JP5778174B2 - ラジカル増進薄膜堆積のための酸素ラジカルの発生 - Google Patents
ラジカル増進薄膜堆積のための酸素ラジカルの発生 Download PDFInfo
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- JP5778174B2 JP5778174B2 JP2012547256A JP2012547256A JP5778174B2 JP 5778174 B2 JP5778174 B2 JP 5778174B2 JP 2012547256 A JP2012547256 A JP 2012547256A JP 2012547256 A JP2012547256 A JP 2012547256A JP 5778174 B2 JP5778174 B2 JP 5778174B2
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- 229910052760 oxygen Inorganic materials 0.000 title claims description 124
- 239000001301 oxygen Substances 0.000 title claims description 119
- 238000000427 thin-film deposition Methods 0.000 title description 4
- 239000002243 precursor Substances 0.000 claims description 200
- 239000007789 gas Substances 0.000 claims description 92
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 75
- 239000000758 substrate Substances 0.000 claims description 73
- 238000000034 method Methods 0.000 claims description 59
- 150000003254 radicals Chemical class 0.000 claims description 58
- -1 Oxygen radical species Chemical class 0.000 claims description 48
- 238000007254 oxidation reaction Methods 0.000 claims description 35
- 230000003647 oxidation Effects 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 238000012546 transfer Methods 0.000 claims description 21
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 21
- 238000005192 partition Methods 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 17
- 239000010408 film Substances 0.000 claims description 15
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- GIRKRMUMWJFNRI-UHFFFAOYSA-N tris(dimethylamino)silicon Chemical compound CN(C)[Si](N(C)C)N(C)C GIRKRMUMWJFNRI-UHFFFAOYSA-N 0.000 claims description 5
- 238000005137 deposition process Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 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 claims description 3
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- LXEXBJXDGVGRAR-UHFFFAOYSA-N trichloro(trichlorosilyl)silane Chemical compound Cl[Si](Cl)(Cl)[Si](Cl)(Cl)Cl LXEXBJXDGVGRAR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims 4
- 230000001681 protective effect Effects 0.000 claims 4
- 239000012530 fluid Substances 0.000 claims 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 2
- 239000001569 carbon dioxide Substances 0.000 claims 2
- 230000002401 inhibitory effect Effects 0.000 claims 2
- 239000001272 nitrous oxide Substances 0.000 claims 2
- 238000013022 venting Methods 0.000 claims 2
- 238000004891 communication Methods 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 34
- 238000000231 atomic layer deposition Methods 0.000 description 17
- 238000010926 purge Methods 0.000 description 13
- 238000002955 isolation Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 230000007723 transport mechanism Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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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
- C23C16/22—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 deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
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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
- C23C16/44—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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
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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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- C23C16/24—Deposition of silicon only
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- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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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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- 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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- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/45538—Plasma being used continuously during the ALD cycle
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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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- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
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- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
- C23C16/45548—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction
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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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- 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
- C23C16/511—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 using microwave 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
- C23C16/44—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
- C23C16/54—Apparatus specially adapted for continuous coating
- C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
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- H—ELECTRICITY
- 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
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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- Metallurgy (AREA)
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- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Electromagnetism (AREA)
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Dispersion Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Formation Of Insulating Films (AREA)
Description
本出願は、米国特許法第119条(e)に基づき、2009年12月29日出願の米国特許仮出願61/290,826号の恩典を主張し、その仮出願は、本明細書で参照することにより組み込まれる。
金属酸化物膜のALD処理用の酸素源として酸素ラジカルを使用する場合、他のものよりも好ましい、いくつかの特定の化学物質及びシステム構成がある。特に、サーマル(非ラジカル)ALDにおいて酸素の前駆体として水を使用することが最適なものとは、異なる構成である。
(1)基板表面に化学吸着する第1前駆体であって、酸素及び酸素ラジカルと反応する化学吸着種が基板表面に残留するようになる、該第1前駆体と、
(2)酸素ラジカル種、例えば、単原子の酸素ラジカル(O・)であって、酸素含有の気体状化合物(又は混合物)を含むが、O2はほとんど含まない第2前駆体から形成されたプラズマ中で発生する、該酸素ラジカル種と
に交互に被曝させる。
例えば、ほとんどO2を含まない適切な気体状の化合物又は混合物は、3%未満(モル分率)のO2しか含まないものとする。いくつかの実施形態では、適切な気体状の化合物又は混合物は、モル分率で2%未満、1%未満、0.1%未満又は0.01%未満のO2しか含まない場合もある。いくつかの実施形態において、適切な化合物又は混合物は、ほとんどO2を含まないと言える場合があり、それは、モル分率で0.001%未満しかO2を含まない場合である。いくつかの実施形態では、適切な気体状の化合物又は混合物は、10ppm未満又は1ppm未満のO2しか含まない。
基板:PETを巻き付けたローラにおける2.2メートルのバンド(ループ)を、図2に示す種類の3ゾーン式反応器システム(但し、通路254,256はそれぞれ2箇所しかない)において、前駆体ゾーン及び酸化ゾーンを循環するよう案内する。
酸化温度:70℃
動作圧力:公称160Pa(1.2Torr)
ラジカル発生器:直流プラズマ、電力約200W、基板1cm以内の範囲に電極を配置
酸素含有ガス:清浄で乾燥した圧縮空気を酸化ゾーンに注入(注記:TiCl4は、容易にはオゾンと反応せず、ポリマー表面において70℃でTiO2を形成する。)
成長速度:約1Å/サイクル
基板:PETを巻き付けたローラにおける2.2メートルのバンド(ループ)を、図2に示す種類の3ゾーン式反応器システム(但し、通路254,256はそれぞれ2箇所しかない)において、前駆体ゾーン及び酸化ゾーンを循環するよう案内する。
基板温度:90℃
動作圧力:公称160Pa(1.2Torr)
ラジカル発生器:直流プラズマ、電力約200W、基板1cm以内の範囲に電極を配置
酸素含有ガス:CO2(注記:TMAは、高濃度のO2とわずかに反応し、O3と適度に反応する。)
成長速度:約1.6Å/サイクル
基板:PETを巻き付けたローラにおける2.2メートルのバンド(ループ)を、図2に示す種類の3ゾーン式反応器システム(但し、通路254,256はそれぞれ2箇所しかない)において、前駆体ゾーンと酸化ゾーンを循環するよう案内する。
基板温度:90℃
動作圧力:公称160Pa(1.2Torr)
ラジカル発生器:直流プラズマ、電力約200W、基板1cm以内の範囲に電極を配置
酸素含有ガス:高純度のCO2(注記:DEZは、O2及びO3と高い反応性を有する。)
成長速度:約1.2Å/サイクル
Claims (31)
- 保護薄膜を堆積する方法において、
第1前駆体ガスを前駆体チャンバに導入するステップであって、該第1前駆体ガスはオゾンと反応する、該第1前駆体ガス導入ステップと、
第2前駆体ガスの流れを、前記前駆体チャンバとは異なりかつ前駆体チャンバから仕切り体で分離した酸化ゾーンに注入する第2前駆体ガス注入ステップであって、前記仕切り体には、流れを制限する1つ又はそれ以上の通路を延在させ、また該第2前駆体ガスは、酸素含有化合物を含み、室温で気体となり、前記第1前駆体ガスと反応せず、さらに該第2前駆体ガスはモル分率で酸素(O2)を3%未満しか含まないものである、該第2前駆体ガス注入ステップと、
前記前駆体チャンバから排出する排出ステップであって、前記第2前駆体ガスの少なくとも一部が、前記酸化ゾーンから前記通路を経て前記前駆体チャンバに流入するようにし、これによって前記第1前駆体ガスが前記酸化ゾーンへ移動することを抑止する、該排出ステップと、
基板を移送経路に沿って前記前駆体チャンバと前記酸化ゾーンとの間で複数回出入りするよう移送する移送ステップであって、該移送経路は、前記通路のうち少なくとも一部を貫通して前記前駆体チャンバに至るものとし、前記前駆体チャンバでは、前記第1前駆体ガスが前記基板の表面に化学吸着種として化学的に吸着する、該移送ステップと、
前記移送経路近傍における前記酸化ゾーンで、前記第2前駆体ガスからプラズマを形成することにより、オゾンを発生させることなく、前記酸素含有化合物から不安定な酸素ラジカル種を発生させる酸素ラジカル種発生ステップであって、前記基板が前記酸化ゾーンを経て移送されるとき、オゾンに被曝されることなく、前記基板が該不安定な酸素ラジカル種に被曝されて、該不安定な酸素ラジカル種が前記化学吸着種と反応し、前記基板上に保護薄膜を堆積する、該酸素ラジカル種発生ステップと、
を有する、方法。 - 請求項1に記載の方法において、前記第2前駆体ガスは、モル分率で通常の酸素(O2)を0.1%未満しか含まない、方法。
- 請求項1に記載の方法において、前記第2前駆体ガスは、二酸化炭素(CO2)を含む、方法。
- 請求項1に記載の方法において、前記第2前駆体ガスは、亜酸化窒素(N2O)を含む、方法。
- 請求項1に記載の方法において、前記第2前駆体ガスは、CO2、CO、NO、N2O及びNO2から選んだ2種又はそれ以上の混合物を含む、方法。
- 請求項1に記載の方法において、前記不安定な酸素ラジカル種は、主として単原子の酸素ラジカル(O・)からなる、方法。
- 請求項1に記載の方法において、前記第1前駆体ガスは、トリメチルアルミニウム(TMA)、四塩化チタン(TiCl4)、六塩化二ケイ素(Si2Cl6)、四塩化ケイ素(SiCl4)、ジエチル亜鉛(DEZ)、トリスジメチルアミノシラン(TDMAS)及び四塩化スズ(SnCl4)からなるグループから選択する、方法。
- 請求項1に記載の方法において、前記基板が前記酸化ゾーンを経て移送される際に、前記基板表面がプラズマに被曝される、方法。
- 請求項1に記載の方法は、さらに、前記基板を加熱するが内部温度は摂氏150度未満となるようにするステップを有する、方法。
- 請求項1に記載の方法は、さらに、前記基板を加熱するが内部温度は摂氏80度未満となるようにするステップを有する、方法。
- 請求項1に記載の方法において、
前記基板は可撓性とし、
前記基板を移送経路に沿って前記前駆体チャンバと前記酸化ゾーンとの間を出入りするように移送する前記移送ステップは、波形の移送経路に沿って案内する一連の回転ガイドの周りに移送して前記基板を巻き取るステップを有する、方法。 - 請求項1に記載の方法において、
前記不安定な酸素ラジカル種の発生ステップは、高周波又はマイクロ波エネルギーを加えることにより、前記酸化ゾーン内で前記酸素含有化合物のガスを励起するステップを含み、また
前記通路は、前記酸化ゾーン内に前記プラズマを閉じ込めることができるほど十分に狭いものとする、方法。 - 請求項1に記載の方法は、さらに、前記酸化ゾーンをバッファゾーンにより前記前駆体チャンバから分離するステップを有し、
前記酸化ゾーンは、第2仕切り体により前記バッファゾーンから分離し、該第2仕切り体には、1つ又はそれ以上の流れを制限する一連の第2の通路が貫通する、方法。 - 請求項1に記載の方法において、前記前駆体チャンバからの前記排出ステップは、前記前駆体チャンバからポンプで排出するステップを含む、方法。
- 基板上に保護薄膜を堆積させるシステムにおいて、
少なくとも1個の仕切り体によって分離して互いに異なる第1前駆体チャンバ及び第2前駆体チャンバを有する反応チャンバであって、前記仕切り体は、該第1前駆体チャンバと該第2前駆体チャンバとの間で前記基板が通過するサイズの1個又はそれ以上の通路を有するものとした、該反応チャンバと、
第1前駆体ガスを前記第1前駆体チャンバに導入するため、前記第1前駆体チャンバに流体連通する、第1前駆体源と
酸素を含有する前駆体ガスの流れを前記第2前駆体チャンバに注入するため、前記第2前駆体チャンバに接続した酸素含有前駆体ガス源であって、該酸素含有前駆体ガスは、酸素含有化合物を含み、室温で気体となり、前記第1前駆体ガスと反応せず、また第2前駆体ガスはモル分率で酸素(O2)を3%未満しか含まないものである、酸素含有前駆体ガス源と、
前記第1前駆体チャンバに接続した排出ポートであって、該排出ポートは前記反応チャンバ及び前記第1前駆体チャンバと前記第2前駆体チャンバの間の流れを制限する通路からの流体出口をなし、また前記第2前駆体チャンバからの唯一の流体出口をなすものであり、したがって、前記酸素含有の前駆体ガスを前記第2前駆体チャンバに注入するとき、
前記酸素含有の前駆体ガスの少なくとも一部は、前記第2前駆体チャンバから前記通路を経て前記第1前駆体チャンバに流入し、前記第1前駆体チャンバで、該排出ポートを経て前記反応チャンバから排出されることになり、このことにより前記第1前駆体ガスが前記第2前駆体チャンバに移動するのを抑止する、該排出ポートと、
基板を移送経路に沿って前記第1前駆体チャンバと前記第2前駆体チャンバとの間を複数回出入りするよう移送するキャリッジであって、該移送経路は、少なくとも一部の前記通路を貫通し、また前記第1前駆体チャンバ及び前記第2前駆体チャンバに延在する、該キャリッジと、
前記第2前駆体チャンバと連係動作するように設けたラジカル発生器であって、該ラジカル発生器を付勢するとき、前記移送経路の近傍で前記酸素含有前駆体ガスからプラズマを形成することにより、オゾンを発生させることなく、前記酸素含有化合物から不安定な酸素ラジカル種を発生させ、前記基板が前記キャリッジにより前記第2前駆体チャンバを通過するよう移送されるとき、オゾンに被曝させることなく、該不安定なラジカル種に前記基板を被曝させる、該ラジカル発生器と、
を備えた、システム。 - 請求項15に記載のシステムにおいて、前記ラジカル発生器は、高周波(RF)プラズマ発生器又はマイクロ波プラズマ発生器とした、システム。
- 請求項16に記載のシステムにおいて、前記通路は、前記第2前駆体チャンバ内に前記プラズマを閉じ込めることができる程度に十分に狭いものとした、システム。
- 請求項15に記載のシステムは、さらに、
前記第1前駆体チャンバと前記第2前駆体チャンバとの間に介在させたバッファゾーンであって、前記第2前駆体チャンバと該バッファゾーンとの間に仕切り体を介在させた、該バッファゾーンと、
前記バッファゾーンと前記第1前駆体チャンバとの間に介在させた第2仕切り体であって、該第2仕切り体は、前記移送経路が貫通する1個又はそれ以上の通路を有する、該第2仕切り体と、
を備えた、システム。 - 請求項15に記載のシステムにおいて、
前記仕切り体は、複数個の通路を有し、
前記キャリッジは、前記第1前駆体チャンバ内で互いに離して設けた複数個の第1回転ガイド、及び前記第2前駆体チャンバ内で互いに離して設けた複数個の第2回転ガイドを有し、
前記第1回転ガイド及び前記第2回転ガイドは、可撓性の基板用の移送経路を画定し、前記第1回転ガイド及び前記第2回転ガイドは、それぞれ前記基板の進行方向が変化する間に、前記可撓性の基板を支持及び案内するよう構成した、システム。 - 請求項15に記載のシステムにおいて、さらに、前記排出ポートに接続したポンプを備えた、システム。
- 基板に酸化物の保護薄膜を堆積するプロセスにおいて、
第1前駆体ガスを前駆体チャンバに導入するステップであって、該第1前駆体ガスはオゾンと反応する、該第1前駆体ガス導入ステップと、
第2前駆体ガスの流れを、前記前駆体チャンバとは異なりかつ前駆体チャンバから仕切り体で分離した酸化ゾーンに注入する第2前駆体ガス注入ステップであって、前記仕切り体には、流れを制限する1つ又はそれ以上の通路を延在させ、また該第2前駆体ガスは、酸素含有化合物を含む、該第2前駆体ガス注入ステップと、
前記前駆体チャンバから排出する排出ステップであって、前記第2前駆体ガスの少なくとも一部が、前記酸化ゾーンから前記通路を経て前記前駆体チャンバに流入するようにし、これによって前記第1前駆体ガスが前記酸化ゾーンへ移動することを抑止する、該排出ステップと、
酸素含有化合物からオゾンを発生させることなく、不安定な酸素ラジカル種を発生させる酸素ラジカル種発生ステップであって、該酸素含有化合物は室温のときに気体であり、また前記第2前駆体ガスはモル分率で酸素(O2)を3%未満しか含まないものである、該酸素ラジカル種発生ステップと、
基板を移送経路に沿って前記前駆体チャンバと前記酸化ゾーンとの間で複数回出入りするよう移送する移送ステップであって、該移送経路は、前記通路のうち少なくとも一部を貫通して前記前駆体チャンバに至るものとし、前記前駆体チャンバでは、前記第1前駆体ガスが前記基板の表面に化学吸着種として化学的に吸着し、前記不安定な酸素ラジカル種は前記表面における化学吸着種と反応し、これにより、前記表面上に酸化物の薄膜を形成する、該移送ステップと、
を有する、方法。 - 請求項21に記載のプロセスにおいて、前記第2前駆体ガスは、モル分率で通常の酸素(O2)を1%未満しか含まない、プロセス。
- 請求項21に記載のプロセスにおいて、前記第2前駆体ガスは、モル分率で通常の酸素(O2)を0.01%未満しか含まない、プロセス。
- 請求項21に記載のプロセスにおいて、前記酸素含有化合物は、二酸化炭素(CO2)からなる、プロセス。
- 請求項21に記載のプロセスにおいて、前記酸素含有化合物は、亜酸化窒素(N2O)からなる、プロセス。
- 請求項21に記載のプロセスにおいて、前記酸素含有化合物は、CO2、CO、NO、N2O及びNO2から選んだ2種又はそれ以上の混合物からなる、プロセス。
- 請求項21に記載のプロセスにおいて、前記第1前駆体ガスは、トリメチルアルミニウム(TMA)、四塩化チタン(TiCl4)、六塩化二ケイ素(Si2Cl6)、四塩化ケイ素(SiCl4)、ジエチル亜鉛(DEZ)、トリスジメチルアミノシラン(TDMAS)及び四塩化スズ(SnCl4)からなるグループから選択する、プロセス。
- 請求項21に記載のプロセスにおいて、前記不安定な酸素ラジカル種は、主として、前記酸素含有化合物から形成したプラズマにより発生した、単原子の酸素ラジカル(O・)からなる、プロセス。
- 請求項21に記載のプロセスにおいて、前記基板の移送ステップは、前記基板を、前記酸素含有化合物から形成したプラズマに被曝させるステップを有する、プロセス。
- 請求項21に記載のプロセスにおいて、
前記第1前駆体ガスは、トリメチルアルミニウム(TMA)、又は四塩化チタン(TiCl4)、又はトリスジメチルアミノシラン(TDMAS)を含み、
前記基板の内部温度を、堆積プロセスにわたり摂氏150度以下に維持する、プロセス。 - 請求項21に記載のプロセスにおいて、前記基板の内部温度を、堆積プロセスにわたり摂氏80度以下に維持する、プロセス。
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WO2011090737A3 (en) | 2011-09-22 |
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BR112012015000A2 (pt) | 2017-03-01 |
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US20110159204A1 (en) | 2011-06-30 |
WO2011090737A2 (en) | 2011-07-28 |
CN102753726A (zh) | 2012-10-24 |
CN102753726B (zh) | 2015-04-29 |
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US8637123B2 (en) | 2014-01-28 |
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