CN105684099A - Laminate, method for manufacturing same, and electronic device - Google Patents
Laminate, method for manufacturing same, and electronic device Download PDFInfo
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- CN105684099A CN105684099A CN201580002351.9A CN201580002351A CN105684099A CN 105684099 A CN105684099 A CN 105684099A CN 201580002351 A CN201580002351 A CN 201580002351A CN 105684099 A CN105684099 A CN 105684099A
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- metal
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- duplexer
- compound layer
- metal compound
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- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 288
- 239000002184 metal Substances 0.000 claims abstract description 288
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 201
- 239000000463 material Substances 0.000 claims abstract description 75
- 239000004065 semiconductor Substances 0.000 claims abstract description 60
- 239000000758 substrate Substances 0.000 claims abstract description 43
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 32
- 239000000956 alloy Substances 0.000 claims abstract description 32
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 32
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 150000002739 metals Chemical class 0.000 claims abstract description 11
- 239000010410 layer Substances 0.000 claims description 326
- 238000002310 reflectometry Methods 0.000 claims description 184
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 144
- 239000010949 copper Substances 0.000 claims description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 101
- 150000001875 compounds Chemical class 0.000 claims description 56
- 230000003287 optical effect Effects 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 50
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 34
- 230000008033 biological extinction Effects 0.000 claims description 31
- 229910052802 copper Inorganic materials 0.000 claims description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- 230000000007 visual effect Effects 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 229910052709 silver Inorganic materials 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000838 Al alloy Inorganic materials 0.000 claims description 6
- 229910001182 Mo alloy Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 2
- 230000004313 glare Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 154
- 239000011787 zinc oxide Substances 0.000 description 69
- 238000005530 etching Methods 0.000 description 57
- 238000004544 sputter deposition Methods 0.000 description 38
- 238000012360 testing method Methods 0.000 description 35
- 239000011521 glass Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 21
- 239000003153 chemical reaction reagent Substances 0.000 description 20
- 230000008676 import Effects 0.000 description 19
- 238000010521 absorption reaction Methods 0.000 description 18
- 230000009467 reduction Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 11
- 229910044991 metal oxide Inorganic materials 0.000 description 11
- 150000004706 metal oxides Chemical class 0.000 description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910003399 ZnO-Cu Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 229910000765 intermetallic Inorganic materials 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 150000004767 nitrides Chemical class 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QWARLPGIFZKIQW-UHFFFAOYSA-N hydrogen peroxide;nitric acid Chemical compound OO.O[N+]([O-])=O QWARLPGIFZKIQW-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 208000003351 Melanosis Diseases 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 230000003321 amplification Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000003199 nucleic acid amplification method Methods 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 5
- 229910007565 Zn—Cu Inorganic materials 0.000 description 4
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 230000007261 regionalization Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 229910002668 Pd-Cu Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/02—Physical, chemical or physicochemical properties
- B32B7/025—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Landscapes
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Electroluminescent Light Sources (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Provided are a laminate in which glare (reflectance) due to the inherent gloss of metals is reduced, a method for manufacturing the laminate, and an electronic device. A laminate (1) comprising a transparent substrate, a metal layer (20) formed on the substrate, and a metal compound layer (30a, 30b) formed on at least one surface of the metal layer (20) so as to be in contact with the surface. The metal layer (20) has a specific resistance of 10 mu omega*cm or less, and is provided with at least one layer of a metal having a specific resistance of 1.0-10 mu omega*cm or an alloy having this metal as a main component. The metal compound layer (30a, 30b) comprises a mixture of a transparent oxide semiconductor material and at least one metal having a free energy of oxide formation equivalent to or greater than that of zinc (Zn).
Description
Technical field
The present invention relates to metal electrode for electronics and optical device etc. and comprise the duplexer of metal and conductive metal compound, its manufacture method and electronics.
Background technology
For the electrode (comprising the supporting electrode improving electroconductibility) of the various electronicss for employing liquid crystal, organic EL etc., in recent years, particularly it is arranged on the maximization as the touch sensing device etc. of input-output unit before display element etc. to carry out. Among detecting electrode contained in touch sensing device (panel), distribution electrode, connection electrode, particularly for detecting electrode, if touch sensing device maximizes, then resistance components increases, the electrode therefore more and more needing resistance lower.
In the past, the electrode of contact panel guaranteed the visuality of display with the use of the conductive metal oxide that the transparencies such as the oxide semiconductor using In, Zn, Sn, Ti etc. as main component are high. But, there is the limit in the conductive metal oxide that transparency is high, it is difficult to reach the low resistance of level required in recent years in reduction resistance value. Therefore, material as an alternative, it is desired to guarantee the practical of visual low resistive metal by fine pattern.
Further, contact panel etc. is had in the former configuration of display element for the electronics of electroded substrate, do not hinder the visuality of display to become prerequisite, therefore, for electrode, it is desired to cover, scattering, stray light, reflection etc. to be lacked as much as possible.
But, by means of only being replaced into, metal can produce to dazzle (ギ ラ Star キ) because of the distinctive high-reflectivity of metal to the existing electrode being made up of conductive metal oxide, it is thus desirable to make reflectance reduction. In addition, by resistance low as far as possible and the electrical conductor that can be electrically connected to form this point very important.
For the metal that reflectivity is low, have molybdenum (Mo), chromium (Cr), titanium (Ti), tantalum (Ta), tungsten (W) or its alloy, but these metals belong to the high classification of resistance value. On the other hand, the resistance value of silver (Ag), aluminium (Al), copper (Cu) etc. or its alloy is low, but reflectivity height.
Although proposing the method utilizing stacking resistance value height on the characteristic of these metals is low in resistance value and reflectivity is high metal and the low metal of reflectivity, but for reducing reflectivity by laminated metal, there is the limit.
In addition, even if can reduce reflectivity to a certain extent by laminated metal, but the etch-rate of each metal is different separately, therefore, particularly in Wet-type etching operation, it is difficult to each layer carries out microfabrication in the lump.In addition, can implement well if being adjusted to Wet-type etching operation, then be difficult on the contrary fully reduce reflectivity.
Therefore, as the method reducing reflectivity, it is proposed that: on metal level, form dielectric substance or metal oxide, metal nitride, metal oxynitrides, metal carbide layer, make 2 layers or 3 layers of method formed; Semi-permeable for the metal of antiradar reflectivity film is configured on metal level, then, forms the method (such as patent documentation 1～7) of dielectric substance or metal oxide, metal nitride, metal oxynitrides, metal carbide layer.
Namely, in patent documentation 1, disclose a kind of transparent and electrically conductive film, the duplexer that its blackening layer being made up of with oxygen nitrogenize copper for being formed on base material becomes as plasma display anti electromagnetic wave film functional membrane, this transparent and electrically conductive film can not make the visual reduction of the indicating meter of configuration under contact panel because of the metalluster reflected light in distribution portion.
In patent documentation 2, disclosing a kind of film shape contact panel sensor, it, by forming the cupric oxide tunicle of black in the visible side of the striped being arranged on film or latticed copper wiring, thus suppresses the reflection from distribution.
In patent documentation 3, disclose a kind of low-resistance contact panel sensor, its sensor electrode being made up of metallic substance by being formed on insulating substrate and the absorption layer having closely sealed layer concurrently being made up of inorganic oxide material formed on sensor electrode, thus can carry out high meticulous etching.
In patent documentation 4, disclose: more than one absorption layers as blackening layer formed in the group that stacking is made up of the carbide being selected from dielectricity material, metal, the alloy of metal, the oxide compound of metal, the nitride of metal, the oxynitride of metal and metal on the transparent substrate and comprise more than one the conductive layer being selected from Ni, Mo, Ti, Cr, Al, Cu, Fe, Co, V, Au and Ag, hence improve conductive layer visuality and to the reflection characteristic of exterior light.
In addition, in patent documentation 5, disclose the blackening layer arranging in the transparent resin substrate side of the conductor layer being made up of copper coating and being made up of copper and mickel and oxygen; Patent Document 6 discloses by possess successively blackening layer, metal level, base material, blackening layer, metal level and utilize nitrogenize copper to form blackening layer, thereby inhibiting the visual reduction of the indicating meter caused because of metalluster reflected light; Patent Document 7 discloses metal level uses Ni-Zn film, conductive layer to use Cu film.
So, in patent documentation 1～7, as the material forming absorption layer, disclose high refractive index transparent film, nesa coating, functional transparent layer, metal oxide, metal nitride, metal oxynitrides, dielectric substance material etc.
According to the method for patent documentation 1～7 grade, it is possible to absorb, by blackening layer or absorption layer, the reflection caused by metal, and by stacking multilayer repeatedly, it is possible to reduce reflectivity further.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2013-169712 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2013-206315 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2013-149196 publication
Patent documentation 4: Japanese Unexamined Patent Application Publication 2013-540331 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2008-311565 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2013-129183 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2007-308761 publication
Summary of the invention
Invent problem to be solved
But, the specific refractory power (n) of the material used in the absorption layer of patent documentation 1～7 or blackening layer in viewing area is about 1.4～2.5, optical extinction coefficient (k) is 0.01～0.25, therefore, absorption layer or blackening layer are absorb few transparent film or layer.
Therefore, for the object of the reflectivity reducing viewing area, even if the absorption layer of patent documentation 1～7 or blackening layer being laminated in the surface of metal level, also can produce reflectivity very big or minimum of viewing area because of the dry of light and produce interference color, and the effect of the reflectance reduction of expected degree can not be obtained.
In addition, in patent documentation 1～7, in order to by the stacking repeatedly of each layer, the difference of the etch-rate of each layer increases, selection material is produced restriction.
The absorption layer of patent documentation 1～7 or blackening layer are metal compound film, therefore following phenomenon is produced: in patterning operation, can not etch together with metal level, need the etching reagent different from metal level, or, namely allowing to etch, the etch-rate of metal level and metal compound layer is also inconsistent, the film of the one party in stacking formation turned into etching or owed etching, and the formation of fine pattern can not as imagined.
In addition, as absorption layer or blackening layer, when using the metallic compound except the nesa coating as transparent oxide semiconductor material, presence or absence according to absorption layer or the electroconductibility of blackening layer or value, sometimes need with the connection of other connection electrode in increase operation or need change film form, when being used as electrode, produce restriction.
The present invention completes in view of above-mentioned problem, it is an object of the invention to provide a kind of duplexer, its manufacture method and electronics, and described duplexer reduces and dazzles (reflectivity) because of what the distinctive gloss of metal caused.
Other object of the present invention is to provide a kind of duplexer, its manufacture method and electronics, described duplexer is formed, is reduced to as far as possible gently by the reflectivity of the metal in viewing area the reflectivity of (Off ラ ッ ト) and formed the tone of visual melanism with less layer, even if Wet-type etching also can be utilized together to form fine pattern and possess the optimal absorption layer with the electroconductibility corresponding with low-resistance metal level when being laminated for stratiform.
For the means dealt with problems
Above-mentioned problem is solved by the duplexer of the present invention, described duplexer is by transparent substrate, the metal level formed on the substrate, formed with the metal compound layer formed in the way of contacting with this face at least one face of this metal level, above-mentioned metal level possesses the layer that at least one layer resistivity is the metal of 1.0 μ Ω cm～10 μ Ω cm, or using this metal as the layer of the alloy of main component, the resistivity of above-mentioned metal level is 10 μ below Ω cm, above-mentioned metal compound layer is by transparent oxide semiconductor material, form with the mixture with the metal that equal above oxide compound generates free energy with zinc (Zn) more than at least one.
So form, therefore, the transparent oxide semiconductor material with electroconductibility can be combined arbitrarily and there is the equal above oxide compound with zinc (Zn) and generate the metal of free energy, it is possible to freely control electrical characteristic (electroconductibility), optical characteristics (specific refractory power and optical extinction coefficient), etch the value that characteristic (solvability in etching reagent, etch-rate) reaches expectation.
Therefore, can be formed by less layer and realize following described conductive laminate: connect easily to the electric distribution of other metal wiring, good electroconductibility can be guaranteed, from the metallic surface reflectivity of visible side and carry out melanism by reduction simultaneously, that can suppress to produce because of metal level dazzles, it is possible to form arbitrary fine pattern together by Wet-type etching.
The duplexer of the present invention is when for the electrode materials of electronics, response speed can improve, and by based on the improvement of the visuality of microfabrication and reflectance reduction, based on etching in the lump, the patterning that carries out is formed, the layer of bottom line is formed, raising and the cost that thus can realize productivity reduce.
In addition, metal compound layer is made up of transparent oxide semiconductor material and the mixture with the metal that equal above oxide compound generates free energy with zinc (Zn), therefore, on the basis guaranteeing electroconductibility, can realizing the optimization of optical constant (specific refractory power, optical extinction coefficient and absorption), the design of duplexer becomes easy. In addition, it is possible to obtain possessing the duplexer of the light absorbing zone with good electroconductibility.
In addition, compared with situation about being only made up of compounds such as metal oxide, metal nitride, metal oxynitrides, metallic carbide, big layer is absorbed owing to becoming, therefore, can the reflectivity of much slower layer on surface of metal, even if when forming for 2 layers that are set to only be made up of metal level and layer of metal compound layer, dazzling of duplexer also reduces, when the duplexer of the present invention being used for indicating meter etc., visual improve.
Owing to visuality improves, therefore the duplexer of the present invention can be suitable for various display element or contact panel etc., need the indicating meter etc. of equipment attractive in appearance in appearance, it is possible to as the electrode of display equipment with, luminous element, contact panel, used for solar batteries, other electronics etc.
In addition, above-mentioned metal level possess at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, the resistivity of above-mentioned metal level is 10 μ below Ω cm, due to the metal using resistance low in the metal layer, therefore, when forming Wiring pattern by metal level and metal compound layer, it is possible to make Wiring pattern thinner, therefore, the contact panel etc. being namely used in display surface also can remain visual.
Metal level and metal compound layer or metal compound layer and metal level and metal compound layer can be carried out pattern formation together by the duplexer of the present invention in wet etch process, it is also possible to form the fine pattern of 4 μm. Therefore, good function can be played as the main electrodes of contact panel, display element, luminous element, photo-electric conversion element etc., supporting electrode and the connection electrode with terminal.
Having the metal that equal above oxide compound generates free energy with zinc (Zn) is to guarantee electroconductibility and not oxidizable metal. Therefore, be there is the metal of the oxide compound generation free energy equal above with zinc (Zn) by mixing in metal compound layer, and can effectively utilize that not oxidizable metal has, absorb big such character.
In addition, being not only metal level, metal compound layer is also electroconductibility, accordingly, it may be possible to easily be electrically connected with other distribution, it is possible to form Wiring pattern by the metal level of the present invention and metal compound layer, as distribution.
Now, the layer that above-mentioned metal level can be the above-mentioned alloy of above-mentioned at least one layer becomes with dissimilar metal layer stackup, and this dissimilar metal layer is made up of the metal different from the above-mentioned metal species of the main component of the layer as above-mentioned alloy.
Due to formation like this, therefore the adjustment of the characteristic such as the optical constant of duplexer, etch-rate becomes easy.
Now, above-mentioned metal level can be single layer and two layers be selected from the group being made up of molybdenum (Mo) layer, Mo alloy, aluminium (Al) layer, aluminium alloy layer or three layer stackup by forming by the alloy of copper (Cu), aluminium (Al), silver (Ag) or these metals and become.
Due to formation like this, therefore, it is possible to make metal level be low resistance, when forming Wiring pattern by metal level and metal compound layer, it is possible to make Wiring pattern relatively thin, the contact panel etc. being therefore namely used in display surface also can remain visual.
Now, the specific refractory power (n) of above-mentioned metal compound layer in viewing area (400～700nm) can be 2.0～2.8, optical extinction coefficient (k) can be 0.6～1.6.
Due to formation like this, therefore, reflection is inhibited, it is possible to forming can not rubescent, the duplexer of furvous that turns to be yellow, turn blue etc.
Now, the layer that above-mentioned metal compound layer can be made up of the mixture of one or both transparent oxide semiconductor materials and the metal with the oxide compound generation free energy above on an equal basis with zinc (Zn) is formed, and above-mentioned transparent oxide semiconductor material can be Indium sesquioxide (In2O3), zinc oxide (ZnO) or stannic oxide (SnO2) or with Indium sesquioxide (In2O3), zinc oxide (ZnO) or stannic oxide (SnO2) as main component and containing additive.
Due to formation like this, therefore, it is possible to the difference forming the average reflectance in viewing area and maximum reflectivity and minimum reflectance little, can not rubescent, the duplexer of furvous that turns to be yellow, turn blue etc.
In addition, metal compound layer uses two kinds of transparent oxide semiconductor materials, by changing the ratio of two kinds of transparent oxide semiconductor materials, it is possible to select the optical constant of duplexer, etch-rate etc. in a wide range.
Now, any one the above metal in the group that the above-mentioned metal with the equal above oxide compound generation free energy with zinc (Zn) comprises zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), plumbous (Pb), molybdenum alloy for being selected from.
So, owing to electroconductibility can being guaranteed in metal compound layer and adds these not oxidizable metals, accordingly, it may be possible to increase the absorption of metal compound layer, it is possible to reduce the reflectivity of duplexer.
Now, above-mentioned metal compound layer can be that above-mentioned transparent oxide semiconductor material and the metal with the equal above oxide compound generation free energy with zinc (Zn) mix with the volume ratio of 8:2～5:5.
Due to formation like this, therefore, on the basis that ensure that electroconductibility, the optimization of optical constant (specific refractory power, optical extinction coefficient and absorption) can also be realized, it is possible to form the difference of the average reflectance in viewing area and maximum reflectivity and minimum reflectance little, can not rubescent, the duplexer of furvous that turns to be yellow, turn blue etc.
Now, above-mentioned metal compound layer is containing more than one in the group being made up of oxygen (O), nitrogen (N), carbon (C), and the thickness of above-mentioned metal compound layer can be the scope of 30nm～60nm.
Due to formation like this, therefore, by the amount of the nitrogen in adjustment metal compound layer, oxygen or carbon, it is possible to suitably control forms the optical constant (specific refractory power, optical extinction coefficient, absorption) of the metal compound layer of duplexer. In addition, nitrogen in metal compound layer, oxygen or carbon have adjustment electroconductibility and the function of etching characteristic (etch-rate) concurrently, accordingly, it may be possible to be adjusted to electricity, optics and chemically best film matter. In addition, reactant gas contained by utilization, it is possible to the scope of adjustment etching characteristic and optical characteristics becomes wide, can use a greater variety of metal or transparent oxide semiconductor material in metal compound layer. Moreover, it is possible to the sandwich of metal compound layer and metal level is formed fine pattern.
In addition, when forming metal compound layer on the face with substrate opposition side of metal level, the surface of duplexer is coated to by the conductive material being made up of the nitride of metal, oxide compound or carbide, therefore, it is possible to make the duplexer of environment patience excellence.
In addition, can have any one above arbitrary combination in the transparent oxide semiconductor material of electroconductibility, the metal with the equal above oxide compound generation free energy with zinc (Zn) and oxygen (O), nitrogen (N), carbon (C), it is possible to freely will control electrical characteristic (electroconductibility), optical characteristics (specific refractory power and optical extinction coefficient), etch the value that characteristic (solvability in etching reagent, etch-rate) reaches expectation.
Therefore, can be formed with less layer and be guaranteed following described conductive laminate: be connected easily to the electric distribution of other metal wiring, good electroconductibility can be guaranteed, can suppress twinkling by reducing from the metallic surface reflectivity (antiradar reflectivity and melanism) of visible side simultaneously, arbitrary fine pattern can be formed together by Wet-type etching in addition.
The duplexer of the present invention is when for the electrode materials of electronics, response speed can improve, and by based on the improvement of the visuality of microfabrication and reflectance reduction, based on etching in the lump, the patterning that carries out is formed, the layer of bottom line is formed, raising and the cost that thus can realize productivity reduce.
Now, in viewing area (400～700nm), above-mentioned duplexer for the light reflectance from above-mentioned metal compound layer side incidence be on average less than more than 1.0% 15%, the difference of maximum reflectivity and minimum reflectance be less than 10%, visually can in dark-coloured.
Due to formation like this, therefore, the twinkling reduction of duplexer, when the duplexer of the present invention is used for indicating meter etc., visual improves.
Owing to visuality improves, therefore the duplexer of the present invention can be suitable for the indicating meter etc. that various display element or contact panel etc. need equipment attractive in appearance in appearance, it is possible to as the electrode of display equipment with, luminous element, contact panel, used for solar batteries, other electronics etc.
In order to make duplexer further in furvous, select the material that the difference of maximum reflectivity and minimum reflectance is little as far as possible very important, in the present invention, the difference of maximum reflectivity and minimum reflectance is adjusted to and reaches less than 10%, therefore can obtain the duplexer of good furvous.
Now, possess the duplexer of the present invention, above-mentioned metal level can also be formed at the metal compound layer formed in the way of contacting with this face at least one face of this metal level on aforesaid substrate at least partially or patterned and formed.
Due to formation like this, therefore the duplexer of the present invention can be suitable for the indicating meter etc. that various display element or contact panel etc. need equipment attractive in appearance in appearance, it is possible to as the electrode of display equipment with, luminous element, contact panel, used for solar batteries, other electronics etc.
Above-mentioned problem is solved by the manufacture method of the duplexer of the present invention, this manufacture method carries out following operation: metal level formation process, on transparent substrate film forming go out at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, forming resistivity is the metal level of 10 μ below Ω cm; With metal compound layer formation process, before this metal level formation process, afterwards at least one situation under, the equal above oxide compound with zinc (Zn) that has more than film forming transparent oxide semiconductor material and at least one generates the mixture of the metal of free energy, forms the metal compound layer as the light absorbing zone with electroconductibility.
Metal compound layer is made up of the mixture of transparent oxide semiconductor material and the metal with the oxide compound generation free energy above on an equal basis with zinc (Zn).Therefore, on the basis guaranteeing electroconductibility, additionally it is possible to realizing the optimization of optical constant (specific refractory power, optical extinction coefficient and absorption), the design of duplexer becomes easy.
In addition, compared with situation about being only made up of compounds such as metal oxide, metal nitride, metal oxynitrides, metallic carbide, big layer is absorbed owing to becoming, therefore, can the reflectivity of much slower layer on surface of metal, even if when forming for 2 layers that are set to only be made up of metal level and layer of metal compound layer, dazzling of duplexer also reduces, when the duplexer of the present invention being used for indicating meter etc., visual improve.
Owing to visuality improves, therefore the duplexer of the present invention can be suitable for various display element or contact panel etc., need the indicating meter etc. of equipment attractive in appearance in appearance, it is possible to as the electrode of display equipment with, luminous element, contact panel, used for solar batteries, other electronics etc.
In addition, above-mentioned metal level possess at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, the resistivity of above-mentioned metal level is 10 μ below Ω cm, due to the metal using resistance low in the metal layer, therefore, when forming Wiring pattern by metal level and metal compound layer, it is possible to make Wiring pattern thinner, therefore, the contact panel etc. being namely used in display surface also can remain visual.
Invention effect
According to the present invention, more than at least one of the metal of free energy can be generated combine there is the transparent oxide semiconductor material of electroconductibility and there is the equal above oxide compound with zinc (Zn) arbitrarily, it is possible to freely control electrical characteristic (electroconductibility), optical characteristics (specific refractory power and optical extinction coefficient), etching characteristic (solvability in etching reagent, etch-rate) and reach the value of expectation.
Therefore, can be formed with less layer and be realized following described conductive laminate: be connected easily to the electric distribution of other metal wiring, good electroconductibility can be guaranteed, from the metallic surface reflectivity of visible side and carry out melanism by reduction simultaneously, that can suppress to produce because of metal level dazzles, it is possible to form arbitrary fine pattern together by Wet-type etching.
The duplexer of the present invention is when for the electrode materials of electronics, response speed can improve, and by based on the improvement of the visuality of microfabrication and reflectance reduction, based on etching in the lump, the patterning that carries out is formed, the layer of bottom line is formed, raising and the cost that thus can realize productivity reduce.
Accompanying drawing explanation
Fig. 1 is the summary section of the duplexer 1 involved by an embodiment of the invention.
Fig. 2 represents changing the ratio of ZnO and Cu and film forming goes out the graphic representation of measured value of the specific refractory power in 400～700nm of the substrate being formed with metal compound layer in the embodiment 1～4 of metal compound layer.
Fig. 3 represents to change the ratio of ZnO and Cu and film forming goes out the graphic representation of calculated value of optical extinction coefficient of substrate of band metal compound layer of embodiment 1～4 of metal compound layer.
Fig. 4 be represent change the ratio of ZnO and Cu and film forming go out metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 1～4 of the metal level being made up of Cu.
Fig. 5 be represent change the ratio of ZnO and Cu and film forming go out metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 1～4 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Fig. 6 represents to change nitrogen or oxygen import volume and film forming goes out the graphic representation of specific refractory power of substrate of band metal compound layer of embodiment 5～14 of Zn-Cu (5:5) metal compound layer.
Fig. 7 represents to change nitrogen or oxygen import volume and film forming goes out the graphic representation of optical extinction coefficient of substrate of band metal compound layer of embodiment 5～14 of Zn-Cu (5:5) metal compound layer.
Fig. 8 be represent change nitrogen or oxygen import volume and film forming go out Zn-Cu (5:5) metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 5～14 of the metal level being made up of Cu.
Fig. 9 be represent change nitrogen or oxygen import volume and film forming go out Zn-Cu (5:5) metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 5～14 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Figure 10 represents to change In2O3With the ratio of Mo and film forming go out metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 15～19 of the metal level being made up of Cu.
Figure 11 represents to change In2O3With the ratio of Mo and film forming go out metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 15～19 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Figure 12 represents to change ZnO-Cu and In2O3Ratio and film forming go out metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 21～25 of the metal level being made up of Cu.
Figure 13 represents to change ZnO-Cu and In2O3Ratio and film forming go out metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 21～25 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Figure 14 represents to change ZnO-Cu and SnO2Ratio and film forming go out metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 26～30 of the metal level being made up of Cu.
Figure 15 represents to change ZnO-Cu and SnO2Ratio and film forming go out metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 26～30 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Figure 16 represents to change nitrogen import volume and film forming goes out ZnO-Cu and SnO2Metal compound layer after, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 31～36 of the metal level being made up of Cu.
Figure 17 represents to change nitrogen import volume and film forming goes out ZnO-Cu and SnO2Metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 31～36 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu.
Figure 18 be represent after changing nitrogen import volume and film forming goes out the metal compound layer of ZnO and Cu, the graphic representation of the measured value of the reflectivity of the duplexer of the embodiment 37～41 of metal level that bilayer that film forming goes out MoNb film and AlNd film is formed.
Figure 19 be represent after changing nitrogen import volume and film forming goes out the metal compound layer of ZnO and Cu, the average reflectance of duplexer of embodiment 37～41 of metal level that bilayer that film forming goes out MoNb film and AlNd film is formed and the graphic representation of the difference of maximum reflectivity and minimum reflectance.
Figure 20 be represent after changing thickness and film forming goes out the metal compound layer of ZnO and Cu, the graphic representation of the measured value of the reflectivity of the duplexer of embodiment 42～47 that film forming goes out the metal level being made up of AlNd film or APC film.
Figure 21 be represent after changing thickness and film forming goes out the metal compound layer of ZnO and Cu, the average reflectance of duplexer of embodiment 42～47 and the graphic representation of the difference of maximum reflectivity and minimum reflectance that film forming goes out the metal level being made up of AlNd film or APC film.
Figure 22 be represent film forming go out for the two kinds of metals (Ni:Cu=1:1) there is the oxide compound above on an equal basis with Zn generating free energy make ZnO ratio vary be 1～5 metal compound layer after, film forming go out the average reflectance of duplexer of embodiment 54～58 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of Cu.
The average reflectance of duplexer of embodiment 54,59,60 of oxygen flow change when Figure 23 represents the film forming making to be set as the metal compound layer of Ni:Cu:ZnO=1:1:1 and the graphic representation of the difference of maximum reflectivity and minimum reflectance.
Figure 24 is the graphic representation of the measured value of the reflectivity of the duplexer represented in the embodiment 54～60 of Figure 22 and Figure 23.
Figure 25 represents one metal (Mo) and oxide compound (ZnO+Al2O3) ratio be set as 1:2, make ZnO and Al2O3Ratio turns into (5:1), (4.5:1.5), (4:2) and film forming go out 50nm metal compound layer the average reflectance of duplexer of embodiment 61～63 and the graphic representation of the difference of maximum reflectivity and minimum reflectance.
Figure 26 represents one metal (Mo) and oxide compound (ZnO+Al2O3) ratio be set as 1:2, make ZnO and Al2O3The graphic representation of measured value of reflectivity of duplexer of the embodiment 61～63 that ratio turns into (5:1), (4.5:1.5), (4:2) and film forming go out 50nm metal compound layer.
Figure 27 represents with ZnO: a kind of metal (Mo): Al2O3Ratio be 4.5:3:1.5 film forming go out metal compound layer (50nm) afterwards, film forming go out the average reflectance of duplexer of embodiment 64,65 and the graphic representation of the difference of maximum reflectivity and minimum reflectance of the metal level being made up of Cu or Al.
Figure 28 represents with ZnO: a kind of metal (Mo): Al2O3Ratio be 4.5:3:1.5 film forming go out metal compound layer (50nm) afterwards, film forming go out the graphic representation of measured value of reflectivity of duplexer of embodiment 64,65 of the metal level being made up of Cu or Al.
Figure 29 represents with ZnO: a kind of metal (Mo): Al2O3Ratio be 4.5:3:1.5 film forming go out metal compound layer (using the amplification of 5nm between 40nm～60nm) afterwards, film forming go out the metal level (100nm) that is made up of AlNd alloy as the graphic representation of the average reflectance of the duplexer of the embodiment 66～70 of metal level and the difference of maximum reflectivity and minimum reflectance.
Figure 30 represents with ZnO: a kind of metal (Mo): Al2O3Ratio be 4.5:3:1.5 film forming go out metal compound layer (using the amplification of 5nm between 40nm～60nm) afterwards, film forming go out the metal level (100nm) that is made up of the AlNd alloy graphic representation as the measured value of the reflectivity of the duplexer of the embodiment 66～70 of metal level.
Figure 31 represents ZnO:Cu=1:1 and Al2O3Ratio be set as (ZnO:Cu): (Al2O3)=10:3.5 and film forming go out metal compound layer (using the amplification of 15nm between 35nm～65nm) afterwards, film forming go out Cu as the graphic representation of the average reflectance of the duplexer of the embodiment 71～73 of metal level and the difference of maximum reflectivity and minimum reflectance.
Figure 32 represents ZnO:Cu=1:1 and Al2O3Ratio be set as (ZnO:Cu): (Al2O3)=10:3.5 and film forming go out metal compound layer (using the amplification of 15nm between 35nm～65nm) afterwards, film forming go out the graphic representation of Cu as the measured value of the reflectivity of the duplexer of the embodiment 71～73 of metal level.
Embodiment
Below, duplexer involved by an enforcement mode for the present invention, it may also be useful to accompanying drawing is described in detail.
The formation > of < duplexer 1
The duplexer 1 of present embodiment is used as: the electroded substrate being loaded into the contact panel of the display unit such as the liquid-crystal display of the various electronicss such as mobile telephone, portable information terminal, game machine, ticketing machine, ATM equipment, onboard navigation system, plasma display. In addition, in addition, additionally it is possible to as the connection electrode of the main electrodes of display element, luminous element, photo-electric conversion element etc., supporting electrode and terminal.
As shown in Figure 1, the duplexer 1 of present embodiment be formed successively on the transparent substrate 10 metal compound layer 30a, metal level 20, metal compound layer 30b and become.
But, the duplexer 1 of present embodiment can also be configured to do not possess metal compound layer 30b according to the purposes applied. In this case, transparent substrate 10 forms metal level 20, between transparency carrier 10 and metal level 20, form the metal compound layer 30a with electroconductibility as metal compound layer.
In addition, the duplexer 1 of present embodiment can also be configured to do not possess metal compound layer 30a, directly forms metal level 20 on the transparent substrate 10, forms metal compound layer 30b on metal level 20.
Substrate 10 is known transparency carrier, is made up of transparent glass material, transparent resin etc., it is possible to think transparent resin molding.
Metal level 20 possess one or more layers resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using resistivity as the metal of 1.0 μ Ω cm～10 μ Ω cm as the layer of the alloy of main component.
Such as, as the metal that resistivity is 1.0 μ Ω cm～10 μ Ω cm, it is possible to use metal simple-substances such as silver (Ag), copper (Cu), aluminium (Al). Its reason is, duplexer 1 is used as electrode, therefore, except the situation specifying high resistance especially and use, and the material that resistance value is low, metallics that is that can freely carry out pattern formation is suitable as metal level 20.
In addition, metal level 20 can be made up of the alloy of the metals such as Ag, Cu, Al.
In addition, although electroconductibility is slightly poor, but with in the combination of metal compound layer 30a, 30b, in order to reduce reflectivity efficiently, as the material of metal level 20, it is possible to use molybdenum (Mo), nickel (Ni) or its alloy etc.
But, if considering electroconductibility and etching, when for metal level 20, from the aspect of electroconductibility and etching, as more effective material, it is possible to enumerate Cu.
It is 10 μ below Ω cm that metal level 20 is adjusted to the resistivity of layer entirety.
About metal level 20, it is possible to be form one layer of the metal of 1.0 μ Ω cm～10 μ Ω cm or its alloy and dissimilar metal layer stackup by resistivity such as Ag, Cu, Al, this dissimilar metal layer is formed by with the different types of metal of the metal forming a layer. Such as, it is possible to by stacking, such as lower floor more than two layers are formed, and described layer is: form one layer of the metal of Ag, Cu, Al or its alloy; With comprise the layer formed with this layer of different types of metal and by any person in Mo, Mo alloy, Al, Al alloy.
Metal compound layer 30a, 30b of present embodiment by transparent oxide semiconductor material and have the oxide compound equal above with zinc (Zn) generate free energy metal at least one more than mixture form, for having the light absorbing zone of electroconductibility.
In transparent oxide semiconductor material, it is possible to use Indium sesquioxide (In2O3), zinc oxide (ZnO), stannic oxide (SnO2) or respectively using above-mentioned oxide compound as main component and in comprising the transparent oxide semiconductor material of the additives such as Sn one or both or there are the dielectric substance of the specific refractory power (n) 1.7～2.7 equal with these transparent oxide semiconductor materials, metal oxide, metal nitride, metal oxynitrides, metallic carbide etc. But, owing to metal compound layer 30a, 30b need electroconductibility, it is preferred to use transparent oxide semiconductor material.
There is the metal that the oxide compound equal above with zinc (Zn) generate free energy and comprise copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), plumbous (Pb) etc., it is possible to select transverse axis is set to temperature, to be set to by the longitudinal axis in Ai Linhanmu (Ellingham) figure of the general oxide compound of the standard free energy of formation of oxide compound with Cu equal or is positioned at the metal of the upside of Cu.
The reason that the metal of mixing in metal compound layer 30a, 30b is set as having the metal of equal above oxide compound generation free energy with zinc (Zn) is, if using oxide compound to generate the free energy metal lower than Zn, when being mixed in transparent oxide semiconductor material and form film, with oxygen overreact, only simple additive as transparent oxide semiconductor material plays a role, it is difficult to obtain absorbing the big film with suitable optical constant as target.
In addition, in metal compound layer 30a, 30b, mixing has the metal of the oxide compound generation free energy equal above with zinc (Zn) is based on following reason.
That is, metal level 20 is the main layer guaranteeing electroconductibility, and metal compound layer 30a, 30b are the layers dazzled reducing the gloss caused by high-reflectivity of this metal level 20 and causing. Therefore, for metal compound layer 30a, 30b, it is necessary to suitably absorb metallic reflection. When only utilizing transparent oxide semiconductor material, dielectric substance, various metallic compound to form metal compound layer 30a, 30b, these materials absorb few, therefore can not fully obtain reflectance reduction effect. In this case, metal compound layer 30a, 30b individual layer is insufficient, consequently, it is desirable to configure the semi-permeable layer of metal between metal level 20 and metal compound layer 30a, 30b in addition or semi-permeable layer and metal compound layer are replaced stacking repeatedly.
In addition, for metal compound layer 30a, 30b of being only made up of transparent oxide semiconductor material, dielectric substance, various metallic compound, the controls such as temperature when only utilizing film forming, pressure, speed, plasma body or reactant gases, certain characteristic in the flatness of the dichroism of reflectance reduction, viewing area, electroconductibility, etching as expected, cannot can not become a layer of the duplexer with sufficient function.
Therefore, in the present embodiment, be there is the metal of the oxide compound generation free energy equal above with zinc (Zn) by mixing in metal compound layer 30a, 30b, thus, the flatness of dichroism in reflectance reduction, viewing area, electroconductibility, etching all in can obtain sufficient performance. Therefore, it is not necessary to the semi-permeable layer of metal.
In addition, for metal compound layer 30a, 30b of present embodiment, the specific refractory power (n) in viewing area (400～700nm) is 1.5～3.0, optical extinction coefficient (k) is 0.30～2.5, thickness 30～60nm time absorption (α) be the scope of 20～60%.
In order to while reducing reflectivity, make visually in melanism, it is necessary to the shape of the graphic representation change of the spectral reflectance factor in viewing area is diminished, namely needs to make the longitudinal axis is set to spectral reflectance factor, being set to by transverse axis in the scope of the viewing area of wavelength becomes smooth shape as much as possible and needs the reflectivity reducing viewing area entirety.
In metal compound layer 30a, 30b, transparent oxide semiconductor material and the volume ratio with the metal that the oxide compound equal above with zinc (Zn) generates free energy are set as: transparent oxide semiconductor material: have the equal above oxide compound with zinc (Zn) and generate the scope of the metal=8:2～5:5 of free energy. Thus, it is possible to make all aspects of the electroconductibility of metal compound layer 30a, 30b, optical constant and etching be applicable scope.
In addition, by two kinds of transparent oxide semiconductor materials used in combination or two kinds of metals with the equal above oxide compound generation free energy with zinc (Zn) used in combination, thus the combination of material becomes abundant, therefore, it is possible to control fine to reflectivity, etching, electroconductibility.
In addition, for metal compound layer 30a, 30b, when film forming by importing oxygen (O2), nitrogen (N2), carbonic acid gas (CO2) in any one above reactant gases, it is possible to make the film that electroconductibility, etching are good.
In addition, by selecting the combination of optical constant and thickness, and reaching viewing area for the light reflectance from metal compound layer 30a, 30b side incidence and being on average less than more than 1.0% 15%, make the difference of maximum reflectivity and minimum reflectance be less than 10% of duplexer 1 can be made, it is possible to formed visual in dark-coloured duplexer 1.
The manufacture method > of < duplexer 1
By carrying out, following operation manufactures the duplexer 1 of present embodiment: metal level formation process, on transparent substrate 10 film forming go out at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, forming resistivity is the metal level 20 of 10 μ below Ω cm; With metal compound layer formation process, before this metal level formation process, afterwards at least one situation under, the equal above oxide compound with zinc (Zn) that has more than film forming transparent oxide semiconductor material and at least one generates the mixture of the metal of free energy, forms metal compound layer 30a, 30b as the light absorbing zone with electroconductibility.
Below, the manufacture method of the duplexer 1 of present embodiment is described.
First, carry out metal compound layer formation process, that is, film forming go out by transparent oxide semiconductor material and have the mixture of metal that the oxide compound equal above with zinc (Zn) generate free energy form, as the metal compound layer 30a of the light absorbing zone with electroconductibility.
In this operation, the target of transparent oxide semiconductor material will be bonded with, with the target being bonded with the metal with the oxide compound generation free energy above on an equal basis with zinc (Zn), it is placed in sputter equipment with transparent substrate 10, taking transparent oxide semiconductor material and there is the oxide compound generation free energy equal above with zinc (Zn) the volume ratio of metal in film as the mode in the scope of 8:2～5:5, adjustment is bonded with the target of transparent oxide semiconductor material and is bonded with has the input electric power (original text: drop into power) that the equal above oxide compound with zinc (Zn) generates the target of the metal of free energy, by sputtering, two sources film forming goes out metal compound layer 30a.
It should be noted that, now, can use and in advance the single target that transparent oxide semiconductor material and the metal with the equal above oxide compound generation free energy with zinc (Zn) mix with the volumetric ratio of 8:2～5:5 be sputtered, the target that transparent oxide semiconductor material mixes with the volumetric ratio of 8:2～5:5 can also be used with the metal with the equal above oxide compound generation free energy with zinc (Zn), with other transparent oxide semiconductor material and/or the target with the metal of equal above oxide compound generation free energy with zinc (Zn), carry out two sources film forming.
Then, carry out metal level formation process, that is, film forming go out at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, forming resistivity is the metal level of 10 μ below Ω cm.
In this operation, it is the metal of 1.0 μ Ω cm～10 μ Ω cm by resistivity or is undertaken sputtering and film forming by known method to reach thickness as the mode of about 120nm using this metal as the alloy of main component. In addition, can also by resistivity be the metal of 1.0 μ Ω cm～10 μ Ω cm or undertaken sputtering using this metal as the alloy of main component by known method and after film forming, it is other metal of 1.0 μ Ω cm～10 μ Ω cm by resistivity or is sputtered by known method using this other metal as the alloy of main component, thus make by 2 layers of metal level formed 20. In addition, it is also possible to make the multilayer film of more than 3 layers.
Then, carry out metal compound layer formation process, that is, film forming go out by transparent oxide semiconductor material and have the mixture of metal that the oxide compound equal above with zinc (Zn) generate free energy form, as the metal compound layer 30b of the light absorbing zone with electroconductibility.
This operation is undertaken by forming the step of the metal compound layer formation process of metal compound layer 30a.
By above-mentioned steps, complete the formation of the duplexer 1 of present embodiment.
It should be noted that, in the present embodiment, the metal compound layer formation process of metal compound layer 30a, metal level formation process, the metal compound layer formation process that forms metal compound layer 30b are carried out being formed successively, but being not defined in this, metal compound layer formation process can also only carry out wherein any one.
Embodiment
Below, based on specific embodiment, the present invention is described more in detail. But, the present invention is not limited to the mode of following embodiment.
(transparent oxide semiconductor material and the research of the ratio of metal) in test example 1 metallic compound
In this test example, on the transparency carrier 10 being made up of glass substrate, make that the ratio of ZnO and the Cu in metal compound layer 30a turns into 8:2,7:3,6:4,5:5 four-stage and film forming goes out the metal compound layer 30a being made up of zinc oxide (ZnO) and copper (Cu) and the metal level 20 being made up of Cu, for the duplexer 1 of the embodiment 1～4 thus obtained, carry out the research of optical characteristics.
First, on the transparency carrier 10 being made up of transparent glass substrate, the target being bonded with the target of the commercially available transparent oxide semiconductor material ZnO using ZnO as main component and being bonded with the Cu generating the high metal of free energy as oxide compound is placed in sputter equipment, by 8:2 (embodiment 1) of ZnO:Cu (volume ratio), the mode of 7:3 (embodiment 2), 6:4 (embodiment 3), 5:5 (embodiment 4), change input electric power and carry out two sources film forming, produce the metal compound layer 30a of embodiment 1～4.
Sputtering condition be without heating, arrive in pressure 5.00E-4Pa, sputtering pressure 4.40E-1Pa, argon gas atmosphere and for DC input electric power, ZnO target is 1.66～0.75kw, Cu target be 0.11～0.2kw when, taking thickness 40nm as target film forming goes out metal compound layer 30a.
The thickness of the metal compound layer 30a that film forming goes out is 37.2～44.7nm.
According to the measured value of thickness, surface resistance value, calculate resistivity, in addition, according to the measured value of the specific refractory power of thickness, transmissivity, reflectivity and substrate, calculate specific refractory power (n) and the optical extinction coefficient (k) of metal compound layer.
The calculated value of the measured value of specific refractory power and optical extinction coefficient is shown in Fig. 2,3.
According to Fig. 2, Fig. 3, resistivity is 7.32E-2～4.58E+0 Ω cm, and specific refractory power is 2.17～2.7 in viewing area (400nm～700nm), and optical extinction coefficient is 0.475～1.53.
Then, on the respective metal compound layer 30a film of embodiment 1～4, gone out the Cu of 120nm by DC sputtering film-forming, measure the reflectivity from rear side (glass surface side) thus calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance. It should be noted that, when calculating the difference of average reflectance and maximum reflectivity and minimum reflectance, the value of reflectivity gets rid of the reflectivity of the glass surface as light entrance face.
Show the result in Fig. 4, Fig. 5.
As shown in Figure 5, in embodiment 2～4, obtain that average reflectance is less than 10%, the difference of maximum reflectivity and minimum reflectance be the antiradar reflectivity of less than 5.72% and the reflection of furvous, but in embodiment 1, difference greatly to 24.69% of maximum reflectivity and minimum reflectance, obtains rubescent reflection.
In embodiment 1, the reflectivity height under 700nm is because the thickness of metal compound layer is thin, and compared with other embodiment 2～4, specific refractory power is low, and optical extinction coefficient is little.
It should be noted that, in embodiment 1, by calculating according to the specific refractory power calculated and optical extinction coefficient, and thickness is moved to 50nm, consequently, it is possible to confirm that maximum reflectivity is 8.33%, average reflectance be 4.08%, maximum with minimum reflection differences be 6.57%.
For optical constant, it is seen that demonstrate following tendency: the ratio of the Cu in metal compound layer 30a is more high from 20% to 50% more high then specific refractory power, and optical extinction coefficient is also more high.
In addition, it is seen that measuring wavelength from 400nm to 700nm, the value of the more long then specific refractory power of wavelength and optical extinction coefficient is more high. Think that its reason is: this determines by the optical constant (particularly optical extinction coefficient k) of Cu, about the reflectivity of Cu, as boundary at long wavelength region internal reflection rate height, low in short wavelength region internal reflection rate near 550nm.
In embodiment 1, difference greatly to 24.69% of maximum reflectivity and minimum reflectance, obtains rubescent reflection, and in addition, in example 4, the ratio of the Cu in film improves, and therefore, the specific refractory power height of 500nm～700nm, optical extinction coefficient also improves. Thus, the reflectivity height in long wavelength region, the reflectivity in short wavelength region are low. For the ratio of ZnO and Cu, it is seen that the 7:3 of the embodiment 2 and 6:4 of embodiment 3 demonstrates good result, specific refractory power be about 2.17～2.54 scope and optical extinction coefficient be 0.66～1.20.
(research of test example 2 nitrogen dependency)
In this example, when using ZnO to go out metal compound layer 30a as transparent oxide semiconductor material by spatter film forming, impact optical characteristics brought for nitrogen import volume has been studied.
By the step same with the embodiment 4 of test example 1, produce and generate, using transparent oxide semiconductor material ZnO with as oxide compound, the target that the Cu of the high metal of free energy is obtained by mixing with the volume ratio of 5:5.
Use this target, without under heating, arriving pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, input electric power DC0.3kw and make the flow of nitrogen be 0sccm (embodiment 5), 10sccm (embodiment 6), 20sccm (embodiment 7), 30sccm (embodiment 8), 40sccm (embodiment 9), 50sccm (embodiment 10), 60sccm (embodiment 11), 100sccm (embodiment 12) condition respectively, taking thickness 40nm as target, film forming goes out metal compound layer 30a.
In addition, replace nitrogen, import oxygen with flow 5sccm (embodiment 13), 10sccm (embodiment 14), carry out film forming equally.
For the metal compound layer 30a of embodiment 5～14, according to the specific refractory power of thickness, transmissivity, reflectivity, substrate, calculate specific refractory power (n) and the optical extinction coefficient (k) of metal compound layer 30a samely with test example 1.
Show the result in Fig. 6, Fig. 7.
As shown in Figure 6, Figure 7, for the metal compound layer 30a of embodiment 5～14, specific refractory power is the scope of 1.95～2.71 in viewing area (400nm～700nm), and optical extinction coefficient is the scope of 0.90～1.57.
Then, Cu film forming is formed by DC sputtering method the metal level 20 of 120nm by the metal compound layer 30a of embodiment 5～14, produces the duplexer 1 of embodiment 5～14. From rear side (glass surface side), measure the reflectivity of the duplexer 1 of embodiment 5～14, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
By shown in Figure 8 for the measurement result of the reflectivity of the duplexer 1 of embodiment 5～12, by shown in Figure 9 for the difference of the average reflectance of the duplexer 1 of embodiment 5～14 and maximum reflectivity and minimum reflectance.
As shown in Figure 9, average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance be less than 10% be the nitrogen flow of embodiment 6～12 be the scope of 10sccm～100sccm, average reflectance is less than 10%, the difference of maximum reflectivity and minimum reflectance be less than 5% be the nitrogen flow of embodiment 7～12 be the scope of 20sccm～100sccm and the oxygen flow of embodiment 14 be 10sccm time.
In addition, it is shown that average reflectance is less than 10%, the difference of maximum reflectivity and minimum reflectance is less than 2.5% reflectivity better like this be the nitrogen flow of embodiment 8～11 is the scope of 30sccm～60sccm. Use that average reflectance is less than 10%, the difference of maximum reflectivity and minimum reflectance be less than 2.5% value as the benchmark of good reflectivity be because of, when average reflectance is less than 10%, reflection is adequately suppressed, when the difference of maximum reflectivity and minimum reflectance is less than 2.5%, it is possible to obtaining can not rubescent, the furvous turning to be yellow, turn blue etc.
Equally, refractive index and optical extinction coefficient are observed, known in embodiment 7～12,14, specific refractory power be 2.17～2.71 scope and optical extinction coefficient be the scope of 0.9～1.57, in lower reflection and the embodiment 8～11 in furvous, specific refractory power is 2.25～2.66, optical extinction coefficient is the scope of 1.20～1.57.
In addition, known: when importing oxygen when sputtering, it is that 5sccm phase contrasts with the oxygen flow of embodiment 13, when the oxygen flow of embodiment 14 is 10sccm, average reflectance is reduced to about 4% from the level of 10%, and the difference of maximum reflectivity and minimum reflectance is also reduced to about 3% from about 5%, therefore, by selecting best importing gas volume, it is possible to control specific refractory power and optical extinction coefficient, it is possible to make low reflection and the duplexer 1 in furvous.
(example of other constitute of test example 3 metallic compound)
In this example, as the transparent oxide semiconductor material forming metal compound layer 30a, it may also be useful to Indium sesquioxide (In2O3) replace the ZnO of test example 1,2, generate the high metal of free energy as oxide compound, it may also be useful to Mo replaces Cu, studies.
To be bonded with In2O3It is placed in respectively in sputter equipment as the target of transparent oxide semiconductor material of main component and the target that is bonded with Mo, by transparent oxide semiconductor material: in the way of the volume ratio of both Mo becomes 10:1 (embodiment 15), 10:2 (embodiment 16), 10:3 (embodiment 17), 10:4 (embodiment 18), 10:5 (embodiment 19), 10:10 (embodiment 20), change input electric power and carry out two sources film forming, produce the metal compound layer 30a of embodiment 15～19.
Sputtering condition be without heating, arrive in pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, Ar atmosphere and make the DC input electric power of transparent oxide semiconductor material be 0.18kw～0.46kw scope, make the DC input electric power of Mo be 0.1kw～0.45kw scope when, taking thickness 40nm as target, go out metal compound layer 30a by two sources spatter film forming.
Then, the film of the metal compound layer 30a of embodiment 15～19 is gone out by DC sputtering film-forming the Cu of 120nm respectively, measures the reflectivity from rear side (glass surface side) thus calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
By shown in Figure 10 for the measured value of reflectivity, by the differential of average reflectance, maximum reflectivity and minimum reflectance in Figure 11.
The embodiment 17,18 of to be the DC input electric power ratio of transparent oxide semiconductor material and Mo be 10:3,10:4 that average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance is less than 10%. In embodiment 17, average reflectance is 11.56%, the difference of maximum reflectivity and minimum reflectance is 3.40%, in embodiment 18, average reflectance be 14.02% and the difference of maximum reflectivity and minimum reflectance be 3.13%.
For the embodiment 16,19 of 10:2,10:5, average reflectance is up to being slightly smaller than 17%, but the difference of maximum reflectivity and minimum reflectance is 3.71% and 4.16%, and outward appearance is furvous.
(research of the constitute of test example 4 metal compound layer)
In this example, ZnO and Cu and In is changed2O3Ratio and film forming goes out by ZnO, Cu, In2O3Alloy form metal compound layer 30a, applicable ratio is studied.
Using target and In that the ZnO as transparent oxide semiconductor material and the ratio of Cu that generates the high metal of free energy as oxide compound take volume basis as 5:52O3Target be placed in sputter equipment, with ZnO Cu mixture and In2O3Volume ratio be that 10:1 (embodiment 21), 10:2 (embodiment 22), 10:3 (embodiment 23), 10:4 (embodiment 24), ratio that the mode of 10:5 (embodiment 25) changes input electric power carry out two sources film forming, produce the metal compound layer 30a of embodiment 21～25.
It is without heating at sputtering condition, arrives in pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, argon (Ar) atmosphere and make the DC input electric power of ZnO Cu mixture target be the scope of 0.14kw～0.72kw, make In2O3When the DC input electric power of target is 0.1kw, taking thickness 40nm as target, go out metal compound layer 30a by two sources spatter film forming.
Then, the film of the metal compound layer 30a of embodiment 21～25 is gone out by DC sputtering film-forming the Cu of 120nm respectively, measures the reflectivity from rear side (glass surface side) thus calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
The measured value of reflectivity is shown in Figure 12, by the differential of maximum reflectivity and minimum reflectance in Figure 13.
Average reflectance is less than 15%, maximum reflectivity with the difference of minimum reflectance be less than 10% be ZnO Cu mixing target and In2O3The DC input electric power ratio of target is the embodiment 23～25 of 10:3～10:5. In embodiment 23, average reflectance is 12.92%, the difference of maximum reflectivity and minimum reflectance is 6.17%, in embodiment 24, average reflectance is 11.79%, the difference of maximum reflectivity and minimum reflectance is 5.80%, in embodiment 25, average reflectance is 9.38%, the difference of maximum reflectivity and minimum reflectance is 4.64%.
In the scope of this test example, along with In2O3Ratio increase, the subtractive of average reflectance and maximum reflectivity and minimum reflectance is little, it is possible to obtain the duplexer 1 with good optical characteristics of object more according to the invention.
(research of the constitute of test example 5 metal compound layer)
In this example, it may also be useful to SnO2Replace the In of test example 42O3, change ZnO and Cu and SnO2Ratio and film forming goes out by ZnO, Cu, SnO2Alloy form metal compound layer 30a, applicable ratio is studied.
Replace the In of test example 42O3Target, by SnO2Target is placed in sputter equipment, with ZnO Cu mixture and SnO2Volume ratio be that 10:1 (embodiment 26), 10:2 (embodiment 27), 10:3 (embodiment 28), 10:4 (embodiment 29), ratio that the mode of 10:5 (embodiment 30) changes input electric power carry out two sources film forming, produce the metal compound layer 30a of embodiment 26～30.
It is make the DC input electric power of ZnO Cu mixture target be the scope of 0.15kw～0.75kw, make SnO at sputtering condition2When the DC input electric power of target is 0.1kw, go out metal compound layer by target of thickness 40nm by two sources spatter film forming.
Then, the film of the metal compound layer 30a of embodiment 21～25 is gone out by DC sputtering film-forming the Cu of 120nm respectively, measures the reflectivity from rear side (glass surface side) thus calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
The measured value of reflectivity is shown in Figure 14, by the differential of maximum reflectivity and minimum reflectance in Figure 15.
Average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance be less than 10% be ZnO Cu mixture target and SnO2The DC input electric power ratio of target is the embodiment 28～30 of 10:3～10:5.
In embodiment 28, average reflectance is 13.12%, the difference of maximum reflectivity and minimum reflectance is 6.17%, in embodiment 29, average reflectance is 9.94%, the difference of maximum reflectivity and minimum reflectance is 5.44%, in embodiment 30, average reflectance is 8.69%, the difference of maximum reflectivity and minimum reflectance is 6.99%.
With the use In of test example 42O3Target situation equally, along with SnO2Ratio increase and average reflectance reduce, but when the ratio 10:4 of embodiment 29 produce bottom, therefore, it is seen that ZnO Cu mixture and SnO2Ratio be 10:4 be applicable.
(test example 6 uses nitrogen Study on Dependence when two kinds of transparent oxide semiconductor materials)
In this example, at use ZnO and SnO2Two kinds when going out metal compound layer 30a as transparent oxide semiconductor material by spatter film forming, impact optical characteristics brought for nitrogen import volume is studied.
Produce as the ZnO of transparent oxide semiconductor material, Cu and SnO that generate the high metal of free energy as oxide compound2The target mixed in the way of becoming the volume ratio of 2:3:1, and be placed in sputter equipment.
Sputtering condition is made to be without under heating, arrival pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, DC input electric power 0.3kw, Ar gas 120sccm imports nitrogen with 0sccm (embodiment 31), 20sccm (embodiment 32), 40sccm (embodiment 33), 60sccm (embodiment 34), 80sccm (embodiment 35), 100sccm (embodiment 36) respectively, carries out film forming respectively by target of thickness 40nm.
Then, Cu film forming is formed by DC sputtering method the metal level 20 of 120nm by the metal compound layer 30a of embodiment 31～36, produces the duplexer 1 of embodiment 31～36. Measure the reflectivity of the duplexer 1 of embodiment 31～36 from rear side (glass surface side), calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
The measurement result of the reflectivity of the duplexer 1 of embodiment 31～36 is shown in Figure 16, by the differential of average reflectance and maximum reflectivity and minimum reflectance in Figure 17.
As shown in figure 16, average reflectance be less than 15%, the difference of maximum reflectivity and minimum reflectance be less than 10% be the nitrogen flow of embodiment 32～36 be the situation of 20sccm～100sccm. In embodiment 32 (nitrogen 20sccm), average reflectance is 13.17%, the difference of maximum reflectivity and minimum reflectance is 2.78%, in embodiment 36 (nitrogen 100sccm), average reflectance is 2.54%, the difference of maximum reflectivity and minimum reflectance is 6.76%. Along with the increase of nitrogen flow, average reflectance reduces gradually, and on the contrary, the difference of maximum reflectivity and minimum reflectance increases.
In addition, in embodiment 31 (nitrogen 0sccm), the reflectivity of more than wavelength 550nm is up to more than 23%. This is because, the characteristic of the reflectivity of Cu produces a very large impact.
In addition, along with the import volume of nitrogen increases, reflectance reduction, therefore, it is seen that when forming metallic compound, Cu, because importing nitrogen, nitrogenize occurs.
(test example 7 makes metal level be that the nitrogen to metal compound layer when forming of two layers of MoNb film and AlNd film imports quantifier elimination)
When the two layers of formation making the metal level 20 of Fig. 1 be MoNb film and AlNd film, for nitrogen flow during metal compound layer 30a film forming, the impact that the characteristic of the reflectivity of duplexer 1 is brought is studied.
Produce the target that the ZnO as transparent oxide semiconductor material and the ratio of Cu generating the high metal of free energy as oxide compound take volume basis as 5:5, it is placed in sputter equipment.
Sputtering condition is made to be without heating, arrive pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, DC input electric power 0.3kw, Ar gas 120sccm imports nitrogen with 20sccm (embodiment 37), 40sccm (embodiment 38), 60sccm (embodiment 39), 80sccm (embodiment 40), 100sccm (embodiment 41) respectively, carries out film forming respectively by target of thickness 40nm.
Then, the molybdenum alloy (MoNb) that film forming goes out 25nm on the metal compound layer 30a of embodiment 37～41 as metal level 20 after, then film forming goes out the aluminium alloy (AlNd) of 100nm, and film forming goes out two layers of metal level formed 20 by MoNb film and AlNd film. Measure the reflectivity of the duplexer 1 of embodiment 37～41 from rear side (glass surface side), calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
The measurement result of the reflectivity of the duplexer 1 of embodiment 37～41 is shown in Figure 18, by the differential of average reflectance and maximum reflectivity and minimum reflectance in Figure 19.
As shown in figure 19, average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance be less than 10% be the nitrogen flow of embodiment 39～41 be the situation of 60sccm～100sccm, in embodiment 39 (nitrogen flow 60sccm), average reflectance is 13.71%, the difference of maximum reflectivity and minimum reflectance is 5.71%. In addition, in embodiment 41 (nitrogen flow 100sccm), average reflectance is 7.46%, the difference of maximum reflectivity and minimum reflectance is 2.61%.
In this example, different from the result of test example 5, along with nitrogen flow when forming metal compound layer 30a is increased to 20sccm～100sccm, the value of the difference of average reflectance, maximum reflectivity, minimum reflectance, maximum reflectivity and minimum reflectance all reduces, it is shown that better optical characteristics. According to the above results it will be seen that imported by nitrogen during sputtering, there is nitrogenize in the Cu dispersed from target.
In addition, known in the scope that flow is 20sccm～100sccm, while nitrogen flow increases, reflectivity continues to reduce, under the nitrogen flow of the peak flow as this example is 100sccm situation, the value of the difference of average reflectance, maximum reflectivity, minimum reflectance, maximum reflectivity and minimum reflectance does not all reach bottom, therefore by further nitrogen import volume being increased to more than 100sccm, it is possible to obtain the stacked film of better antiradar reflectivity.
(test example 8 makes metal level be AlNd film or the research of metallic compound thickness when APC film)
When making the metal level 20 of Fig. 1 for Al alloy (AlNd) film or Ag alloy (APC:Ag-Pd-Cu alloy) film, the impact that the characteristic of the reflectivity of duplexer 1 is brought is studied by the thickness for metal compound layer 30a.
The ratio making the ZnO as transparent oxide semiconductor material and generating the Cu of the high metal of free energy as oxide compound take volume basis as the target of 5:5, is placed in sputter equipment.
Sputtering condition is made to be without heating, arrive pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, DC input electric power 0.3kw, Ar gas 120sccm import in the atmosphere of 60sccm nitrogen, it is that the mode film forming of 40nm, 50nm, 60nm goes out the ZnO-Cu film for metallic compound taking thickness, obtains metal compound layer 30a.
Then, being that on the metal compound layer 30a of 40nm, 50nm, 60nm, film forming goes out aluminium alloy (AlNd) 100nm or Ag alloy (APC) 100nm as metal level 20 respectively at thickness, film forming goes out metal level 20.
Using the situation of the thickness of metal compound layer 30a to be 40nm, 50nm, 60nm and metal level 20 be AlNd as embodiment 42～44, using the situation of the thickness of metal compound layer 30a to be 40nm, 50nm, 60nm and metal level 20 be APC as embodiment 45～47.
From rear side (glass surface side), measure the reflectivity of the duplexer 1 of embodiment 42～47, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance.
The measurement result of the reflectivity of the duplexer 1 of embodiment 42～47 is shown in Figure 20, by the differential of average reflectance and maximum reflectivity and minimum reflectance in Figure 21.
On the metal compound layer 30a of thickness 40nm, film forming goes out in the embodiment 42 of AlNd, the difference of maximum reflectivity and minimum reflectance is 10.68%, in embodiment 43～47, average reflectance is 6.22%～11.0%, the difference of maximum reflectivity and minimum reflectance is in the scope of 4.36%～6.71%, it is possible to obtaining visual is also dark tint and the duplexer 1 of reflectivity Characteristics that is applicable to.
(test example 9 etching evaluation)
In this example, to the evaluation carrying out etching in the embodiment 6 (nitrogen flow 10sccm) of test example 2, embodiment 11 (nitrogen flow 60sccm) and the duplexer 1 that makes when embodiment 12 (nitrogen flow 100sccm).
By the same condition of embodiment 11,12 with test example 2, with the nitrogen flow of 60sccm, 100sccm on the substrate 10 being made up of glass substrate, sputter by by the target that ZnO and Cu is obtained by mixing with the volume ratio of 5:5, thus form the metal compound layer 30a of thickness 40nm, metal compound layer 30a is formed by sputtering the metal level 20 being made up of Cu of thickness 120nm, obtains the duplexer 1 of embodiment 48,49 respectively.
In addition, by the condition same with the embodiment 6 of test example 2, with the nitrogen flow of 10sccm on the substrate 10 being made up of glass substrate, sputter by by the target that ZnO and Cu is obtained by mixing with the volume ratio of 5:5, thus form the metal compound layer 30a of thickness 40nm, metal compound layer 30a is formed by sputtering the metal level 20 being made up of Cu of thickness 120nm, obtains the duplexer 1 of embodiment 50.
By the condition same with the embodiment 11 of test example 2, with the nitrogen flow of 60sccm on the substrate 10 being made up of PET film, sputter by by the target that ZnO and Cu is obtained by mixing with the volume ratio of 5:5, thus form the metal compound layer 30a of thickness 40nm, metal compound layer 30a is formed by sputtering the metal level 20 being made up of Cu of thickness 120nm, obtains the duplexer 1 of embodiment 51.
By the condition same with the embodiment 6 of test example 2, with the nitrogen flow of 60sccm on the substrate 10 being made up of PET film, use and the target that ZnO and Cu is obtained by mixing with the volume ratio of 5:5 is sputtered, thus form the metal compound layer 30a of thickness 40nm, on metal compound layer 30a, the metal level 20 being made up of Cu of thickness 120nm is formed by sputtering, further, with the nitrogen flow of 60sccm, use and the target that ZnO and Cu is obtained by mixing with the volume ratio of 5:5 is sputtered, thus form the metal compound layer 30b of thickness 40nm, obtain the duplexer 1 of embodiment 52.
For the duplexer of embodiment 48～52, it may also be useful to nitric acid hydrogen peroxide system (Ech-1, Geomatec Co., Ltd. system) and phosphoric acid nitroacetyl system (Ech-2, Geomatec Co., Ltd. system) two kinds of etching reagents etch.
In an etching step, the duplexer 1 of embodiment 48～52 is cut into 50 millimeters × 50 millimeters respectively, is immersed in each etching reagent, controls in the way of liquid temperature is constant, confirm etching end time (terminal).
For the etching end point of the embodiment 48～50 employing glass substrate, when the etching reagent of nitric acid hydrogen peroxide system (Ech-1), it is 20 seconds, for the identical time, when the etching reagent of phosphoric acid nitroacetyl system (Ech-2), it it is 45～50 seconds, it is necessary to the time of more than 2 times of Ech-1.
For the etching end point of the embodiment 51,52 employing film substrate, it it is 17～18 seconds when the etching reagent of nitric acid hydrogen peroxide system (Ech-1), it it is 38～44 seconds when the etching reagent of phosphoric acid nitroacetyl system (Ech-2), compared with the embodiment 48～50 employing glass substrate, result slightly fast about 10%.
(the etching evaluation of test example 10 test pattern)
Use the duplexer 1 of the embodiment 48～52 made samely with test example 9, the test patterns of 20 μm, 10 μm, 4 μm are used in version, utilize the etching reagent of nitric acid hydrogen peroxide system (Ech-1) and phosphoric acid nitroacetyl system (Ech-2) implements Wet-type etching so that it is determined that the pattern dimension of each sample.
Show the result in table 1.
[table 1]
Glass substrate
Film
In Table 1, pattern width is the measured value of the pattern width obtained after etching, retreat width be by by the mean value of the difference of the measured value of the resist width under each resist width and pattern width divided by 2, thus calculate the value of the mean value of the single side size relative to the retrogressing of resist pattern.
As shown in table 1, for the etching reagent of nitric acid hydrogen peroxide system (Ech-1), produce the retrogressing (crossing etching) that single side size relative to resist pattern is on average about 0.5～0.6 μm, but can be formed taking 20 μm, 10 μm, 4 μm as basic pattern. From the pattern that the observation of pros and cons any surface is all good.
For the etching reagent of phosphoric acid nitroacetyl system (Ech-2), although 20 μm of patterns can be confirmed, but can not confirming 10 μm, 4 μm patterns, in addition, the pattern of metal level 20 becomes catenary (オ バ Ha Application グ shape) etc. and can not obtain sufficient result.
But, it is seen that by adjusting concentration, the proportioning of etching reagent, reliable pattern formation all can be carried out when any one etching reagent.
(the etching evaluation of test example 11 test pattern)
In this example, to embodiment 30 (ZnO Cu mixture and the SnO in test example 52Volume ratio be 10:5) when the duplexer 1 that makes carry out the evaluation of etching.
By the condition same with the embodiment 30 of test example 5, on the substrate 10 being made up of glass substrate, with ZnO Cu mixture and SnO2Volume ratio be that the mode of 10:5 carries out sputtering the metal compound layer 30a forming thickness 40nm, on metal compound layer 30a, formed the metal level 20 being made up of Cu of thickness 120nm by sputtering, further, with ZnO Cu mixture and SnO2Volume ratio be that the mode of 10:5 carries out sputtering thus forms the metal compound layer 30b of thickness 40nm, obtain the duplexer 1 of embodiment 53.
Use the duplexer 1 of embodiment 53, utilize the etching reagent of nitric acid hydrogen peroxide system (Ech-1) and the etching reagent (Ech-3, Geomatec Co., Ltd. system) of iron(ic) chloride, use the version of the test pattern of 20 μm, 10 μm, 4 μm to implement etching, thus the pattern dimension of sample is confirmed.
Show the result in table 2.
[table 2]
Result according to table 2, utilize the etching reagent of nitric acid hydrogen peroxide system (Ech-1), single side size is had relative to resist pattern to be on average the retrogressing (crossing etching) of about 0.2 μm, the etching reagent (Ech-3) of iron(ic) chloride is utilized then to have the retrogressing (crossing etching) of about 0.5 μm, it is possible to be formed taking 20 μm, 10 μm, 4 μm as basic pattern.But, when utilizing etching reagent (Ech-3) of iron(ic) chloride, metal compound layer 30a, 30b etch-rate is fast, therefore, and the reflection all confirming slightly in patterned sides edge observing from positive and negative any surface and causing by Cu.
(example that test example 12 metal compound layer is made up of the mixture with two kinds of metals)
On the substrate 10, film forming goes out the metal compound layer 30a being made up of Cu and Ni two kinds of metals and ZnO, then uses Cu as metal level 20. First, the alloys target of Cu and Ni (1:1) and ZnO target are placed in device, in the way of the ratio of Cu:Ni:ZnO=1:1:1～5, adjust the output rating of each target, formed the metal compound layer 30a of five kinds of roughly thickness 55nm by the sputtering of two source.
Sputtering condition be without heating, arrive in pressure 5.00E-4Pa, sputtering pressure 4.3E-1Pa, argon gas atmosphere and for DC input electric power, ZnO target is 1.66～0.35kw, Cu target be 0.2kw under, form metal compound layer 30a by target of thickness 55nm. Then, on metal compound layer 30a, it may also be useful to other Cu target forms the metal level 20 being made up of Cu of thickness 120nm thus the duplexer obtaining embodiment 54～58 by sputtering.
In addition, when the ratio of Cu:Ni:ZnO=1:1:1, import the oxygen of 2sccm and 4sccm during film forming thus obtain the duplexer of embodiment 59～60.
From metal compound layer 30a side (glass surface side), measure the reflectivity of the duplexer of embodiment 54～60, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance. By the differential of the average reflectance of the duplexer of embodiment 54～60 and maximum reflectivity and minimum reflectance in Figure 22 and Figure 23, the measurement result of reflectivity is shown in Figure 24.
The embodiment 55～57 of to be the ratio of Cu:Ni:ZnO as shown in figure 23 be 1:1:2～4 that when not importing oxygen when film forming, average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance is less than 10%.
When not importing oxygen during film forming, in the embodiment 54 of ratio 1:1:1 and the embodiment 58 of 1:1:5, reflectivity does not reach the level less than 15% of the reflectivity expected. In the embodiment 58 of oxide ratio up to ratio 1:1:5, it is believed that the absorption of metal compound layer reduces, therefore reflectivity increases.
On the other hand, it is seen that when ratio is 1:1:1, in the embodiment 59,60 of Figure 23, Figure 24, film forming imports oxygen O2The reactant gases such as=2sccm, 4sccm adjusts, result is in embodiment 59, average reflectance is 15.75%, the difference of maximum reflectivity and minimum reflectance is 5.65%, in embodiment 60, average reflectance is 14.78%, the difference of maximum reflectivity and minimum reflectance is reduced to 6.12%, it is seen that obtain good reflectivity.
(example that test example 13 metal compound layer is made up of a kind of metal (Mo) and two kinds of dielectric substances)
As the transparent oxide semiconductor material forming metal compound layer 30a, produce ZnO and aluminum oxide (Al2O3) and the ratio of Mo be the oxide compound mixing target of (5:1:3), (4.5:1.5:3), (4:2:3).
Oxide compound mixing target is placed in device, make sputtering condition be without heating, arrive pressure 8.00E-4Pa, sputtering pressure 1.60E-1Pa, under the Ar gas of 120sccm, input electric power are 0.3kW, after film forming goes out metal compound layer 30a, the AlNd alloy of stacking 120nm thus film forming goes out metal level 20, obtain the duplexer of embodiment 61～63.
From metal compound layer 30a side (glass surface side), measure the reflectivity of the duplexer of embodiment 61～63, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance. By the differential of the average reflectance of the duplexer of embodiment 61～63 and maximum reflectivity and minimum reflectance in Figure 25, the measurement result of reflectivity is shown in Figure 26.
As shown in Figure 25, Figure 26, the difference of the average reflectance of embodiment 61～63 and maximum reflectivity and minimum reflectance is less than 10%, observes the film that can obtain good furvous from visible side. Do not find because of ZnO and Al2O3The larger difference that causes of ratio.
In addition, to ZnO and the Al of embodiment 622O3The metal compound layer 30a being 4.5:1.5:3 with the ratio of Mo forms Cu, Al of 50nm respectively, makes metal level 20 for bilayer structure, obtains the duplexer of embodiment 64,65.
In embodiment 64,65, it is seen that the difference of average reflectance and maximum reflectivity and minimum reflectance is less than 10%, during thickness 50nm, in the big multizone of viewing area 400～700nm, it is antiradar reflectivity when film forming goes out Al compared with Cu. This is presumably because, due to the specific refractory power of Cu, Al and the impact of optical extinction coefficient, reach the peak skew of the minimum reflectivity of the bottom of reflectivity. When forming Cu film, it is possible to by making the thickness of metal compound layer 30a be as thin as 35nm～40nm, the average reflectance of embodiment 64 and the difference of maximum reflectivity and minimum reflectance are reduced.
In addition, at ZnO and the Al making embodiment 622O3And the ratio of Mo is that on the film that changes with the amplification of 5nm between 40nm～60nm of the thickness of the metal compound layer 30a of 4.5:1.5:3, film forming goes out the metal level 20 being made up of AlNd alloy, obtains the duplexer of embodiment 66～70.
From metal compound layer 30a side (glass surface side), measure the reflectivity of the duplexer of embodiment 66～70, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance. By the differential of the average reflectance of the duplexer of embodiment 66～70 and maximum reflectivity and minimum reflectance in Figure 29, the measurement result of reflectivity is shown in Figure 30.
As shown in figure 29, in embodiment 66～69, average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance is less than 10%. In embodiment 70, the difference of maximum reflectivity and minimum reflectance is 12.78%, average reflectance is the 7.50% of less than 15%. In Figure 29, it is clear that thickness dependency is shown clearly. For this kind of situation, as mentioned above, it is necessary, can easily expect for making metal level 20 also be applicable to for during Cu.
(example that test example 14 is made up of metal compound layer (ZnO:Cu=1:1) and a kind of metal oxide)
As the transparent oxide semiconductor material forming metal compound layer 30a, it is target and the Al of 1:1 by the ratio of ZnO and Cu2O3Target be arranged in device, as metal compound layer 30a, with (ZnO:Cu=1:1) and a kind of metal oxide (Al2O3) ratio be (ZnO-Cu): (Al2O3The mode of)=10:3.5 adjusts the output rating of respective shielding power supply, and goes out three kinds of metal compound layer 30a by target film forming of thickness 35nm, 50nm, 65nm. Then the Cu of stacking 120nm is as metal level 20, obtains the duplexer of embodiment 71～73.
From metal compound layer 30a side (glass surface side), measure the reflectivity of the duplexer of embodiment 71～73, calculate the difference of the average reflectance in viewing area (400nm～700nm), maximum reflectivity and minimum reflectance. By the differential of the average reflectance of the duplexer of embodiment 71～73 and maximum reflectivity and minimum reflectance in Figure 31, the measurement result of reflectivity is shown in Figure 32.
The thickness of metal compound layer 30a be 35, in the embodiment 71,72 of 50nm, average reflectance is less than 15%, the difference of maximum reflectivity and minimum reflectance is less than 10%. Be in the embodiment 73 of 65nm at the thickness of metal compound layer 30a, the difference of maximum reflectivity and minimum reflectance be less than 10% 2.41%, average reflectance be 16.25%.
When being any one thickness band of thickness 35nm, 50nm, 65nm when making metal compound layer 30a, it is also possible to obtain the reflectivity that flatness is good. It is in the embodiment 73 of 65nm at the thickness of metal compound layer 30a, the reflectivity height of viewing area entirety, but the difference of maximum reflectivity and minimum reflectance is little, therefore black dullization, in appearance well.
For the duplexer of the only layer of composition transparent oxide semiconductor material and the conventional of metal level, because of the relation of specific refractory power and optical extinction coefficient, it is clear that easily formed based on the reduction of reflectivity and the interference color of bottom. According to above-described embodiment, if the metal compound layer of the application and metal level are combined, then can obtaining the preferred stacked film in furvous, this metal compound layer is formed by with the mixture with the metal that the oxide compound above on an equal basis with zinc oxide generates free energy.
Nomenclature
1 duplexer
20 metal levels
30a, 30b metal compound layer
Claims (11)
1. a duplexer, it is characterised in that, it is made up of with the metal compound layer formed in the way of contacting with this face at least one face of this metal level transparent substrate, the metal level that formed on the substrate,
Described metal level possess at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, the resistivity of described metal level is 10 μ below Ω cm,
Described metal compound layer is made up of the mixture with the metal that equal above oxide compound generates free energy with zinc (Zn) more than transparent oxide semiconductor material and at least one.
2. duplexer as claimed in claim 1, it is characterized in that, the layer that described metal level is the described alloy of described at least one layer becomes with dissimilar metal layer stackup, and this dissimilar metal layer is made up of the metal different from the described metal species of the main component of the layer as described alloy.
3. duplexer as claimed in claim 2, it is characterised in that, described metal level is by inciting somebody to action
The single layer that is made up of copper (Cu), aluminium (Al), silver (Ag) or the alloy of these metals,
With two layers or three layers be selected from the group being made up of molybdenum (Mo) layer, Mo alloy, aluminium (Al) layer, aluminium alloy layer
It is laminated.
4. duplexer as according to any one of claims 1 to 3, it is characterized in that, the specific refractory power (n) of described metal compound layer in viewing area (400～700nm) is 2.0～2.8, optical extinction coefficient (k) is 0.6～1.6.
5. duplexer as according to any one of Claims 1 to 4, it is characterized in that, the layer that described metal compound layer is made up of the mixture of one or both transparent oxide semiconductor materials and the metal with the oxide compound generation free energy above on an equal basis with zinc (Zn) is formed, and described transparent oxide semiconductor material is Indium sesquioxide (In2O3), zinc oxide (ZnO) or stannic oxide (SnO2) or with Indium sesquioxide (In2O3), zinc oxide (ZnO) or stannic oxide (SnO2) as main component and containing additive.
6. duplexer as claimed in claim 5, it is characterized in that, described in there is the oxide compound equal above with zinc (Zn) generate any one the above metal in the group that the metal of free energy comprises zinc (Zn), copper (Cu), nickel (Ni), molybdenum (Mo), cobalt (Co), plumbous (Pb), molybdenum alloy for being selected from.
7. duplexer as claimed in claim 6, it is characterized in that, described metal compound layer is that described transparent oxide semiconductor material and the metal with the equal above oxide compound generation free energy with zinc (Zn) mix with the volume ratio of 8:2～5:5.
8. duplexer as according to any one of claim 1～7, it is characterised in that,
Described metal compound layer contains more than one in the group being made up of oxygen (O), nitrogen (N), carbon (C),
The thickness of described metal compound layer is the scope of 30nm～60nm.
9. duplexer as according to any one of claim 1～8, wherein, in viewing area (400～700nm), described duplexer for the light reflectance from described metal compound layer side incidence be on average less than more than 1.0% 15%, the difference of maximum reflectivity and minimum reflectance be less than 10%, visual in dark-coloured.
10. an electronics, it is characterised in that,
Possess the duplexer according to any one of claim 1～9,
Described metal level with at least one face of this metal level by the metal compound layer formed in the way of contacting with this face be formed on described substrate at least partially or patterned and formed.
The manufacture method of 11. 1 kinds of duplexers, it is characterised in that, carry out following operation:
Metal level formation process, on transparent substrate film forming go out at least one layer resistivity be 1.0 μ Ω cm～10 μ Ω cm metal layer or using this metal as the layer of the alloy of main component, forming resistivity is the metal level of 10 μ below Ω cm; With
Metal compound layer formation process, before this metal level formation process, afterwards at least one situation under, the equal above oxide compound with zinc (Zn) that has more than film forming transparent oxide semiconductor material and at least one generates the mixture of the metal of free energy, forms the metal compound layer as the light absorbing zone with electroconductibility.
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| JP2014-125422 | 2014-06-18 | ||
| JP2014125422 | 2014-06-18 | ||
| PCT/JP2015/067443 WO2015194587A1 (en) | 2014-06-18 | 2015-06-17 | Laminate, method for manufacturing same, and electronic device |
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| KR (1) | KR101681878B1 (en) |
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| CN108776563A (en) * | 2018-06-29 | 2018-11-09 | 信利光电股份有限公司 | A kind of black touch screen of one and preparation method thereof |
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| TWI746603B (en) * | 2016-08-09 | 2021-11-21 | 南韓商東友精細化工有限公司 | Transparent electrode, touch sensor and image display device including the same |
| KR102545420B1 (en) * | 2016-11-25 | 2023-06-19 | 동우 화인켐 주식회사 | Touch sensor integrated with oled and oled display device comprising the same |
| WO2022163546A1 (en) * | 2021-01-27 | 2022-08-04 | Ａｇｃ株式会社 | Optical thin film laminate and method for producing same |
| WO2024117069A1 (en) * | 2022-11-30 | 2024-06-06 | 日東電工株式会社 | Reflective film |
| WO2024117068A1 (en) * | 2022-11-30 | 2024-06-06 | 日東電工株式会社 | Reflective film |
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| CN105684099B (en) | 2018-01-19 |
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| TWI595507B (en) | 2017-08-11 |
| JPWO2015194587A1 (en) | 2017-04-20 |
| KR20160043154A (en) | 2016-04-20 |
| TW201601169A (en) | 2016-01-01 |
| KR101681878B1 (en) | 2016-12-01 |
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