CN103510059A - Method for preparing novel copper alloy protection layer material and film laminated layer - Google Patents
Method for preparing novel copper alloy protection layer material and film laminated layer Download PDFInfo
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- CN103510059A CN103510059A CN201310494844.1A CN201310494844A CN103510059A CN 103510059 A CN103510059 A CN 103510059A CN 201310494844 A CN201310494844 A CN 201310494844A CN 103510059 A CN103510059 A CN 103510059A
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Abstract
The invention provides a method for preparing a novel copper alloy protection layer material and a film laminated layer. The method comprises the following steps: firstly, sputtering coating a transparent conductive film (zinc aluminum gallium oxide) and a metal layer on glass or PET (Polyethylene Glycol Terephthalate) with an absorbing layer, further sputtering coating a copper alloy protection layer, and forming a film laminated layer structure (base material/ZAGO/metal or alloy/Cu-alloy) of an upper electrode of a film photo battery. The film can be formed into a membrane in the low-temperature (less than 150 DEG C) in a sputtering coating mode, the application requirements of glass and various flexibly base materials are met, the low resistance of a lead is ensured because of sputtering coating of pure aluminum pure silver-aluminum alloy or silver alloy, the weather resistance of the lead is improved with the combination of the copper alloy film on the upper surface, a film structure with low cost, low resistance and good weather resistance is formed, the resistance can be maintained to be less than 6*10<-6>omega cm, and the production requirements on the electrode of the film photo battery are met.
Description
Technical field
The present invention relates to a kind of new copper alloy protecting layer material and the laminated preparation method of film, belong to the Application Areas of thin film photocell.
Background technology
Along with advancing by leaps and bounds of social development and science and technology, the mankind are day by day urgent to the demand of functional materials.New functional materials has become the key of new technology and infant industry's development.Along with the development of the industries such as indicating meter, touchscreen, semi-conductor, sun power, a kind of new functional materials---transparent conductive oxide film (transparent conducting oxide, referred to as TCO film) thereupon Emergence and Development gets up.So-called transparent conductive film refers to that the transmittance of a thin-film material in visible-range reaches more than 80%, and electroconductibility is high, than resistance value lower than 1x10
-3Ω .cm.The metals such as known Au, Ag, Pt, Cu, Rh, Pd, Al, Cr, when forming the thick film of 3-15nm, all have light transmission to a certain degree, are all once applied to transparent membrane electrode.But these metallic films are too large to the absorption of light, low and the poor stability of hardness, therefore gradually develop into and take metal oxide as transparent conductive film material (Transparent Conduction Oxide, TCO) be main, this class film has the common light electrical characteristic such as optical transmittance high and resistivity in Kuan, visible range, forbidden band is low, at solar cell, plane demonstration, specific function window coating and other field of photoelectric devices, has broad application prospects.The most ripe, the most widely used In that surely belongs to of technology of preparing wherein
2o
3base (In
2o
3: Sn is called for short ITO) film, but because Indium sesquioxide price is high, therefore in thin film photocell, still take the nesa coating of zinc oxide series at present as main, as materials such as AZO (ZnO:Al) and GZO (ZnO:Ga).
For reaching the technique of film large-area uniformity and production vacuum degree of spattering, be first-selected, so the quality of film Coating Materials (target) for sputter and performance just become extremely important.Target is to have solid shape for the mother metal of sputter coating.If target can be divided into metal and pottery two large classes simply according to materials classification, if conventionally can generally divide into melting processing procedure and the large class of powder metallurgy processing procedure two according to processing procedure classification.Most metals target is adopted melting processing procedure (Al, Sb, Bi, Cd, Ce, Co, Cu, Ge, Au, Hf, In, Ir, Fe, Pb, Mg, Ni, Ni-Cr, Ni-Fe, Ni-V, Nb, Pd, Pt, Se, Si, Ag, Sn, Ti, V, Y, Zn, Zr) obtain, minority target grain size when using is controlled, alloy ingredient fusing point gap is too large etc., and factors just adopt powder metallurgy processing procedure (As, B, Cr, Co, Mn, Mo, Ni-Cr, Permalloy, Re, Ru, Te, W, 90W-10Ti).In ceramic target, only has SiO
2with ThF
4, Na
3alF
6adopt melting processing procedure, great majority are adopted powder metallurgy processing procedure (compacting+sintering, hot pressing, heat are all pressed), comprise oxide compound (Al
2o
3, BaTi O
3, PbTi O
3, Ce O
2, ITO, LiNbO
3, SiO, Ta
2o
5, TiO
2, ZrO
2, Hf O
2, MgO), carbide (SiC, TiC, TaC, WC), boride (TiB
2, Zr B
2, LaB
6), nitride (Si
3n
4, TaN, TiN), fluorochemical (CaF
2, CeF
3, MgF
2), sulfide (CdS, MoS
2, TaS
2), selenide (CdSe, PbSe, MoSe), telluride (CdTe, MoTe) and silicide (MoSi
2, TaSi
2, TiSi
2, WSi
2).
Nesa coating in the development of large-sized touch screen, LCD TV and thin film photocell (TCO) is crucial in large-area electroconductibility and transparence, and the transparence of TCO and the electrical efficiency of conversion of battery and the speed of reaction of touch screen of to a certain degree affecting, at present still there is visible ray and the problem such as long wavelength region transparence is lower and low temperature plated film is not electrically good in Indium sesquioxide series nesa coating, needs thermal treatment to obtain preferably electrical.Because traditional ITO (90% Indium sesquioxide) film design need just can reach preferably electrical at higher temperature plated film, be also unfavorable for the use of flexible substrate, and the high usage quantity that how to reduce of Indium sesquioxide price is also crucial.Aspect traditional electrode and wire, mostly use the materials such as fine aluminium and fine silver in addition, adopting the modes such as sputter or silk screen printing to form required film wire and membrane electrode.But fine silver and pure aluminum material weathering resistance are poor, in following use procedure, easily because of thermogenesis electronic migration, life-time service causes film to produce abnormal projection or broken string, causes the life-span of assembly to reduce.How extending the life-span of film wire and electrode and reduce production costs, is also the important key of the enlargement of application, to produce low cost and to meet the electronic product of consumer demand.
Summary of the invention
The object of the invention is to provide a kind of new copper alloy protecting layer material and laminated method of film prepared; first having the glass of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the top electrode of thin film photocell or the film layered structure of wire.Adopt method self-control fine silver, fine aluminium, silver alloys, aluminium alloy and the copper alloy target of vacuum melting, the composition aspect of copper alloy is controlled fine copper and is added nickel content 10-49wt%, add zirconium content 0-1.0 wt%, add chromium content 0-1.0 wt%, add pure titanium content 0.1-1.0 wt%.<b TranNum="85">adopt the mode of injection forming, the target of self-control zinc oxide gallium aluminium series, controls alumina content at 0.1-5.0wt% in zinc oxide gallium aluminium target, and gallium oxide content is at 0.1-5.0wt%</b>.Pioneering fine silver, silver alloys, fine aluminium and the aluminium alloy of using is used as main traverse Coating Materials, adding that copper alloy protects laminated composite structure to make film layered structure and lead.First (TCO) film of the electrically conducting transparent of first sputter 15-200nm on glass and pliability pet substrate, follow the fine silver of sputter 30-500nm, silver alloys, fine aluminium or aluminum alloy films, the last copper alloy thin films at sputter 10-150nm, form multilayer film layered structure, film can be under low temperature (< 150 ℃) state forming sputtering film, meet glass and various flexible substrate must be used, fine silver, silver alloys, the sputter of fine aluminium or aluminium alloy has been guaranteed the low resistance of wire, the copper alloy plated film of collocation upper surface increases the weathering resistance of electrode, form a kind of, low resistance, the membrane structure that weathering resistance is good, the Production requirement that meets the electrode of thin film photocell.Resistance value can maintain 6x10<sup TranNum="86">-6</sup>below Ω cm.
Prepare the laminated method of new copper alloy protecting layer material and film, copper alloy protective layer material is followed successively by conductive zinc oxide gallium aluminium thin film layer, fine silver or thin film silver alloy layers from bottom to up, copper alloy thin films layer forms; In the material of wherein said conductive zinc oxide gallium aluminium thin film layer, alumina content massfraction is 0.1
-5.0%, the content massfraction 0.1-5.0% of gallium oxide, surplus is zinc oxide; Using respectively zirconia ball, pure water and dispersion agent metal carboxylate to grind fully above-mentioned raw materials mixes, milling time 24 hours, then slurry is poured in porousness mould, through super-dry rear demoulding, form the low density idiosome that multivariant oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become zinc oxide gallium aluminium (ZAGO) target with surface grinding;
The design of employing multilayered structure, first on glass or pliability pet substrate, the zinc oxide aluminum of first sputter 15-200nm is transferred film, follow fine silver, fine aluminium, aluminium alloy or the silver alloy film of sputter 15-500nm, the last copper alloy thin films at sputter 10-200nm, the electrode film that forms multilayer layered structure, makes film forming sputtering film under < 150 ℃ of states.
Described zinc oxide aluminum is transferred in target, and the total content that aluminum oxide adds is not more than 5wt%, and the total content that gallium oxide adds is not more than 5wt%, and the total content that aluminum oxide and gallium oxide add is not more than 10wt%.
Described copper alloy is by nickel massfraction content 10-49wt%, zirconium massfraction content 0.1-1.0 wt%, chromium massfraction content 0.1-1.0 wt%, pure titanium massfraction content 0.1-1.0 wt%, and surplus is that copper forms.
The composition aspect of described silver alloys is controlled fine silver interpolation titanium content and is not more than 3wt%, adds copper content and is not more than 50wt%.
The composition aspect of described aluminium alloy is controlled fine aluminium interpolation titanium content and is not more than 3wt%, adds chromium content and is not more than 3wt%, adds neodymium content and is not more than 5wt%.
The preparation of copper alloy target for described sputter, is used cycle stove, at 1200 ℃, dissolves fine copper or a copper alloy material, is then cast in cast iron die, and the target of machining desired size is standby; Fine silver and silver alloys target for described sputter, used cycle stove, at 1100 ℃, dissolves fine silver and silver-colored titanium copper material, is then cast in cast iron die, and the target of machining desired size is standby; Fine aluminium and aluminium alloy target for described sputter, used cycle stove, at 850 ℃, dissolves fine aluminium and aluminium titanium chromium neodymium material, is then cast in cast iron die, and the target of machining desired size is standby.
Described its sputter process is: first, by glass or pet substrate, metal targets, alloy target material and zinc oxide gallium aluminium target are put into vacuum splashing and plating machine, and vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate or pet substrate do not heat, and then carry out sputter.
In described conductive zinc oxide gallium aluminium material, preferred content is: quality of alumina mark content is 0.5-3.0%, and gallium oxide content is 0.5-3.0%, and surplus is zinc oxide.
Mass ratio is: conductive zinc oxide gallium aluminium material: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02.
Intermediate conductive layer is selected fine aluminium, fine silver, aluminium alloy or silver alloys.
A kind of new copper alloy protecting layer material and laminated method of film prepared; first having the glass (healthy and free from worry 7095) of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the film layered structure of the top electrode of thin film photocell.
adopt the mode of injection forming, the target of self-control zinc oxide gallium aluminium series, controls alumina content at 0.1-5.0wt% in zinc oxide gallium aluminium target, and gallium oxide content is at 0.1-5.0wt%, and surplus is zinc oxide.Powder in blending ratio: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02, grind abundant composite dependency powdered material, milling time approximately 24 hours, then slurry is poured in porousness mould, dry rear demoulding through after a while forms the low density idiosome that multivariant oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become self-control with surface grinding
zinc oxide gallium aluminium(ZAGO) target.Cycle stove is used in the preparation of copper alloy target, at 1200 ℃ of dissolved copper alloy material, then be cast in cast iron die standby at the target that is processed into desired size, the composition aspect of copper alloy is controlled fine copper and is added nickel content 10-49wt%, add zirconium content 0-1.0 wt%, add chromium content 0-1.0 wt%, add pure titanium content 0-1.0 wt%.
cycle stove is used in the preparation of fine aluminium and aluminium alloy target, at 850 ℃, dissolve the materials such as fine aluminiums and titanium, chromium, neodymium, then be cast in cast iron die standby at the target that is processed into desired size, cycle stove is used in the preparation of fine silver and silver alloys target, at 1100 ℃, dissolve the materials such as fine silver, titanium, copper, be then cast in cast iron die standby at the target that is processed into desired size.First by glass substrate, fine aluminium target, copper alloy target and
zinc oxide gallium aluminium(ZAGO) target is put into vacuum splashing and plating machine (science and technology/north, Taiwan scholar extensively continues science and technology), vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then first thick with DC power supply sputter the first layer 15-200nm
zinc oxide gallium aluminium(ZAGO) film, then with the thick fine aluminium film of DC power supply sputter second layer 15-500nm, last with the 3rd layer of thick copper alloy thin films of 10-200nm of DC power supply sputter, form required Glass (PET)/ZAGO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
A kind of new copper alloy protecting layer material and laminated method of film prepared; first having the glass (healthy and free from worry 7095) of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the top electrode of thin film photocell or the film layered structure of wire.
adopt the mode of injection forming, the target of self-control zinc oxide gallium aluminium series, controls alumina content at 0.1-5.0wt% in zinc oxide gallium aluminium target, and gallium oxide content is at 0.1-5.0wt%, and surplus is zinc oxide.Powder in blending ratio: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02, grind abundant composite dependency powdered material, milling time approximately 24 hours, then slurry is poured in porousness mould, dry rear demoulding through after a while forms the low density idiosome that ternary oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become self-control with surface grinding
zinc oxide gallium aluminium(ZAGO) target.Cycle stove is used in the preparation of copper alloy target, at 1200 ℃ of dissolved copper alloy material, then be cast in cast iron die standby at the target that is processed into desired size, the composition aspect of copper alloy is controlled fine copper and is added nickel content 10-49wt%, add zirconium content 0-1.0 wt%, add chromium content 0-1.0 wt%, add pure titanium content 0-1.0 wt%.
cycle stove is used in the preparation of fine aluminium and aluminium alloy target, at 850 ℃, dissolve the materials such as fine aluminiums and titanium, chromium, neodymium, then be cast in cast iron die standby at the target that is processed into desired size, cycle stove is used in the preparation of fine silver and silver alloys target, at 1100 ℃, dissolve a material such as fine silver, titanium, copper, be then cast in cast iron die standby at the target that is processed into desired size.First by substrate, aluminium alloy target, copper alloy target and
zinc oxide gallium aluminium(ZAGO) target is put into vacuum splashing and plating machine (science and technology/north, Taiwan scholar extensively continues science and technology), vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, substrate does not heat.Then first thick with DC power supply sputter the first layer 15-200nm
zinc oxide gallium aluminium(ZAGO) film, then with the thick aluminum alloy films of DC power supply sputter second layer 15-500nm, last with the 3rd layer of thick copper alloy thin films of 10-200nm of DC power supply sputter, form required Glass (PET)/ZAGO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
A kind of new copper alloy protecting layer material and laminated method of film prepared; first having the glass (healthy and free from worry 7095) of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the top electrode of thin film photocell or the film layered structure of wire.
adopt the mode of injection forming, the target of self-control zinc oxide gallium aluminium series, controls alumina content at 0.1-5.0wt% in zinc oxide gallium aluminium target, and gallium oxide content is at 0.1-5.0wt%, and surplus is zinc oxide.Powder in blending ratio: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02, grind abundant composite dependency powdered material, milling time approximately 24 hours, then slurry is poured in porousness mould, dry rear demoulding through after a while forms the low density idiosome that ternary oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become self-control with surface grinding
zinc oxide gallium aluminium(ZAGO) target.Cycle stove is used in the preparation of copper alloy target, at 1200 ℃ of dissolved copper alloy material, then be cast in cast iron die standby at the target that is processed into desired size, the composition aspect of copper alloy is controlled fine copper and is added nickel content 10-49wt%, add zirconium content 0-1.0 wt%, add chromium content 0-1.0 wt%, add pure titanium content 0-1.0 wt%.
cycle stove is used in the preparation of fine aluminium and aluminium alloy target, at 850 ℃, dissolve the materials such as fine aluminiums and titanium, chromium, neodymium, then be cast in cast iron die standby at the target that is processed into desired size, cycle stove is used in the preparation of fine silver and silver alloys target, at 1100 ℃, dissolve a material such as fine silver, titanium, copper, be then cast in cast iron die standby at the target that is processed into desired size.First by substrate, fine silver target, copper alloy target and
zinc oxide gallium aluminium(ZAGO) target is put into vacuum splashing and plating machine (science and technology/north, Taiwan scholar extensively continues science and technology), vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, substrate does not heat.Then first thick with DC power supply sputter the first layer 15-200nm
zinc oxide gallium aluminium(ZAGO) film, then with the thick fine silver film of DC power supply sputter second layer 15-500nm, last with the 3rd layer of thick copper alloy thin films of 10-100nm of DC power supply sputter, form required Glass (PET)/ZAGO/Ag/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
A kind of new copper alloy protecting layer material and laminated method of film prepared; first having the glass (healthy and free from worry 7095) of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the top electrode of thin film photocell or the film layered structure of wire.
adopt the mode of injection forming, the target of self-control zinc oxide gallium aluminium series, controls alumina content at 0.1-5.0wt% in zinc oxide gallium aluminium target, and gallium oxide content is at 0.1-5.0wt%, and surplus is zinc oxide.Powder in blending ratio: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02, grind abundant composite dependency powdered material, milling time approximately 24 hours, then slurry is poured in porousness mould, dry rear demoulding through after a while forms the low density idiosome that ternary oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become self-control with surface grinding
zinc oxide gallium aluminium(ZAGO) target.Cycle stove is used in the preparation of copper alloy target, at 1200 ℃ of dissolved copper alloy material, then be cast in cast iron die standby at the target that is processed into desired size, the composition aspect of copper alloy is controlled fine copper and is added nickel content 10-49wt%, add zirconium content 0-1.0 wt%, add chromium content 0-1.0 wt%, add pure titanium content 0-1.0 wt%.
cycle stove is used in the preparation of fine aluminium and aluminium alloy target, at 850 ℃, dissolve the materials such as fine aluminiums and titanium, chromium, neodymium, then be cast in cast iron die standby at the target that is processed into desired size, cycle stove is used in the preparation of fine silver and silver alloys target, at 1100 ℃, dissolve a material such as fine silver, titanium, copper, be then cast in cast iron die standby at the target that is processed into desired size.First by substrate, aluminium alloy target, copper alloy target and
zinc oxide gallium aluminium(ZAGO) target is put into vacuum splashing and plating machine (science and technology/north, Taiwan scholar extensively continues science and technology), vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then first thick with DC power supply sputter the first layer 15-150nm
zinc oxide gallium aluminium(ZAGO) film, then with the thick silver alloy film of DC power supply sputter second layer 15-500nm, last with the 3rd layer of thick copper alloy thin films of 10-200nm of DC power supply sputter, form required Glass (PET)/ZAGO/Ag-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Feature of the present invention is in preparing the laminated process of copper alloy protective layer material and film; first having the glass of absorption layer or first sputter nesa coating (zinc oxide gallium aluminium) and metal level above PET; at sputter copper alloy protective layer, form the top electrode of thin film photocell or the film layered structure of wire.。Film can be under low temperature (<150 ℃) state forming sputtering film, meet glass and various flexible substrate must be used, the sputter of the metals such as fine silver, fine aluminium, silver alloys, aluminium alloy has been guaranteed the low resistance of electrode, the copper alloy plated film of collocation upper surface increases the weathering resistance of electrode, form a kind of low cost, low resistance, the good film layered structure of weathering resistance, resistance value can maintain 6x10<sup TranNum="139">-6</sup>below Ω cm, meet the Production requirement of the electrode of thin film photocell.
embodiment:
Embodiment 1:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-15wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-15wt%Ni) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 2:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-ˇ 30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.。
Embodiment 3:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-45wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-45wt%Ni) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 4:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni-0.3Cr) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni-0.3Cr) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 5:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni-0.3Ti) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni-0.3Ti) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 6:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni-0.3Zr) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni-0.3Zr) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 7:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+3wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+3wt%Al2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 8:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni) and zinc oxide gallium aluminium
(ZnO+2wt%Al2O3+1wt%Ga2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide gallium aluminium of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3+1wt%Ga2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAGO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 9:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni) and zinc oxide gallium aluminium
(ZnO+2wt%Al2O3+3wt%Ga2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide gallium aluminium of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3+3wt%Ga2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAGO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 10:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-30wt%Ni) and zinc-gallium oxide
(ZnO+1wt%Ga2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc-gallium oxide of DC power supply order sputter the first layer 100nm
(ZnO+1wt%Ga2O3)film, the fine aluminium film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZGO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 11:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), aluminium titanium (Al-1.0wt%Ti) target, copper alloy (Cu-30wt%Ni) and zinc oxide gallium aluminium
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide gallium aluminium of DC power supply order sputter the first layer 100nm
(ZnO+0.1wt%Al2O3+1wt%Ga2O3)film, aluminium titanium (Al-1.0wt%Ti) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 12:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), aluminium chromium (Al-1.0wt%Cr) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium chromium (Al-1.0wt%Cr) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 13:
A kind of new copper alloy protecting layer material and laminated method of film prepared; the design of employing multilayered structure; first by glass substrate (healthy and free from worry 7095), aluminium chromium (Al-1.0wt%Cr-0.5wt%Ti) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium chromium (Al-1.0wt%Cr-0.5wt%Ti) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 14:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), aluminium neodymium (Al-1.0wt%Nd) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium neodymium (Al-1.0wt%Nd) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 15:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), aluminium neodymium (Al-3.0wt%Nd) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium neodymium (Al-3.0wt%Nd) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 16:
A kind of new copper alloy protecting layer material and laminated method of film prepared; the design of employing multilayered structure; first by glass substrate (healthy and free from worry 7095), aluminium neodymium titanium (Al-2.0wt%Nd-1.0wt%Ti) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium neodymium titanium (Al-2.0wt%Nd-1.0wt%Ti) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 17:
A kind of new copper alloy protecting layer material and laminated method of film prepared; the design of employing multilayered structure; first by glass substrate (healthy and free from worry 7095), aluminium neodymium chromium (Al-2.0wt%Nd-1.0wt%Cr) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, aluminium neodymium chromium (Al-2.0wt%Nd-1.0wt%Cr) film that second layer 200nm is thick, the 3rd layer of copper alloy that 50nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 18:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate (healthy and free from worry 7095), fine aluminium target, copper alloy (Cu-ˇ 30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required Glass/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.。
Embodiment 19:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by PET, fine aluminium target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine aluminium film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Al/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.。
Embodiment 20:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate, fine silver target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine silver film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 21:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate, silver-colored titanium (Ag-0.5wt%Ti) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, silver-colored titanium (Ag-0.5wt%Ti) film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 22:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate, silver-colored titanium copper (Ag-0.3wt%Ti-1.0wt%Cu) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, silver-colored titanium copper (Ag-0.3wt%Ti-1.0wt%Cu) film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 23:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by glass substrate, silver-bearing copper (Ag-15wt%Cu) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the silver-bearing copper that second layer 300nm is thick (Ag-15wt%Cu) film, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 24:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by PET, silver-bearing copper (Ag-45wt%Cu) target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the silver-bearing copper that second layer 300nm is thick (Ag-45wt%Cu) film, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag-alloy/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Embodiment 25:
Prepare the laminated method of new copper alloy protecting layer material and film, adopt multilayered structure design, first by PET, fine silver target, copper alloy (Cu-30wt%Ni) and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply order sputter the first layer 100nm
(ZnO+2wt%Al2O3)film, the fine silver film that second layer 300nm is thick, the 3rd layer of copper alloy that 100nm is thick (Cu-30wt%Ni) film, form required PET/ZAO/Ag/Cu-alloy multi-layer film structure, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
Comparative example 1:
The method of preparing electric conductive oxidation zinc-aluminium target in prior art, will add aluminum oxide 2wt% in zinc oxide, use the mode of cold isostactic pressing and high temperature sintering to make base substrate, is then processed into target.First by glass substrate, fine aluminium and zinc oxide aluminum
(ZnO+2wt%Al2O3)target is put into vacuum splashing and plating machine, vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate does not heat.Then with the thick zinc oxide aluminum of DC power supply sputter one deck 100nm
(ZnO+2wt%Al2O3)film, then form the tunic structure of required Glass/ZAO/Al with the fine aluminium film of DC power supply sputter second layer 200nm, use four-point probe resistance meter to carry out electrical measurement, and carry out the weather-proof test of 85%/200 hour of 60 ℃/humidity.
The laminated electrode of copper alloy protective layer film that each embodiment and comparative example make performance as shown in the table:
From upper table result, can find out, in the making processes of electrode of the present invention, first with fine aluminium, fine silver, aluminium alloy or silver alloys, reach low-resistance object, and the weathering resistance of the film of sputter copper alloy thin films raising subsequently, after weather-proof test, resistivity still can maintain quite low numerical value, the multilayer film layered structure that the present invention proposes, can meet the performance requriements of thin film photocell electrode.
Claims (10)
1. prepare the laminated method of new copper alloy protecting layer material and film, copper alloy protective layer material is followed successively by conductive zinc oxide gallium aluminium thin film layer, fine silver or thin film silver alloy layers from bottom to up, copper alloy thin films layer forms; It is characterized in that being: in the material of wherein said conductive zinc oxide gallium aluminium thin film layer, alumina content massfraction is 0.1
-5.0%, the content massfraction 0.1-5.0% of gallium oxide, surplus is zinc oxide; Using respectively zirconia ball, pure water and dispersion agent metal carboxylate to grind fully above-mentioned raw materials mixes, milling time 24 hours, then slurry is poured in porousness mould, through super-dry rear demoulding, form the low density idiosome that multivariant oxide mixes, then pass through the high temperature sintering of 1400-1550 ℃, can form high-density target idiosome for sputter, through cutting, become zinc oxide gallium aluminium (ZAGO) target with surface grinding;
The design of employing multilayered structure, first on glass or pliability pet substrate, the zinc oxide aluminum of first sputter 15-200nm is transferred film, follow fine silver, fine aluminium, aluminium alloy or the silver alloy film of sputter 15-500nm, the last copper alloy thin films at sputter 10-200nm, the electrode film that forms multilayer layered structure, makes film forming sputtering film under < 150 ℃ of states.
2. a kind of novel conductive new copper alloy protecting layer material and laminated method of film prepared according to claim 1; it is characterized in that: zinc oxide aluminum is transferred in target; the total content that aluminum oxide adds is not more than 5wt%; the total content that gallium oxide adds is not more than 5wt%, and the total content that aluminum oxide and gallium oxide add is not more than 10wt%.
3. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1; it is characterized in that: copper alloy is by nickel massfraction content 10-49wt%, zirconium massfraction content 0.1-1.0 wt%, chromium massfraction content 0.1-1.0 wt%, pure titanium massfraction content 0.1-1.0 wt%, and surplus is that copper forms.
4. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1, is characterized in that: the composition aspect of silver alloys is controlled fine silver interpolation titanium content and is not more than 3wt%, adds copper content and is not more than 50wt%.
5. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1; it is characterized in that: the composition aspect of aluminium alloy is controlled fine aluminium interpolation titanium content and is not more than 3wt%; add chromium content and be not more than 3wt%, add neodymium content and be not more than 5wt%.
6. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1, it is characterized in that: the preparation of copper alloy target for described sputter, use cycle stove, at 1200 ℃, dissolve fine copper or a copper alloy material, then be cast in cast iron die, the target of machining desired size is standby; Fine silver and silver alloys target for described sputter, used cycle stove, at 1100 ℃, dissolves fine silver and silver-colored titanium copper material, is then cast in cast iron die, and the target of machining desired size is standby; Fine aluminium and aluminium alloy target for described sputter, used cycle stove, at 850 ℃, dissolves fine aluminium and aluminium titanium chromium neodymium material, is then cast in cast iron die, and the target of machining desired size is standby.
7. a kind of method of preparing new copper alloy protecting layer material and film distribution according to claim 1; it is characterized in that its sputter process is: first by glass or pet substrate, metal targets; alloy target material and zinc oxide gallium aluminium target are put into vacuum splashing and plating machine, and vacuum-pumping system is evacuated to 0.7 * 10 by sputter cavity background pressure
-5-0.9 * 10
-5after torr, utilize argon gas to be used as working gas, seeing through throttling valve is 3 * 10 by the operating pressure that passes into argon gas control sputter cavity
-3torr, glass substrate or pet substrate do not heat, and then carry out sputter.
8. a kind of method of preparing new copper alloy protecting layer material and film distribution according to claim 1; it is characterized in that in conductive zinc oxide gallium aluminium material, preferred content is: quality of alumina mark content is 0.5-3.0%; gallium oxide content is 0.5-3.0%, and surplus is zinc oxide.
9. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1, is characterized in that mass ratio is: conductive zinc oxide gallium aluminium material: zirconia ball: pure water: dispersion agent=1:3:0.25:0.02.
10. a kind of new copper alloy protecting layer material and laminated method of film prepared according to claim 1, is characterized in that intermediate conductive layer selection fine aluminium, fine silver, aluminium alloy or silver alloys.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105274486A (en) * | 2015-11-18 | 2016-01-27 | 南京迪纳科光电材料有限公司 | Preparing method for amorphous AlGaZnO transparent electrode material |
| CN110747494A (en) * | 2019-11-11 | 2020-02-04 | 上海纯米电子科技有限公司 | Electroplating cavity and manufacturing method |
| CN110923636A (en) * | 2019-11-29 | 2020-03-27 | 南京航空航天大学 | Electron beam composite plasma alloying treatment method for surface of gamma-TiAl alloy |
| CN113122885A (en) * | 2021-04-05 | 2021-07-16 | 莫日根 | Application of aluminum alloy composite board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105274486A (en) * | 2015-11-18 | 2016-01-27 | 南京迪纳科光电材料有限公司 | Preparing method for amorphous AlGaZnO transparent electrode material |
| CN110747494A (en) * | 2019-11-11 | 2020-02-04 | 上海纯米电子科技有限公司 | Electroplating cavity and manufacturing method |
| CN110923636A (en) * | 2019-11-29 | 2020-03-27 | 南京航空航天大学 | Electron beam composite plasma alloying treatment method for surface of gamma-TiAl alloy |
| CN113122885A (en) * | 2021-04-05 | 2021-07-16 | 莫日根 | Application of aluminum alloy composite board |
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| CN103510059B (en) | 2016-08-17 |
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