CN105185843B - A kind of transparent conductive film of taking off arbitrary graphic and its application - Google Patents
A kind of transparent conductive film of taking off arbitrary graphic and its application Download PDFInfo
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- CN105185843B CN105185843B CN201410273143.XA CN201410273143A CN105185843B CN 105185843 B CN105185843 B CN 105185843B CN 201410273143 A CN201410273143 A CN 201410273143A CN 105185843 B CN105185843 B CN 105185843B
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Abstract
The invention belongs to field of photoelectric devices, a kind of transparent conductive film of taking off arbitrary graphic is disclosed, it includes having set gradually substrate, transparent conductive film layer, conductive membrane layer from bottom to top；Adhesive force between the substrate and transparent conductive film layer is more than the adhesive force between transparent conductive film layer and conductive membrane layer；The conductive membrane layer is peelable.The present invention further comprises intermediate layer, ultra-thin interface-modifying layer or substrate interface decorative layer.Conductive membrane layer can be peeled off as needed during present invention application, retains transparent conductive film layer, form the transparent conductive film of taking off arbitrary graphic.The present invention has wide application prospect in terms of the transparent window that the transparency electrode as photoelectric device or anti-electromagnetic wave are disturbed.
Description
Technical field
The invention belongs to field of photoelectric devices, and in particular to a kind of transparent conductive film of taking off arbitrary graphic and its
Using.
Background technology
Led using tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO) and Al-Doped ZnO (AZO) film as the transparent of representative
Electroxidation thing (TCO) generally has wide forbidden band, visible range light transmission height and the low common photoelectric characteristic of resistivity, wide
Shown generally applied to solar cell, plane, the interference of specific function window coating, anti-electromagnetic wave and other photoelectric devices are led
Domain.In recent years, oxide-metal-oxide (such as ITO | Ag | ITO, AZO | Ag | AZO, NiO | Ag | NiO etc.) and metal nano knot
The transparent conductive film of the developments such as structure base transparent conductive composite films is also progressively applied to solar cell, display and electromagnetism interference
Deng field.Usually require that at least one side electrode is transparent conductive film in photoelectric fields such as solar cell, displays, it is desirable to high saturating
Light rate and high conductivity.But some special dimensions, such as translucent solar cell or all-transparent are shown, it is desirable to which upper/lower electrode is all
There is transparent requirement.In the place of anti-electromagnetic interference, using nontransparent nickeline metal composite coating or metallic film generally all
With good electromagnetism antijamming capability, but should high light transmittance strong anti-electromagnetic interference capability again window material and window film
Still there are very strong application field, such as military aircraft window, instrument window and the observation for requiring good electromagnetic shielding field place
Window etc..High printing opacity and highly conductive film are typically mutual restriction and contradictory, and generally increase film thickness can be improved
Thin film conductive ability, but light transmittance can be reduced.In solar cells, increase translucency can improve battery light absorbs, but film
Square resistance increase causes high series resistance, reduces battery efficiency.In luminescence display such as organic luminescent device (OLED),
High euphotic electrode can improve the light effusion of OLED, but high value electrode needs more high driving voltage and causes higher energy to consume
Dissipate.Place is disturbed in anti electromagnetic wave, low resistance thin film is conducive to improving anti-electromagnetic interference capability, and high value transparent window will be reduced
Anti electromagnetic wave interference performance.In order to reduce its negative effect in practical application, high value transparent membrane area coverage is reduced as far as possible,
Increase the area coverage of low resistance film, typically a kind of feasible solution.At present conventional transparent conductive film such as ITO, FTO and
AZO, oxide-metal-oxide electroconductive film such as AZO | Ag | AZO, metal Nano structure base composition transparent conductive composite films etc.
Prepared on substrate after transparent conductive film, prior art means are difficult to flexibly be schemed as needed in subsequent applications
Shapeization is adjusted, and this is that application cost is made troubles and improved in later stage application.
The content of the invention
The present invention overcomes the disadvantages mentioned above of prior art, it is proposed that a kind of electrically conducting transparent of taking off arbitrary graphic is thin
Film, can peel off Upper conductive film as needed in actual use and expose lower floor's transparent conductive film window, and other
Unstripped part still keeps the film with satisfactory electrical conductivity, and the transparent conductive film of taking off arbitrary graphic of the present invention makes
There is very strong flexibility and operability in.
The present invention proposes a kind of transparent conductive film of taking off arbitrary graphic, and it includes substrate and described
The transparent conductive film and conductive membrane layer being sequentially depositing from bottom to up on substrate.Wherein, the substrate and transparent conductive film
Adhesive force between layer is more than the adhesive force between transparent conductive film layer and conductive membrane layer；The conductive membrane layer is peelable
From.
In the present invention, conductive membrane layer can be peeled off as needed.Due to the attachment between substrate and transparent conductive film layer
Power is significantly greater than the adhesive force between transparent conductive film layer and conductive membrane layer, therefore, transparent when peeling off conductive membrane layer
Not peeling off phenomenon between conductive membrane layer and substrate, so as to form the transparent conductive film of arbitrary graphic.
The transparent conductive film of taking off arbitrary graphic of the present invention further comprises intermediate layer.By transparent being led described
Intermediate layer is introduced between thin film layer and the conductive membrane layer, so as to weaken the transparent conductive film layer and the conduction
Adhesive force between film layer.Preferably, the intermediate layer includes LiF, common salt, carbon film, organic molecule, polymeric material
Material, molybdenum oxide, silane etc..
The transparent conductive film of taking off arbitrary graphic of the present invention further comprises ultra-thin interface-modifying layer.It is described ultra-thin
Interface-modifying layer is by using formed by the modifying interface mode to transparent conductive film layer, so that described transparent to weaken
Adhesive force between conductive membrane layer and conductive membrane layer.Wherein, be to the modifying interface of transparent conductive film layer using nitrogen,
Oxygen, Ar, methane, acetylene, hydrogen, steam etc. carry out surface plasma processing, or are passed through the methods such as silane gas, so that shape
Into self-assembling ultrathin interface-modifying layer etc., the adhesive force between the transparent conductive film layer and conductive membrane layer is weakened.
The transparent conductive film of taking off arbitrary graphic of the present invention further comprises substrate interface decorative layer.By in lining
Basal surface is chemically or physically modified to form substrate interface decorative layer, so as to strengthen the substrate and transparent conductive film
Adhesive force between layer.It is wherein, described that in substrate surface progress, chemically or physically modification is included in substrate surface deposition buffering
Layer, substrate surface roughening, are passed through gas and carry out the methods such as surface plasma processing, form substrate interface decorative layer.Preferably, institute
It is the functionalised silica gel layer coated in substrate surface to state substrate interface decorative layer.Preferably, coating functions on the surface of a substrate
Layer of silica gel, is handled with oxygen/argon surface plasma or with alkaline solution treatments such as NaOH in substrate surface formation hydroxyl.It is described
" functionalised silica gel layer " refers to contain silane coupler in layer of silica gel, makes transparent conductive film by " functionalised silica gel layer " effect
It is connected with substrate by covalent bond or ionic bond；" silane coupler " refers to the silane containing alkoxy grp, typical silane
Coupling agent is such as：Methacryloxypropyl trimethyl silane, tetraethoxysilance, propyl silane and (three second of 1,2- bis-
Epoxide silicyl) ethane etc..
In the present invention, substrate can be any one of any transparent material such as glass, plastics, quartz and sapphire.
In the present invention, transparent conductive film layer is the transparent metal film that metal or metal alloy is constituted, and can be transparent
Conductive oxide film, can also be the THIN COMPOSITE of transparent conductive oxide/metal/transparent conductive oxide (O/M/O) composition
Film.
Wherein, metal or metal alloy constitute transparent metal film for aluminium, titanium, chromium, nickel, iron, copper, silver, gold, titanium chromium,
The unitary such as silver-colored aluminium, magnalium, titanium silver, magnesium silver, nickeline, Ag-Cu-Zn or multicomponent alloy formation transparent metal film it is any one
Kind.
Wherein, transparent conductive oxide film is Al-Doped ZnO (AZO), gallium-doped zinc oxide (GZO), indium-doped zinc oxide
(IZO), any one of the transparent conductive film of formation such as tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO).
Wherein, transparent conductive oxide/metal/transparent conductive oxide (O/M/O) multi-layered composite system formation is transparent
Conductive film is AZO | Ag | AZO, ZnO | and Ag | ZnO, GZO | Ag | any one of the system such as GZO.
In the present invention, conductive membrane layer be metal or metal alloy for example aluminium, titanium, chromium, nickel, iron, copper, silver, titanium chromium, silver-colored aluminium,
The translucent or opaque metal film of the formation of the unitary such as magnalium, titanium silver, magnesium silver, nickeline, Ag-Cu-Zn or multicomponent alloy
Any one.
In the present invention, intermediate layer is used for the tack for weakening transparent conductive film and conductive membrane layer.Intermediate layer can be selected
With one layer of physics film of formation such as LiF, common salt, carbon film.
In the present invention, weaken the tack between transparent conductive film and conductive membrane layer, physical chemistry can also be used
Method such as corona treatment, hydride modified processing transparent conductive film interface, for example, being passed through nitrogen, oxygen, Ar, methane, second
Alkynes, hydrogen or steam carry out surface plasma processing or are passed through silane gas forming ultra-thin interface-modifying layer, so as to weaken
Chemical bond is contacted between bright conductive film and conductive membrane layer, the attachment between reduction transparent conductive film and conductive membrane layer
Property.
The invention also provides the preparation method of the transparent conductive film of above-mentioned taking off arbitrary graphic, vacuum thermal evaporation
Plated film, magnetron sputtering deposition, chemical vapor deposition (CVD), solwution method spin coating, print, scrape figure film forming etc., obtaining taking off any
Patterned transparent conductive film.
In a specific embodiment, preparation method of the present invention is comprised the following specific steps that：From high-transparent glass, elder generation
It is with cleaning procedure that glass surface is clearly clean, surface coarsening and hydroxyl then are carried out to glass with NaOH solution or HF solution
Change, then dry.Ready glass is put into vacuum thermal evaporation system to vacuumize, then steaming degree TiCr or NiCr alloy is saturating
Bright conductive film, then evaporates LiF films and Ag layers.
It is preferred that, metal or metal alloy film, transparent conductive oxide and intermediate layer can pass through magnetron sputtering, vacuum
Prepared by the modes such as thermal evaporation, electron beam evaporation and laser deposition, it is also possible to print, print and prepared by the mode such as spin coating.Such as with heat
Evaporation prepares transparent conductive film, and transparent conductive film, then depositing inter-layer and conductive membrane layer are first deposited on substrate.For
Raising substrate and transparent conductive film adhesive force, substrate surface can be modified by corona treatment, silane chemistries, chemistry is clear
Wash the raisings such as roughening and plus substrate temperature and transparent conductive film adhesive force.Such as using magnetron sputtering deposition transparency conducting layer,
Intermediate layer and conductive membrane layer, sputter transparent conductive film layer, intermediate layer and conductive membrane layer successively on substrate.Substrate table
Face cleaning, physical chemistry processing and the parameter such as underlayer temperature and bias are close to improving substrate and transparent conductive film adhesive force
Correlation, sputtering parameter such as power, air pressure, sputter rate, O2 to Ar ratio, each layer film thickness, target and substrate spacing and angle etc.
It can be adjusted as needed.Adhesive force between substrate and transparent conductive film will be significantly greater than transparent conductive film and conduction
Adhesive force between film layer, is easy to follow-up when peeling off conductive film with sticky instrument, only peels off Upper conductive film and lower floor is saturating
Bright conductive film is not influenceed by stripping.In the present invention, the adhesive force between the transparent conductive film layer and conductive membrane layer is bright
The aobvious adhesive force less than between the substrate and transparent conductive film.Intermediate layer insert LiF, organic molecule layer, it is non-functional
Change silylation layer etc..Herein refer to the transparent conductive film layer that " non-functionalized silylation layer " refers to the middle silylation layer that must be formed and lower floor
It is main with van der Waals interaction, covalent bond and ionic bond effect negligible amounts or weaker between Upper conductive film layer.
The invention also provides the transparent conductive film of taking off arbitrary graphic is in the transparency electrode as photoelectric device
Or the application of each side such as transparent window of anti-electromagnetic wave interference.
In the present invention, the adhesive force between substrate and transparent conductive film is significantly greater than transparent conductive film layer and conductive thin
When adhesive force between film layer refers to peel off Upper conductive film, Upper conductive film can be peeled off thoroughly and lower floor's electrically conducting transparent is thin
Film layer any will not come off.In the present invention, as long as the adhesive force between substrate and transparent conductive film will be significantly greater than transparent lead
Adhesive force between thin film layer and conductive membrane layer, transparent conductive film is not influenceed by conductive membrane layer stripping, intermediate layer and/
Or ultra-thin interface-modifying layer can be omitted.
Present invention innovation is, intermediate layer is introduced between transparent conductive film layer and conductive membrane layer or to electrically conducting transparent
Film layer carries out modifying interface, so that the adhesive force between transparent conductive film layer and conductive membrane layer is weakened, and electrically conducting transparent
Enough adhesive force is kept between film layer and substrate, lower floor's transparent conductive film is unaffected when peeling off Upper conductive film.
The position of electrically conducting transparent window as needed, flexibly peels off Upper conductive film and intact reservation lower floor transparent conductive film, from
And form the transparent conductive film window that figure can be arbitrarily devised.
Present invention innovation is, by carrying out chemistry or physical modification in substrate surface so that transparent conductive film layer
There is very strong adhesive force between substrate, and intermediate layer is introduced between transparent conductive film and conductive membrane layer or to transparent
The modifying interface of conductive membrane layer, adhesive force is led significantly lower than substrate with transparent between transparent conductive film layer and conductive membrane layer
Adhesive force between conductive film, lower floor's transparent conductive film is not by shadow when peeling off Upper conductive film with adhesive tape and seal
Ring, be derived from can with arbitrarily devised patterned transparent conductive film window, and unstripped full structural membrane still with figure
The conductive film of transparent conductive film the linking into an integrated entity of window of shape.The patterned electrically conducting transparent obtained with above-mentioned design
Membrane structure, all should belong to the scope of the present invention.
Brief description of the drawings
Fig. 1 is the schematic cross-section of the transparent conductive film of the taking off arbitrary graphic of the present invention in embodiment 1.
Fig. 2 is the schematic cross-section of the transparent conductive film of the taking off arbitrary graphic of the present invention in embodiment 2.
Fig. 3 is the schematic cross-section of the taking off arbitrary graphic transparent conductive film of the present invention in embodiment 3.
Fig. 4 is the schematic cross-section of the taking off arbitrary graphic transparent conductive film of the present invention in embodiment 4.
Embodiment
With reference to specific examples below and accompanying drawing, the present invention is described in further detail, protection content of the invention
It is not limited to following examples.Under the spirit and scope without departing substantially from inventive concept, those skilled in the art it is conceivable that change
Change and advantage is all included in the present invention, and using appended claims as protection domain.The process of the implementation present invention,
Condition, reagent, experimental method etc., are the universal knowledege and common knowledge of this area in addition to the following content specially referred to,
The present invention is not particularly limited.
Such as Fig. 1-Fig. 4,1 expression substrate, 10 represent substrate interface decorative layers, and 2 represent transparent conductive film layers, and 21 represent super
Thin interface-modifying layer, 3 represent intermediate layer, and 4 represent conductive membrane layer.
As shown in Fig. 1 (a) and (b), the transparent conductive film of taking off arbitrary graphic of the present invention is wrapped successively from bottom to up
Include substrate 1, transparent conductive film layer 2, intermediate layer 3 and conductive membrane layer 4.Between the substrate 1 and transparent conductive film layer 2
Adhesive force is more than the adhesive force between transparent conductive film layer 2 and conductive membrane layer 4.
Wherein, substrate 1 is glass, and substrate 1 can also be any one of plastics, quartz or sapphire.Electrically conducting transparent is thin
Film layer 2 is the transparent metal film of aluminium formation；It can also be aluminium, titanium, chromium, nickel, iron, copper, silver, gold, titanium chromium, silver-colored aluminium, magnalium, titanium
Any one of the unitary such as silver, magnesium silver, nickeline, Ag-Cu-Zn or the transparent metal film of multicomponent alloy formation；Can also be AZO
The transparent conductive film of transparent conductive oxide formation, can also be the transparent conductive oxides such as AZO, GZO, IZO, ITO, FTO
Any one of the transparent conductive film of formation.Conductive membrane layer 4 is aluminium, titanium, chromium, nickel, iron, copper, silver, titanium chromium, silver-colored aluminium, magnesium
The unitary such as aluminium, titanium silver, magnesium silver, nickeline, Ag-Cu-Zn or transparent, the translucent or opaque metal film of multicomponent alloy formation
Any one.Intermediate layer 3 is LiF；LiF, common salt, carbon film, organic molecule, polymeric material, oxidation can also be selected
Any one of molybdenum, silane etc..
In a specific embodiment, method for carrying out modifying interface to transparent conductive film layer 2 etc. can also be used to be formed
The transition zone of one layer of reduction transparent conductive film 2 and the adhesive force of conductive membrane layer 4, i.e., ultra-thin interface-modifying layer 21, such as Fig. 2 institutes
Show.The modifying interface method to transparent conductive film layer 2, which includes using, is passed through nitrogen, oxygen, Ar, methane, acetylene, hydrogen
Or steam carries out surface plasma processing or is passed through silane gas formation self-assembling ultrathin interface-modifying layer.
The present invention can also be by introducing intermediate layer 3 between transparent conductive film layer 2 and conductive membrane layer 4 so that thoroughly
Adhesive force is significantly lower than the attachment between transparent conductive film layer 2 and substrate 1 between bright conductive membrane layer 2 and conductive membrane layer 4
Power, is then partially stripped the conductive membrane layer 4 on upper strata using adhesive tape or graphical seal, and the electrically conducting transparent of lower floor
Film layer 2 is not influenceed by stripping, obtains patterned transparent conductive film.
The present invention is also possible to form substrate interface decorative layer 10 by carrying out chemically or physically modification on the surface of substrate 1, its
Strengthen the adhesive force between the substrate 1 and transparent conductive film layer 2.E.g., including in the surface coating functions silica gel of substrate 1
Layer or functional silane layers.
In the present invention, as long as the adhesive force between substrate 1 and transparent conductive film 2 will be significantly greater than transparent conductive film layer
Adhesive force between 3 and conductive membrane layer 4, transparent conductive film 2 is not influenceed by the stripping of conductive membrane layer 4, intermediate layer 3 and/or
Ultra-thin interface-modifying layer 21 can be omitted.In the present invention, the adhesive force between substrate 1 and transparent conductive film 2 is significantly greater than
When adhesive force between bright conductive membrane layer 3 and conductive membrane layer 4 refers to peel off Upper conductive film, Upper conductive film can be thorough
Bottom is peeled off and lower floor's transparent conductive film layer any will not come off.Because the adhesive force between substrate and transparent conductive film layer is bright
The aobvious adhesive force being more than between transparent conductive film layer and conductive membrane layer is therefore, transparent to lead when peeling off conductive membrane layer 4
Not peeling off phenomenon between thin film layer 2 and substrate 1.In the transparent conductive film of taking off arbitrary graphic of the present invention,
Conductive membrane layer 4 can be peeled off by adhesive tape or sticky seal, and transparent conductive film layer 2 is not influenceed by stripping, is appointed
Anticipate patterned transparent conductive film.
Embodiment 1
As shown in Fig. 1 (a), the transparent conductive film of taking off arbitrary graphic is included from down to up successively in the present embodiment
Substrate 1, transparent conductive film layer 2, intermediate layer 3 and conductive membrane layer 4.Wherein, substrate 1 is glass, transparent conductive film layer
2 be aerdentalloy film, and intermediate layer 3 is LiF, and conductive membrane layer 4 is silverskin.Conductive membrane layer 4 be partially stripped after leave it is saturating
Shown in bright conductive film such as Fig. 1 (b).Single specific material is provided in the present embodiment, other materials selection is not limited, simply lifts
The example explanation present invention.The glass surface of substrate 1 is handled by surface coarsening and surface plasma, the silver-colored aluminium of electrically conducting transparent in hot evaporation
The silverskin of conductive membrane layer 4 in alloy film 2, then thermal evaporation intermediate layer 3LiF transition zones, last thermal evaporation.Above-mentioned the present embodiment system
The structure of standby obtained product is Glass/AgAl/LiF/Ag, and the adhesive force of glass and aerdentalloy film is significantly greater than silver-colored aluminium and closed
Adhesive force between golden film and silverskin, by adhesive tape or patterned seal, the silver-colored aluminium of lower floor in silverskin stripping process
Film is unaffected, forms conductive by the patterned transparent of Glass/AgAl or Glass/AgAl/LiF structure compositions after stripping
Film.Transparent conductive film made from the present embodiment can as photoelectric device transparent cathode or transparent anode, it is unstripped
Conductive film can be used as the lower connecting wire of resistance in photoelectric device without transparent requirement.The present embodiment electrically conducting transparent is thin
Film is also used as the transparent window of anti-electromagnetic wave interference, that is, requires that conductive film, stripping are peeled off in transparent position with adhesive tape
The patterned transparent conductive film of Glass/AgAl or Glass/AgAl/LiF compositions is formed from after as watch window,
Unstripped film is full structural membrane Glass/AgAl/LiF/Ag, realizes the anti-electromagnetic interference capability of greater degree.
Embodiment 2
As shown in Fig. 2 the present embodiment transparent conductive film includes substrate 1 from down to up successively, transparent conductive film layer
2 and conductive membrane layer 4, and the ultra-thin interface-modifying layer 21 that modifying interface is formed in transparent conductive film layer 2.Wherein,
Substrate 1 is glass or PET, and transparent conductive film layer 2 is NiCr alloy films, and conductive membrane layer 4 is silver film.This implementation
Example provides single specific material, does not limit other materials selection, of the invention solely for the purpose of illustration.Manufacturing process is with implementation
Example 1.After the roughened processing with surface plasma of substrate 1, NiCr transparent conductive film layers 2 have very strong adhesive force with substrate 1.
Surface plasma processing is carried out to NiCr films 2 using steam mode, ultra-thin interface-modifying layer 21 is formed on NiCr films 2, is led
The energy rapid decrease under steam effect of the adhesive force between silverskin 4 and NiCr films 2 is caused, therefore can be very well stripping Ag with adhesive tape
Layer and obtain patterned Glass/NiCr or PET/NiCr transparent conductive films.Can be with to the modifying interfaces of NiCr films 2
Silane gas formation self-assembling ultrathin interface-modifying layer is passed through, or is passed through nitrogen, oxygen, Ar, methane, acetylene, hydrogen carry out table
Surface plasma processing.The present embodiment transparent conductive film may be used as the transparent window of anti-electromagnetic wave interference, i.e., with graphical
Glass/NiCr or PET/NiCr transparent conductive films as watch window, unstripped film Glass/NiCr/Ag or
Person PET/NiCr/Ag as greater degree electromagnetism interference protection film.Transparent conductive film window and unstripped conduction
Film forms continuous integrated electromagnetic wave interference protecting film together.
Embodiment 3
As shown in figure 3, the present embodiment transparent conductive film includes substrate 1, substrate interface decorative layer from down to up successively
10th, transparent conductive film layer 2 and conductive membrane layer 4.Wherein, substrate 1 is glass or PET, substrate interface decorative layer 10
For transparent silicon glue-line, transparent conductive film layer 2 is TiCr alloy films, and conductive membrane layer 4 is silver film.The present embodiment provides single
Specific material, does not limit other materials selection, is intended merely to that the present invention is better described.Manufacturing process be the same as Example 1.Substrate
Layer of transparent layer of silica gel 10, TiCr transparent conductive film layers 2 and the lining after the modification of transparent silicon glue-line are coated after 1 roughened processing
There is very strong adhesive force between bottom 1.Surface plasma processing is carried out to TiCr transparent conductive film layers 2 using steam mode,
Ultra-thin interface-modifying layer is formed in TiCr transparent conductive film layers 2, causes between silverskin 4 and TiCr films 2 adhesive force in steam
The lower energy rapid decrease of effect, therefore can obtain patterned Glass/ layer of silica gel/TiCr peeling off Ag layers very well with adhesive tape
Or PET/ layer of silica gel/TiCr transparent conductive films.Can also be in the surface of substrate 1 coating clear silane layer.It is transparent to TiCr to lead
The modifying interface of thin film layer 2 can also be passed through silane gas formation self-assembling ultrathin interface-modifying layer, or be passed through nitrogen, oxygen
Gas, Ar, methane, acetylene, hydrogen carry out surface plasma processing.The transparent conductive film of the present embodiment may be used as anti-electromagnetism
The transparent window of wave interference, i.e., with patterned Glass/ layer of silica gel/TiCr or PET/ layer of silica gel/TiCr transparent conductive films
As watch window, unstripped film is as the electromagnetism interference protection film of greater degree, and both films still connect
Continuous.
Embodiment 4
As shown in figure 4, the present embodiment transparent conductive film includes substrate 1, substrate interface decorative layer from down to up successively
10th, transparent conductive film layer 2, intermediate layer 3 and conductive membrane layer 4.Wherein, substrate 1 is glass, and substrate interface decorative layer 10 is
Bright layer of silica gel, transparent conductive film layer 2 is AgAl alloy films, and intermediate layer 3 is LiF layers, and conductive membrane layer 4 is silver film.Herein
Single specific material is provided, other materials selection is not limited, is intended merely to that the present invention is better described.Manufacturing process is with implementation
Example 1.Layer of transparent layer of silica gel 10 is coated after the roughened processing of substrate 1, AgAl transparent conductive film layers 2 through transparent silicon glue-line with repairing
Substrate 1 after decorations has very strong adhesive force, between silverskin 4 and AgAl films 2 adhesive force behind the 3LiF intervals of intermediate layer can quickly under
Drop, therefore can obtain patterned Glass/ layer of silica gel/AgAl or Glass/ silica gel peeling off Ag layers very well with adhesive tape
The transparent conductive film of layer/AgAl/LiF structures.The transparent conductive film of the present embodiment may be used as the saturating of anti-electromagnetic wave interference
Bright window, can also use the transparency electrode of photoelectric device, that is, peel off after conductive membrane layer Ag, with patterned Glass/ silica gel
Layer/AgAl or Glass/ layer of silica gel/AgAl/LiF is as the transparent conductive electrode of device, and unstripped film, which can be used as, connects
Connecting wire between the lower photoelectric device of resistance.
Above-described is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art
For, without departing from the concept of the premise of the invention, various modifications and improvements can be made, these belong to the present invention
Protection domain.
Claims (9)
1. a kind of transparent conductive film of taking off arbitrary graphic, it is characterised in that it includes substrate (1), in the substrate
(1) transparent conductive film layer (2) and conductive membrane layer (4) being sequentially depositing on；The substrate (1) and transparent conductive film layer
(2) adhesive force between is more than the adhesive force between transparent conductive film layer (2) and conductive membrane layer (4)；The conductive film
Layer (4) is peelable；It includes intermediate layer (3)；The intermediate layer (3) is located at the transparent conductive film layer (2) and the conduction
Between film layer (4), it weakens the adhesive force between the transparent conductive film layer (2) and the conductive membrane layer (4).
2. the transparent conductive film of taking off arbitrary graphic as claimed in claim 1, it is characterised in that the intermediate layer
(3) LiF, common salt, carbon film, organic molecule, polymeric material, molybdenum oxide or silane are included.
3. a kind of transparent conductive film of taking off arbitrary graphic, it is characterised in that it includes substrate (1), in the substrate
(1) transparent conductive film layer (2) and conductive membrane layer (4) being sequentially depositing on；The substrate (1) and transparent conductive film layer
(2) adhesive force between is more than the adhesive force between transparent conductive film layer (2) and conductive membrane layer (4)；The conductive film
Layer (4) is peelable；It includes ultra-thin interface-modifying layer (21)；The ultra-thin interface-modifying layer (21) is to transparent conductive film layer
(2) modifying interface and formed, it weakens the adhesive force between described transparent conductive film layer (2) and conductive membrane layer (4).
4. the transparent conductive film of taking off arbitrary graphic as claimed in claim 3, it is characterised in that described to be led to transparent
The modifying interface of thin film layer (2) be using be passed through nitrogen, oxygen, Ar, methane, acetylene, hydrogen or steam carry out surface etc. from
Daughter handles or is passed through silane gas formation self-assembling ultrathin interface-modifying layer (21).
5. the transparent conductive film of the taking off arbitrary graphic as described in claim 1 or 3, it is characterised in that it includes lining
Bottom interface decorative layer (10)；The substrate interface decorative layer (10) is by chemically or physically being modified on substrate (1) surface
Formed, it strengthens the adhesive force between the substrate (1) and transparent conductive film layer (2).
6. the transparent conductive film of taking off arbitrary graphic as claimed in claim 5, it is characterised in that the substrate interface
Decorative layer (10) is included in the functionalised silica gel layer of substrate (1) surface coating.
7. the transparent conductive film of the taking off arbitrary graphic as described in claim 1 or 3, it is characterised in that
The substrate (1) is transparent material；
The transparent conductive film layer (2) is that transparent metal film, transparent conductive oxide that metal or metal alloy is constituted are thin
The laminated film of film or transparent conductive oxide/metal/transparent conductive oxide composition；
The conductive membrane layer (4) is the translucent or opaque metal film that metal or metal alloy is constituted.
8. the transparent conductive film of taking off arbitrary graphic as claimed in claim 7, it is characterised in that
The transparent metal film that the metal or metal alloy is constituted is aluminium, titanium, chromium, nickel, iron, copper, silver, gold, titanium chromium, silver-colored aluminium,
Any one for the transparent metal film that magnalium, titanium silver, magnesium silver, nickeline, Ag-Cu-Zn unitary or multicomponent alloy are formed；
The transparent conductive oxide film is Al-Doped ZnO, gallium-doped zinc oxide, indium-doped zinc oxide, tin-doped indium oxide, fluorine doped
Any one of the transparent conductive film of tin oxide formation；
The laminated film of the transparent conductive oxide/metal/transparent conductive oxide composition is AZO | Ag | AZO, ZnO | and Ag |
ZnO, ITO | Ag | ITO, GZO | Ag | GZO, AZO | AgAl | any one of AZO multi-layered composite systems；
The conductive film (4) is aluminium, titanium, chromium, nickel, iron, copper, silver, titanium chromium, silver-colored aluminium, magnalium, titanium silver, magnesium silver, nickeline, silver-bearing copper
Any one of zinc unitary or transparent, the translucent or opaque metallic film of multicomponent alloy formation.
9. the application of the transparent conductive film of the taking off arbitrary graphic as shown in claim 1 or 3, it is characterised in that institute
The transparent conductive film for stating taking off arbitrary graphic is used as the transparency electrode of photoelectric device or as the saturating of anti-electromagnetic wave interference
Bright window.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273143.XA CN105185843B (en) | 2014-06-18 | 2014-06-18 | A kind of transparent conductive film of taking off arbitrary graphic and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410273143.XA CN105185843B (en) | 2014-06-18 | 2014-06-18 | A kind of transparent conductive film of taking off arbitrary graphic and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105185843A CN105185843A (en) | 2015-12-23 |
| CN105185843B true CN105185843B (en) | 2017-07-25 |
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| CN107393979B (en) * | 2017-06-09 | 2019-07-16 | 中国科学院宁波材料技术与工程研究所 | A kind of transparent electrode and its preparation method and application based on ultrathin metallic film |
| CN109545979A (en) * | 2018-10-19 | 2019-03-29 | 杭州电子科技大学 | The organic photovoltaic cell of metallic transparent electrode and preparation method and composition |
| CN109830545B (en) * | 2019-02-14 | 2021-10-15 | 中国科学院半导体研究所 | Aluminum-doped zinc oxide film surface modification material, preparation method and battery |
| CN111816365B (en) * | 2019-04-10 | 2022-04-19 | 中国科学院苏州纳米技术与纳米仿生研究所 | Method for transferring conductive polymer onto flexible substrate and flexible electrode |
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| US6040521A (en) * | 1996-11-08 | 2000-03-21 | Showa Shell Sekiyu K.K. | N-type window layer for a thin film solar cell and method of making |
| CN201302999Y (en) * | 2009-02-02 | 2009-09-02 | 信义玻璃工程（东莞）有限公司 | Transparent conductive film glass |
| CN103151394A (en) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin-film solar cell and manufacture method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6040521A (en) * | 1996-11-08 | 2000-03-21 | Showa Shell Sekiyu K.K. | N-type window layer for a thin film solar cell and method of making |
| CN201302999Y (en) * | 2009-02-02 | 2009-09-02 | 信义玻璃工程（东莞）有限公司 | Transparent conductive film glass |
| CN103151394A (en) * | 2012-12-14 | 2013-06-12 | 广东志成冠军集团有限公司 | Thin-film solar cell and manufacture method thereof |
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