CN108878058B - Three-decker transparent conductive film and preparation method thereof for dimming glass - Google Patents
Three-decker transparent conductive film and preparation method thereof for dimming glass Download PDFInfo
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- CN108878058B CN108878058B CN201810658119.6A CN201810658119A CN108878058B CN 108878058 B CN108878058 B CN 108878058B CN 201810658119 A CN201810658119 A CN 201810658119A CN 108878058 B CN108878058 B CN 108878058B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
Abstract
The three-decker transparent conductive film and preparation method thereof that the present invention relates to a kind of for dimming glass.Its technical solution is: oxide target material and metal targets are packed on magnetic control sputtering system target stand；In the mixed gas or argon gas of argon gas or argon gas and hydrogen and the mixed-gas atmosphere of oxygen, sputtering method deposition oxide is used in substrate surface, obtains oxide skin(coating)；Then in the mixed-gas atmosphere of argon gas and hydrogen, sputtering method deposited metal is used in oxide layer surface, obtains metal layer；Finally in the mixed gas or argon gas of argon gas or argon gas and hydrogen and the mixed-gas atmosphere of oxygen, the oxide is deposited using sputtering method on the metal layer, the three-decker transparent conductive film for dimming glass is made.Present invention process is simple and production cost is low, made product optics, electricity and good mechanical performance.The present invention is made of oxide skin(coating), metal layer and oxide skin(coating), and oxide skin(coating) and metal layer are corresponding with a thickness of 20~100nm and 3~20nm.
Description
Technical field
The invention belongs to transparent conductive film technical fields.In particular to a kind of three-decker for dimming glass is transparent
Conductive film and preparation method thereof.
Background technique
Dimming glass is made of transparent conductive electrode and liquid crystal layer.Its working principle is that: in the feelings of not electric field action
Under condition, dimming glass is in light transmission opaque state；When being passed through alternating current, liquid crystal molecule realizes ordered arrangement, at this moment dims
Glass is just converted to pellucidity from light transmission opaque state.By electric field action, can be realized in transparent and opaque state
Between quick random conversion.Transparent conductive electrode in current dimming glass product mainly uses tin indium oxide (ITO) thin
Membrane material has many advantages, such as that translucency is good, surface resistance is low, technical maturity.But ito thin film is not resistant to bending, in production, transports and makes
It is scrapped with fracture is easy to happen in the process, and indium ore reserves is rare and disperse, exploitation and recycling difficulty, not with resource
Disconnected consumption, the cost of ito thin film will constantly rise.Therefore, it is thin to try hard to find a kind of ITO that is cheap and haveing excellent performance by people
Film alternate material.
Current more potential ito thin film alternative materials have graphene, carbon nanotube, metal grill and Ag nano wire
The thin-film material of equal formation.But current graphene is still in development phase, and apart from volume production, there are also far distances.Nano-sized carbon plumber
Industry volume production technology is not perfect enough, and manufactured film product electric conductivity can't reach the level of common ito thin film.Metal mesh
Lattice are to be made using metal materials such as common Ag, Cu as original material using traditional coining method, raw material and system
Though it is all very low to make cost, products made thereby has unsurmountable unauspicious interference problem, using being restricted.If reducing metal
The line width of metal in grid needs more to be converted into technique, and cost can increase therewith, and the problems such as have easy broken string.Nanometer Ag
There are serious diffusing reflections, i.e. mist degree (Haze) problem for line film.
The transparent conductive film of prior art preparation, mostly the oxidic transparent conductive film of single layer structure, this single layer
The oxidic transparent conductive film translucency of structure is good, but there are resistivity when the preparation of flexible substrate surface is not high, resistant to bending etc.
Defect.Single layer ultra-thin conductive metallic film can also be used as transparent conductive film, but translucency and stability are to be improved.It answers at present
Super thin metal thin-film material only has the noble metal that resistivity are low and chemical stability is good such as Au, Ag silver and Pt, but Au and Pt
It is expensive, it limits its application.
Oxide/metal/oxide three-decker film, reaches the characteristics of combining oxide and metal well
The balance of translucency and electric conductivity, and the defects of resistivity is not high, resistant to bending when overcoming the preparation of flexible substrate surface, it can
To carry out industrialization quantization production.In oxide/metal/oxide three-decker, the characteristic of metal layer is thin to three-decker
The electrically conducting transparent performance of film plays a crucial role.It has been generally acknowledged that: metal layer is capable of forming continuous film under thin thickness, has simultaneously
Big crystallite dimension and small surface roughness can make three-decker film obtain high electrically conducting transparent performance.In current research
In, metal layer usually deposits under an ar atmosphere, and by low temperature or high speed deposition, metal layer can reach in thin film thickness
Continuous film forming [T.C.Zhang, Z.X.Mei, Y.Guo, Q.K.Xue, X.L.Du, Influence of growth
temperature on formation of continuous Ag thin film on ZnO surface by ultra-
high vacuum deposition,Journal of Physics D:Applied Physics,2009,42(6):
065303-065307；L.Cattin,Y.Lare,M.Makha,M.Fleury,F.Chandezon,T.Abachi,M.Morsli,
K.Napo,M.Addou,J.C.Bernede,Effect of the Ag deposition rate on the properties
of conductive transparent MoO3/Ag/MoO3 multilayer,Solar Energy Materials&Solar
Cells, 2013,117 (4): 103-109], low temperature depositing needs additional refrigerating plant, increases without the preparation suspected of film
Cost.Although improving deposition rate makes metallic film reach continuous and derivable in thin film thickness, but because the thickness of film is thin, brilliant
Grain is tiny, and crystallinity is poor.And thin crystal grain increases the scattering to electronics and photon, and high transparent conductivity is obtained to trilamellar membrane
It can be unfavorable.In identical film thickness, the metal film that the metal film of high speed deposition is deposited relative to low speed, crystallinity is mentioned
Height [D.Ebner, M.Bauch, T.Dimopoulos, High performance and low cost transparent
electrodes based on ultrathin Cu layer,Optics Express,2017,25(8):A240-A252]。
But high deposition rate is unfavorable for the control of ultra-thin metal layer thickness, and crystallinity improves, i.e., meeting while crystal grain increases
Increase roughness of film, this will increase the scattering to electronics or photon, and high electrically conducting transparent performance is obtained to trilamellar membrane
It is unfavorable.To enable metal layer continuous film forming in relatively thin film thickness, can by pre-deposition the second phase metal as wetting layer,
But this needs to increase additional evaporation source or target, and cost improves.In addition, though this method can get the metal of continuous and derivable
Film, but these the second phase metal (such as Al, Ge) electrically conducting transparent performances are often than the transparent conductivity of deposited metal (such as Ag or Cu)
It is poor to want, to influence the translucency of monolithic film membrane, and the segregation of the second phase metal is also possible to will cause under Thin film conductive performance
Drop [L.Vj N.P.Kobayashi, M.S.Islam, W.Wu, P.Chaturvedi, N.X.Fang, S.Y.Wang,
R.S.Williams,Ultrasmooth silver thin films deposited with a germanium
nucleation layer,Nano Letters,2009,9(1):178-182].Pre-deposition monolayer or polymer conduct
Although the method for wetting layer and effective, should not be used in vacuum deposition system [J.Y.Zou, C.Z.Li,
C.Y.Chang,H.L.Yip,A.K.Y.Jen,Interfacial engineering of ultrathin metal film
transparent electrode for flexible organic photovoltaic cells,Advanced
Materials,2014,26(22):3618-3623].Alloying element is added in a metal or O is introduced in deposition atmosphere2、N2Though
The wetability that metal film can be increased makes film form continuous film in lower film thickness, but needs careful control addition element
Content or O2、N2Content；Otherwise, excessive addition element or O2、N2Content will lead to film performance deteriorate [G.Zhao,
W.Wang, T.S.Bae, S.G.Lee, C.W.Mun, S.Lee, H.Yu, G.H.Lee, M.Song, J.Yun, Stable
ultrathin partially oxidized copper film electrode for highly efficient
flexible solar cells,Nature Communications,2015,6:8830-8837；G.Zhao,S.M.Kim,
S.G.Lee, T.S.Bae, C.W.Mun, S.Lee, H.Yu, G.H.Lee, H.S.Lee, M.Song, J.Yun, Bendable
solar cells from stable,flexible,and transparent conducting electrodes
fabricated using a nitrogen-doped ultrathin copper film,Advanced Functional
Materials,2016,26(23):4180-4191].In addition, increasing metal film wetability, its minimal continuous thickness is reduced, it is real
It is also to reach the formation continuous and derivable film in lower film thickness by refining metal grain on border.But metal grain refinement is
It is unfavorable for the promotion of thin-film transparent electric conductivity.In short, accurate control of the existing means to metal layer thickness such as Ag, Cu, simultaneously
Place is still had several drawbacks to the regulation aspect of crystallite dimension and surface roughness.
Summary of the invention
The present invention is directed to overcome the deficiencies in the prior art, and it is an object of the present invention to provide a kind of simple process, production cost be low and energy
The preparation method for the three-decker transparent conductive film for dimming glass being enough mass produced is used for prepared by this method
Optics, electricity and the good mechanical performance of the three-decker transparent conductive film of dimming glass.
To achieve the above object, the step of the technical solution adopted by the present invention is:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system.
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3Pa, in argon atmosphere or in argon
The mixed atmosphere of gas and oxygen or in the mixed atmosphere of argon gas and hydrogen, in sputtering pressure be 0.2~3Pa and sputtering power is
Oxide target material is sputtered under the conditions of 60~150W, in substrate surface deposition oxide, deposition rate is 0.25~
1.0nm/s, sedimentation time are 60~160s, obtain oxide skin(coating).
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.35).
Step 3: in the mixed-gas atmosphere of argon gas and hydrogen, with sputtering pressure for 0.2~0.8Pa and sputtering power
To be sputtered under the conditions of 10~150W to metal targets, in the oxide layer surface deposited metal, deposition rate 0.04
~0.3nm/s, sedimentation time are 20~150s, obtain metal layer.
The flow-rate ratio of the argon gas and hydrogen is 1: (0.15~0.35).
Step 4: in argon atmosphere or in the mixed atmosphere of argon gas and oxygen or in the mixed atmosphere of argon gas and hydrogen,
Oxide target material is sputtered under the conditions of sputtering pressure is 0.2~3Pa and sputtering power is 60~150W, in the metal
Layer surface deposits the oxide, and deposition rate is 0.25~1.0nm/s, and sedimentation time is 60~160s；It is made for dimming
The three-decker transparent conductive film of glass.
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.35).
The operating temperature of step 1 to step 4 is room temperature.
The oxide target material: purity is higher than 99.9%, and consistency is higher than 95%；The material of the oxide target material is two
Tin oxide, zinc oxide, indium sesquioxide, Fluorin doped stannic oxide, three oxygen of aluminium-doped zinc oxide, Ga-doped zinc oxide and tin dope
Change one of two indiums.
The metal targets: purity is higher than 99.9%, and consistency is higher than 95%；The material of the metal targets be silver, copper,
One of silver alloy and copper alloy.
The substrate is glass substrate or is flexible substrate, and the material of the flexible substrate is ultra-thin glass, gathers to benzene two
One of formic acid glycol ester, polyethylene naphthalate, polyether-ether-ketone and polymethyl methacrylate；The glass lined
The substitute mode at bottom is mode of the piece to piece；The substitute mode of the flexible substrate is the mode for reel-to-reel.
The three-decker transparent conductive film for dimming glass is by oxide skin(coating), metal layer and oxide skin(coating) structure
At；The metal layer is one of silver-colored simple substance membrane, copper simple substance film, silver alloy film and copper alloy thin films；The oxidation
Nitride layer is tin dioxide thin film, zinc-oxide film, indium sesquioxide film, Fluorin doped tin dioxide thin film, aluminium-doped zinc oxide
One of film, Ga-doped zinc oxide film and tin dope indium sesquioxide film.
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 20~100nm, metal
Layer with a thickness of 3~20nm.
Due to the adoption of the above technical scheme, compared with the prior art, the invention has the advantages that:
(1) the three-decker transparent conductive film prepared by the present invention for dimming glass is oxide/metal/oxide
Three-decker, due to used oxide be N-shaped wide bandgap semiconductor materials, forbidden energy gap be greater than 3.3eV；In addition,
The price of Ag, Cu that the present invention uses are cheap relative to metal prices such as Au and Pt.Therefore, prepared for dimming glass
Three-decker transparent conductive film compared with the existing technology in single layer structure transparent conductive film resistivity is low, light transmittance
High, good mechanical performance and at low cost etc..
(2) present invention oxide layer deposition is carried out using sputtering method in substrate surface, on the oxide skin(coating) using splashing
Method deposited metal is penetrated, the oxide is deposited using sputtering method on the metal layer, oxide/metal/oxide is made
Three-decker transparent conductive film.Relative to metal layer is deposited under usual Ar atmosphere, the present invention uses Ar+H2Gold is deposited under atmosphere
The deposition rate of metal layer can be reduced by belonging to layer, and improve its crystallinity simultaneously.The reduction of deposition rate is conducive to metal thickness
The control of degree has been better achieved and has accurately controlled the thickness of the metallic films such as Ag, Cu.And the raising of metal film crystallinity, energy
The scattering to photon or electronics is reduced, so that eventually lead to thick " quasi-continuous " film has more preferably than thin continuous and derivable film
Electrically conducting transparent performance.
(3) provided by the present invention for the preparation method of the three-decker transparent conductive film of dimming glass, only in metal
Ar+H is used when layer deposition2Mixed atmosphere does not need to increase the equal outer processing step of preliminary sedimentation lamination, H therein2It is a kind of go back
Originality gas pollutes target without having to worry about reacting with metal targets, while can also eliminate remnants O present in sputter chamber2
Influence, reduce requirement to system condition of high vacuum degree and cleannes.So a kind of three for dimming glass provided by the invention
The preparation method of layer structured transparent conductive film has that preparation is simple, and production cost is low, and can be suitable for big rule
The characteristics of mould produces.
(4) the three-decker transparent conductive film prepared by the present invention for dimming glass: oxide skin(coating) with a thickness of 20
~100nm, metal layer with a thickness of 3~20nm.
Therefore, the present invention has the characteristics that simple process, production cost are low and can be mass produced, and prepared is used for
Optics, electricity and the good mechanical performance of the three-decker transparent conductive film of dimming glass.
Specific embodiment
The invention will be further described With reference to embodiment, not to the limitation of its protection scope.
In present embodiment:
Operating temperature is room temperature；The metal targets: purity is higher than 99.9%, and consistency is higher than 95%；The oxide
Target: purity is higher than 99.9%, and consistency is higher than 95%.
The substitute mode of the glass substrate is mode of the piece to piece；The substitute mode of the flexible substrate is for reel-to-reel
Mode.
It is repeated no more in embodiment.
Embodiment 1
A kind of three-decker transparent conductive film and preparation method thereof for dimming glass.Preparation side described in the present embodiment
The step of method, is:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system.
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3Pa is splashing in argon atmosphere
Pressure of emanating is to sputter under the conditions of 1.5~2.5Pa and sputtering power are 60~90W to oxide target material, heavy in substrate surface
Product oxide, deposition rate are 0.25~0.55nm/s, and sedimentation time is 60~130s, obtain oxide skin(coating).
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.12).
Step 3: in the mixed-gas atmosphere of argon gas and hydrogen, with sputtering pressure for 0.2~0.5Pa and sputtering power
To be sputtered under the conditions of 10~60W to metal targets, in the oxide layer surface deposited metal, deposition rate is 0.04~
0.12nm/s, sedimentation time are 20~120s, obtain metal layer.
The flow-rate ratio of the argon gas and hydrogen is 1: (0.15~0.2).
Step 4: in argon atmosphere, it is right under the conditions of sputtering pressure is 1.5~2.5Pa and sputtering power is 60~90W
Oxide target material is sputtered, and deposits the oxide in the layer on surface of metal, deposition rate is 0.25~0.55nm/s, is sunk
The product time is 60~130s；The three-decker transparent conductive film for dimming glass is made.
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.12).
The material of the oxide target material is stannic oxide.
The material of the metal targets is silver.
The substrate is glass substrate.
The three-decker transparent conductive film for dimming glass is by oxide skin(coating), metal layer and oxide skin(coating) structure
At.The metal layer is silver-colored simple substance membrane；The oxide skin(coating) is tin dioxide thin film.
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 20~65nm, metal
Layer with a thickness of 3~12nm.
Embodiment 2
A kind of three-decker transparent conductive film and preparation method thereof for dimming glass.Preparation side described in the present embodiment
The step of method, is:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system.
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3Pa, in the mixed of argon gas and oxygen
It closes in atmosphere, oxide target material is sputtered under the conditions of sputtering pressure is 1~2Pa and sputtering power is 80~110W, In
Substrate surface deposition oxide, deposition rate are 0.4~0.7nm/s, and sedimentation time is 70~140s, obtain oxide skin(coating).
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.1~0.2).
Step 3: in the mixed-gas atmosphere of argon gas and hydrogen, with sputtering pressure for 0.3~0.6Pa and sputtering power
To be sputtered under the conditions of 40~90W to metal targets, in the oxide layer surface deposited metal, deposition rate is 0.10~
0.18nm/s, sedimentation time are 30~130s, obtain metal layer.
The flow-rate ratio of the argon gas and hydrogen is 1: (0.2~0.25).
Step 4: in the mixed atmosphere of argon gas and oxygen, sputtering pressure be 1~2Pa and sputtering power be 80~
Oxide target material is sputtered under the conditions of 110W, deposits the oxide in the layer on surface of metal, deposition rate is 0.4~
0.7nm/s, sedimentation time are 70~140s；The three-decker transparent conductive film for dimming glass is made.
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.1~0.2).
The material of the oxide target material is zinc oxide.
The material of the metal targets is copper.
The substrate is flexible substrate, and the material of the flexible substrate is ultra-thin glass.
The three-decker transparent conductive film for dimming glass is by oxide skin(coating), metal layer and oxide skin(coating) structure
At.The metal layer is copper simple substance film；The oxide skin(coating) is zinc-oxide film.
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 30~75nm, metal
Layer with a thickness of 5~14nm.
Embodiment 3
A kind of three-decker transparent conductive film and preparation method thereof for dimming glass.Preparation side described in the present embodiment
The step of method, is:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system.
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3The mixing of Pa, argon gas and hydrogen
In atmosphere, oxide target material is sputtered under the conditions of sputtering pressure is 0.2~1.5Pa and sputtering power is 100~130W,
In substrate surface deposition oxide, deposition rate is 0.55~0.85nm/s, and sedimentation time is 80~150s, obtains oxide
Layer.
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.18~0..28).
Step 3: in the mixed-gas atmosphere of argon gas and hydrogen, with sputtering pressure for 0.4~0.7Pa and sputtering power
To be sputtered under the conditions of 70~120W to metal targets, in the oxide layer surface deposited metal, deposition rate 0.16
~0.24nm/s, sedimentation time are 40~140s, obtain metal layer.
The flow-rate ratio of the argon gas and hydrogen is 1: (0.25~0.30).
Step 4: in sputtering pressure be 0.2~1.5Pa and sputtering power is 100 in the mixed atmosphere of argon gas and hydrogen
Oxide target material is sputtered under the conditions of~130W, deposits the oxide in the layer on surface of metal, deposition rate is
0.55~0.85nm/s, sedimentation time are 80~150s；The three-decker transparent conductive film for dimming glass is made；
The flow-rate ratio of the argon gas and hydrogen is 1: (0.18~0.28).
The material of the oxide target material is indium sesquioxide.
The material of the metal targets is silver alloy.
The substrate is flexible substrate, and the material of the flexible substrate is polyethylene terephthalate.
The three-decker transparent conductive film for dimming glass is by oxide skin(coating), metal layer and oxide skin(coating) structure
At.The metal layer is silver alloy film；The oxide skin(coating) is indium sesquioxide film.
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 42~89nm, metal
Layer with a thickness of 8~17nm.
Embodiment 4
A kind of three-decker transparent conductive film and preparation method thereof for dimming glass.Preparation side described in the present embodiment
The step of method, is:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system.
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3Pa, in the mixed of argon gas and hydrogen
It closes in atmosphere, oxide target material is sputtered under the conditions of sputtering pressure is 2~3Pa and sputtering power is 120~150W, In
Substrate surface deposition oxide, deposition rate are 0.7~1.0nm/s, and sedimentation time is 90~160s, obtain oxide skin(coating).
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.25~0.35).
Step 3: in the mixed-gas atmosphere of argon gas and hydrogen, with sputtering pressure for 0.5~0.8Pa and sputtering power
To be sputtered under the conditions of 100~150W to metal targets, in the oxide layer surface deposited metal, deposition rate 0.2
~0.3nm/s, sedimentation time are 50~150s, obtain metal layer.
The flow-rate ratio of the argon gas and hydrogen is 1: (0.3~0.35).
Step 4: in the mixed atmosphere of argon gas and hydrogen, sputtering pressure be 2~3Pa and sputtering power be 120~
Oxide target material is sputtered under the conditions of 150W, deposits the oxide in the layer on surface of metal, deposition rate is 0.7~
1.0nm/s, sedimentation time are 90~160s；The three-decker transparent conductive film for dimming glass is made.
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.25~0.35).
The material of the oxide target material is that Fluorin doped stannic oxide, aluminium-doped zinc oxide, Ga-doped zinc oxide and tin are mixed
One of miscellaneous indium sesquioxide.
The material of the metal targets is copper alloy.
The substrate is flexible substrate, the material of the flexible substrate be polyethylene naphthalate, polyether-ether-ketone and
One of polymethyl methacrylate.
The three-decker transparent conductive film for dimming glass is by oxide skin(coating), metal layer and oxide skin(coating) structure
At；The metal layer is copper alloy thin films；The oxide skin(coating) is indium sesquioxide film, Fluorin doped tin dioxide thin film, aluminium
One of doping zinc-oxide film, Ga-doped zinc oxide film and tin dope indium sesquioxide film.
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 60~100nm, metal
Layer with a thickness of 10~20nm.
Due to the adoption of the above technical scheme, the beneficial effect of present embodiment compared with prior art is:
(1) the three-decker transparent conductive film for dimming glass of present embodiment preparation is oxide/gold
Category/oxide three-decker, since used oxide is N-shaped wide bandgap semiconductor materials, forbidden energy gap is greater than
3.3eV；In addition, the price of Ag, Cu that present embodiment uses are cheap relative to metal prices such as Au and Pt.Therefore, institute
Preparation the three-decker transparent conductive film for dimming glass compared with the existing technology in single layer structure electrically conducting transparent
Film resiativity is low, light transmittance is high, good mechanical performance and at low cost etc..
(2) present embodiment carries out oxide layer deposition using sputtering method, in the oxide skin(coating) in substrate surface
It is upper to use sputtering method deposited metal, the oxide is deposited using sputtering method on the metal layer, be made oxide/metal/
The three-decker transparent conductive film of oxide.Relative to metal layer is deposited under usual Ar atmosphere, present embodiment is used
Ar+H2Metal layer is deposited under atmosphere can reduce the deposition rate of metal layer, and improve its crystallinity simultaneously.The reduction of deposition rate
Be conducive to the control to metal layer thickness, be better achieved and the thickness of the metallic films such as Ag, Cu is accurately controlled.And metal film
The raising of crystallinity can reduce the scattering to photon or electronics, so that it is more continuous than thin to eventually lead to thick " quasi-continuous " film
Smooth film has better electrically conducting transparent performance.
(3) preparation method for the three-decker transparent conductive film for dimming glass that present embodiment provides,
Ar+H is only used in deposition of metal2Mixed atmosphere does not need to increase the equal outer processing step of preliminary sedimentation lamination, H therein2
It is a kind of reducibility gas, pollutes target without having to worry about reacting with metal targets, while can also eliminate in sputter chamber and exist
Remaining O2Influence, reduce requirement to system condition of high vacuum degree and cleannes.So one kind that present embodiment provides
The preparation method of three-decker transparent conductive film for dimming glass have preparation is simple, production cost is low,
And the characteristics of large-scale production can be suitable for.
(4) the three-decker transparent conductive film for dimming glass of present embodiment preparation: oxide skin(coating)
With a thickness of 20~100nm, metal layer with a thickness of 3~20nm.
Therefore, present embodiment has the characteristics that simple process, production cost are low and can be mass produced, made
The standby optics thin for the three-decker electrically conducting transparent of dimming glass, electricity and good mechanical performance.
Claims (5)
1. a kind of preparation method of the three-decker transparent conductive film for dimming glass, it is characterised in that the preparation method
The step of be:
Step 1: oxide target material and metal targets are packed on the target stand of magnetic control sputtering system；
Step 2: the cavity of magnetic control sputtering system is evacuated to pressure less than 3 × 10-3Pa, in argon atmosphere or in argon gas with
The mixed atmosphere of oxygen or in the mixed atmosphere of argon gas and hydrogen, sputtering pressure be 0.2~3Pa and sputtering power be 60~
Oxide target material is sputtered under the conditions of 150W, in substrate surface deposition oxide, deposition rate is 0.25~1.0nm/s,
Sedimentation time is 60~160s, obtains oxide skin(coating)；
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.35)；
Step 3: with sputtering pressure be 0.2~0.8Pa and sputtering power is 10 in the mixed-gas atmosphere of argon gas and hydrogen
Metal targets are sputtered under the conditions of~150W, in the oxide layer surface deposited metal, deposition rate is 0.04~
0.3nm/s, sedimentation time are 20~150s, obtain metal layer；
The flow-rate ratio of the argon gas and hydrogen is 1: (0.15~0.35)；
Step 4: being splashed in argon atmosphere or in the mixed atmosphere of argon gas and oxygen or in the mixed atmosphere of argon gas and hydrogen
Pressure of emanating is to sputter under the conditions of 0.2~3Pa and sputtering power are 60~150W to oxide target material, in the metal layer table
Face deposits the oxide, and deposition rate is 0.25~1.0nm/s, and sedimentation time is 60~160s；It is made for dimming glass
Three-decker transparent conductive film；
The flow-rate ratio and the argon gas of the argon gas and oxygen and the flow-rate ratio of hydrogen are 1: (0.02~0.35)；
The operating temperature of step 1 to step 4 is room temperature.
2. the preparation method of the three-decker transparent conductive film according to claim 1 for dimming glass, feature
Be the oxide target material: purity is higher than 99.9%, and consistency is higher than 95%；
The material of the oxide target material is stannic oxide, zinc oxide, indium sesquioxide, Fluorin doped stannic oxide, aluminium doping oxygen
Change one of zinc, Ga-doped zinc oxide and tin dope indium sesquioxide.
3. the preparation method of the three-decker transparent conductive film according to claim 1 for dimming glass, feature
Be the metal targets: purity is higher than 99.9%, and consistency is higher than 95%；
The material of the metal targets is one of silver, copper, silver alloy and copper alloy.
4. the preparation method of the three-decker transparent conductive film according to claim 1 for dimming glass, feature
It is that the substrate is glass substrate or is flexible substrate, the material of the flexible substrate is ultra-thin glass, poly terephthalic acid
One of glycol ester, polyethylene naphthalate, polyether-ether-ketone and polymethyl methacrylate；
The substitute mode of the glass substrate is mode of the piece to piece；The substitute mode of the flexible substrate is the side for reel-to-reel
Formula.
5. a kind of three-decker transparent conductive film for dimming glass, it is characterised in that three layers for dimming glass
Structured transparent conductive film be any one of according to claim 1~4 described in transparent led for the three-decker of dimming glass
The three-decker transparent conductive film of dimming glass is used for prepared by the preparation method of conductive film；
The three-decker transparent conductive film for dimming glass is made of oxide skin(coating), metal layer and oxide skin(coating)；Institute
Metal layer is stated as one of silver-colored simple substance membrane, copper simple substance film, silver alloy film and copper alloy thin films, the oxide skin(coating) is
Tin dioxide thin film, zinc-oxide film, indium sesquioxide film, Fluorin doped tin dioxide thin film, aluminum-doped zinc oxide films, gallium
One of doping zinc-oxide film and tin dope indium sesquioxide film；
The three-decker transparent conductive film for dimming glass: oxide skin(coating) with a thickness of 20~100nm, metal layer
With a thickness of 3~20nm.
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| CN111651099A (en) | 2020-04-28 | 2020-09-11 | 北京载诚科技有限公司 | Touch device |
| CN112538344B (en) * | 2020-12-28 | 2022-11-11 | 淮阴师范学院 | Germanium-erbium-doped tin dioxide multilayer composite film and preparation method thereof |
| CN112941476B (en) * | 2021-01-28 | 2022-09-16 | 山东省科学院能源研究所 | Tin dioxide/copper/tin dioxide multilayer transparent conductive film and preparation method and application thereof |
| CN112941479B (en) * | 2021-01-29 | 2022-11-04 | 山东省科学院能源研究所 | Method for adjusting thickness of silver layer by tin dioxide/silver/tin dioxide transparent conductive film and application |
| CN112951930B (en) * | 2021-01-29 | 2022-11-04 | 山东省科学院能源研究所 | Titanium dioxide/silver/titanium dioxide transparent conductive film and preparation method and application thereof |
| CN114050223A (en) * | 2021-11-24 | 2022-02-15 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of transparent conductive structure |
| CN114914311B (en) * | 2022-04-18 | 2023-03-07 | 通威太阳能（安徽）有限公司 | Conductive layer, solar cell and preparation method thereof |
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