TW201608048A - 金屬膜形成方法 - Google Patents
金屬膜形成方法 Download PDFInfo
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- TW201608048A TW201608048A TW104128055A TW104128055A TW201608048A TW 201608048 A TW201608048 A TW 201608048A TW 104128055 A TW104128055 A TW 104128055A TW 104128055 A TW104128055 A TW 104128055A TW 201608048 A TW201608048 A TW 201608048A
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- Prior art keywords
- metal film
- forming
- metal
- organic solvent
- film according
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 135
- 239000002184 metal Substances 0.000 title claims abstract description 135
- 238000000034 method Methods 0.000 title claims abstract description 75
- 239000003960 organic solvent Substances 0.000 claims abstract description 57
- 239000012159 carrier gas Substances 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000003595 mist Substances 0.000 claims abstract description 40
- 239000007800 oxidant agent Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 31
- 238000000889 atomisation Methods 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 46
- -1 amine compound Chemical class 0.000 claims description 42
- 239000004065 semiconductor Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011651 chromium Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000010948 rhodium Substances 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
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- 239000011733 molybdenum Substances 0.000 claims description 3
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- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
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- 125000003158 alcohol group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 20
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 4
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- YNOGYQAEJGADFJ-UHFFFAOYSA-N oxolan-2-ylmethanamine Chemical compound NCC1CCCO1 YNOGYQAEJGADFJ-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940100684 pentylamine Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 1
- TXQWFIVRZNOPCK-UHFFFAOYSA-N pyridin-4-ylmethanamine Chemical compound NCC1=CC=NC=C1 TXQWFIVRZNOPCK-UHFFFAOYSA-N 0.000 description 1
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 description 1
- MIROPXUFDXCYLG-UHFFFAOYSA-N pyridine-2,5-diamine Chemical compound NC1=CC=C(N)N=C1 MIROPXUFDXCYLG-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- NGXSWUFDCSEIOO-UHFFFAOYSA-N pyrrolidin-3-amine Chemical compound NC1CCNC1 NGXSWUFDCSEIOO-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- BHRZNVHARXXAHW-UHFFFAOYSA-N sec-butylamine Chemical compound CCC(C)N BHRZNVHARXXAHW-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
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- C30B19/00—Liquid-phase epitaxial-layer growth
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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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
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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
- C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4486—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by producing an aerosol and subsequent evaporation of the droplets or particles
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Abstract
提供一種能夠有利於工業上形成密合性優良的金屬膜的金屬膜形成方法以及藉由其方法形成的金屬膜。
【解決手段】一種在基體上形成金屬膜的金屬膜形成方法,包括在氧化劑、胺化合物或者質子酸的有機溶劑中,使金屬溶解或分散形成原料溶液,將原料溶液霧化產生霧的霧化製程,將載氣提供給所述霧的載氣供給製程,藉由所述載氣將所述霧提供給所述基體的供給製程和使所述霧熱反應,在所述基體表面的一部分或者全部層積金屬膜的金屬膜形成製程。
Description
本發明涉及對半導體裝置的電極形成等有用的金屬膜形成方法。
在現有技術中,蒸鍍或者濺射法被用於金屬膜形成方法。應用電子束或者高頻的真空蒸鍍法等被廣泛用於蒸鍍,並且,用直流電源或者交流電源產生等離子體,隨後,用等離子體濺射陽極金屬,在陰極沉積金屬的手法等被廣泛用於濺射法中。但是,蒸鍍或者濺射法需要真空製程,為此,在成本花費、大型化、量產化上還存在課題。
並且,熟知塗敷方法等被廣泛用於金屬膜形成方法。塗敷金屬膏,乾燥之後煆燒的手法被用於塗敷方法。但是,這樣的塗敷方法中,煆燒需要650℃以上的高溫,金屬膜形成方法未必令人滿意。另外,已知有有機金屬氣相沉積法等,和塗敷方法一樣需要高溫製程,並且未必能充分獲得密合性。
對此,近年來嘗試使用膏體來分散超微粒子,在基板上形成圖案化金屬膜。例如專利文獻1中,已知一種手法,使由金屬芯部和有機物塗敷層
構成的複合金屬超微粒子分散在溶劑中調製成金屬膏,使該金屬膏附著在半導體元件的電極上低溫煆燒形成超微粒子電極。但是,Ag或者Au等貴金屬超微粒子形成的金屬薄膜難與平滑的無機酸化物基板發生反應,不能得到充分的密合性,尤其在為了增加導電性在薄金屬排線上形成金屬鍍覆被膜時,由於電鍍前處理或者電鍍液導致的化學反應,存在金屬排線從無機酸化物基板剝離的問題。
並且,在近年,正在研究藉由氣溶膠沉積法形成金屬膜。專利文獻2中記載一種方法,將金屬離子氣霧化,藉由將所述氣霧化金屬粒子吹到基板上,在所述基板上形成由金屬薄膜構成的電極或者排線圖案,專利文獻3中記載了一種方法,在透明電極表面藉由氣溶膠沉積法形成有金屬薄膜構成的輔助電極。但是,根據氣溶膠沉積法,電極和基板的密合性非常差,尤其不適用於在電極上形成需要的厚膜,並且,因為成膜時需要真空製程,成膜之後需要高溫熱處理,並不令人滿意。
【背景技術文獻】
【專利文獻】
【專利文獻1】日本專利 特開2001-168141號公報
【專利文獻2】日本專利 特開2011-153329號公報
【專利文獻3】日本專利 特開2013-129887號公報
本發明的目的是提供一種能夠有利於工業成膜的密合性優良的金屬膜形成方法以及藉由其方法形成的金屬膜。
本發明人等為了達到上述目的進行了認真的研究,結果發現,使用含有氧化劑、胺化合物或者質子酸的有機溶劑作為溶劑,霧化CVD法形成金屬膜的話,與金屬酸化物膜成膜時不同,容易形成密合性優良的金屬膜。
並且,本發明人等得到了上述見解後,加以研究,完成了本發明。
即,本發明涉及到以下發明。
[1]一種在基體上形成金屬膜的金屬膜形成方法,特徵是包括在含有氧化劑、胺化合物或者質子酸的有機溶劑中,使金屬溶解或分散形成原料溶液,將原料溶液霧化產生霧的霧化製程,將載氣提供給所述霧的載氣供給製程,藉由所述載氣將所述霧提供給所述基體的供給製程和使所述霧熱反應,在所述基體表面的一部分或者全部層積金屬膜的金屬膜形成製程。
[2]如所述[1]中所述的金屬膜形成方法,所述有機溶劑包括氧化劑。
[3]如所述[2]中所述的金屬膜形成方法,所述氧化劑與所述有機溶劑的體積比在1:99~50:50範圍內。
[4]如所述[2]或[3]中所述的金屬膜形成方法,所述氧化劑為水或過氧化氫。
[5]如所述[1]中所述的金屬膜形成方法,所述有機溶劑包括胺化合物。
[6]如所述[5]中所述的金屬膜形成方法,所述胺化合物為二胺。
[7]如所述[1]中所述的金屬膜形成方法,所述有機溶劑包括質子酸。
[8]如所述[7]中所述的金屬膜形成方法,所述質子酸為鹵化氫酸。
[9]如所述[1]~[8]中任意一項所述的金屬膜形成方法,所述熱反應在200℃~650℃的溫度進行。
[10]如所述[1]~[9]中任意一項所述的金屬膜形成方法,所述熱反應惰性氣體或在還原氣體的環境下進行。
[11]如所述[1]~[10]中任意一項所述的金屬膜形成方法,所述金屬從金(Au),銀(Ag),白金(Pt)、銅(Cu)、鐵(Fe)、錳(Mn)、鎳(Ni)、鈀(Pd)、鈷(Co)、銠(Rh)、釕(Ru)、鉻(Cr)、鉬(Mo),鎢(W)以及鋁(Al)中選出的1種或兩種以上金屬的。
[12]如所述[1]~[11]中任意一項所述的金屬膜形成方法,所述有機溶劑為乙醇。
[13]如所述[1]~[12]中任意一項所述的金屬膜形成方法,所述原料溶液為為如下溶液a)和b)的混合物,a)含有氧化劑,胺化合物或包括質子酸的有機溶劑,b)含有所述金屬的金屬絡化物溶液或金屬鹽溶液。
[14]一種利用所述[1]~[13]中任意一項記載的金屬膜形成方法形成的金屬膜
[15]如所述[14]中所述的金屬膜作為電極。
[16]如所述[15]中所述的金屬膜作為電極時,還至少具備半導體層的半導體裝置。
[17]一種用於形成金屬膜的霧之前體溶液,特徵為含有氧化劑,胺化合物或質子酸的有機溶劑中,使金屬溶解或分散形成溶液。
[18]如所述[17]中所述的用於形成金屬膜的霧之前體溶液,所述有機溶劑包括氧化劑。
[19]如所述[18]中所述的用於形成金屬膜的霧之前體溶液,所述氧化劑和所述有機溶劑的體積比在1:99~50:50範圍內。
[20]如所述[17]中所述的用於形成金屬膜的霧之前體溶液,所述有機溶劑包括胺化合物或質子酸。
根據本發明的金屬膜形成方法,能夠形成密合性優良的有利於工業成膜的金屬膜。並且,本發明的金屬膜密合性優良。
1‧‧‧霧化發生裝置
2a‧‧‧載氣源
2b‧‧‧載氣(稀釋)源
3a‧‧‧流量調節閥
3b‧‧‧流量調節閥
4‧‧‧霧發生源
4a‧‧‧原料溶液
4b‧‧‧霧
5‧‧‧容器
5a‧‧‧水
6‧‧‧超聲波振子
7‧‧‧成膜室
8‧‧‧熱板
9‧‧‧供給管
10‧‧‧基板
11‧‧‧排氣口
19‧‧‧霧化發生裝置
20‧‧‧基板
21‧‧‧基座
22a‧‧‧載氣供給裝置
22b‧‧‧載氣供給(稀釋)裝置
23a‧‧‧流量調節閥
23b‧‧‧流量調節閥
24‧‧‧霧發生起源
24a‧‧‧原料溶液
25‧‧‧容器
25a‧‧‧水
26‧‧‧超聲波振子
27‧‧‧供給管
28‧‧‧加熱器
29‧‧‧排氣口
【圖1】實施例1使用的霧化發生裝置的構成圖。
【圖2】表示實施例1中橫截面SEM像的圖。
【圖3】表示實施例1中金屬膜表面的SEM像的圖。
【圖4】實施例4使用的霧化發生裝置的概略構成圖。
【圖5】表示實施例4中XRD測量結果的圖。
【圖6】表示實施例5中XRD測量結果的圖。
【圖7】表示實施例6中XRD測量結果的圖。
【圖8】表示實施例5中金屬膜表面照片的圖。
本發明的金屬膜形成方法是一種在基體上形成金屬膜的金屬膜形成方法,特徵是包括:在含有氧化劑、胺化合物或者質子酸的有機溶劑中,使金屬溶解或分散形成原料溶液,將原料溶液霧化產生霧的霧化製程;將載氣提供給所述霧的載氣供給製程;藉由所述載氣將所述霧提供給所述基體的供給製程和使所述霧熱反應,在所述基體表面的一部分或者全部層積金屬膜的金屬膜形成製程。
所述霧化製程是在含有氧化劑、胺化合物或者質子酸的有機溶劑中使金屬溶解或分散調製成原料溶液,使原料溶液霧化產生霧。
本製程中使用的含有氧化劑的有機溶劑(以下,也說成「含有氧化劑的有機溶劑」),有機溶劑中沒有特別限定含有氧化劑,例如,可以藉由公知的有機溶劑和氧化劑混合得到。所述氧化劑和所述有機溶劑的體積比,優選1:99~50:50範圍內,更優選1:99~40:60範圍內,更優選1:99~10:90範圍內,最優選1:99~5:95範圍內。藉由這樣的優選範圍,霧更適於成膜,並且膜質更加良好。
作為所述氧化劑可以是例如水,水溶性或非水溶性的公知的氧化劑
等,不過,在本發明中,所述氧化劑優選水或水溶性的氧化劑,更優選水或過氧化氫更好,最優選水。並且,使用水溶性氧化劑作為所述氧化劑時,優選和水混合的水溶液形態(例如過氧化氫水等)。
作為所述氧化劑,更具體的可以是例如水,過氧化氫(H2O2),過氧化鈉(Na2O2),過氧化鋇(BaO2),過氧化苯甲醯(C6H5CO)2O2等過氧化物,次亞氯酸(HClO),過氯酸,硝酸,過醋酸或者硝基苯等的有機過氧化物等。
作為所述水,更具體的可以是例如純水,超純水,自來水,井水,礦泉水,礦物水,溫泉水,泉水,淡水,海水等,也包括對這些水進行例如精製,加熱,殺菌,過濾,離子交換,電解,滲透壓調整,緩衝化等處理之後的水(例如,臭氧水,純淨水,熱水,離子交換水,生理鹽水,磷酸緩衝液,磷酸緩衝生理食鹽水等)。
所述有機溶劑只要不妨礙本發明的目的,沒有特別的限定,作為這樣的溶劑,可以是例如醇(例如甲醇,乙醇,丙醇,異丙醇,丁醇,叔丁醇等),醚(例如二噁烷,四氫呋喃,二乙基醚(Diethyl ether),叔丁基甲基醚(t-butyl methyl ether),二異丙醇醚,乙二醇-二甲基醚等),酯(例如甲酸乙基,醋酸乙基,醋酸正丁酯等),羧酸(例如甲酸,醋酸,丙酸等),鹵化烴(例如二氯甲烷,氯仿,四氯化碳,三氯乙烯,1,2-二氯甲烷,氯苯等),烴(例如正己烷,苯,甲苯等),醯胺(例如甲醯氨基,N,N-二甲基
甲醯氨基,N,N-二甲基乙醯胺等),酮(例如丙酮,甲乙酮,甲基異丁基酮等),腈類(例如乙腈,丙腈等),環丁碸,六甲基磷醯胺等的單獨使用或它們的混合溶劑。本發明中,所述有機溶劑優選醇,酮或者它們的混合溶劑,更優選醇,最優選低級醇(優選C1~3)。
本製程中用使用的含有胺化合物的有機溶劑(以下又叫做含有胺化合物的有機溶劑),在有機溶劑中含有胺化合物的話就沒有特別限定,例如,可以藉由將公知的有機溶劑和胺化合物混合而得到。所述胺化合物和所述有機溶劑的混合物的配合比例,在所述有機溶劑中,所述胺化合物優選0.001摩爾/L~10摩爾/L範圍內,更優選0.005摩爾/L~1摩爾/L範圍內,最優選0.01摩爾/L~0.1摩爾/L範圍內。在這樣的優選範圍,霧更適於成膜,並且膜質能更加良好。
所述胺化合物只要不妨礙本發明的目的沒有特別的限定,可以是含有氧原子、硫原子、氮原子等的化合物。作為所述胺化合物,可以是例如,甲胺,乙胺,丙基胺,異丙基胺,正丁胺,異丁胺,仲丁基胺,叔丁胺,己基胺,2-甲氧基乙胺,2-乙氧乙基胺,3-甲氧基丙基胺,3-甲基硫代丙胺,乙二胺,丙二胺,丁二胺,己二胺,二亞乙基三胺,三亞乙基四胺,四乙烯五胺,亞氨基二丙胺,甲基亞氨基二丙胺,十二烷基亞氨基二丙胺,N,N’-二氨基丙基-1,3-丙二胺,N,N’-二氨基丙基-1,3-丁二胺,1,2-二氨基丙烷,二-(3-氨基丙基)醚,1,2-雙(3-氨基丙氧基)乙烷,1,3二-(3-氨基丙氧基)-2,2-二甲基丙烷,N-月桂基丙二胺,N,N’-N,N′-二叔丁
基乙二胺,N-甲基乙二胺,N-乙基乙二胺,N,N-二甲基乙撐二胺,烯丙基胺等具有C1~C16碳數的脂肪族化合物;環戊胺,環己胺,環庚胺,環辛基胺,氨基甲基環己烷,4-甲基環己胺,1-環己基乙胺,3,3,5-三甲基環己胺,異佛爾酮二胺,己二氨基甲基環等具有C1~C16碳數的脂環化合物;苄胺,苯乙胺,4-甲基苄基胺,N-氨基丙基苯胺,2-氨基-1,2-二苯基乙醇,9-氨基芴,二苯甲基胺,苯二甲胺,苯二胺,二氨基二苯甲烷,N-二苄基乙二胺,2-氨基吡啶,3-氨基吡啶,4-氨基吡啶,2,3-二氨基吡啶,2,5-二氨基吡啶,2,3,6-鳥氨基吡啶,N-氨基丙基苯胺,2-氨基-3-甲基吡啶,2-氨基-4-甲基吡啶,2-氨基-6-甲基吡啶,2-氨基-3-乙基吡啶,2-氨基-3-丙基吡啶,2-氨基-4,6-二甲基吡啶,2,6-二氨基-4-甲基吡啶,3-氨基-6-異丙基吡啶,2,6-二氨基吡啶等具有C1~C16碳數的芳香族化合物;呱嗪,N-氨基丙基呱嗪,2-甲基呱嗪,2,6-二甲基呱嗪,2,5-二甲基呱嗪,3-甲基氨基呱啶,2-氨基甲基呱嗪,3-氨基吡咯烷,同型呱嗪,N-氨基丙基呱嗪,1,4-(雙-氨基丙基)呱嗪,N-氨基乙基呱啶,N-氨基丙基呱啶,2-氨基甲基呱啶,4-氨基甲基呱啶,糠胺,四氫糠胺,3-(甲基氨基基)吡咯烷,5-甲基糠胺,2-(硫代乙酸糠)乙胺,2-吡啶甲基胺,3-吡啶甲基胺,4-吡啶甲基胺等具有C1~C16碳數的雜環化合物;2-羥基乙基胺,甲基(2-羥乙基)胺,1-氨基-2-丙醇,3-氨基-1-丙醇,2-氨基-1-丙醇,1-氨基-2-丙醇,二乙醇胺,3-氨基-1,2--丙二醇,2-(2-氨基乙氧基)乙醇,N-(2-羥乙基)乙二胺,2-氨基-1,3-丙二醇等含有一個以上經基的化合物。本發明中,所述胺化合物優選多胺,更優選二胺。另外,所述多胺可以是例如乙二胺,二亞乙基,三亞乙基四胺,四亞乙基五胺,聚氧丙烯二胺,聚氧化丙烯三胺等脂肪族多胺;異佛爾酮二胺,
烯二胺,雙(4-氨基-3-甲基二環己基)甲烷,二氨基二環己基甲烷,雙(氨基甲基)環己烷,N-氨基乙基呱嗪,3,9-雙(3-氨基丙基)-2,4,8,10-四惡螺(5.5)十一烷脂環式多胺等;間-苯二胺,對苯二胺,甲苯-2,4-二胺,甲苯-2,6-二胺,均三甲苯-2,4-二胺,均三甲苯-2,6-二胺,3-,5-二乙基甲苯-2,4-二胺,3,5-單核多胺如二乙基甲苯-2,6-二胺;亞聯苯基二胺,4,4-二氨基二苯甲烷,2,5-萘二胺,2,6-萘二胺等芳香族多胺;2-咪唑氨丙基等的咪唑等。
用在含有胺化合物的有機溶劑中的有機溶劑只要不妨礙本發明的目的,就沒有特別的限定,作為這樣的溶劑,可以是例如醇(例如甲醇,乙醇,丙醇,異丙醇,丁醇,叔丁醇等),醚(例如二噁烷,四氫呋喃,二乙基醚(Diethyl ether),叔丁基甲基醚(t-butyl methyl ether),二異丙醇醚,乙二醇-二甲基醚等),酯(例如甲酸乙基,醋酸乙基,醋酸正丁酯等),羧酸(例如甲酸,醋酸,丙酸等),鹵化烴類(例如二氯甲烷,氯仿,四氯化碳,三氯乙烯,1,2-二氯甲烷,氯苯等),烴(例如正己烷,苯,甲苯等),酮(例如丙酮,甲乙酮,甲基異丁基酮等)等的單獨使用或它們的混合溶劑。本發明中,所述有機溶劑優選醇,酮或者它們的混合溶劑,更優選醇,最優選低級醇(優選C1~3)。
本製程中使用的含有質子酸的有機溶劑(以下,也說成「含有質子酸的有機溶劑」),有機溶劑中含有質子酸的話就沒有特別限定,例如,可以藉由公知的有機溶劑和質子酸混合得到。所述質子酸和所述有機溶劑的混合物的配合比例,在所述有機溶劑中,所述質子酸優選0.001摩爾/L~10摩
爾/L範圍內,更優選0.005摩爾/L~1摩爾/L範圍內,最優選0.01摩爾/L~0.1摩爾/L範圍內。在這樣的優選範圍,霧更適於成膜,並且膜質更加良好。
所述質子酸只要不妨礙本發明的目的沒有特別的限定,公知的質子酸就可以。所述質子酸可以是例如鹽酸、硫酸、硝酸、磷酸、氟硼酸、氫氟酸、高氯酸等無機酸或有機羧酸、酚類、有機磺酸等。而且,有機羧酸可以是例如甲酸、乙酸、草酸(Oxalic acid)、苯甲酸、鄰苯二甲酸、馬來酸、富馬酸、丙二酸、酒石酸、檸檬酸、乳酸、琥珀酸、一氯乙酸、二氯乙酸、三氯乙酸、三氟乙酸、乙酸硝基、三苯基酯等。有機磺酸可以是例如烷基苯磺酸,烷基萘磺酸,烷基萘二磺酸,萘磺酸福馬林縮聚物,三聚氰胺磺酸鹽福馬林縮聚物,萘二磺酸,萘三磺酸,二萘甲烷二磺酸,蒽醌磺酸,蒽醌二磺酸,蒽磺酸,芘磺酸等。並且,可以使用它們的金屬鹽。在本發明中,所述質子酸優選無機酸,更優選氫鹵酸。氫鹵酸可以是例如鹽酸,氫溴酸,氫碘酸,氫氟酸等。
用在含有質子酸的有機溶劑中的有機溶劑只要不妨礙本發明的目的,就沒有特別的限定,作為這樣的溶劑,可以是例如醇(例如甲醇,乙醇,丙醇,異丙醇,丁醇,叔丁醇等),醚(例如二噁烷,四氫呋喃,二乙基醚(Diethyl ether),叔丁基甲基醚(t-butyl methyl ether),二異丙醇醚,乙二醇-二甲基醚等),酯(例如甲酸乙基,醋酸乙基,醋酸正丁酯等),酮(例如丙酮,甲乙酮,甲基異丁基酮等)等的單獨使用或它們的混合溶劑。本發明中,所述有機溶劑優選醇,酮或者它們的混合溶劑,更優選醇,最優選
低級醇(優選C1~3)。
本製程中使用的金屬只要不妨礙本發明的目的沒有特別限定,優選從金(Au),銀(Ag),白金(Pt)、銅(Cu)、鐵(Fe)、錳(Mn)、鎳(Ni)、鈀(Pd)、鈷(Co)、銠(Rh)、釕(Ru)、鉻(Cr)、鉬(Mo),鎢(W)以及鋁(Al)中選出的1種或兩種以上金屬。
本製程中,所述含有氧化劑的有機溶劑中,含有胺化合物的有機溶劑中或者含有質子酸的有機溶劑中,使金屬溶解或分散調製成原料溶液。
所述原料溶液中,所述金屬只要能在含有氧化劑的有機溶劑中,含有胺化合物的有機溶劑中或者含有質子酸的有機溶劑中溶解或分散的話沒有特別限定,本發明中優選:含有氧化劑,胺化合物或質子酸的有機溶劑與含有所述金屬的金屬絡化物溶液或金屬鹽溶液之混合溶液。
所述金屬的配合比例沒有特別限定,對原料溶液整體來說,優選0.01~70質量%,更優選0.12~50質量%。
在含有氧化劑,胺化合物或質子酸的有機溶劑中,使金屬溶解或分散形成溶液作為用於形成金屬膜的霧之前體(Precursor)溶液特別有用。
本製程中,所述原料溶液霧化產生霧。霧化方法,只要能使所述原料霧化的話沒有特別限定,可以是公知的霧化方法,本發明中,優選使用超聲波的霧化方法。
所述載氣供給製程,將載氣供給所述霧。載氣種類只要不妨礙本發明的目的沒有特別限定,合適的實例是例如氧,氮或氬氣等惰性氣體,再者氫氣或成膜氣體(Forming gas)等還原性氣體。並且,載氣的種類可以是一種,也可以是兩種以上,改變載氣濃度後的稀釋氣體(例如10倍稀釋氣體等)等可以作為第二載氣使用。並且,載氣的供給部位不只限於一處,可以是是兩處以上。
供給製程藉由所述載氣將所述霧提供給所述基體。載氣的流量沒有特別限定,優選0.01~20L/分鐘,更優選1~10L/分鐘。
所述基體只要能夠支援金屬膜的話沒有特別限定。所述質子酸只要不妨礙本發明的目的沒有特別的限定,公知的質子酸就可以,有機化合物也可以,無機化合物也可以。所述基體的形狀可以是例如平板或圓板、纖維狀、棒狀、圓柱狀,棱柱狀、筒狀、螺旋狀、球狀、環狀等,本發明中優選基板。
所述基板為板狀,只要能作為膜的支持體沒有特別限定。可以是絕緣體基板、半導體基板、導電性基板,所述基板優選絕緣體基板,優選表面有金屬膜的基板。本發明中,所述基板優選具有剛玉結構的結晶物為主要成分的基板,或者具有β-高盧結構的結晶物為主要成分的基板。具有剛玉結構的結晶物為主要成分的基板,基板組成比中,具有剛玉結構的結晶物
只要含量在50%以上,沒有特別限定,本發明中,優選含量70%以上,更優選含量90%以上。具有剛玉結構的結晶物為主要成分的基板可以是例如藍寶石基板(例:c面藍寶石基板)或者α型氧化鎵基板等。具有β-高盧結構的結晶物為主要成分的基板,基板組成比中,具有β-高盧結構的結晶物只要含量在50%以上,沒有特別限定,本發明中,優選含量70%以上,更優選含量90%以上。具有β-高盧結構的結晶物為主要成分的基板,可以是例如β-Ga2O3基板或者含有Ga2O3和Al2O3,Al2O3比0wt%多且在60wt%以下的混晶體基板等。其他的底層基板可以是含有六方晶體結構的基板(例:SiC基板、ZnO基板、GaN基板)等。含有六方晶體結構的基板上,優選直接或者藉由其他的層(例:緩衝層)形成膜。基板的厚度在本發明中沒有特別的限定,優選50~2000μm,更優選200~800μm。
金屬膜形成製程中,使所述霧熱反應,在所述基體表面的一部分或者全部層積金屬膜。所述熱反應中,藉由熱使所述霧反應即可,反應條件等只要不妨礙本發明的目的沒有特別限制。本製程中,所述熱反應優選在200℃~650℃的溫度,更優選在300℃~600℃的溫度,最優選在400℃~550℃的溫度下進行。並且,所述熱反應優選在無氧環境下進行,更優選氮氣或氬氣等惰性氣體,或是成膜氣體(Forming gas)或氫氣等還原性氣體環境下進行,最優選惰性氣體下進行。並且,可在加壓下、減壓下、常壓下以及大氣壓下的任何條件下反應,本發明中,優選常壓下或者大氣壓下反應。另外,膜厚可以藉由調整成膜時間來設定,本發明中
因為膜越厚密合性越優良,成膜時間優選設定長一些。成膜時間優選10分鐘以上,更優選30分鐘以上,最優選1小時以上。
根據本發明,能否斷續地結晶生長還是未知的,但無論如何,能形成密合性優良的金屬膜。並且,根據本發明,保持密合性優良的狀態下,能夠容易形成膜厚200nm以上的金屬膜(優選膜厚300nm以上,更優選500nm以上,更優選1μm以上,最優選10μm以上的金屬膜)。為此,根據本發明的金屬膜形成方法製得的金屬膜適用於電極或接觸層,這樣的金屬膜也包括在本發明內,本發明的金屬膜可作為電極或接觸層使用。並且,本發明的金屬膜構成的電極適用於半導體裝置,至少能和半導體層一起用於半導體裝置。
所述半導體層可以是例如氧化物半導體層,氮化物半導體層,含有矽的半導體層。所述氧化物半導體層優選主要成分為含有銦、鋁和鎵中一種或兩種以上元素的氧化物的半導體層。所述氮化物半導體層優選為含有氮化物半導體作為主要成分之半導體層,該氮化物半導體含有銦、鋁和鎵中的一種或兩種以上的元素。所述含有矽的半導體層優選為:含有矽或碳化矽作為主要成分之半導體層。
本發明的金屬膜可用於傳統金屬膜的各種用途,例如作為電極或接觸層,適用於各種半導體層,尤其適用於功率器件。並且,所述半導體裝置可以分為電極在半導體層的一側形成的橫型元件(橫型設備)和電極在半
導體層的表裏兩面側形成的縱型元件(縱型設備),本發明的金屬膜在橫型設備和縱型設備中都適用。
本發明中,所述金屬膜作為電極優選用於縱型設備。
所述半導體裝置可以是例如肖特基勢壘二極體(SBD)、金屬半導體場效應電晶體(MESFET)、高電子遷移率電晶體(HEMT)、金屬氧化物半導體場效應電晶體(MOSFET)、靜電感應電晶體(SIT)、結型場效應電晶體(JFET)、絕緣柵型雙極電晶體(IGBT)或者發光二極體等。本發明中,所述半導體裝置優選SBD、MOSFET、SIT、JFET或者IGBT,更優選SBD、MOSFET或者SIT。
另外,所述半導體裝置還可以含有其他層等(例如絕緣體層、半導體層、導體層、半導體層、緩衝層、或者其他中間層等)。
【實施例1】
用圖1說明實施例中使用的霧化發生裝置。圖1的霧化發生裝置19具有載置基板20的基座21、提供載氣的載氣供給裝置22a、調節載氣供給裝置22中送出載氣流量的流量調節閥23a、提供載氣(稀釋)的載氣供給裝置22b、調節載氣(稀釋)供給裝置22中送出載氣流量的流量調節閥23b、容納原料溶液的霧發生源24,水25a的容器25、安裝在容器25底面的超聲波振子26、內徑為40mm的石英管構成的供給管27、設置在供給管27周圍的加熱器28和排出熱反應後的霧、液滴以及廢氣的排氣口29。基座21由
石英構成,載置基板20的面相對水平面傾斜。成膜室的供給管27和基座21都是由石英製作成的,因此抑制:於基板20上形成的膜內混入來自裝置的雜質。
使用將乙醯丙酮酸銠(Rhodium acetylacetonate,0.01mol/L)加入到甲醇和水的混合溶劑(甲醇:水=9.5:0.5)而被分散的溶液作為原料溶液。用c面藍寶石作為基板。用氮氣作為載氣。載氣流量為5L/分鐘,載氣(稀釋)的流量設定為0.5L/分鐘。成膜在氮氣環境下以500℃進行。對於得到的金屬膜,用x射線衍射裝置確認銠金屬膜的形成。並且對於得到的銠金屬膜,在斷面SEM處測定膜厚。結果約11.7μm。另外這個斷面的SEM像如圖2所示。並且,用SEM觀察金屬膜表面。結果具有凹凸少,光滑的表面。另外這個金屬膜表的SEM像如圖3所示。並且,對於密合性,施加應力,藉由目視來觀察剝離狀況,完全沒有發生剝離等,密合性也優良。
【實施例2】
除了將水合甲醇的配合比例(體積比)設定為如表1所示比例之外,和實施例1一樣形成金屬膜,觀察其成膜狀態,進一步評價密合性。
【實施例3】
除了使用乙醯丙酮鋁代替乙醯丙酮酸銠以外,和實施例1一樣形成金屬膜。發現使用鋁能和使用銠時一樣能成膜。
【實施例4】。
1.成膜裝置
實施例4中,使用圖4所示霧化發生裝置1代替實施例1中使用的霧化發生裝置。用圖4說明實施例中使用的CVD裝置。霧CVD裝置1具有提供載氣的載氣源2a、提供載氣的載氣供給源2a、調節載氣供給源2a中送出載氣流量的流量調節閥3a、提供載氣(稀釋)的載氣(稀釋)源2b、調節載氣(稀釋)源2b中送出載氣(稀釋)流量的流量調節閥3b、容納原料溶液的霧發生源4,裝水5a的容器5、安裝在容器5底面的超聲波振子6、成膜室7、霧發生源4連接成膜室7的供給管9、成膜室7內設置的熱板8、熱反應後的霧、排出液滴和廢氣的排氣口11。另外,熱板8上設置有基板10。
2.原料溶液的製備
使乙醯丙酮酸銅0.05摩爾/L、在甲醇中混合乙醯丙酮酸銅,進一步,作為螯合劑(Chelating agent),添加混合溶液0.5%體積的乙二胺(Ethylenediamine),調製成原料溶液4a。
3.成膜準備
將上述2.中得到的原料溶液4a容納在霧發生源4內。其次,用玻璃基板作為基板10,玻璃基板設置在熱板8上,使熱板8工作將成膜室7內的溫度升到500℃。其次,打開流量閥3a、3b,將載氣從作為載氣源的載氣供給裝置2a、2b供給到成膜室7中,用載氣充分置換成膜室7
的氣體環境後,分別調節載氣的流量為5.0L/分鐘,載氣(稀釋)的流量為0.5L/分鐘。另外,使用氮氣作為載氣。
4.金屬膜的形成。
其次,使超聲波振子6以2.4MHz振動,其振動藉由水5a傳播到原料溶液4a,因此使原料溶液4a霧化產生霧4b。這個霧4b由載氣藉由供給管9內導入到成膜室7內,大氣壓下400℃在成膜室7內霧發生熱反應,在基板10上形成銅膜。成膜時間在30分鐘內。對於銅膜,用X射線測定裝置進行確認。XRD測定結果如圖5所示。並且和實施例1一樣對密合性進行評價,結果良好。
【實施例5】
除了成膜溫度用500℃代替400℃以外,和實施例4一樣得到了銅膜。對於銅膜,用X射線測定裝置進行確認。XRD測定結果如圖6所示。並且,膜厚為925nm。並且和實施例1一樣對密合性進行評價,結果良好。
【實施例6】
使乙醯丙酮酸銅為0.05摩爾/L、在甲醇中混合乙醯丙酮酸銅,進一步,作為質子酸,添加混合溶液0.25%體積的鹽酸,調製成原料溶液。除了用這個原料溶液代替實施例4中的原料溶液4a以外,和實施例4一樣而製得銅膜。對於銅膜,用X射線測定裝置進行確認。XRD測定結果如圖7所示。
並且,膜厚為799nm。並且和實施例1一樣對密合性進行評價,結果良好。
實施例4以及5中使用螯合劑時,金屬膜的光澤更加良好。作為參考,實施例5中得到的銅膜的表面圖片如圖8所示。並且,如實施例6,用質子酸時成膜速率更加良好。
【產業上的利用可能性】
本發明的金屬膜形成方法可以使用在半導體(例如化合物半導體電子設備等)電子部件、電機器部件、光學‧電子照相相關裝置、工業部件等所有領域,能夠形成優良的電極,因此尤其適用於半導體裝置的製造。
19‧‧‧霧化發生裝置
20‧‧‧基板
21‧‧‧基座
22a‧‧‧載氣供給裝置
22b‧‧‧載氣供給(稀釋)裝置
23a‧‧‧流量調節閥
23b‧‧‧流量調節閥
24‧‧‧霧發生起源
24a‧‧‧原料溶液
25‧‧‧容器
25a‧‧‧水
26‧‧‧超聲波振子
27‧‧‧供給管
28‧‧‧加熱器
29‧‧‧排氣口
Claims (20)
- 一種在基體上形成金屬膜的金屬膜形成方法,其特徵為,含有如下製程:在含有氧化劑、胺化合物或者質子酸的有機溶劑中,使金屬溶解或分散而形成原料溶液,將該原料溶液霧化產生霧的霧化製程;將載氣提供給所述霧的載氣供給製程;藉由所述載氣將所述霧提供給所述基體的供給製程;以及使所述霧發生熱反應,在所述基體表面的一部分或者全部層積金屬膜的金屬膜形成製程。
- 如權利要求1中所述的金屬膜形成方法,所述有機溶劑含有氧化劑。
- 如權利要求2中所述的金屬膜形成方法,所述氧化劑與所述有機溶劑的體積比在1:99~50:50範圍內。
- 如權利要求2所述的金屬膜形成方法,所述氧化劑為水或過氧化氫。
- 如權利要求1中所述的金屬膜形成方法,所述有機溶劑含有胺化合物。
- 如權利要求5中所述的金屬膜形成方法,所述胺化合物為二胺。
- 如權利要求1中所述的金屬膜形成方法,所述有機溶劑含有質子酸。
- 如權利要求7中所述的金屬膜形成方法,所述質子酸為鹵化氫酸。
- 如權利要求1中所述的金屬膜形成方法,所述熱反應在200℃~650℃的溫度下進行。
- 如權利要求1中所述的金屬膜形成方法,所述熱反應在惰性氣體或還原氣體的環境下進行。
- 如權利要求1中所述的金屬膜形成方法,所述金屬為從金(Au),銀(Ag),白金(Pt)、銅(Cu)、鐵(Fe)、錳(Mn)、鎳(Ni)、鈀(Pd)、鈷(Co)、銠(Rh)、釕(Ru)、鉻(Cr)、鉬(Mo),鎢(W)以及鋁(Al)中選出的1種或兩種以上。
- 如權利要求1中所述的金屬膜形成方法,所述有機溶劑為醇。
- 如權利要求1中所述的金屬膜形成方法,所述原料溶液為下述a)和b)的混合溶液,a)含有氧化劑,胺化合物或質子酸的有機溶劑b)含有所述金屬的金屬絡化物溶液或金屬鹽溶液。
- 一種利用權利要求1~13中任意一項所述的金屬膜形成方法而形成的金屬膜。
- 如權利要求14中所述的金屬膜作為電極。
- 一種半導體裝置,具備如權利要求15中所述的金屬膜作為電極,並且還至少具備半導體層。
- 一種用於形成金屬膜的霧之前體溶液,特徵在為含有氧化劑,胺化合物或質子酸的有機溶劑中,使金屬溶解或分散形成溶液。
- 如權利要求17中所述的用於形成金屬膜的霧之前體溶液,所述有機溶劑含有氧化劑。
- 如權利要求18中所述的用於形成金屬膜的霧之前體溶液,所述氧化劑和所述有機溶劑的體積比在1:99~50:50範圍內。
- 如權利要求17中所述的用於形成金屬膜的霧之前體溶液,所述有機溶劑含有胺化合物或質子酸。
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- 2015-05-27 JP JP2015108025A patent/JP6945120B2/ja active Active
- 2015-08-27 EP EP15182652.6A patent/EP2990503B1/en active Active
- 2015-08-27 US US14/838,126 patent/US9828694B2/en active Active
- 2015-08-27 KR KR1020150121117A patent/KR101807544B1/ko active IP Right Grant
- 2015-08-27 TW TW104128055A patent/TWI597381B/zh active
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TWI627886B (zh) * | 2016-05-13 | 2018-06-21 | Suzhou Weipeng Electrical Technology Co Ltd | 一種超薄金屬層的印刷線路板的製備方法 |
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KR101807544B1 (ko) | 2017-12-11 |
EP2990503A1 (en) | 2016-03-02 |
CN105386008B (zh) | 2020-01-21 |
EP2990503B1 (en) | 2022-01-12 |
CN110952077A (zh) | 2020-04-03 |
TWI597381B (zh) | 2017-09-01 |
US9828694B2 (en) | 2017-11-28 |
KR20160026761A (ko) | 2016-03-09 |
JP6945120B2 (ja) | 2021-10-06 |
JP2016050357A (ja) | 2016-04-11 |
CN110952077B (zh) | 2022-09-13 |
US20160060788A1 (en) | 2016-03-03 |
CN105386008A (zh) | 2016-03-09 |
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