CN105814647B - Transparent conductive laminate, the manufacture method of transparent conductive laminate and the electronic installation that is formed using transparent conductive laminate - Google Patents
Transparent conductive laminate, the manufacture method of transparent conductive laminate and the electronic installation that is formed using transparent conductive laminate Download PDFInfo
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- CN105814647B CN105814647B CN201580003087.0A CN201580003087A CN105814647B CN 105814647 B CN105814647 B CN 105814647B CN 201580003087 A CN201580003087 A CN 201580003087A CN 105814647 B CN105814647 B CN 105814647B
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000009434 installation Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 358
- 239000011787 zinc oxide Substances 0.000 claims abstract description 179
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052738 indium Inorganic materials 0.000 claims abstract description 116
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 101
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000011701 zinc Substances 0.000 claims abstract description 72
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 53
- 239000001301 oxygen Substances 0.000 claims abstract description 53
- 238000004544 sputter deposition Methods 0.000 claims abstract description 31
- 238000004458 analytical method Methods 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 20
- 238000000921 elemental analysis Methods 0.000 claims description 22
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- 229960001296 zinc oxide Drugs 0.000 description 148
- 239000010410 layer Substances 0.000 description 29
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 19
- 229910003437 indium oxide Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 9
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- 229910052786 argon Inorganic materials 0.000 description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 6
- 229910001195 gallium oxide Inorganic materials 0.000 description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 102000036435 Zincins Human genes 0.000 description 1
- 108091007139 Zincins Proteins 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 238000009738 saturating Methods 0.000 description 1
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- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Physical Vapour Deposition (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
The present invention provides a kind of transparent conductive laminate with excellent damp and hot characteristic, the manufacture method of transparent conductive laminate and the electronic installation that is formed using the transparent conductive laminate.It is characterized in that, it is to possess at least one side of base material by sputtering method transparent conductive laminate of Zinc oxide film for being formed etc., Zinc oxide film is to include zinc oxide, the Zinc oxide film that doped gallium and indium form simultaneously, the Zinc oxide film includes zinc amount, gallium amount, oxygen amount and the indium amount on being determined by the XPS analysis of film thickness direction, multiple regions with uneven concentration distribution, i.e. the different first area of the value comprising [In]/[Ga] and second area.
Description
Technical field
Led the present invention relates to transparent conductive laminate, the manufacture method of transparent conductive laminate and using transparent
The electronic installation that electrical lamilate forms, more particularly to the transparent conductive laminate of damp and hot excellent, transparent conductivity layer
Fit manufacture method and the electronic installation formed using the transparent conductive laminate.
Background technology
In the past, in the portrait display device for possessing liquid-crystal apparatus, Organnic electroluminescent device (organic EL element), by tin
The transparent conductive laminate that doped indium oxide uses as the formation material of transparency conducting layer is widely used.
On the other hand, replacing as the transparency conducting layer using a large amount of tin-doped indium oxides comprising high price rare metal indium
Generation, motion have transparent conductive laminate (such as the patent document using the transparency, the excellent zinc oxide of surface smoothness
1)。
More specifically, it is that one kind forms Al on organic polymer lamilate base material2O3Film, and be formed on mixing
Miscellaneous Ga ZnO is the transparent conductive film of GZO films.
In addition, motion has using zinc oxide as principal component, by the dopant of concentration easy-regulating, the reduction of resistivity is made
For the purpose of low resistivity, transparent electric conductor (such as patent document 2).
More specifically, be a kind of transparent conductive body being made up of zinc oxide, indium oxide and gallium oxide, its be by indium and
The concentration of element of gallium is set to the low resistivity, transparent electric conductor of the value in prescribed limit respectively.
On the other hand, motion has also can obtain excellent moisture-proof thermal characteristics as purpose, doping even if for very thin films level
The transparent conductivity Zinc oxide film (such as patent document 3) of element-specific.
More specifically, be it is a kind of to zinc oxide addition by Ga and/or Al the first element formed and by selected from by
The transparent conductivity zinc oxide of at least one formed second element in the group that In, Bi, Se, Ce, Cu, Er and Eu are formed
Film, it is the value in particular range in the ratio resistance before and after defined damp heat test, by zinc and the atomic quantity of second element ratio
And thickness is defined as the value in prescribed limit.
And then it is more in order to solve the content of indium or gallium, the problem of the sputtering target material such as easy thick-film, even if motion has to be thin
Film humidity resistance also the ion plating target of excellent transparent conductivity zinc-oxide film, formed obtained by ion plating target
Transparent conductivity zinc-oxide film (such as patent document 4).
More specifically, it is a kind of sintered body institute of the gallium by including ormal weight in zinc oxide and indium into and resulting
Transparent conductivity zinc-oxide film in In/Ga quality ratio be the value less than 0.01~0.6 ion plating target.
Prior art literature
Patent document
Patent document 1：No. 4917897 publications of Japanese Patent No. (claims etc.)
Patent document 2：Japanese Patent Publication 2006-147325 publications (claims etc.)
Patent document 3：Japanese Patent Publication 2013-147727 publications (claims etc.)
Patent document 4：Japanese Patent Publication 2011-74779 publications (claims etc.)
The content of the invention
(1) technical problems to be solved
However, the transparent conductive laminate disclosed on patent document 1, it is found that there are the following problems, i.e. either
It is no must be by Al2O3Film is still not abundant enough as priming coat, the moisture-proof thermal characteristics of the only Zinc oxide film of doped gallium.
In addition, on the low resistivity, transparent electric conductor disclosed in patent document 2, it is found that there are the following problems, i.e. though it is real
The improvement of resistivity is showed, but any consideration is not carried out to damp and hot characteristic.
In addition, on the transparent conductivity Zinc oxide film disclosed in patent document 3, it is found that there are the following problems, i.e. though
Damp and hot characteristic to a certain degree has been arrived, but membrance casting condition is excessively harsh, and thickness is necessary for below 140nm, purposes is defined
It is narrow.
And then on the transparent conductivity Zinc oxide film disclosed in patent document 4, it is found that there are the following problems, i.e. it is special
Sign is, it is impossible to formed, and need to be formed by the ion plating of high price in general sputter equipment, therefore, the big rule of manufacturing equipment
Modelling, it is economically disadvantageous.
Therefore, as a result the present inventor etc. has found, the oxidation even formed by sputtering method by furtheing investigate these problems
Zinc film, by making it include zinc amount, gallium amount, oxygen amount and indium amount on being determined by XPS analysis, there is uneven concentration
Multiple regions (first area and second area) of distribution, and by the combination in the plurality of region, damp and hot excellent can be made, from
And it is over into the present invention.
That is, it is an object of the present invention to provide it is a kind of can be by the saturating of the damp and hot excellent that general sputter equipment is formed
Bright conductive laminate, the transparent conductive laminate manufacture method and formed using the transparent conductive laminate
Electronic installation.
(2) technical scheme
According to the present invention, there is provided a kind of transparent conductive laminate, it is characterised in that had at least one side of base material
It is standby that zinc oxide, while doped gallium are included the transparent conductive laminate of Zinc oxide film that is formed, Zinc oxide film by sputtering method
And indium, the Zinc oxide film include zinc amount, gallium amount, oxygen amount and the indium amount on being determined by the XPS analysis of film thickness direction, had
Multiple regions of uneven concentration distribution, and the plurality of region includes on the film thickness direction from Zinc oxide film towards base material
The different first area of [In]/[Ga] value and second area, can solve the above problems.
That is, due to comprising multiple regions (first area and second area) as described below, therefore zinc oxide can be improved
The damp and hot characteristic of film, wherein in the multiple region, on zinc amount, gallium amount, oxygen amount and the indium in the Zinc oxide film of the present invention
Amount, on the film thickness direction from Zinc oxide film towards substrate side, there is the indium amount increase of relativity, what is then reduced is uneven dense
Degree distribution.
Conversely, relatively more region (the firstth area of indium amount is set by the near surface of the Zinc oxide film in the opposite side of base material
Domain), and first area that Zinc oxide film included and each region of second area is met the relation of amount of element described above, by
This, the Zinc oxide film of damp and hot excellent while the initial resistance for keeping relatively low can be made.
In addition, it is combined into by using the next specific first area of XPS measure and matching somebody with somebody for second area, so as to higher
Specific precision easily will match somebody with somebody be combined into regulation and control into ormal weight, to meet prescribed relationship, therefore stable performance can be obtained
Transparent conductive laminate.
In addition, the dopant as Zinc oxide film, the reasons why selecting gallium and indium, is as described below.
That is, it is due to by comprising two or more added dopants, it is possible to increase the chemical stability of zinc oxide.
In addition, be due to Group IIIA (boron family) element for generally believing the periodic table of elements situation compared with Group IIB (zinc race) member
The zinc of element has a valence electron more, and assumes in zinc when occupying side draw for dopant, aluminium, gallium and respective first electricity of indium
Small from energy, the occurring source as carrier is effective.
And then on dopant zinc occupy side as above it is assumed that and the first ionization energy it is small, therefore to such as aoxidize
The combination energy indexes of ion-binding ionic crystal as zinc, i.e. Madelung energy (Madelung energy) are carried out
When comparing, aluminium is -6.44eV, and gallium is -13.72eV, and indium is -9.73eV.
Therefore, it is the stability because as dopant relative to zinc oxide, it is believed that be followed successively by gallium, indium, aluminium from low to high.
In addition, for covalent radius, it is in the case of zincIt is in the case of aluminiumThe situation of gallium
Under beIt is in the case of indiumIn addition, for ionic radius, it is in the case of zincIn the case of aluminium
ForIt is in the case of galliumIt is in the case of indium
If so doing, using zinc oxide as in the crystallization of main component, it is assumed that in zinc side draw for dopant, consider its structure
When making stability, from the viewpoint of covalent radius, thus it is speculated that gallium is most stably substituted, from the viewpoint of ionic radius,
Speculate that indium is most stably substituted, therefore, select them to wait and be used as dopant.
But the first area that is included of Zinc oxide film and the interface of second area are not necessarily required to clearly, and can be
Ratio of components continuity or the part of phasic Chang in each region be present.
In other words, in Zinc oxide film, in a thickness direction, the ratio of components continuity of the inside comprising relativity indium amount or
Phasic Chang, as illustrated in Fig. 1 etc., or be able to confirm that in XPS measure, form the different first area of ratio of components
And the degree of second area.
Moreover, as described later, the formation of the first area different on ratio of components and second area can be by once
The implementation of sputter step is formed, or can be formed by the implementation of sputter step more than twice.
That is, even if being a sputter step, as sputtering target material, the ternary system of zinc oxide-gallium oxide-indium oxide is used
Sintered body, the mixing ratio by suitably adjusting its each composition etc., as illustrated in Fig. 1 etc., it can be formed in zinc oxide to continuity
The relatively large number of region of indium amount (first area) of the near surface of the side opposite with substrate-side of film and in Zinc oxide film
Inside the relatively small number of region of indium amount (second area).
On the reason, from the viewpoint of above-mentioned Ma get Long energy, thus it is speculated that gallium is larger, is stably incorporated to crystal grain,
To be unstable when another aspect indium is compared with gallium, in addition, from the viewpoint of covalent radius, estimation is due to
It is larger when indium is compared with zinc and gallium.That is, because prediction indium is small for the solubility of zinc oxide, therefore speculate except maintaining crystal structure
Outside, the indium of relative surplus is segregated in surface.
In addition, it was confirmed that with using ion plating method, vacuum vapour deposition situation compared with, use and show in the case of sputtering method
Write and produce such segregation, therefore the present invention uses sputtering method.
It is of course also possible to by the implementation of sputter step more than twice, and make the species of sputtering condition, sputtering target material
Etc. difference, the different first area of ratio of components and second area are formed.
In addition, when forming of the invention, [In]/[Ga] value gradually decreases preferably in the first region, and second
[In]/[Ga] value is shown as certain value in region.
By so making each region of first area that Zinc oxide film included and second area meet member as described above
The relation of element amount, excellent damp and hot characteristic can be obtained while relatively low initial resistance is kept.
In addition, shown in Fig. 3 as be described hereinafter, according to the first area to Zinc oxide film based on SIMS (Secondary Ion
Mass Spectrometry) determination of elemental analysis, on the figure of gained, on indium, exist raised to upside as display
The situation of the distribution curve of maximum.But this is the influence in so-called of short duration region, even if in this case, as
With the value of [In]/[Ga] obtained by XPS analysis measure, can be included in the phenomenon gradually decreased.
In addition, when forming of the invention, it is preferable that in the Zinc oxide film formed comprising first area and second area,
With respect to the total amount (100atom%) of the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount, indium amount is set to
Value in the range of 0.01~8atom%, and gallium amount is set to the value in the range of 0.1~10atom%.
It by the value being so set to the indium of Zinc oxide film and gallium concentration in prescribed limit, can improve damp and hot characteristic.
In addition, when forming of the invention, it is preferable that in the first region, with respect to XPS determination of elemental analysis
Zinc amount, gallium amount, the total amount (100atom%) of oxygen amount and indium amount, are set to the value in the range of 20~60atom%, by gallium amount by zinc amount
The value being set in the range of 0.1~10atom%, oxygen amount is set to the value in the range of 22~79.89atom%, and indium amount is set to
Value in the range of 0.01~8atom%.
Transparent conductive laminate is formed by so considering each composition amounts of first area, can be obtained more excellent
Damp and hot characteristic.
In addition, when forming of the invention, it is preferable that in the second area, with respect to XPS determination of elemental analysis
Zinc amount, gallium amount, the total amount (100atom%) of oxygen amount and indium amount, are set to the value in the range of 35~65atom%, by gallium amount by zinc amount
The value being set in the range of 0.1~10atom%, oxygen amount is set to the value in the range of 17~64.89atom%, and indium amount is set to
Value in the range of 0.01~8atom%.
Transparent conductive laminate is formed by so considering each composition amounts of second area, can be obtained more excellent
Damp and hot characteristic.
In addition, when forming of the invention, preferably [In] of first area/[Ga] value is set to more than second area
[In]/[Ga] value.
By so forming first area~second area, more excellent damp and hot characteristic can be obtained.
In addition, when forming of the invention, preferably will be by ρ0The initial ratio resistance of represented Zinc oxide film is set to 1 × 10-4~1
×10-1Value in the range of Ω cm, and thickness is set to the value in the range of 20~300nm.
By so forming, can be made with specific thickness, and it is damp and hot while relatively low initial ratio resistance is kept
The Zinc oxide film of excellent.
In addition, when forming of the invention, it is preferable that the initial ratio resistance of Zinc oxide film is being set into ρ0, will be in 60 DEG C, phase
Under conditions of humidity 95%, the ratio resistance after taking care of 500 hours is set to ρ500When, by ρ500/ρ0Represented ratio is set to 1.5
Following value.
By so forming, the electrically conducting transparent of damp and hot excellent while the relatively low initial ratio resistance that can be maintained
Property lamilate.
In addition, the another way of the present invention is a kind of electronic installation, it is characterised in that by any of the above-described kind of transparent conductivity
Lamilate forms for transparency electrode.
So, by the way that the transparent conductive laminate for keeping damp and hot excellent while relatively low initial ratio resistance is used
In transparency electrode, the long-time stability of electronic installation can be suitably realized.
In addition, the another mode of the present invention is a kind of manufacture method of transparent conductive laminate, it is characterised in that it is
Possess at least one side of base material by sputtering method the manufacture method of the transparent conductive laminate of Zinc oxide film that is formed,
Include following step (1)~(2)；
The step of (1) preparing base material and sintered body respectively,
(2) the step of forming Zinc oxide film, the Zinc oxide film is at least one side of base material, by sintered body by splashing
The Zinc oxide film of doped gallium and indium while including zinc oxide that the method for penetrating forms, in the Zinc oxide film, on by towards base
Zinc amount, gallium amount, oxygen amount and the indium amount that the XPS analysis of the thickness direction of material are determined, as with the more of uneven concentration distribution
Individual region, the different first area of the value comprising [In]/[Ga] and second area.
That is, by so being manufactured, damp and hot characteristic while can stably manufacturing the initial ratio resistance for keeping relatively low
Excellent transparent conductive laminate.
In addition, when implementing of the invention, preferably the temperature of base material when forming Zinc oxide film is set to 10 on base material~
Value in the range of 150 DEG C.
By so being manufactured, the species increase of workable base material, therefore can not only manufacture available for multipurpose
Transparent conductive laminate, it is also favourable on economic face.
Brief description of the drawings
(a) in Fig. 1 is for illustrating to pass through film thickness direction to the Zinc oxide film of the transparent conductive laminate of embodiment 2
The figure of amount of element (zinc amount, oxygen amount, gallium amount and indium amount) that is determined of XPS analysis, (b) in Fig. 1 be enlarged representation gallium amount and
The figure of the distribution curve of indium amount, (c) in Fig. 1 are the figures for being used to illustrate the change of [In]/[Ga] value.
(a)~(c) in Fig. 2 is the figure for illustrating the section of the transparent conductive laminate of the present invention, and this is transparent to lead
Electrical lamilate includes the Zinc oxide film being made up of multiple regions with uneven concentration distribution.
Fig. 3 is for illustrating the Zinc oxide film for the transparent conductive laminate in embodiment 3, by the member based on SIMS
The figure of the amount of element (zinc amount, oxygen amount, gallium amount and indium amount) of the film thickness direction of element analysis measure gained.
Fig. 4 is the Zinc oxide film that doped gallium and indium form while including zinc oxide of the present invention based on In Plane methods
X-ray diffractogram.
Fig. 5 is the X-ray diffractogram on 002 face based on Out of Plane methods of the Zinc oxide film of the present invention.
Fig. 6 is the photo for illustrating the crystal structure of GZO films.
Fig. 7 is the figure for illustrating the damp and hot characteristic of the transparent conductive laminate of the present invention.
(a) in Fig. 8 is for illustrating to pass through film thickness direction to the Zinc oxide film of the transparent conductive laminate of embodiment 1
The figure of amount of element (zinc amount, oxygen amount, gallium amount and indium amount) that is determined of XPS analysis, (b) in Fig. 8 be amplification show gallium amount and
The figure of the distribution curve of indium amount, (c) in Fig. 8 are the figures for being used to illustrate the change of [In]/[Ga] value.
(a) in Fig. 9 is for illustrating to pass through film thickness direction to the Zinc oxide film of the transparent conductive laminate of embodiment 3
The figure of amount of element (zinc amount, oxygen amount, gallium amount and indium amount) that is determined of XPS analysis, (b) in Fig. 9 be amplification show gallium amount and
The figure of the distribution curve of indium amount, (c) in Fig. 9 are the figures for being used to illustrate the change of [In]/[Ga] value.
(a) in Figure 10 is for illustrating to pass through thickness side to the Zinc oxide film of the transparent conductive laminate of embodiment 4
To the figure of amount of element (zinc amount, oxygen amount, gallium amount and indium amount) that is determined of XPS analysis, (b) in Figure 10 is that amplification shows gallium amount
And the figure of the distribution curve of indium amount, (c) in Figure 10 are the figures for being used to illustrate the change of [In]/[Ga] value.
(a) in Figure 11 is for illustrating to pass through thickness side to the Zinc oxide film of the transparent conductive laminate of comparative example 1
To the figure of amount of element (zinc amount, oxygen amount, gallium amount and indium amount) that is determined of XPS analysis, (b) in Figure 11 is that amplification shows gallium amount
And the figure of the distribution curve of indium amount.
Embodiment
(first embodiment)
First embodiment is a kind of transparent conductive laminate, it is characterised in that is had at least one side of base material
It is standby by sputtering method and the transparent conductive laminate of Zinc oxide film formed, Zinc oxide film is to include zinc oxide, is adulterated simultaneously
The Zinc oxide film that gallium and indium form, as shown in figure 1, the Zinc oxide film is included on being determined by the XPS analysis of film thickness direction
Zinc amount, gallium amount, oxygen amount and indium amount, there are multiple regions of uneven concentration distribution, and the plurality of region is from Zinc oxide film
The different first area of value comprising [In]/[Ga] and second area on towards the film thickness direction of base material.
Below, the transparent conductive laminate of first embodiment is specifically described with reference to appropriate accompanying drawing.
1. Zinc oxide film
Shown in (a) in Zinc oxide film (sometimes referred to as transparency conducting layer) 10 such as Fig. 2, it is characterised in that by including oxidation
Zinc, while the Zinc oxide film that doped gallium and indium form is formed, on the film thickness direction towards base material, on passing through film thickness direction
Zinc amount, gallium amount, oxygen amount and the indium amount that XPS analysis are determined, as uneven concentration distribution, from Zinc oxide film towards base material
On film thickness direction, the value comprising [In]/[Ga] different first area 10a and second area 10b.
That is, the first area and each region of second area that Zinc oxide film is included meet Elemental redistribution as described above
Relation, it thus can be made into the Zinc oxide film being made up of the excellent Zinc oxide film of damp and hot characteristic or the transparency.
(1) crystal structure
Known Zinc oxide film has the crystal structure of hexagonal crystal system wurtzite-type, be doped gallium Zinc oxide film (hereinafter referred to as
For GZO films), but as shown in fig. 6, the crystal structure with hexagonal crystal system wurtzite-type, is the strong film of c-axis orientation.
In addition, though the Zinc oxide film of the present invention is comprising zinc oxide, while the Zinc oxide film that doped gallium and indium form is (following
Sometimes referred to as In-GZO films), even if doped indium, because indium amount is relatively more a small amount of, it can speculate that it will be high as c-axis orientation
Prismatical structure.
More specifically, the X based on In plane methods when Fig. 4 represents to make the concentration of the indium in Zinc oxide film change
X ray diffration pattern x.
Here, it by weight ratio is ZnO that characteristic curve A, which is,：Ga2O3：In2O3=94.0：5.7：Obtained by 0.3 sintered body
The X-ray diffractogram of In-GZO films, it by weight ratio is ZnO that characteristic curve B, which is,：Ga2O3：In2O3=93.3：5.7：1.0 sintering
The X-ray diffractogram of In-GZO films obtained by body.
In addition, it by weight ratio is ZnO that characteristic curve C, which is,：Ga2O3：In2O3=89.3：5.7：Obtained by 5.0 sintered body
The X-ray diffractogram of In-GZO films, it by weight ratio is ZnO that characteristic curve D, which is,：Ga2O3：In2O3=84.3：5.7：10.0 burning
The X-ray diffractogram of In-GZO films obtained by knot body.
Moreover, characteristic curve E is the X-ray diffractogram for not including indium, i.e. GZO films.
In addition, Fig. 5 represents the X-ray diffractogram based on Out of Plane methods on 002 face of Zinc oxide film.
Here, characteristic curve A~E in Fig. 5 is identical with the sample of the X-ray diffractogram corresponding to Fig. 4.
Therefore, as shown in Fig. 4 and Fig. 5 X-ray diffractogram, because In-GZO films show the diffraction same with GZO films
Peak, therefore can speculate that crystal structure is also similar.
(2) form
In addition, in Zinc oxide film, with respect to the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
Total amount (100atom%), indium amount is preferably set to the value in the range of 0.01~8atom%, and gallium amount is set to 0.1~
Value in the range of 10atom%.
That is, because in Zinc oxide film, if indium amount turns into the value less than 0.01atom%, existing cannot be suitable wet
The situation of thermal characteristics, on the other hand, if indium amount turns into the value more than 8atom%, electrical characteristic reduction be present.
In addition, if gallium amount turns into the value beyond above range, that electrical characteristic is bad be present.
Therefore, from the point of view of this good point of damp and hot characteristic is made, in Zinc oxide film, surveyed with respect to XPS elementary analysis
Fixed zinc amount, gallium amount, the total amount (100atom%) of oxygen amount and indium amount, are more preferably set to 0.02~7atom% models by indium concentration
Interior value is enclosed, and gallium concentration is set to the value in the range of 0.5~10atom%.
In addition, each element amount for the determination of elemental analysis for passing through above-mentioned XPS, refers in Zinc oxide film on the whole, pass through film
The average value for the amount of element in each depth that the XPS analysis in thick direction are determined.
(3) first area
Such as (a)~(c) in Fig. 1 and as shown in (a) in Fig. 2, it is preferable that the first area 10a of Zinc oxide film 10, be
On zinc amount, gallium amount, oxygen amount and indium amount, there are one of multiple regions of uneven concentration distribution, and from substrate surface furthermost
Formed, in the XPS analysis of film thickness direction, the value of indium amount/gallium amount ([In]/[Ga]) gradually decreases.
Here, for Zinc oxide film 10, the result that the XPS analysis by film thickness direction are determined is for example shown in Figure 1
(a)~(b).
In addition, by the result that [In]/[Ga] is calculated from (a) in Fig. 1~(b) (c) shown in Figure 1.
That is, by Fig. 1, it is recognized that in the first region, towards base material, gallium amount is significantly increased compared to indium amount.
In addition, in first area, indium amount also increases compared with second area.
Turned into by each element of first area and second area and so formed, can obtain as described later good damp and hot
Characteristic.
In addition, in the first region, it is preferable that with respect to the zinc amount, gallium amount, oxygen amount of XPS determination of elemental analysis
And the total amount (100atom%) of indium amount, zinc amount is set to the value in the range of 20~60atom%, gallium amount is set to 0.1~
Value in the range of 10atom%, oxygen amount is set to the value in the range of 22~79.89atom%, and indium amount is set to 0.01~
Value in the range of 8atom%.
That is, if because the indium amount of first area turns into the value less than 0.01atom%, damp and hot characteristic be present significantly reduces
Situation.
On the other hand, if because the indium amount of first area turns into the value more than 8atom%, zinc amount be present and gallium amount is relative
Property reduce, gradation composition disequilibrium and make crystal structure change situation.
Therefore, from the point of view of this good point of damp and hot characteristic is made, in the first region, it is further preferred that with respect to XPS's
The zinc amount of determination of elemental analysis, gallium amount, the total amount (100atom%) of oxygen amount and indium amount, are set to 25~55atom% models by zinc amount
Interior value is enclosed, gallium amount is set to the value in the range of 0.1~5atom%, oxygen amount is set in the range of 33~74.88atom%
It is worth, and indium amount is set to the value in the range of 0.02~7atom%.
Therefore, in the first region, particularly preferably, with respect to the zinc amount of XPS determination of elemental analysis, gallium amount,
The total amount of oxygen amount and indium amount (100atom%), value zinc amount being set in the range of 30~55atom%, gallium amount is set to 1~
Value in the range of 5atom%, value oxygen amount being set in the range of 35~68atom%, and indium amount is set to 1~5atom%
In the range of value.
In addition, each element amount of the first area for the determination of elemental analysis for passing through XPS, though refer to by film thickness direction
In the measure of XPS analysis, the average value of the amount of element for the scope that [In]/[Ga] value gradually decreases, but because first area is
Very thin films, therefore in the case where measured value only has at 1 point, refer to its value.
(4) second area
As shown in (a) in (a)~(c) and Fig. 2 in Fig. 1, the second area 10b of Zinc oxide film 10, is on passing through
Zinc amount, gallium amount, oxygen amount and the indium amount that the XPS analysis of film thickness direction are determined, have uneven concentration distribution multiple regions it
One, it is located at substrate side, relative to the value of the total amount (100atom%), preferably [In]/[Ga] of zinc amount, gallium amount, oxygen amount and indium amount
It is shown as certain value.
Its reason is, because so second area as the ratio of components in film thickness direction by not having significantly change
Region, therefore can obtain good damp and hot characteristic.
In addition, [In]/[Ga] value is shown as certain value, refer to for [In]/[Ga], by by the mark of second area
Coefficient of alteration obtained from quasi- deviations divided by average value turns into less than 50%.
Therefore, in the second area, it is preferable that with respect to the zinc amount, gallium amount, oxygen amount of XPS determination of elemental analysis
And the total amount (100atom%) of indium amount, zinc amount is set to the value in the range of 35~65atom%, gallium amount is set to 0.1~
Value in the range of 10atom%, oxygen amount is set to the value in the range of 17~64.89atom%, and indium amount is set to 0.01~
Value in the range of 8atom%.
That is, if because the indium amount of second area turns into the value less than 0.01atom%, damp and hot characteristic be present significantly reduces
Situation.
On the other hand, if because the indium amount of second area exceedes 8atom% value, with zinc amount and gallium amount relativity being present
Reduce, gradation composition disequilibrium and make crystal structure change situation.
Therefore, from the point of view of this good point of damp and hot characteristic is made, in the second area, it is further preferred that with respect to XPS's
The zinc amount of determination of elemental analysis, gallium amount, the total amount (100atom%) of oxygen amount and indium amount, are set to 40~60atom% models by zinc amount
Interior value is enclosed, gallium amount is set to the value in the range of 0.5~10atom%, oxygen amount is set in the range of 23~59.48atom%
It is worth, and indium amount is set to the value in the range of 0.02~7atom%.
Therefore, in the second area, particularly preferably, with respect to the zinc amount of XPS determination of elemental analysis, gallium amount,
The total amount of oxygen amount and indium amount (100atom%), value zinc amount being set in the range of 30~55atom%, is set to 2.3 by gallium amount
Value in the range of~5atom%, value oxygen amount being set in the range of 36.5~67.2atom%, and indium amount is set to 0.5
Value in the range of~3.5atom%.
In addition, each element amount of the second area for the determination of elemental analysis for passing through XPS, refers to by film thickness direction
In the measure of XPS analysis, [In]/[Ga] value is shown as the average value of the amount of element of the scope of certain value.
(5)[In]/[Ga]
In addition, in first area and second area, preferably [In] of first area/[Ga] value is more than second area
[In]/[Ga] value.
I.e., it is preferable that by from first area towards second area, making gallium amount change with indium amount, so as to as described above, make
[In] of first area/[Ga] value is more than [In]/[Ga] of second area value.
More specifically, it is preferable that from first area towards second area, as described above, make gallium amount be significantly increased and
Indium amount is reduced, or it is any.
More specifically, it is further preferred that [In] of first area/[Ga] value is more than [In]/[Ga] of second area
(σ of average value+3).
Its reason is that, because by making [In]/[Ga] of first area and second area be such numerical difference, can obtain
More good damp and hot characteristic.
(6) thickness
In addition, for the thickness comprising first area and the Zinc oxide film of second area, though and it is not particularly restricted, generally
Preferably below 300nm value.
Its reason is, because if the thickness of Zinc oxide film turns into the value more than 300nm, to exist and carry out through the visible of light
The absolute magnitude of light reduces, and the transparency reduces or the formation of Zinc oxide film is excessively time-consuming, the situation that productivity reduces.
But if the thickness of Zinc oxide film is excessively thinning, such as the value less than 20nm, then exist and include first area
And the significantly reduced situation such as the electrical characteristic of the Zinc oxide film of second area or damp and hot characteristic.
It is therefore preferable that make the thickness of the Zinc oxide film comprising first area and second area in the range of 20~300nm
It is worth, the value in the range of the value more preferably in the range of 25~250nm, more preferably 30~200nm.
And then the thickness in each region for Zinc oxide film, though and not particularly restricted, the film of generally preferable first area
Thickness is below 15nm.
Its reason is, if because the thickness of first area on the contrary in the film formation step of a step, exists more than 15nm
Thickness adjustment becomes difficult or forms the time and increases, or and then ratio resistance situation about uprising.
But if the thickness of first area is excessively thinning, such as the value less than 0.1nm, then exist damp and hot characteristic or
Mechanicalness characteristic significantly reduces, or is difficult to situation about being stably formed.
It is therefore preferable that for the thickness of first area to be set to the value in the range of 0.1~15nm, more preferably it is set to 0.3
Value in the range of~10nm, the value being even more preferably set in the range of 0.5~5nm.
And then for the thickness of second area, it is often preferred that the value in the range of 15~295nm, more preferably 20
Value in the range of value in the range of~245nm, more preferably 25~195nm.
(7) damp and hot characteristic
Additionally, it is preferred that the initial ratio resistance of the Zinc oxide film 10,10 ' illustrated in (a) in fig. 2~(c) is set to ρ0,
Will be under conditions of 60 DEG C, relative humidity 95%, the ratio resistance after taking care of 500 hours is set to ρ500When, will be by ρ500/ρ0It is represented
Ratio be set to less than 1.5 value.
In addition, ratio resistance (the ρ of Zinc oxide film0、ρ500) as illustrating in embodiment 1, sheet resistance can be used
Device is determined to determine.
Here, reference picture 7, illustrates the ratio before and after the composition and environmental test of the Zinc oxide film of transparent conductive laminate
The relation of resistance variations.
That is, the transverse axis of Fig. 7 represents the elapsed time when being taken care of under conditions of 60 DEG C, relative humidity 95%, and the longitudinal axis represents
Using under conditions of 60 DEG C, relative humidity 95% take care of X hours after ratio resistance as ρXCalculated with ρX/ρ0It is represented
Ratio.
Moreover, characteristic curve A~E in Fig. 7 is identical with the sample of the X-ray diffractogram corresponding to Fig. 4.
By these characteristic curves A~E comparison, there is following trend in discovery, in the Zinc oxide film of GZO films, even if adding
Add the indium that comparison is a small amount of, damp and hot characteristic can be also increased sharply, and by making indium addition further increase, damp and hot characteristic further carries
It is high.
Therefore, compared with the GZO films corresponding to characteristic curve E, corresponding to characteristic curve A~D In-GZO films, wet
The changing ratio of ratio resistance under thermal environment for a long time it is relatively low, it can be said that its through when damp and hot excellent.
(8) initial ratio resistance
Additionally, it is preferred that the initial ratio resistance (ρ by the Zinc oxide film 10,10 ' illustrated in (a) in Fig. 2~(c)0) it is set to 1
×10-4~1 × 10-1Value in the range of Ω cm, is more preferably set to 1 × 10-4~1 × 10-2Value in the range of Ω cm.
In addition, the initial ratio resistance (ρ) of Zinc oxide film is as illustrating in embodiment 1, can be by transparent conductivity
The surface resistivity (R) of the thickness (d) of lamilate and measure calculates.
Pass through the indium amount for being included the first area of the Zinc oxide film of transparent conductive laminate and second area
(atom%) value being set in prescribed limit, initial ratio resistance can be made to turn into the value in above-mentioned preferred scope.
2. base material
(1) species
As the base material 12 illustrated in Fig. 1, as long as the transparency is excellent, and it is not particularly limited, glass, ceramics, tree can be enumerated
Membrane of lipoprotein etc..As the material of resin film, polyimides, polyamide, polyamidoimide, polyphenylene oxide can be enumerated
(Polyphenylene ether), polyether-ketone, polyether-ether-ketone, polyolefin, polyester, makrolon, polysulfones, polyether sulfone, polyphenylene sulfide
Ether (Polyphenylene sulfide), polyarylate, acrylic resin, cycloolefin polymer, aromatic series birds of the same feather flock together compound,
Polyurethane polymer etc..
Excellent especially for the flexibility for the transparent conductive laminate for making the present invention, base material is preferably resin film.
It is excellent based on the transparency and have versatility in addition, in these resin films, it is preferably selected from by polyester, polyamides
At least one of group that imines, polyamide, cycloolefin polymer are formed, more preferably polyester or cyclenes hydrocarbon-based polymeric
Thing.
More specifically, as polyester, can enumerate polyethylene terephthalate, polybutylene terephthalate (PBT),
PEN, polyarylate etc..
In addition, as polyamide, fully aromatic polyamide, nylon 6, nylon66 fiber, nylon copolymer etc. can be enumerated.
In addition, as cycloolefin polymer, norbornene polymer, monocyclic cyclic olefin Type of Collective can be enumerated
Thing, cyclic conjugated diene are birdsed of the same feather flock together compound, alicyclic vinyl ring type hydrocarbon polymer and their hydride.Such as Appel can be enumerated
(the ethylene-cycloolefin hydrocarbon copolymer of Mitsui Chemicals, Inc.'s system), Arton (norbornene polymer of JSR company systems), ZEONOR
(norbornene polymer of Nippon Zeon) etc..
(2) thickness
In addition, though the thickness of the base material 12 illustrated in Fig. 2 determines according to application target etc., from flexibility and behaviour
From the point of view of making readily point, the value preferably in 1~1000 μ m, the more preferably value in 5~250 μ ms, further
Value more preferably in 10~200 μ ms.
(3) additive
In addition, in the substrate, in addition to above-mentioned resin component, in the range of not damaging the transparency and waiting, it can include
The various additives such as antioxidant, fire retardant, lubricant.
3. other layers
And then in the transparent conductive laminate of the present invention, as needed, various other layers can be set.
As other such layers, for example, can enumerate gas-barrier layer, priming coat, planarization layer, hard conating, protective layer,
Antistatic layer, stain-proofing layer, antiglare layer, colour filter, adhesive phase, decorative layer, printing layer etc..
Here, priming coat is the layer for improving the cohesive of base material and Zinc oxide film and setting, as material, such as can
Use polyurethane based resin, acrylic resin, silane coupler, epoxylite, polyester resin, ultraviolet hardening tree
The well known materials of fat etc..
In addition, gas-barrier layer is preferably provided between base material and Zinc oxide film, as the material for forming gas-barrier layer,
As long as preventing oxygen and vapor from passing through then and be not particularly limited, but it is preferably that the transparency is good, and barrier properties for gases is good.
More specifically, as constituent material, such as the metals such as aluminium, magnesium, zirconium, titanium, zinc, tin are preferably selected from；Silica,
The inorganic oxides such as aluminum oxide, zinc oxide, zirconium oxide, titanium oxide, indium oxide, tin oxide, zinc-tin oxide；The inorganic nitrogens such as silicon nitride
Compound；Inorganic oxynitrides；Inorganic carbide；Inorganic sulphide；Inorganic oxynitriding carbide；High-molecular compound and they
At least one of complex.
In addition, the gas-barrier layer can include various macromolecule resins, curing agent, age resister, light stabilizer, fire-retardant
Other gradation compositions such as agent.
In addition, as forming the method for gas-barrier layer, and be not particularly limited, such as can enumerate and pass through above-mentioned material
Vapour deposition method, sputtering method, ion plating method, thermal cvd, plasma CVD method etc. and the method that is formed on base material will make above-mentioned
Solution is coated on base material by known coating method obtained from material is dissolved or dispersed in organic solvent, and is moderately dried
The film of gained and formed method, for gained film carry out atmospheric plasma treatment, ion implantation, lamp anneal
Method that the surface of processing etc. is modified and is formed etc..
In addition, the thickness of gas-barrier layer and not particularly restricted, it is often preferred that the value in the μ m of 20nm~50.
Its reason is that, because by the gas-barrier layer as such regulation thickness, can further obtain excellent gas
Body barrier, cohesive, and flexibility can be taken into account and by film-strength.
Therefore it is more preferable to which the thickness of gas-barrier layer is set into the value in the μ m of 30nm~1, further preferably it is set to
Value in the range of 40nm~500nm.
Additionally, it is preferred that the moisture-vapor transmission that gas-barrier layer is determined under 40 DEG C, the atmosphere of relative humidity 90%
It is set to 0.1g/m2/ below day value, is more preferably set to 0.05g/m2/ below day value, more preferably 0.01g/m2/
Below day value.
Its reason is because the value by being set to such moisture-vapor transmission, can prevent Zinc oxide film from deteriorating, and to obtain
The excellent barrier properties for gases of humidity resistance.
In addition, the moisture-vapor transmission as gas-barrier layer, can be determined with known method, such as commercially available water can be used
Vapor transmission rates determine device to determine.
4. transparent conductive laminate
(1) mode
Transparent conductive laminate 50,50 ', 50 " illustrated in (a)~(c) in Fig. 2 is the one side or double in base material 12
Face forms Zinc oxide film 10,10 ' and formed, and Zinc oxide film includes on the film thickness direction from Zinc oxide film towards base material passes through XPS
The determined specific composition of analysis than first area 10a and second area 10b.
In addition, as shown in (c) in Fig. 2, the situation of gas-barrier layer 14 is included between base material 12 and Zinc oxide film 10
Also it is preferable mode.
In addition, in the present invention, on the transparency of Zinc oxide film, in specific thickness, such as any in 20~600nm
In value, preferably make wavelength 550nm light penetration be more than 70% value, more preferably more than 80% value, further
Preferably more than 90% value.
In addition, the transparency on transparent conductive laminate, in specific thickness, such as any in 10 μm~1mm
In value, optimal wavelength 550nm light penetration is more than 50% value, and more preferably more than 60% value is further excellent
Elect more than 70% value as.
(2) ratio resistance
The ratio resistance (ρ) of transparent conductive laminate 50,50 ', 50 " illustrated in (a)~(c) in Fig. 2 in fact with
The ratio resistance of Zinc oxide film 10,10 ' is identical, therefore omits and illustrate again.
(second embodiment)
Second embodiment is a kind of manufacture method of transparent conductive laminate, it is characterised in that it is in base material
Possess at least one side by sputtering method the manufacture method of the transparent conductive laminate of Zinc oxide film that is formed, comprising following
Step (1)~(2).
(1) the step of preparing base material and sintered body
(2) the step of forming Zinc oxide film, the Zinc oxide film is at least one side of base material, by sintered body by splashing
The Zinc oxide film of doped gallium and indium while including zinc oxide that the method for penetrating forms, comprising on the XPS analysis by film thickness direction
Zinc amount, gallium amount, oxygen amount and the indium amount determined, there are multiple regions of uneven concentration distribution, and the plurality of region is from oxygen
Change zinc film surface to the different first area of the value comprising [In]/[Ga] on the thickness direction of base material and second area.
Below, the manufacture method of the transparent conductive laminate of second embodiment is specifically described.
1. step (1)：The step of preparing base material and sintered body
Step (1) is the step of preparation as the sintered body of base material and sputtering target material.
That is, the Zinc oxide film illustrated in (a)~(c) in Fig. 2 further wraps preferably by using zinc oxide as principal component
Film forming is carried out containing the sintered body of gallium oxide and indium oxide.
In addition, in the sintered body for forming Zinc oxide film, it is preferable that relative to the total amount of the sintered body, by zinc oxide
Use level is set to the value in the range of 70~99.98 weight % (being 56~80 weight % as zinc), and the use level of gallium oxide is determined
For the value in the range of 0.01~15 weight % (being 0.007~11.2 weight % as gallium), and the use level of indium oxide is set to
Value in the range of 0.01~15 weight % (being 0.008~12.4 weight % as indium).
Its reason is, because being sintered by using the ternary system for the zinc oxide-gallium oxide-indium oxide for having regulated and controled use level
Body, comprising first area and second area, the Zinc oxide film of damp and hot excellent expeditiously film forming can be made, can finally make life
Efficiency is produced to improve.
More specifically, be because relative to sintered body total amount, indium oxide use level less than 0.01 weight %'s
In the case of, the amount that the indium that the Zinc oxide film after film forming is included be present substantially reduces, and can not be sufficiently formed first area, cannot
The situation of damp and hot characteristic.
On the other hand, be because indium oxide amount more than 15 weight % in the case of, though exist formed first area and
Second area, but the amount relativity of the indium included by the Zinc oxide film after film forming increase, therefore ratio resistance turns into very
The situation of big value.
Therefore it is more preferable to ground, relative to the total amount of sintered body, is set to 76~99.4 weight % by the use level of zinc oxide
Value in the range of (being 61~80 weight % as zinc), the use level of gallium oxide is set into 0.5~12 weight % (is as gallium
0.37~8.9 weight %) in the range of value, and using the use level of indium oxide be set to 0.1~12 weight % (as indium be 0.08~
9.9 weight %) in the range of value.
In addition, it is further preferred that relative to sintered body total amount, the use level of zinc oxide is set to 80~98.7 weights
The value in the range of % (being 64~79 weight % as zinc) is measured, the use level of gallium oxide is set into 1~10 weight % (is as gallium
0.74~7.4 weight %) in the range of value, and using the use level of indium oxide be set to 0.3~10 weight % (as indium be 0.25~
8.3 weight %) in the range of value.
And then it is further preferred that relative to sintered body total amount, the use level of zinc oxide is set to 80~94.3 weights
The value in the range of % (being 64~79 weight % as zinc) is measured, the use level of gallium oxide is set to 5.4~10 weight % (as gallium
For 4.1~7.4 weight %) in the range of value, and using the use level of indium oxide be set to 0.3~10 weight % (as indium be 0.25
~8.3 weight %) in the range of value.
In addition, the details on base material, as described in the above description, therefore is omitted.
2. step (2)：The forming method of Zinc oxide film
Step (2) is the step of forming Zinc oxide film.
I.e., it is characterised in that as the method for forming Zinc oxide film, physics facture can be enumerated and with chemical vapor deposition
Method is the chemical facture of representative, among those, from can from the aspect of easy and efficiency forms transparent conductor layer well,
Use sputtering method.
Its reason is, because by sputtering method, even if only 1 step, to be combined into by adjusting matching somebody with somebody for target, can efficiency
The Zinc oxide film formed comprising the different first area of composition and second area is formed well.
Here, as more specifically sputtering method, DC sputtering methods, DC magnetron sputtering methods, RF sputtering methods, RF magnetic controls can be enumerated and splashed
Penetrate the overlapping sputtering method of method, DC+RF, the overlapping magnetron sputtering methods of DC+RF, facing targets sputtering method, ECR sputtering methods, double magnetron sputtering methods
Deng.
In addition, as sputtering condition, though and be not particularly limited, be used as back pressure, preferably 1 × 10-2Below Pa value,
More preferably 1 × 10-3Below Pa value.
In addition, when selection is by forming method in argon gas import system, pressure turns into 0.1~5Pa scopes in optimum decision system
Interior value, the value more preferably in the range of 0.2~1Pa.
And then when implementing sputtering method, on the gaseous species in import system, use argon (Ar) or argon (Ar) and oxygen
(O2) mixed gas, though this on production cost preferably, can also use Ar beyond rare gas, nitrogen (N2) etc..Make
In the case of with mixed gas, preferably by the mixing ratio (O2/(Ar+O2)) it is set to the value in the range of 0.01~20, be more preferably
Value in the range of 0.1~10.
Its reason is that, because if the mixing ratio of argon and oxygen is above range, can easily regulate and control formed zinc oxide
The composition of film, thus can film forming be that ratio resistance is low and humidity resistance is excellent, and then the conductive layer that reflectivity is low.
Additionally, it is preferred that for the temperature of base material when forming Zinc oxide film is being set in the range of 10~150 DEG C on base material
Value.
Its reason is, if because the temperature of base material is the value in the range of 10~150 DEG C, as base material, even in use
It in the case of resin film, will not also change base material, can easily regulate and control the composition of formed Zinc oxide film, Neng Goushi
Locality forms Zinc oxide film.
(the 3rd embodiment)
3rd embodiment is a kind of electronic installation, it is characterised in that uses above-mentioned any transparent conductive laminate
Formed in transparency electrode.
More specifically, carrying can be enumerated and possess the liquid crystal that the transparency electrode of defined transparent conductive laminate forms
Show device, organic el display, inorganic EL display, Electronic Paper, solar cell, organic transistor, organic EL illuminating, inorganic EL
Illumination, thermoelectric conversion device, gas sensor etc..
That is, electronic installation of the invention is therefore transparent due to possessing the transparent conductive laminate described in first embodiment
The excellent, ratio resistance of property is very small, and can play the electric conductivity for the rising that can suppress ratio resistance for a long time.
Embodiment
Below, by embodiment, further the present invention is described in detail.But the following description is exemplary earth's surface
Show the present invention, the present invention is not restricted to these records.
(embodiment 1)
1. the manufacture of transparent conductive laminate
(1) step 1：The step of preparing base material and sintered body
As base material, prepare alkali-free glass (Corning Incorporated's system, EagleXG, thickness：700μm).
In addition, prepare the ternary system sintered body (ZnO of zinc oxide-gallium oxide-indium oxide：Ga2O3：In2O3=94.0 weights
Measure %：5.7 weight %：0.3 weight %).
(2) step 2：The forming step of Zinc oxide film
Then, for alkali-free glass, by DC magnetron sputtering methods, using above-mentioned ternary system sintered body, in following sputterings
Under the conditions of, with 1 substantial step, form the Zinc oxide film (thickness for possessing first area and second area：100nm), obtain
To transparent conductive laminate.
Base material temperature：20℃；
DC is exported：500W；
Carrier gas：Argon (Ar)；
Film pressure：0.6Pa；
Film formation time：35sec.
2. the evaluation of transparent conductive laminate
To determining and evaluating below the transparent conductive laminate progress of gained.
(1) XPS analysis of film thickness direction
While determining device using following XPS, under following condition determinations, the transparent conductivity layer of gained is carried out
The elementary analysis of fit zinc on the film thickness direction of Zinc oxide film, gallium, indium, oxygen and silicon.By the member based on XPS measure of gained
Plain spirogram is shown in Fig. 8.
(XPS determines device)
Model name：PHI Quantera SXM (ULVAC-PHI company systems)；
X-ray source：AlKα(1486.6eV)；
X-ray beam diameter：100μm.
(condition determination)
Power value：25W；
Voltage：15kV；
Take out angle：45 degree；
Vacuum：5.0×10-8Pa；
Pass Energy：112eV；
Time Per Step：20msec；
eV step：0.1eV.
(sputtering condition)
Sputter gas：Argon；
Apply voltage：-4kV；
Sputtering time：5min；
Interval time：0.2min.
(measure element peak value)
O：O1s；
In：In3d5/2；
Zn：Zn2p3/2；
Ga：Ga2p3/2。
In addition, according to the element spirogram, whether can confirm in Zinc oxide film formed with comprising possessing composition requirement respectively
The first area of ratio and multiple regions of second area.
That is, confirm with composition requirement than first~second area whole, from Zinc oxide film towards the thickness of base material
On direction, will confirm that the situation of the first area of [In]/[Ga] value reduction is designated as zero evaluation, by it is unconfirmed to [In]/
The situation of the first area of the value reduction of [Ga] is designated as × evaluated.The result of gained is shown in table 1.
(2) X-ray diffraction measure
It is right using X-ray diffraction device ((strain) system of science, full-automatic horizontal Multi-functional X ray diffractometer Smart Lab)
The crystal structure of the Zinc oxide film of resulting transparent conductive laminate is given by In Plane methods and Out of plane methods
To confirm.Resulting result is shown in Fig. 4 and Fig. 5 characteristic curve A.
(3) thickness (d) of Zinc oxide film
The transparent conductivity of gained is determined using spectroscopic ellipsometers M-2000U (J.A.WoollamJapan company systems)
The thickness (d) of the Zinc oxide film of lamilate.
(4)ρ500/ρ0Calculate
To the initial surface resistivity (R of the Zinc oxide film of the transparent conductive laminate of gained0), using being used as surface
The LORESTA-GP MCP-T600 (Mitsubishi Chemical's (strain) system) of the resistance measurement device and PROBE TYPE ASP as probe
(Mitsubishi Chemical Analytic (strain) systems), is determined under 23 DEG C of temperature, 50%RH environmental condition.
And then the transparent conductive laminate of gained is placed 500 hours under 60 DEG C, 95%RH environment, after taking-up
23 DEG C, carry out temperature adjustment/damping in 1 day under 50%RH environment, determine the surface resistivity (R after damp heat test500)。
Then, from the surface resistivity (R of gained0And R500) and thickness (d) by following formula (1) and (2), calculate initial ratio
Resistance (ρ0) and damp heat test after ratio resistance (ρ500), obtain ρ500/ρ0Ratio.The result of gained is shown in table 1.
In addition, Fig. 7 represents the damp heat test elapsed time of the grade of embodiment 1, the ratio with the ratio resistance before and after damp heat test
(ρX/ρ0) relation.
R0=ρ0/d (1)；
R500=ρ500/d (2)。
(embodiment 2)
In example 2, except the weight ratio for the ternary system sintered body of sputtering is changed into ZnO：Ga2O3：In2O3
=93.3：5.7：Outside 1.0, other manufacture, evaluate transparent conductive laminate similarly to Example 1.By the result of gained
While being shown in table 1, the amount of element based on XPS measure of gained is illustrated in Fig. 1, the X-ray diffraction peak of gained is shown in Fig. 4
And Fig. 5 characteristic curve B.
(embodiment 3)
In embodiment 3, except the weight ratio for the ternary system sintered body of sputtering is changed into ZnO：Ga2O3：In2O3
=89.3：5.7：Outside 5.0, other manufacture, evaluate transparent conductive laminate similarly to Example 1.By the result of gained
While being shown in table 1, Fig. 9 will be illustrated in based on the amount of element that XPS is determined, X-ray diffraction peak is shown in Fig. 4 and Fig. 5 characteristic
Curve C.
And then for the transparent conductive laminate of gained, with following condition determinations, carry out being based on SIMS (Secondary
Ion Mass Spectrometry) determination of elemental analysis, the elementary analysis of gained is illustrated in Fig. 3.
Determine device：ADEPT1010 (Physical electronics, inc.s system)；
Primary ions：O2+；
Primary ions energy：0.75keV；
Scanning area：500μm×700μm；
Detection zone：9%；
Secondary ion polarity：Positive；
Depth conversion：Crater Depth.
(embodiment 4)
In example 4, except the weight ratio for the ternary system sintered body of sputtering is changed into ZnO：Ga2O3：In2O3
=84.3：5.7：Outside 10.0, other manufacture, evaluate transparent conductive laminate similarly to Example 1.By the result of gained
While being shown in table 1, the amount of element based on XPS measure of gained is illustrated in Figure 10, the X-ray diffraction peak of gained is shown in figure
4 and Fig. 5 characteristic curve D.
(comparative example 1)
In comparative example 1, as the sintered body for sputtering, except being changed to ZnO using weight ratio：Ga2O3=94.3：
Outside 5.7 sintered body, other manufacture, evaluate transparent conductive laminate similarly to Example 1.The result of gained is shown in
While table 1, amount of element of the gained based on XPS measure is illustrated in Figure 11, by the X-ray diffraction peak of gained be shown in Fig. 4 and
Fig. 5 characteristic curve E.
According to table 1, can confirm the Zinc oxide film of the transparent conductive laminate of gained in embodiment has specific crystallization
Construction, and comprising the different first area of the ratio of components based on XPS analysis and second area, and each region possesses specific structure,
So as to efficiently obtain the extremely excellent transparent conductive laminate of damp and hot characteristic.
On the other hand, the transparent conductive laminate for including the GZO films not containing indium of comparative example 1, not comprising defined
First~second area, and the ratio resistance after environmental test significantly increases.
Industrial applicibility
More than, as described in detail, according to the transparent conductive laminate of the present invention, it is that have at least one side of base material
The transparent conductive laminate of the standby Zinc oxide film formed by sputtering method, while Zinc oxide film is by comprising zinc oxide, doping
The Zinc oxide film that gallium and indium form is formed,
Moreover, the Zinc oxide film includes, on determined by the XPS analysis of film thickness direction zinc amount, gallium amount, oxygen amount and
Indium amount, there are multiple regions (first area and second area) of uneven concentration distribution.
That is, by the structure, excellent damp and hot characteristic is efficiently obtained while relatively low initial resistance is kept.
Moreover, manufacturing method according to the invention, the sputtering methods of 2 steps it is of course possible to, even if being the sputtering method of 1 step,
Only adjust and be combined into matching somebody with somebody for sputtering target material, determined by XPS, can easily and stably manufacture to include has different compositions
Than and the different first area such as damp and hot characteristic (the relative region for including a large amount of indiums) and second area (indium compares less area
Domain) Zinc oxide film.
Thus, transparent conductive laminate of the invention is needing to provide the electric product, electronic component, figure of damp and hot characteristic
As display device (organic electroluminescence device, inorganic electroluminescence device, liquid crystal display, Electronic Paper etc.) solar cell
Deng various uses in, be expected to effectively serve as transparency electrode etc..
Description of reference numerals
10、10’：Zinc oxide film；
10a：First area, 10b：Second area；
12：Base material；
14：Gas-barrier layer；
20：GZO films；
50、50’、50”：Transparent conductive laminate.
Claims (8)
1. a kind of transparent conductive laminate, it is characterised in that be to possess at least one side of base material by sputtering method and shape
Into Zinc oxide film transparent conductive laminate,
The Zinc oxide film includes zinc oxide, while doped gallium and indium,
In the Zinc oxide film, on the zinc amount, gallium amount, oxygen determined by the XPS analysis of the film thickness direction towards the base material
Amount and indium amount, by indium amount and when being expressed as [In] and [Ga] of gallium amount, as uneven concentration distribution, include [In]/[Ga]
The different first area of value and second area,
[In] of the first area/[Ga] value is set to the value of [In]/[Ga] more than the second area,
In the first area, [In]/[Ga] value internally gradually decreases from surface, meanwhile, in secondth area
In domain, [In]/[Ga] value is shown as certain value,
The thickness of the Zinc oxide film formed comprising the first area and the second area is set to 20~300nm model
Interior value is enclosed, meanwhile, the value thickness of the first area being set in the range of 0.1~15nm,
In the first area, set by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
For 100atom% when, indium amount is set to the value in the range of 0.11~5atom%,
In the second area, it is set to by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
During 100atom%, indium amount is set to the value in the range of 0.01~3.5atom%,
Further, the initial ratio resistance of the Zinc oxide film is set to 1.1 × 10-3~1 × 10-1Value in the range of Ω cm.
2. transparent conductive laminate according to claim 1, it is characterised in that
In the Zinc oxide film, set by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
For 100atom% when, the value that gallium amount is set in the range of 0.1~10atom%.
3. transparent conductive laminate according to claim 1, it is characterised in that
In the first area, set by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
For 100atom% when, zinc amount is set to the value in the range of 20~60atom%, gallium amount is set in the range of 0.1~10atom%
Value, value oxygen amount being set in the range of 22~79.89atom%.
4. transparent conductive laminate according to claim 1, it is characterised in that
In the second area, set by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
For 100atom% when, zinc amount is set to the value in the range of 35~65atom%, gallium amount is set in the range of 0.1~10atom%
Value, value oxygen amount being set in the range of 17~64.89atom%.
5. transparent conductive laminate according to claim 1, it is characterised in that
The initial ratio resistance of the Zinc oxide film is being set to ρ0, will be under conditions of 60 DEG C, relative humidity 95%, keeping 500 is small
When after ratio resistance be set to ρ1When, by ρ1Ratio represented by/ρ 0 is set to less than 1.5 value.
6. a kind of electronic installation, it is characterised in that transparent conductive laminate as claimed in claim 1 is used in transparent electricity
Pole forms.
7. a kind of manufacture method of transparent conductive laminate, it is characterised in that it is formed just at least one side of base material
Beginning ratio resistance is 1.1 × 10-3~1 × 10-1The transparent conductive laminate that the Zinc oxide film of value in the range of Ω cm forms
Manufacture method, include following step (1)~(2)；
The step of (1) preparing the base material and sintered body respectively,
(2) the step of forming the Zinc oxide film, the Zinc oxide film is at least one side of the base material, by the sintering
The Zinc oxide film of doped gallium and indium while including zinc oxide that body is formed by sputtering method, in the Zinc oxide film, on logical
The zinc amount determined towards the XPS analysis of the film thickness direction of the base material, gallium amount, oxygen amount and indium amount are crossed, by indium amount and gallium amount
When being expressed as [In] and [Ga], as uneven concentration distribution, the different first area and second of the value comprising [In]/[Ga]
Region,
[In] of the first area/[Ga] value is set to the value of [In]/[Ga] more than the second area,
In the first area, [In]/[Ga] value internally gradually decreases from surface, meanwhile, in secondth area
In domain, [In]/[Ga] value is shown as certain value,
The thickness of the Zinc oxide film formed comprising the first area and the second area is set to 20~300nm model
Interior value is enclosed, meanwhile, the value thickness of the first area being set in the range of 0.1~15nm,
In the first area, set by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
For 100atom% when, indium amount is set to the value in the range of 0.11~5atom%,
In the second area, it is set to by the total amount by the zinc amount of XPS determination of elemental analysis, gallium amount, oxygen amount and indium amount
During 100atom%, the value that indium amount is set in the range of 0.01~3.5atom%.
8. the manufacture method of transparent conductive laminate according to claim 7, it is characterised in that on the substrate,
The value temperature of base material when forming the Zinc oxide film being set in the range of 10~150 DEG C.
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| CN106200107B (en) * | 2016-09-30 | 2020-06-02 | 京东方科技集团股份有限公司 | Display substrate, display panel and display device |
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Also Published As
| Publication number | Publication date |
|---|---|
| WO2015118724A1 (en) | 2015-08-13 |
| TWI659435B (en) | 2019-05-11 |
| TW201532078A (en) | 2015-08-16 |
| WO2015119238A1 (en) | 2015-08-13 |
| TW201603053A (en) | 2016-01-16 |
| JPWO2015119238A1 (en) | 2017-03-30 |
| CN105814647A (en) | 2016-07-27 |
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