TWI500050B - 導電薄膜的製法 - Google Patents
導電薄膜的製法 Download PDFInfo
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- TWI500050B TWI500050B TW100106318A TW100106318A TWI500050B TW I500050 B TWI500050 B TW I500050B TW 100106318 A TW100106318 A TW 100106318A TW 100106318 A TW100106318 A TW 100106318A TW I500050 B TWI500050 B TW I500050B
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- 238000000034 method Methods 0.000 title claims description 54
- 239000010409 thin film Substances 0.000 title description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 90
- 229910052751 metal Inorganic materials 0.000 claims description 56
- 239000002184 metal Substances 0.000 claims description 56
- 150000004706 metal oxides Chemical class 0.000 claims description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 50
- 239000011787 zinc oxide Substances 0.000 claims description 43
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 33
- 238000004519 manufacturing process Methods 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 18
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- 229910001923 silver oxide Inorganic materials 0.000 claims description 10
- 229920000867 polyelectrolyte Polymers 0.000 claims description 9
- 238000003980 solgel method Methods 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000004065 semiconductor Substances 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 109
- 239000010408 film Substances 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 238000003618 dip coating Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- -1 indium metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VENMTXXQRBCIST-UHFFFAOYSA-N CNC.C=CC=CCC Chemical class CNC.C=CC=CCC VENMTXXQRBCIST-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Thermal Sciences (AREA)
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- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
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- Manufacturing Of Electric Cables (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Description
本發明係關於一種導電薄膜的製造方法。
在許多光電產品或元件中,例如太陽能電池、表面聲波元件、壓電材料元件、氣體偵測器、液晶顯示器等,都需要透明導電薄膜(transparent conductive thin film,TCO)結構。
迄今,透明導電薄膜的構成材質仍以銦錫氧化物(ITO)為大宗。銦在地球上屬於稀有金屬、具有毒性,並且在製造ITO薄膜的氫氣電漿過程中不穩定,造成成本大幅提高。
此外,習知技術以蒸鍍或濺鍍方法製作導電薄膜,具有設備成本高、難以大面積製作等缺點。
因此,亟需提出一種新的透明導電薄膜與其製造方法,可大面積製作、可降低毒性、可降低製造成本。
本發明的目的在於提供一種可在低成本、甚至低溫的
條件下,以大面積方式製作無銦導電薄膜的方法。
根據上述目的,本發明實施例提供一種導電薄膜的製造方法,包含在一基板上,以溶液法形成一第一金屬氧化物層;接著,以非溶液法或溶液法形成一無銦金屬層於第一金屬氧化物層上;接著,以溶液法形成一第二金屬氧化物層於該無銦金屬層上。
在實施例中,溶液法可包含溶膠凝膠法、微奈米粒子堆疊法、水熱法、浸泡塗佈法。
在另一實施例,可省略第一金屬氧化物層。
2‧‧‧基板
4‧‧‧絕緣層
6‧‧‧第一金屬氧化物層
8‧‧‧金屬層
10‧‧‧第二金屬氧化物層
12‧‧‧基板
14‧‧‧絕緣層
16‧‧‧第一金屬氧化物層
18‧‧‧金屬層
20‧‧‧第二金屬氧化物層
22‧‧‧聚電解質溶液
圖1A至1F顯示根據本發明一實施例以較高溫製程形成導電薄膜的方法;圖2A至2F顯示根據本發明另一實施例以較高溫製程形成導電薄膜的方法;以及圖3顯示根據本發明實施例,未經過PDAC溶液與經過PDAC溶液處理後的金屬層表面。
以下將詳述本案的各實施例,並配合圖式作為例示。除了這些詳細描述之外,本發明還可以廣泛地施行在其他的實施例中,任何所述實施例的輕易替代、修改、等效變化都包含在本案的範圍內,並以之後的專利範圍為準。在說明書的描述中,為了使讀者對本發明有
較完整的了解,提供了許多特定細節;然而,本發明可能在省略部分或全部這些特定細節的前提下,仍可實施。此外,眾所周知的步驟或元件並未描述於細節中,以避免造成本發明不必要之限制。此外,於圖示中,相同或相似的符號表示相同或相似的元件。
本發明提供的第一實施例,是以較高溫製程,在一基板上製作一種具有金屬/金屬氧化物,或者金屬氧化物/金屬/金屬氧化物結構、透明或不透明的導電薄膜,其中金屬氧化物層,甚至金屬層,都是以溶液法製作。此處高溫製程指的是,製程的溫度可超過500℃。
圖1A至圖1F顯示根據本發明第一實施例之製作導電薄膜的方法。參照圖1A,提供一基板2,例如一矽基板,並清洗之。參照圖1B,形成一絕緣層4於基板2上。例如,以加熱的方法,使在矽基板上形成一二氧化矽絕緣層。參照圖1C,以溶液法形成一厚度約20nm至50nm的第一金屬氧化物層6在絕緣層4上。此處的溶液法可包含溶膠凝膠(sol-gel)法、微奈米粒子堆疊法、水熱法、浸泡塗佈法(dip coating)等等,較佳者為溶膠凝膠法。第一金屬氧化物層6可包含氧化鋅、氧化鈦、氧化釩、氧化鎳、氧化鉬、氧化銅、氧化銀、氧化鎢等或其他金屬氧化物。以溶膠凝膠方法為例,首先將一包含反應物的第一金屬氧化物溶液,以旋轉塗佈(spin coating)、浸沒塗佈(dip coating)、流動法等方式,塗佈於絕緣層4上,之後加熱第一金屬氧化物溶液塗層,使反應並烘乾成為第一金屬氧化物層6。使反應、烘乾的方式,可包含以烘箱或其他習知技術常用的加熱設備加熱第一金屬氧化物溶液達成。烘乾的環境可以是真空,或是在空氣、氮氣、其他適當氣體,或者前述
氣體的組合氣體環境下進行。
參照圖1D,接著,形成一金屬層8於第一金屬氧化層6上,形成的方法可包含蒸鍍、濺鍍,或前述的溶液法。金屬層8的材質可包含金、銀、鉑、銅、鐵、錳、鈷、其他非銦的金屬,或者前述材質的任意組合的合金。溶液法可包含溶膠凝膠(sol-gel)法、微奈米粒子堆疊法、水熱法、浸泡塗佈法等,較佳者為微奈米粒子堆疊法。例如,將一具有複數個微米/奈米金屬結構的溶液塗佈於第一金屬氧化層6表面,在室溫或低溫(<100℃)條件下,溶液中的微米/奈米金屬結構相互堆疊形成該金屬層8。微奈米粒子堆疊法的細節可進一步參考台灣專利申請案,申請號98128628,申請日2009年8月26日,題為「用於有機光電元件之過渡金屬氧化物的懸浮液或溶液、其製作方法與應用」,該專利申請案的全文併入本文,視為本案說明書的一部分。若需要製備一透明導電薄膜,則金屬層8的厚度可控制在約2nm至10nm之間;並且,若金屬層8的材質為銀或銅,則金屬層8的厚度可控制在約2nm至8nm之間。若需要製備一不透明導電薄膜,則金屬層8的厚度可控制在大於100nm以上。
參照圖1E,接著,可以相同於第一金屬氧化層6的製作方法,形成一第二金屬氧化層10於金屬層8上。第一金屬氧化層6通常與第二金屬氧化層10的材質與厚度相同,但也可選用相似或不同的材料與厚度。
參照圖1F,接著,將圖1E的結構,以約100至1400℃的條件進行退火一段時間。進行退火的設備可包含快速退火系統(RTA)、高溫爐、烘箱、雷射等等。
在上述實施例中,除了矽,基板2也可是任何其他材質,例如石英、金屬、半導體、玻璃、塑膠等等。某些實施例中,可以省略在基板2上形成絕緣層4的步驟,例如,當基板2為絕緣材質,例如石英。另外,可使用其他方法形成絕緣層4,例如,使基板2浸沒於一酸性溶液。另外,如果金屬層8的厚度超過100nm,可省略上述退火步驟。另外,在另一實施例,可省略形成第一金屬氧化物層6的步驟,使金屬層8直接形成在絕緣層4或基板2上。
本發明提供的第二實施例,是以較低溫製程,在一基板上製作一種具有金屬/金屬氧化物,或者金屬氧化物/金屬/金屬氧化物複合結構,其中金屬氧化物層,甚至金屬層,都是以溶液法製作。此處低溫製程指的是,所有製程步驟在小於500℃、甚至在室溫的條件下完成。
圖2A至圖2F顯示根據本發明第二實施例之製作導電薄膜的方法。參照圖2A,提供一基板12,並清洗之。參照圖2B,以如同第一實施例的方法,形成一絕緣層14於基板12上。參照圖2C,以如同第一實施例的方法與材質,形成一第一金屬氧化物層16在絕緣層14上。參照圖2D,接著,以如同第一實施例的方法與材質,形成一金屬層18於第一金屬氧化層16上。
參照圖2E,接著,使金屬層18與一聚電解質(polyelectrolytes)溶液22,例如一聚陽離子(polycation)溶液,例如聚氯化己二烯二甲基胺[poly(diallyldimethylammonium chloride),PDAC]溶液接觸。例如,將聚電解質溶液22滴在金屬層18表
面,或將金屬層18浸沒於聚電解質溶液22。聚電解質溶液22會縮短金屬層18晶粒之間的間距,使改善金屬層18的平坦度與導電性。之後,以自然或人工乾燥方式,使乾燥聚電解質溶液22。此步驟可於室溫下進行。
參照圖2F,接著,可以相同於第一金屬氧化層16的製作方法與材質,形成一第二金屬氧化層20於金屬層18上。之後,可不需再進行退火步驟,完成導電薄膜的製備。此外,本實施例的材質與結構變化,亦與第一實施例相同,不再贅述。
實例1
本實例將以高溫製程,在一矽基板上製作一透明的氧化鋅/銀/氧化鋅三明治結構,作為一導電薄膜。
首先,使用高溫爐以1000℃加熱矽基板3hr,使成長厚度約200nm的氧化層於其表面上,作為絕緣層。
接著,切取約1cm×1cm大小的矽基板,並以標準的清洗過程清洗:把矽基板分別放入丙酮、甲醇、去離子水中,以超音波震盪器震洗15min,之後,以氮***的氮氣吹乾矽基板。
接著,調配無摻雜的氧化鋅溶膠凝膠溶液。將溶質-醋酸鋅(Zn(CH3COOH)2.2H2O)、溶劑-甲氧乙醇(2-Methoxyethanol,2MOE),以莫耳比1:1的比例,再加上穩定劑-單乙醇胺(Monoethanolamine,MEA),置入一燒杯後密封。將燒杯加熱至65℃,並以攪拌子攪拌兩個小時,使其內容物變成透明澄清狀,成為濃度0.5M的氧化鋅溶膠凝膠(sol-gel)溶液。
接著,用旋轉塗佈機(spin coater)把上述氧化鋅溶膠凝膠溶液旋塗於矽基板上。旋塗的轉速與時間會影響成膜厚度。首先,
以1000rpm、10sec加上4000rpm、30sec的條件,將甲醇旋塗於矽基板上。用氮***吹乾甲醇旋塗層,以形成適合氧化鋅溶膠凝膠溶液吸附的氫氧基。接著,以1000rpm、10sec加上4000rpm、30sec的轉速與時間,旋塗氧化鋅溶膠凝膠溶液於表面上具有氫氧基的矽基板上,其中,氧化鋅溶膠凝膠旋塗層的厚度,可隨旋轉次數調變。
接著,烘乾氧化鋅溶膠凝膠旋塗層,形成一初步氧化鋅層。隨後用電磁加熱攪拌機(hot plate),以200℃加熱初步氧化鋅層30min,以去除多餘的有機物而形成一第一氧化鋅層,其厚度大約為30至50nm。可重複上述旋塗、烘乾等步驟使增加薄膜厚度。
接著,使用熱蒸鍍機在第一氧化鋅層上蒸鍍一層厚度約2至10nm的銀金屬層。
接著,以製作第一氧化鋅層的相同方法,立即製作一第二氧化鋅層於銀金屬層上。
最後,將所製備樣品放入高溫爐中,以約400至700℃的條件,退火1hr,完成氧化鋅/銀/氧化鋅(ZnO/Ag/ZnO)結構。
實例2
本實例的製作方法與實例1相同,除了銀金屬層的厚度大於100nm,使成為一不透明的氧化鋅/銀/氧化鋅三明治結構。
實例3
本實例的製作方法與實例1相同,不同處在於省略了第一氧化鋅層,亦即,銀金屬層直接被形成在絕緣層上,再形成第二氧化鋅層於銀金屬層上。
實例4
本實例的製作方法與實例3相同,除了銀金屬層的厚度大於100nm,使成為一具有不透明銀/氧化鋅結構的導電薄膜。
實例5
本實例將以低溫製程,在一玻璃基板上製作一透明的氧化鋅/銀/氧化鋅三明治結構,作為一導電薄膜。
以如同實例1的製造方法,在玻璃基板上形成第一氧化鋅層與第二氧化鋅層,而不同處在於,本實例以微奈米粒子堆疊法取代熱蒸鍍法,形成銀金屬層。將具有濃度約0.1mg/ml的微米/奈米銀粒子的溶液塗佈於第一氧化鋅層上,在室溫條件下,溶液中的微米/奈米銀粒子相互堆疊形成一銀金屬層於第一氧化鋅層上。銀金屬層的厚度控制在約2至8nm或2至10nm。
接著,於室溫下,將聚氯化己二烯二甲基胺(PDAC)溶液滴在銀金屬層表面,再使其自然風乾。圖3顯示銀金屬層在未經PDAC處理與經過PDAC處理後的掃描電子顯微鏡(SEM)圖。經過PDAC處理過的銀金屬層表面有類似燒結作用,會黏結金屬銀晶粒、縮短銀金屬層晶粒之間的間距,使改善銀金屬層的平坦度與導電度。
接著,形成一第二氧化鋅層於銀金屬層上,且不需再進行退火步驟。
實例6
本實例的製作方法與實例5相同,除了銀金屬層的厚度大於100nm,使成為一不透明的氧化鋅/銀/氧化鋅三明治結構。
實例7
本實例的製作方法與實例5相同,不同處在於省略了第一氧化鋅層,亦即,銀金屬層直接被形成在玻璃基板上,再形成第二氧化鋅層於銀金屬層上。
實例8
本實例的製作方法與實例7相同,除了銀金屬層的厚度大於100nm,使成為一具有不透明銀/氧化鋅結構的導電薄膜。
實例9
本實例的製作方法與實例5相同,除了以水熱法取代溶膠凝膠法,作為第一氧化鋅層與第二氧化鋅層的形成方法。首先於所欲形成表面上,亦即,玻璃基板或金屬層表面上,塗佈一氧化鋅種子層;接著,在密閉的反應器內,利用水為介質,控制適當壓力與溫度(低於100℃),使包含反應物一硝酸鋅六水合物(zinc nitratehexahydrate,Zn(NO3)2.6H2O)及四氮六甲圜(methenamine,C6H12N4)的混合溶液,在氧化鋅種子層上成長第一氧化鋅層或第二氧化鋅層。
以上,本發明各實施例所製備的導電薄膜,可應用於各種光電元件或電子元件。例如,所製備的透明導電薄膜,可作為於一太陽能電池的一電極,如此可增加光穿透率,進而增加能源轉換效率。例如,所製備的不透明導電薄膜,當其金屬層的厚度介於100nm至200nm,可作為一發光二極體的一反射層,亦即,n極,使增加發光二極體的出光量。現有發光二極體的n極材質通常為單層結構的金或氧化銦錫(ITO),其中金會吸光,導致發光效率變差,而氧化銦錫的導電性較差,導致發光不均勻。若使用本發明實施例所提供的導電薄膜,例如氧
化鋅/銀/氧化鋅,則銀的導電度優於氧化鋅,且不吸光,而氧化鋅提供保護作用,可避免銀氧化,提高可靠度。
習知技術已經揭露有以傳統的蒸鍍或濺鍍方法,製成由複合層構成的透明導電薄膜。然而,蒸鍍或濺鍍方法必須使用昂貴的設備,並且難以製作大面積的導電薄膜。另一方面,溶液法,例如溶膠凝膠(sol-gel)法等,雖已見於習知技術,但是並未被應用於製作三明治結構的導電薄膜,顯見以溶液法製作導電薄膜,具有一定的困難性。本發明成功以溶液法製造出金屬氧化層/金屬/金屬氧化層,或金屬/金屬氧化層的透明或不透明導電結構。此製作方法的製作成本低廉、製程迅速,所製備的導電結構導電性佳,可應用於各種光電元件,不僅解決業界長久以來存在的問題,也十分具有前瞻性。
以上所述僅為本發明之較佳實施例而已,並非用以限定本發明之申請專利範圍;凡其他未脫離發明所揭示之精神下所完成之等效改變或修飾,均應包含在下述之申請專利範圍內。
12‧‧‧基板
14‧‧‧絕緣層
16‧‧‧第一金屬氧化物層
18‧‧‧金屬層
20‧‧‧第二金屬氧化物層
22‧‧‧聚電解質溶液
Claims (12)
- 一種導電薄膜的製造方法,該導電薄膜作為一電極,該製造方法包含:提供一基板;以一溶液法形成一第一金屬氧化物層在該基板上;以一非溶液法或該溶液法形成一金屬層於該第一金屬氧化物層上;以該溶液法形成一第二金屬氧化物層於該金屬層上;其中該第一金屬氧化物層和該第二金屬氧化物層的材質包含氧化鋅、氧化鈦、氧化釩、氧化鎳、氧化鉬、氧化銅、氧化銀,或氧化鎢。
- 如申請專利範圍第1項的製造方法,尚包含形成一絕緣層於該基板與該第一金屬氧化物層之間。
- 如申請專利範圍第1項的製造方法,其中該基板的材質包含矽、玻璃、石英、半導體、金屬、塑膠。
- 如申請專利範圍第1項的製造方法,其中該溶液法包含一溶膠凝膠法、一微奈米粒子堆疊法、一浸泡塗佈法,或一水熱法。
- 如申請專利範圍第4項的製造方法,其中該溶膠凝膠法包含:形成一溶膠凝膠種子層於所欲成長的表面;塗佈一包含反應物的溶膠凝膠溶液於該溶膠凝膠種子層上;以及加熱使該溶膠凝膠溶液反應成該金屬層、該第一金屬氧化物層,或該第二金屬氧化物層。
- 如申請專利範圍第4項的製造方法,其中該微奈米粒子堆疊法包含: 塗佈一具有複數個微米/奈米金屬或微米/奈米金屬氧化物結構的溶液於所欲成長表面上;以及該溶液中的微米/奈米金屬結構或微米/奈米金屬氧化物結構相互堆疊形成該金屬層、該第一金屬氧化物層,或該第二金屬氧化物層。
- 如申請專利範圍第4項的製造方法,其中該水熱法包含:塗佈一水熱法種子層於所欲成長表面;於一密閉反應器內,控制適當壓力與溫度,使一具有反應物的水溶液在所欲成長表面上成長該金屬層、該第一金屬氧化物層,或該第二金屬氧化物層。
- 如申請專利範圍第1項的製造方法,其中在形成該金屬層之後,尚包含使該金屬層與一聚電解質溶液接觸,使改善該金屬層的平坦度與導電度。
- 如申請專利範圍第8項的製造方法,其中該聚電解質溶液包含聚氯化己二烯二甲基胺。
- 如申請專利範圍第1項的製造方法,其中該金屬層的材質包含金、銀、鉑、銅、鐵、錳、鈷、其他非銦的金屬,或者前述材質的任意組合的合金。
- 如申請專利範圍第1項的製造方法,當形成該第二金屬氧化物層於該金屬層之後,尚包含進行一退火步驟。
- 如申請專利範圍第1項的製造方法,其中該金屬層的厚度介於約2nm至10nm之間,或該金屬層的厚度介於100nm至200nm,且該導電薄膜作為一反射層。
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KR101406721B1 (ko) * | 2013-04-03 | 2014-06-16 | 한국에너지기술연구원 | 성능이 향상된 전극 소재용 분말 제조 방법과 이를 이용한 전극과 그 활용. |
CN103866321A (zh) * | 2014-03-14 | 2014-06-18 | 中国科学院合肥物质科学研究院 | 银纳米颗粒-氧化锌多孔纳米片-碳纤维布复合衬底及其制备方法和用途 |
US9708916B2 (en) | 2014-07-18 | 2017-07-18 | General Electric Company | Turbine bucket plenum for cooling flows |
EP3012348A1 (en) * | 2014-10-22 | 2016-04-27 | Nokia Technologies OY | Multilyer barrier coating and method to produce a multilayer barrier coating |
KR20170040863A (ko) | 2015-10-05 | 2017-04-14 | 삼성디스플레이 주식회사 | 투광성 도전막 및 이를 포함하는 액정 표시 장치 |
CN111128443B (zh) * | 2019-12-30 | 2021-05-28 | 深圳市华科创智技术有限公司 | 一种透明导电膜及其制备方法 |
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CN112563874B (zh) * | 2020-11-27 | 2021-07-30 | 南京大学 | 一种室温光激发氧化锌声子振动太赫兹激光器 |
CN113415780B (zh) * | 2021-06-18 | 2024-01-30 | 合肥工业大学 | 一种一维有序结构的金属氧化物纳米纤维薄膜材料及其制备方法 |
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