記エッチング工程は、プラズマにより活性化されたエッチングガスを前記基板の表面に供給することにより行われる請求項5に記載の保護膜形成方法。
- 前記上方成長工程における前記酸化膜堆積工程の繰り返し周期は、前記犠牲膜形成工程における前記酸化膜堆積工程の繰り返し周期よりも短い請求項7に記載の保護膜形成方法。
- 前記上方成長工程における前記酸化膜堆積工程の繰り返し周期は、1分間に120回以上であり、
前記犠牲膜形成工程における前記酸化膜堆積工程の繰り返し周期は、1分間に80回以下である請求項8に記載の保護膜形成方法。 - 前記基板は、処理室内に設けられた回転テーブル上に周方向に沿って配置され、
該回転テーブルより上方に、該回転テーブルの該周方向に沿って前記原料ガスを前記基板の表面に吸着させる吸着領域、前記基板の表面に吸着した前記原料ガスを酸化する酸化領域、及び前記酸化膜の側面をエッチングするエッチング領域が互いに離間して設けられ、
前記犠牲膜形成工程では、前記回転テーブルを80rpm以下の回転速度で回転させ、前記基板に前記吸着領域及び前記酸化領域を順次通過させることにより、前記原料ガス吸着工程及び前記酸化工程を1分間に80回以下の繰り返し周期で行い、
前記上方成長工程では、前記回転テーブルを120rpm以上の回転速度で回転させ、前記基板に前記吸着領域及び前記酸化領域を順次通過させることにより、前記原料ガス吸着工程及び前記酸化工程を1分間に120回以下の繰り返し周期で行い、
前記エッチング工程は、前記原料ガス及び前記酸化ガスの供給を停止させるとともに前記活性化されたエッチングガスを供給しながら、前記回転テーブルを所定の回転速度で回転させ、前記エッチング領域を所定の周期で通過させることにより行われる請求項9に記載の保護膜形成方法。 - 前記犠牲膜形成工程の前記原料ガス吸着工程において供給される前記原料ガスの流量は、前記上方成長工程の前記原料ガス吸着工程において供給される前記原料ガスの流量よりも大きい請求項8に記載の保護膜形成方法。
- 前記有機金属の酸化膜は、High−k膜である請求項1に記載の保護膜形成方法。
- 前記有機金属は、有機アミノチタニウムである請求項1に記載の保護膜形成方法。
- 前記有機アミノチタニウムは、テトラキスジメチルアミノチタニウムである請求項13に記載の保護膜形成方法。
- 前記有機半金属は、有機シランである請求項1に記載の保護膜形成方法。
- 前記窪み形状は、トレンチである請求項1に記載の保護膜形成方法。
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