CN106756789A - A kind of compound transparent electricity conductive film and preparation method thereof - Google Patents
A kind of compound transparent electricity conductive film and preparation method thereof Download PDFInfo
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- CN106756789A CN106756789A CN201611066277.XA CN201611066277A CN106756789A CN 106756789 A CN106756789 A CN 106756789A CN 201611066277 A CN201611066277 A CN 201611066277A CN 106756789 A CN106756789 A CN 106756789A
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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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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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
- C23C14/06—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
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
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Abstract
A kind of compound transparent electricity conductive film of the present invention and preparation method thereof, described compound transparent electricity conductive film, including substrate, the at least one layer of doped zinc oxide transparent conductive film deposited in substrate, in the ITO layer of top deposition, and at least one layer of heavy doping electrically conducting transparent layer film or nano particle deposited in compound transparent electricity conductive film.Described preparation method, comprises the following steps, step 1, and ground floor doped zinc oxide transparent conductive film layer is deposited on by the substrate of pretreatment；Step 2, then prepares heavy doping electrically conducting transparent layer film of a layer thickness no more than 2000 nanometers, or nano particle of the particle diameter no more than 2000 nanometers；Step 3, deposits one layer of doped zinc oxide transparent conductive film layer on heavy doping electrically conducting transparent layer film or nano particle；Step 4, repeat step 2 and/or 3 reaches the technical parameter of needs, and in one layer of ITO layer of top layer deposition, prepares compound transparent electricity conductive film.
Description
Technical field
The present invention relates to conductive film material, specially a kind of compound transparent electricity conductive film and preparation method thereof.
Background technology
Transparent conductive film is a kind of a kind of good conductivity feature with good transmitance in visible-range again
Film, mainly there is metal membrane system, oxide membrane system, other compound membrane systems, macromolecule membrane system, compound film system etc..Current research
It is metal membrane system and oxide membrane system be most widely used.Transparent conductive film be mainly used in photoelectric device (such as LED, it is thin
Film solar cell etc.) window material.Common transparent conductive film is that (aluminium adulterates for ITO (indium oxide of tin dope three), AZO
Zinc oxide) etc. the electric conductivity that not only requires of transparent conductive film, also to have excellent visible light transmission.It is existing transparent to lead
What conductive film was used is all that simple ITO or AZO are prepared, but simple transparent conductive film is relatively costly, has
By environmental testing, it sometimes appear that spot under high-temperature high-humidity environment, and its aberration is higher for Shi Buneng；Simple AZO
Although more than one the percent of the cost of transparent conductive film only ITO, its electric conductivity is also not so good as ITO, and environmental suitability
It is poor, make it cannot be in many fields (such as display) large-scale application.
The content of the invention
For problems of the prior art, the present invention provides a kind of compound transparent electricity conductive film and preparation method thereof,
With low cost, electric conductivity is remarkable, and translucency is excellent, and aberration is small, environmental testing stabilization.
The present invention is to be achieved through the following technical solutions：
A kind of compound transparent electricity conductive film, including substrate, at least one layer of adulterated zinc oxide transparent deposited in substrate
Conductive film, in the ITO layer of top deposition, and at least one layer of heavy doping deposited in compound transparent electricity conductive film is saturating
Bright membrane of conducting layer or nano particle.
Preferably, the thickness of doped zinc oxide transparent conductive film is 10~2000 nanometers.
Preferably, heavy doping transparency conducting layer film thickness is 0~2000 nanometer, and the particle diameter of nano particle is 0~2000
Nanometer, at least one layer of thickness is not 0.
Preferably, the thickness of heavy doping electrically conducting transparent layer film is 10~30 nanometers, and the particle diameter of nano particle is 1~500
Nanometer.
Preferably, the doped chemical in doped zinc oxide transparent conductive film is any one in boron, gallium and aluminium.
Preferably, also including be deposited on substrate and adjacent doped zinc oxide transparent conductive film layer between preformed layer.
A kind of preparation method of compound transparent electricity conductive film, comprises the following steps,
Step 1, deposits ground floor doped zinc oxide transparent conductive film layer on by the substrate of pretreatment；
Step 2, then prepares heavy doping electrically conducting transparent layer film of a layer thickness no more than 2000 nanometers, or particle diameter is not
Nano particle more than 2000 nanometers；
Step 3, deposits one layer of adulterated zinc oxide transparent conductive thin on heavy doping electrically conducting transparent layer film or nano particle
Film layer；
Step 4, repeat step 2 and/or 3 reaches the technical parameter of needs, and in one layer of ITO layer of top layer deposition, is prepared into
To compound transparent electricity conductive film.
Preferably, temperature when ground floor doped zinc oxide transparent conductive film layer is precipitated in step 1 is 100-500 DEG C；
When depositing remaining transparent conductive film layer in step 2 in deposition of heavily doped electrically conducting transparent layer film or nano particle and step 3
Temperature is 0-300 DEG C.
Preferably, heavy doping electrically conducting transparent layer film is higher than doped zinc oxide transparent conductive film layer using electric conductivity
One kind in metal, oxide or alloy, nano particle is using electric conductivity higher than doped zinc oxide transparent conductive film layer
One kind in metal, oxide or alloy.
Preferably, in step 1, pretreatment includes the surface using plasma treatment to substrate, treatment atmosphere be hydrogen,
One or more in nitrogen, helium, neon and argon gas of mixed gas；
In step 1, the step of depositing preformed layer in substrate is additionally included in, ground floor doping zinc-oxide is deposited on preformed layer
Transparent conductive film layer.
Compared with prior art, the present invention has following beneficial technique effect：
Transparent conductive film of the present invention, by precipitating the transparent conductive film layer of multilayer, and adjacent transparent
Heavy doping electrically conducting transparent layer film or nano particle are added between conductive membrane layer respectively, using heavy doping electrically conducting transparent layer film
Or the transparent conductive film of the cheap preparation low price of nano particle.The electric conductivity of heavy doping electrically conducting transparent layer film or nano particle
Can be stronger than transparent conductive film, and sandwich construction can be utilized to realize being uniformly distributed and conduct to electric field, by this side
Formula improves the electric property of transparent conductive film；And the refractive index of heavy doping electrically conducting transparent layer film and nano particle is between saturating
Between bright conductive film and treated substrate, so that optical property gets a promotion；It is transparent from that can improve
The electric property and optical property of conductive film, and the cost of transparent conductive film can be reduced.Because doping zinc-oxide is in phase
There is the light transmittance higher than ITO under the conditions of, and optics complementation can be formed with ITO, cause our translucency excellent, aberration
It is small；Simultaneously because the moisture pick-up properties of doping zinc-oxide can stable substrate defect such that it is able to so that environmental testing is steady
It is fixed, it is to avoid spot occurs.
Further, limited by the thickness of counterweight doping transparent membrane of conducting layer and nano particle and transparent conductive film layer
System, can be good at meeting the overall translucency requirement of transparent conductive film.
Further, by the system to its each transparent conductive film layer and heavy doping electrically conducting transparent layer film and nano particle
The control of standby temperature, makes it only need to the needs temperature higher in ground floor transparent conductive film layer, and in subsequent layers shape
In the deposition of structure, it is only necessary to even operated at room temperature in low temperature, greatly reduce its operation complexity and
Environmental requirement such that it is able to cost is greatly reduced, and improves the quality of its product, it is to avoid subsequent high temperature is deposited to preceding step
The influence and destruction of the result of layer.
Brief description of the drawings
Fig. 1 is the structure sectional view of the compound transparent electricity conductive film described in present example.
Fig. 2 is the transmission spectra of the compound transparent electricity conductive film described in present example 1.
Fig. 3 is the transmission spectra of the compound transparent electricity conductive film described in present example 2.
Fig. 4 is the transmission spectra of the compound transparent electricity conductive film described in present example 3.
Fig. 5 is the transmission spectra of the compound transparent electricity conductive film described in present example 4.
Fig. 6 is the transmission spectra of the compound transparent electricity conductive film described in present example 5.
Fig. 7 is the transmission spectra of the compound transparent electricity conductive film described in present example 6.
Fig. 8 is the transmission spectra of the compound transparent electricity conductive film described in present example 7.
Fig. 9 is the transmission spectra of the compound transparent electricity conductive film described in present example 8.
Figure 10 is the transmission spectra of the compound transparent electricity conductive film described in present example 9.
The environmental testing figure of the compound transparent electricity conductive film described in Figure 11 present examples.
The environmental testing figure of Figure 12 transparent conductive films in the prior art.
The spectrum comparison diagram of compound transparent electricity conductive film and transparent conductive film described in Figure 13 present examples.
In figure：1 is the substrate by pre-processing；2 is doped zinc oxide transparent conductive film layer；3 doping transparents of attaching most importance to are led
Electric layer film；4 is ITO layer.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
A kind of compound transparent electricity conductive film of the present invention, as shown in figure 1, including substrate 1, at least for depositing on the base 1
Layer doped zinc oxide transparent conductive film 2, top deposition ITO layer 4, and at least one of which heavily doped layer film 3 or
Nano particle；Described heavily doped layer film 3 or nanoparticle deposition the bottom doped zinc oxide transparent conductive film and
Between the ITO layer of top.Illustrated by taking spaced apart deposits as an example in this preferred embodiment.
Specifically, the preparation method of compound transparent electricity conductive film of the present invention is, step 1, on by the substrate of pretreatment
Deposition ground floor doped zinc oxide transparent conductive film layer；Step 2, then deposits a layer thickness heavily doped no more than 2000 nanometers
The nano particle of miscellaneous electrically conducting transparent layer film or particle diameter no more than 2000 nanometers；Step 3, redeposited one layer of adulterated zinc oxide transparent
Conductive membrane layer；Step 4, above-mentioned steps 2 and/or step 3 can be repeated n times；Preferred n=1-10, by doping zinc-oxide
Transparent conductive film layer and heavy doping electrically conducting transparent layer film or acting on for nano particle do not change transparent conductive film
Cost is reduced under behavior pattern.Ground floor, the second layer ..., n-th layer heavy doping transparency conducting layer film thickness arrived for 0
2000 nanometers, nano particle diameter is 0 to 2000 nanometers, and at least one layer of thickness is not 0, and thickness can be differed, material
Also can differ.Pretreatment mode is carried out to substrate for plasma surface treatment, chemical treatment, coating film treatment, heat treatment
Or one or more of mechanical treatment or simple cleaning etc..Substrate can be rigid basement and flexible substrates, rigid basement energy
Enough using glass, quartz, sapphire or silicon base, flexible substrates can use polyester film, such as PET, makrolon；
Tinsel, ultra-thin glass, polyethylene film or other organic material films.Adulterated zinc oxide transparent is deposited in substrate conductive
Film be by the way of thermal evaporation, electron beam evaporation, vacuum sputtering, chemical vapor deposition or the spraying in one kind；Doping
Zinc oxide transparent conductive film can use different species.Ground floor, the second layer ..., n-th layer transparent conductive film layer
Thickness is 10 to 2000 nanometers.The depositing temperature of ground floor adulterated zinc oxide transparent thin film layer is 100 DEG C to 500 DEG C, remaining
Each layer is 0 DEG C to 300 DEG C；Preferably, ground floor is 250-500 DEG C, and remaining each layer is 20-200 DEG C.
Preferably, used in step 1 by atmosphere for hydrogen, nitrogen, helium, neon, argon gas or mixed gas etc. from
Ground floor transparent conductive film layer is deposited on the substrate surface of daughter pretreatment.
By structure of the present invention, product of the present invention can be obtained, with one layer of heavy doping transparency conducting layer
As a example by film or nano particle, structure is as shown in Figure 1；And in its performance, by its thickness, processing technology and temperature
Control, make it that following index, heavy doping electrically conducting transparent layer film or nano particle and transparent conductive film are reached in performance
The average transmittance in limit of visible spectrum of layer is higher than 60%, more preferably higher than 80%, preferably higher than 85%；Resistivity is small
In 10-3Ohmcm (Ω cm), preferably less than 5x10-4Ohmcm (Ω cm).
Figure 11 is picture of the compound transparent electricity conductive film of the present invention after hot and humid environment is tested, without any
Damage, Figure 12 is ito thin film by the picture after hot and humid environment test, spottiness appearance.Figure 13 is conductive composite transparent
The light transmittance collection of illustrative plates of film and ito thin film, can find out compound transparent electricity conductive film of the present invention in visible region from figure
Domain translucency is uniform, and aberration is small；While reduces cost, properties of product are greatly improved from stability and aberration.
Reconciliation is further detailed to preparation method of the invention and properties of product below by way of multiple embodiments
Release.
Embodiment 1：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, ito thin film is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
As a result：Light transmittance 83%, resistivity 6 × 10-4Ω ﹒ cm.
Embodiment 2：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 200 | 120 | 200 |
Step 5, ito thin film is sputtered with sputtering equipment on existing silver nano-grain, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 83%, resistivity 4 × 10-4Ω ﹒ cm.
Embodiment 4：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, the indium oxide transparency conducting layer of heavy doping is sputtered with sputtering equipment on existing doping zinc-oxide film,
Sputtering condition is as follows：
Step 5, ITO layer, sputtering condition are sputtered with sputtering equipment on the indium oxide transparency conducting layer of existing heavy doping
It is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 85%, resistivity 3 × 10-4Ω ﹒ cm.
Embodiment 5：
Step 1, doping zinc-oxide film is sputtered with sputtering equipment on the PET by plasma surface treatment, sputtering
Condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm；
Step 2, Ag films are sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Step 3, ito thin film is sputtered with sputtering equipment on existing Ag films, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 84%, resistivity 2 × 10-4Ω ﹒ cm.
Embodiment 6：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 200 | 120 | 1 |
Step 5, doped ITO layer is sputtered with sputtering equipment on existing silver nano-grain, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 85%, resistivity 2 × 10-4Ω ﹒ cm.
Embodiment 7：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 200 | 120 | 2000 |
Step 5, doping zinc-oxide film is sputtered with sputtering equipment on silver nano-grain, and sputtering condition is as follows：
Step 6, ITO layer is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 81%, resistivity 3 × 10-4Ω ﹒ cm.
Embodiment 8：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, Ag films are sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Step 5, doping zinc-oxide film is sputtered with sputtering equipment on Ag films, and sputtering condition is as follows：
Step 6, ITO layer is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 81%, resistivity 3 × 10-4Ω ﹒ cm.
Embodiment 9：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, the indium oxide film of heavy doping is sputtered with sputtering equipment on existing doping zinc-oxide film, sputters bar
Part is as follows：
Step 5, doping zinc-oxide film is sputtered with sputtering equipment on the indium oxide film of heavy doping, and sputtering condition is such as
Under：
Step 6, ITO layer is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 81%, resistivity 3 × 10-4Ω ﹒ cm.
Embodiment 10：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 150 | 120 | 500 |
Step 5, doping zinc-oxide film is sputtered with sputtering equipment on silver nano-grain, and sputtering condition is as follows：
Step 6, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 220 | 120 | 500 |
Step 7, ITO layer is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 79%, resistivity 8 × 10-5Ω ﹒ cm.
Embodiment 11：
Step 1, uses H2- Ar mixed gas plasmas method is to substrate surface treatment, activating surface；
Step 2, deposits one layer of preformed layer titanium nano metal layer on flexible substrate PET, and its condition is as follows：
Step 3, doping zinc-oxide film is sputtered with sputtering equipment on preformed layer, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity ＞ 10-3Ohmcm
Step 4, the indium oxide film of heavy doping is sputtered with sputtering equipment on existing doping zinc-oxide film, sputters bar
Part is as follows：
Step 5, doping zinc-oxide film is sputtered with sputtering equipment on the indium oxide film of heavy doping, and sputtering condition is such as
Under：
Step 6, silver nano-grain is sputtered with sputtering equipment on existing doping zinc-oxide film, and sputtering condition is as follows：
| Operating air pressure (Pa) | Temperature (DEG C) | Power (W) | Particle diameter (nm) |
| 1.4×10‐4 | 20 | 120 | 500 |
Step 7, ITO layer is sputtered with sputtering equipment on existing silver nano-grain, and sputtering condition is as follows：
Visible region average transmittance>70%, resistivity<10-3Ohmcm；
As a result：Light transmittance 74%, resistivity 7 × 10-5Ω ﹒ cm.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (10)
1. a kind of compound transparent electricity conductive film, it is characterised in that including substrate, at least one layer of doping oxygen deposited in substrate
Change zinc transparent conductive film, top deposition ITO layer, and in compound transparent electricity conductive film deposit it is at least one layer of
Heavy doping electrically conducting transparent layer film or nano particle.
2. a kind of compound transparent electricity conductive film according to claim 1, it is characterised in that adulterated zinc oxide transparent conductive thin
The thickness of film is 10~2000 nanometers.
3. a kind of compound transparent electricity conductive film according to claim 1, it is characterised in that heavy doping electrically conducting transparent layer film
Thickness is 0~2000 nanometer, and the particle diameter of nano particle is 0~2000 nanometer, and at least one layer of thickness is not 0.
4. a kind of compound transparent electricity conductive film structure according to claim 1, it is characterised in that heavy doping transparency conducting layer
The thickness of film is 10~30 nanometers, and the particle diameter of nano particle is 1~500 nanometer.
5. a kind of compound transparent electricity conductive film structure according to claim 1, it is characterised in that adulterated zinc oxide transparent is led
Doped chemical in conductive film is any one in boron, gallium and aluminium.
6. a kind of compound transparent electricity conductive film structure according to claim 1, it is characterised in that also including being deposited on substrate
And the preformed layer between adjacent doped zinc oxide transparent conductive film layer.
7. a kind of preparation method of compound transparent electricity conductive film, it is characterised in that comprise the following steps,
Step 1, deposits ground floor doped zinc oxide transparent conductive film layer on by the substrate of pretreatment；
Step 2, then prepares heavy doping electrically conducting transparent layer film of a layer thickness no more than 2000 nanometers, or particle diameter is no more than
2000 nanometers of nano particle；
Step 3, deposits one layer of doped zinc oxide transparent conductive film layer on heavy doping electrically conducting transparent layer film or nano particle；
Step 4, repeat step 2 and/or 3 reaches the technical parameter of needs, and in one layer of ITO layer of top layer deposition, prepares multiple
Close transparent conductive film.
8. the preparation method of a kind of compound transparent electricity conductive film according to claim 7, it is characterised in that sunk in step 1
Temperature during the ground floor doped zinc oxide transparent conductive film layer of shallow lake is 100-500 DEG C；Deposition of heavily doped electrically conducting transparent in step 2
Temperature when remaining transparent conductive film layer is deposited in layer film or nano particle and step 3 is 0-300 DEG C.
9. the preparation method of a kind of compound transparent electricity conductive film according to claim 7, it is characterised in that heavy doping is transparent
Membrane of conducting layer is using in the metal, oxide or alloy that electric conductivity is higher than doped zinc oxide transparent conductive film layer
Kind, nano particle is using in the metal, oxide or alloy that electric conductivity is higher than doped zinc oxide transparent conductive film layer
Kind.
10. the preparation method of a kind of compound transparent electricity conductive film according to claim 7, it is characterised in that in step 1,
Pretreatment includes the surface using plasma treatment to substrate, and treatment atmosphere is in hydrogen, nitrogen, helium, neon and argon gas
One or more of mixed gas；
In step 1, the step of depositing preformed layer in substrate is additionally included in, ground floor adulterated zinc oxide transparent is deposited on preformed layer
Conductive membrane layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611066277.XA CN106756789A (en) | 2016-11-28 | 2016-11-28 | A kind of compound transparent electricity conductive film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611066277.XA CN106756789A (en) | 2016-11-28 | 2016-11-28 | A kind of compound transparent electricity conductive film and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
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| WO2022007767A1 (en) * | 2020-07-09 | 2022-01-13 | 北京载诚科技有限公司 | Double-sided conductive film, coating method, and touch screen |
| 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 |
| US11269474B2 (en) | 2020-04-28 | 2022-03-08 | Beijing Zenithnano Technology Co., Ltd | Touch devices |
| US11269466B2 (en) | 2020-04-28 | 2022-03-08 | Beijing Zenithnano Technology Co., Ltd. | Touch panels |
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