CN1699262A - Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film - Google Patents
Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film Download PDFInfo
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- CN1699262A CN1699262A CN 200510079183 CN200510079183A CN1699262A CN 1699262 A CN1699262 A CN 1699262A CN 200510079183 CN200510079183 CN 200510079183 CN 200510079183 A CN200510079183 A CN 200510079183A CN 1699262 A CN1699262 A CN 1699262A
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- 239000004020 conductor Substances 0.000 title claims description 156
- 239000011521 glass Substances 0.000 title abstract description 256
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 255
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 247
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 228
- 239000011787 zinc oxide Substances 0.000 claims abstract description 113
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 91
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 78
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 48
- 238000005477 sputtering target Methods 0.000 claims abstract description 47
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 45
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 42
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000011701 zinc Substances 0.000 claims description 402
- 239000000203 mixture Substances 0.000 claims description 109
- 238000005245 sintering Methods 0.000 claims description 30
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 24
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 23
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 claims description 18
- 229910003449 rhenium oxide Inorganic materials 0.000 claims description 18
- -1 stannic oxide metal oxides Chemical class 0.000 claims description 14
- 238000007733 ion plating Methods 0.000 claims description 5
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 35
- 238000004544 sputter deposition Methods 0.000 abstract description 22
- 239000000470 constituent Substances 0.000 abstract description 4
- 238000002347 injection Methods 0.000 abstract description 2
- 239000007924 injection Substances 0.000 abstract description 2
- 229910001887 tin oxide Inorganic materials 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 195
- 238000004519 manufacturing process Methods 0.000 description 177
- 239000011248 coating agent Substances 0.000 description 176
- 238000000576 coating method Methods 0.000 description 176
- 239000002994 raw material Substances 0.000 description 127
- 239000010408 film Substances 0.000 description 102
- 239000000758 substrate Substances 0.000 description 101
- 125000004429 atom Chemical group 0.000 description 83
- 239000010410 layer Substances 0.000 description 51
- 238000005259 measurement Methods 0.000 description 50
- 238000000034 method Methods 0.000 description 45
- 150000001875 compounds Chemical class 0.000 description 38
- 238000002425 crystallisation Methods 0.000 description 33
- 230000008025 crystallization Effects 0.000 description 33
- 238000000227 grinding Methods 0.000 description 33
- 230000000704 physical effect Effects 0.000 description 33
- 238000002834 transmittance Methods 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- 238000005401 electroluminescence Methods 0.000 description 21
- 238000005530 etching Methods 0.000 description 19
- 229910052596 spinel Inorganic materials 0.000 description 16
- 239000011029 spinel Substances 0.000 description 16
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000005755 formation reaction Methods 0.000 description 11
- 150000002894 organic compounds Chemical class 0.000 description 11
- 238000005469 granulation Methods 0.000 description 8
- 230000003179 granulation Effects 0.000 description 8
- 238000005381 potential energy Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229920000515 polycarbonate Polymers 0.000 description 4
- 239000004417 polycarbonate Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920006289 polycarbonate film Polymers 0.000 description 3
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- 239000004431 polycarbonate resin Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- JLUUVUUYIXBDCG-UHFFFAOYSA-N 6-[1-benzyl-6-(4-methylpiperazin-1-yl)benzimidazol-2-yl]-n,3-dimethyl-[1,2,4]triazolo[4,3-a]pyrazin-8-amine Chemical compound C=1N2C(C)=NN=C2C(NC)=NC=1C1=NC2=CC=C(N3CCN(C)CC3)C=C2N1CC1=CC=CC=C1 JLUUVUUYIXBDCG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000012789 electroconductive film Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 125000006617 triphenylamine group Chemical group 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YJZATOSJMRIRIW-UHFFFAOYSA-N [Ir]=O Chemical class [Ir]=O YJZATOSJMRIRIW-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical group [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The present invention includes a sintered product for a transparent conductive film formed in a stable and efficient manner by sputtering or the like, a sputtering target of the sintered product, and a transparent conductive glass and film made of the target. The transparent conductive glass and film have excellent transparency, conductivity and workability into an electrode, and thus are suitable for use in a transparent electrode of an organic electroluminescent device to achieve a good hole injection rate therein. The sintered product contains indium oxide, tin oxide and zinc oxide as constituent components in a specific atomic ratio of the metal atom, and optionally contains a specific metal oxide such as ruthenium oxide, molybdenum oxide, vanadium oxide and the like.
Description
The application entered China's (international filing date: on August 19th, 1999) on June 30th, 2000, application number is 99801982.8, and (international application no: PCT/JP99/04453), denomination of invention is divided an application for the PCT international application of " target for transparent electroconductive film, transparent conductive material, transparent conducting glass and transparent conductive film ".
Technical field
The present invention relates to a kind of in display unit etc., the utmost point is suitable as the burning sintered product of nesa coating blank, is used to form transparent conducting glass and the transparent conductive film of the film forming of nesa coating with target, transparent conductive material and target formation from then on using this sintered product gained.
Background technology
In recent years, various display unit, for example liquid crystal indicator or electroluminescent (electroluminesence) display unit, field emission (field emmission) indicating meter etc. have imported the Controlling System in office's machinery or the factory all.In these display unit, no matter any device all has display unit and is sandwiched in sandwich structure in the nesa coating.
In these transparent electrolemmas, the most use becomes the ITO film with Indium sesquioxide-stannic oxide (being designated hereinafter simply as ITO).This ITO film except that have the preferable transparency, and lower resistance, also have good etching, the splendid close outstanding property good characteristic of substrate, and be extensive use of by this area.And this ITO film is generally by using sputtering method or method film forming such as ion plating method, vapour deposition method.
Though the ITO film has above-mentioned good characteristic, but still have many problems to be solved to exist, when for example in liquid crystal indicator, using, combine or form the electrode processibility that connects when pasting etc. with dissimilar metal about the taper processibility of the surface accuracy of ITO or electrode as transparency carrier.
Particularly, this ITO itself is the metal oxide in crystallization bosom, so when becoming mem stage, the film surface also can produce crystal grain.When the crystal grain of growing up is deposited on ITO film surface, can cause the reduction of surface accuracy.In the etching step that is used to form electrode pair ITO film, the grain to grain boundary is at first etched, and etching electrode surface can produce trickle concavo-convex, so be difficult for carrying out high-precision etching.Therefore, add man-hour for this ITO membrane electrode, the grain to grain boundary of this film is also at first etched, and this can make the ITO particle often remain in etched part, and at this moment, this ITO electrode film easily and produce electric conduction phenomena between electrode and cause and show problems such as bad.
And, for example open that flat 6-234565 communique disclosed in the spy for addressing this problem, in not sacrificing under the transparency and the electroconductibility, and be that purpose has proposed the transparent conductive material that Indium sesquioxide and zinc oxide were constituted with the processibility of improved electrode.But this is by the material that Indium sesquioxide and zinc oxide constituted, and the body resistance of itself is 2～5m Ω cm, thus must control input electric power during film forming, thereby have the shortcoming that is difficult for having competent productivity.
And, when the ITO film uses at the electrode of effect organic electroluminescence device, hole (positive hole) must be transferred to the luminescent layer or hole transporting layer of organic electroluminescence device from the ITO film.Therefore, the work function of the work function of wishing electrode materials and the organic compound that constitutes this luminescent layer or hole transporting layer is much at one level, so the energy gap of anode and cavity conveying interlayer is with few more good more.For reducing this energy gap, must use the work function of anode material as far as possible and reduce as the gap between the organic compound ionization potential energy of hole transporting layer.Proposed various organic compound to form the cavity conveying material of this hole transporting layer, wherein known aromatic amine based compound, particularly triphenylamine derivative have good function.Wherein, the triphenylamine in this triphenylamine derivative, its ionization potential energy is 5.5～5.6 electron-volts.On the other hand, for nesa coating, know Indium sesquioxide-stannic oxide (hereinafter to be referred as ITO) and have the good transparency and have than low resistance.The work function of this ITO is 4.6 electron-volts.Therefore, the anode that constituted of general thus material will exist with electron supplying layer portion and show sizable energy gap.
Under the sort of situation, for example the spy opens in the mean value 9-63771 communique, has disclosed the organic film luminous element that organic compound layer is set between anode and negative electrode.Its anode is the work function metal oxide film bigger than ITO.Yet the anode that film constituted of metal oxide, its transmittance are 10% when for example this metal is for ruthenium oxide, are 20% during for vanadium oxide.In order to improve this than low-transmittance, proposing by ITO film and thickness again is the double-layer structure that the ultrathin membrane below 300 dusts constitutes.Even but under this situation, transmittance also is about 40～60%.So when this bilayer structure was used for display unit, the transparency of its transparency electrode did not still meet the demands.
The present invention is providing a kind of when being carried out to membrane operations with sputtering method etc., can stablize and the sintered product of the metal oxide produced of mode smoothly, and the target that this sintered product constituted, and the transparent conducting glass and the conducting film that form by this target.These conductive glass and conducting film have the good transparency, electroconductibility, electrode processibility, and when using as the transparency electrode in the organic electroluminescence device, the all ionization potential energy gap of its work function and cavity conveying material is less in equipment, and can not cause the reduction of these equipment luminous efficiencies.
The inventor, just address the above problem through all research back result, learn when use contains sintered product by the compound that Indium sesquioxide, stannic oxide and zinc oxide constituted of specified proportion and uses as transparent conductive material, can solve the above problems smoothly, thereby finish the present invention.
Summary of the invention
Particularly, the present invention is made of a first aspect of the present invention～fourth aspect that is summarized as follows:
[I] a first aspect of the present invention
[1] a kind of sintered product wherein contains Indium sesquioxide, stannic oxide and zinc oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.50～0.75
Sn/(In+Sn+Zn)＝0.20～0.45
Zn/(In+Sn+Zn)＝0.03～0.30，
And contain tool In
2O
3(ZnO) m, m is 2～20 integer in the formula, shown hexagonal crystal lamellar compound and tool Zn
2SnO
4Shown spinel structure compound.
[2] as described above [1] record sintered product, its resistivity value is lower than 2m Ω cm.
[3] a kind of sintered product wherein contains Indium sesquioxide, stannic oxide and zinc oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.50～0.75
Sn/(In+Sn+Zn)＝0.20～0.45
Zn/(In+Sn+Zn)＝0.03～0.30，
And contain the positive tetravalence of 0.5～10 atom % that accounts for whole atoms metal total amounts and above polyvalent metal oxides, and contain formula In
2O
3(ZnO) m (m is 2～20 integer in the formula), shown hexagonal crystal lamellar compound and formula Zn
2SnO
4Shown spinel structure compound.
[4] as described above the sintered product of [3] record, wherein, positive tetravalence and above polyvalent metal oxides are ruthenium oxide, molybdenum oxide or vanadium oxide.
[5] a kind of sputtering target of nesa coating, it comprises the sintered product of each record in the item of aforementioned [1]～[4].
[6] a kind of electron bunch target of nesa coating, it comprises the sintered product of each record in the item of aforementioned [1]～[4].
[7] a kind of ion plating target of nesa coating (ion plating target), it comprises the sintered product of each record in the item of aforementioned [1]～[4].
[8] a kind of amorphous, transparent conducting film that is covered on glass surface makes, and conducting film wherein contains Indium sesquioxide, stannic oxide and zinc oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.50～0.75
Sn/(In+Sn+Zn)＝0.20～0.45
Zn/(In+Sn+Zn)＝0.03～0.30，
And contain the positive tetravalence of 0.5～10 atom % that accounts for whole atoms metal total amounts and above polyvalent metal oxides.
[9] as described above the transparent conducting glass of [8] record, wherein, positive tetravalence and above polyvalent metal oxides are ruthenium oxide, molybdenum oxide or vanadium oxide.
[10] as described above [8] or [9] record transparent conducting glass, wherein, transmittance is more than 75%, resistivity is at most 5m Ω cm, and the work function of nesa coating is more than 5.45.
[11] a kind of transparent conductive film that lining amorphous, transparent conductive layer makes on the transparent resin film surface, conducting film wherein contains Indium sesquioxide, stannic oxide and zinc oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.50～0.75
Sn/(In+Sn+Zn)＝0.20～0.45
Zn/(In+Sn+Zn)＝0.03～0.30，
And contain the positive tetravalence of 0.50～10 atom % that accounts for whole atoms metal total amounts and above polyvalent metal oxides.
[12] as described above the transparent conductive film of [11] record, wherein positive tetravalence and above polyvalent metal oxides are ruthenium oxide, molybdenum oxide or vanadium oxide.
[13] as described above [11] or [12] record transparent conductive film, wherein, transmittance is more than 75%, resistivity is at most 5m Ω cm, and the work function of nesa coating is more than 5.45.
[II] a second aspect of the present invention
[1] a kind of sintered product of composition, said composition contains Indium sesquioxide, Indium sesquioxide and zinc oxide and/or stannic oxide, and the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.00～0.20
Sn/(In+Zn+Sn)＝0.03～0.20
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
[2] a kind of composition sintered product, said composition contain Indium sesquioxide and zinc oxide or also contain stannic oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.80～1.00
Zn/(In+Sn+Zn)＝0.05～0.20
Sn/(In+Sn+Zn)＝0.00～0.20，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
[3] a kind of composition sintered product, said composition contains Indium sesquioxide, zinc oxide and stannic oxide, and the atomic ratio between each composition is
In/(In+Sn+Zn)＝0.80～1.00
Zn/(In+Sn+Zn)＝0.05～0.20
Sn/(In+Sn+Zn)＝0.02～0.20，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
[4] a kind of sputtering target, it contains the sintered product of each record in the item of aforementioned [1]～[3].
[5] a kind of electron bunch target (electron-beaming target), it contains the sintered product of each record in the item of aforementioned [1]～[3].
[6] a kind of ion plating target, it contains the sintered product of each record in the item of aforementioned [1]～[3].
[7] a kind of transparent conducting glass that the lining nesa coating that a kind of composition constituted makes on glass surface, said composition contains Indium sesquioxide, zinc oxide and stannic oxide, and the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.00～0.20
Sn/(In+Zn+Sn)＝0.00～0.20，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
[8] as described above [7] record transparent conducting glass, wherein, transmittance is more than 75%, resistivity is at most 5m Ω cm, and the work function of nesa coating is more than 5.45 electron-volts.
[9] a kind of transparent conductive film that the lining transparency conducting layer makes on the transparent resin film surface, conductive layer wherein contains Indium sesquioxide, zinc oxide and stannic oxide, and the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.00～0.20
Sn/(In+Zn+Sn)＝0.00～0.20，
And contain 0.50～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
[10] as described above [9] record transparent conductive film, wherein, transmittance is more than 75%, resistivity is at most 5m Ω cm, and the work function of transparency conducting layer is more than 5.45 electron-volts.
[III] a third aspect of the present invention
[1] a kind of transparent conductive material of composition, said composition comprises one or more metal oxides that are selected from Indium sesquioxide, zinc oxide and stannic oxide, and contains one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.5～20 atom % that accounts for whole atoms metal total amounts.
[2] a kind of transparent conductive material of composition, said composition comprises the metal oxide in Indium sesquioxide, zinc oxide and the stannic oxide, the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.00～1.00
Zn/(In+Zn+Sn)＝0.00～0.25
Sn/(In+Zn+Sn)＝0.00～1.00，
And contain one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.50～20 atom % that accounts for whole atoms metal total amounts.
[3] a kind of transparent conductive material of composition, said composition comprises the metal oxide in Indium sesquioxide, zinc oxide and the stannic oxide, the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.50～1.00
Zn/(In+Zn+Sn)＝0.05～0.25
Sn/(In+Zn+Sn)＝0.00～0.50，
And contain one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.5～20 atom % that accounts for whole atoms metal total amounts.
[4] a kind of transparent conductive material of composition, said composition comprises the metal oxide in Indium sesquioxide, zinc oxide and the stannic oxide, the atomic ratio between each composition is
In/(In+Zn+Sn)＝0.75～0.95
Zn/(In+Zn+Sn)＝0.05～0.20
Sn/(In+Zn+Sn)＝0.00～0.20，
And contain one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.50～20 atom % that accounts for whole atoms metal total amounts.
[5] a kind of sintered product that makes by each composition in aforementioned [1]～[4] of the sintering.
[6] a kind of sputtering target comprises aforementioned [5] sintered product.
[7] a kind of transparent conducting glass that the nesa coating of a kind of composition of lining makes on glass surface, said composition contains one or more metal oxides that are selected from Indium sesquioxide, zinc oxide and stannic oxide, and contains one or more selected in iridium oxide, rhenium oxide and the palladous oxide metal oxides that are selected from of 0.5～20 atom % that accounts for whole atoms metal total amounts.
[8] as described above [7] record transparent conducting glass, its transmittance is more than 70%, and the work function of nesa coating is more than 5.4 ev.
[9] a kind of transparent conductive film that lining layer of transparent conductive layer makes on the transparent resin film surface, this transparency conducting layer comprises one or more metal oxides that are selected from Indium sesquioxide, zinc oxide and stannic oxide, and contain 0.5～20 atom % that accounts for whole atoms metal total amounts by one or more selected in iridium oxide, rhenium oxide and palladous oxide metal oxides.
[10] as described above [9] record transparent conductive film, its transmittance is more than 70%, and the work function of transparency conducting layer is more than 5.4 electron-volts.
[IV] a fourth aspect of the present invention
[1] a kind of transparent conductive material of composition, said composition comprises the metal oxide in stannic oxide, Indium sesquioxide and the zinc oxide, the atomic ratio between each composition is
Sn/(Sn+In+Zn)＝0.55～1.00，
In/(Sn+In+Zn)＝0.00～0.45
Zn/(Sn+In+Zn)＝0.00～0.25
And contain one or more metal oxides of 0.5～10 atom % that accounts for whole atoms metal total amounts by vanadium oxide, molybdenum oxide and ruthenium oxide.
[2] as described above [1] record transparent conductive material, wherein, the atomic ratio between each composition of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.55～0.95
In/(Sn+In+Zn)＝0.00～0.40
Zn/(Sn+In+Zn)＝0.05～0.25
[3] as described above [1] record transparent conductive material, wherein, the atomic ratio between each composition of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.55～0.95
In/(Sn+In+Zn)＝0.00～0.40
Zn/(Sn+In+Zn)＝0.05～0.20
[4] as described above [1] record transparent conductive material, wherein, the atomic ratio between each composition of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.60～0.95
In/(Sn+In+Zn)＝0.00～0.35
Zn/(Sn+In+Zn)＝0.05～0.20
[5] sintered product made in being not less than 1200 ℃ sintering temperature of a kind of each composition by aforementioned [1]～[4].
[6] a kind of sputtering target, it comprises the sintered product of aforementioned [5] record, and resistivity is below the 10m Ω cm.
[7] a kind of on the glass surface substrate, the transparent conducting glass that the nesa coating of a kind of composition that is covered makes, said composition contains the metal oxide in stannic oxide, Indium sesquioxide and the zinc oxide, and the atomic ratio between each composition is
Sn/(Sn+In+Zn)＝0.55～1.00
In/(Sn+In+Zn)＝0.00～0.45
Zn/(Sn+In+Zn)＝0.00～0.25
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by one or more selected in vanadium oxide, molybdenum oxide and ruthenium oxide metal oxides.
[8] as described above [7] record transparent conducting glass, wherein, the transmittance of nesa coating is more than 70%, and work function is more than 5.4 electron-volts.
[9] transparent conductive film that makes of a kind of transparency conducting layer that overlies a kind of composition in the transparent resin film surface, said composition comprises the metal oxide in stannic oxide, Indium sesquioxide and the zinc oxide, and the atomic ratio between each composition is
Sn/(Sn+In+Zn)＝0.55～1.00
In/(Sn+In+Zn)＝0.00～0.45
Zn/(Sn+In+Zn)＝0.00～0.25
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by one or more selected in vanadium oxide, molybdenum oxide and ruthenium oxide metal oxides.
[10] as described above [9] record transparent conductive film, wherein, the transmittance of transparency conducting layer is more than 70%, and work function is more than 5.4 electron-volts.
Embodiment
Below will describe embodiment of the present invention.
[I] a first aspect of the present invention
Sintered product of the present invention is the transparent conductive material of using as the nesa coating film forming, and its basic comprising composition is Indium sesquioxide, stannic oxide and zinc oxide.
The atomic ratio of its moiety is
In/(In+Sn+Zn)＝0.50～0.75
Sn/(In+Sn+Zn)＝0.20～0.45
Zn/(In+Sn+Zn)＝0.03～0.30。
In these proportion of composing scopes, again with
In/(In+Sn+Zn)＝0.60～0.75
Sn/(In+Sn+Zn)＝0.20～0.35
Zn/(In+Sn+Zn)＝0.05～0.20
For preferably.
Again with
In/(In+Sn+Zn)＝0.60～0.70
Sn/(In+Sn+Zn)＝0.25～0.35
Zn/(In+Sn+Zn)＝0.05～0.15
For most preferably.
Among the present invention, as the composition such as the above-mentioned qualification of Indium sesquioxide, stannic oxide and the zinc oxide of constituent, if the mixture of Indium sesquioxide and zinc oxide is under low temperature during sintering, the electroconductibility of sintered product is low.Sintered product of the present invention can prevent that electroconductibility from reducing.The mixture of these Indium sesquioxides and zinc oxide is if during sintering, can form the hexagonal crystal lamellar compound that electroconductibility improves under high temperature.But desire is transformed to the hexagonal crystal lamellar compound with all zinc oxide its difficulty is arranged, so the raising of electroconductibility is also limited.
Therefore, make the zinc oxide and the stannic oxide effect that can't be transformed to the hexagonal crystal lamellar compound among the present invention, to form compound with spinel structure, the electroconductibility of the sintered product of composition gained is improved, can use the sputter process that target carried out of sintered product gained thus more stable.
About the blended ratio of these compositions,, except that the surface resistivity that can cause the gained nesa coating raises, thermotolerance is reduced at 0.50 o'clock if the atomic ratio of Indium sesquioxide is lower than; If this numerical value surpasses at 0.75 o'clock, can make gained nesa coating generation crystallization and cause that the transparency reduces.If the atomic ratio of stannic oxide is lower than at 0.20 o'clock, the spinel structure compound that zinc oxide and stannic oxide form will be not exclusively; If this numerical value surpasses, the surface resistivity of gained nesa coating is improved at 0.45 o'clock.In addition, if the atomic ratio of zinc oxide is lower than at 0.03 o'clock, the nesa coating of gained forms crystallization easily, and this numerical value then can make the thermotolerance of the nesa coating of gained reduce if surpass at 0.30 o'clock.
These constituents still contain with In in these metal oxides except that above-mentioned compositing range
2O
3(ZnO) (m is 2～20 integer to m in the formula.) shown in the hexagonal crystal lamellar compound, and formula Zn
2SnO
4Shown spinel structure compound.
Sintered product of the present invention by above-mentioned structure gained has higher electric conductivity as previously mentioned, and resistivity value is lower than 2m Ω cm.Therefore,, sputter process is carried out under more stable situation, therefore can under extremely good working condition, manufacture membrane product using when carrying out film forming as the sputter equipment of target etc. with this sintered product.
This sintered product comprises constituent Indium sesquioxide, stannic oxide and zinc oxide, and contains in addition and account for wherein all the positive tetravalence of 0.5～10 atom % of atoms metal total amounts or above polyvalent metal oxides, especially is preferably ruthenium oxide, molybdenum oxide or vanadium oxide.This sintered product has the work function between 5.45 and 5.70 ev, so average work function 5.6 ev as the organic compound of luminophore or cavity conveying material are almost same level in its work function and the organic electroluminescence device.Therefore, if be used for organic electroluminescence device, then the nesa coating that forms by this sintered product target of sputter should have high hole input rate.In this sintered product, the ratio of positive tetravalence or above polyvalent metal oxides is preferably 1～5 atom % of whole atoms metal total values.
Secondly, the manufacture method of relevant sintered product of the present invention, it is powder with above-mentioned each metal oxide, use mixing and grinding machine, for example wet-type ball mill or ball mill, ultrasound etc., mix equably, after the grinding, granulation, make required shape in the extrusion forming mode, become sintered product through sintering processes again.Herein with the raw material powder mixed grinding, be it is ground to as far as possible fine, but general so that be that the thing of the following mixed grinding of 1 μ m is good with handling to median size.Sintering condition is generally 1,200～1,500 ℃, is preferably 1,250～1,480 ℃, and the time is 10～72 hours, is preferably 24～48 hours.The temperature rise rate of this moment is 1～50 ℃/minute.
In this sintering processes, when making Indium sesquioxide in the sintered product and zinc oxide form the form of the hexagonal crystal lamellar compound shown in the aforementioned formula, sintering temperature is being good more than 1,250 ℃.When having the compound of spinel structure for zinc oxide and stannic oxide are formed, its sintering temperature is being good more than 1,000 ℃.
When preparation sintered product of the present invention, when these metal oxide three composition systems with positive tetravalence and above polyvalent metal oxides such as ruthenium oxide, molybdenum oxide or vanadium oxide in conjunction with the time, the powder of an amount of additional metals oxide compound such as ruthenium oxide is added in the three composition system metal oxide powders of raw material, carry out sintering by last method again.Equally, the sintering of shaped object can be can to form in the sintered product of gained under the condition of spinel structure compound of six side's lamellar compounds of Indium sesquioxide and zinc oxide and zinc oxide and stannic oxide and carry out.
[II] a second aspect of the present invention
Among the present invention, forming the sintered product that nesa coating is used, is to contain the Indium sesquioxide of following atomic ratio or the composition of Indium sesquioxide and zinc oxide and/or stannic oxide,
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.00～0.20
Sn/(In+Zn+Sn)＝0.00～0.20，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by one or more selected in ruthenium oxide, molybdenum oxide and vanadium oxide metal oxides.
Preferred sintered product is to contain the Indium sesquioxide of following atomic ratio and the composition of zinc oxide or these compounds and stannic oxide,
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.05～0.20
Sn/(In+Zn+Sn)＝0.00～0.20，
Said composition also contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
Most preferred burning product is the composition of the Indium sesquioxide, zinc oxide and the stannic oxide that contain following atomic ratio,
In/(In+Zn+Sn)＝0.80～1.00
Zn/(In+Zn+Sn)＝0.05～0.20
Sn/(In+Zn+Sn)＝0.02～0.20，
Said composition also contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
In the sintered product of the present invention, composition as Indium sesquioxide, stannic oxide and the zinc oxide of basic comprising composition as mentioned above, can use Indium sesquioxide separately, maybe can use the mixture of Indium sesquioxide and small amounts of zinc, or use the mixture of Indium sesquioxide and small amounts of zinc and stannic oxide.
Wherein, in the content of these compositions,, except that the surface resistivity that can cause the gained nesa coating raises, thermotolerance is reduced at 0.80 o'clock if the atomic ratio of Indium sesquioxide is lower than.The atomic ratio of zinc oxide is lower than at 0.05 o'clock, can cause the etching of gained nesa coating not good.At this moment, when spatter film forming, can add water or hydrogen on a small quantity, so that its etching improves.The atomic ratio of zinc oxide can make the electroconductibility of gained nesa coating reduce if surpass at 0.20 o'clock.In addition, if the atomic ratio of stannic oxide is lower than, the electroconductibility of target is reduced at 0.02 o'clock, this numerical value then can make the surface resistivity of the nesa coating of gained raise if surpass at 0.20 o'clock.
Described sintered product comprises the basal component of above-mentioned Indium sesquioxide or Indium sesquioxide and zinc oxide and/or stannic oxide and contains by ruthenium oxide, molybdenum oxide and interpolation metal oxide that vanadium oxide went out earlier that its content is 0.5～10 atom % that accounts for atoms metal total amount in the composition.If these add the content of metal oxides when being lower than 0.5 atom %, and the nesa coating of gained then can't possess enough high work function, if when this content surpasses 10 atom %, can cause the reduction of the transparency.That is, the preferable range of these metal oxide contents is to account for 1～7 atom % of atoms metal total amount in the composition, more preferably 1～5 atom %.
So, be used in and add behind one or more ruthenium oxide or the added ingredientss such as molybdenum oxide, vanadium oxide the nesa coating that the sintered product with gained makes in the basal component such as Indium sesquioxide, can obtain making work function to improve, if the content of this added ingredients can obtain the numerical value more than 5.45 electron-volts when above-mentioned scope.The numerical value of the work function of this nesa coating, with in the organic electroluminescence device as 5.5～5.6 electron-volts of the mean value of the work function of organic compound such as luminophore or cavity conveying material quite.Therefore, when using this nesa coating as the anode of organic electroluminescence device, the energy gap in the time of can making anode injected hole transfer layer thus or the hole injected luminescent layer reduces, so this equipment can guarantee higher hole input rate.Therefore, the driving voltage of organic electroluminescence device is reduced, also can suppress the heating phenomenon that each interlayer energy gap is produced, and can make it have stable luminescence phenomenon for a long time.
Secondly, relevant agglomerating manufacture method of the present invention, it is powder with above-mentioned each metal oxide, use mixing and grinding machine, for example wet-type ball mill or ball mill, ultrasound etc., mix equably, after the grinding, granulation, make required shape in the extrusion forming mode, become sintered product through sintering processes again.Herein with the raw material powder mixed grinding, be it to be ground to fine as far as possible, be below the 1 μ m but be generally mixed grinding to median size.In the sintering stage, molding is 1,200～1, and 500 ℃, be preferably 1,250～1,480 ℃ of sintering, the time is 10～72 hours, is preferably 24～48 hours.The temperature rise rate of this moment is 1～50 ℃/minute.
[III] a third aspect of the present invention
Transparent conductive material of the present invention is a kind of composition, it comprises one or more metal oxides that are selected from Indium sesquioxide, zinc oxide and stannic oxide, and contains and account for wherein all one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.5～20 atom % of atoms metal total amounts.
Transparent conductive material of the present invention with preferred electroconductibility is the composition of the Indium sesquioxide, zinc oxide and the stannic oxide metal oxide that comprise following atomic ratio,
In/(In+Zn+Sn)＝0.00～1.00
Zn/(In+Zn+Sn)＝0.00～0.25
Sn/(In+Zn+Sn)＝0.00～1.00
And contain one or more metal oxides that are selected from iridium oxide, rhenium oxide and palladous oxide of 0.5～20 atom % that accounts for whole atoms metal total amounts.
Preferred transparent conductive material is the composition by the metal oxide in the Indium sesquioxide that comprises following atomic ratio, zinc oxide and the stannic oxide:
In/(In+Zn+Sn)＝0.50～1.00
Zn/(In+Zn+Sn)＝0.05～0.25
Sn/(In+Zn+Sn)＝0.00～0.50
And contain the transparent conductive material of 0.5～20 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in iridium oxide, rhenium oxide and the palladous oxide.
Wherein, have the more preferably transparent conductive material of electroconductibility and be metal oxide by the Indium sesquioxide that comprises following atomic ratio, zinc oxide and stannic oxide,
In/(In+Zn+Sn)＝0.75～0.95
Zn/(In+Zn+Sn)＝0.05～0.20
Sn/(In+Zn+Sn)＝0.00～0.20
And contain the transparent conductive material of 0.5～20 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in iridium oxide, rhenium oxide and the palladous oxide.
Have the transparent conductive material of electroconductibility most preferably and be metal oxide by the Indium sesquioxide that comprises following atomic ratio, zinc oxide and stannic oxide,
In/(In+Zn+Sn)＝0.85～0.95
Zn/(In+Zn+Sn)＝0.07～0.20
Sn/(In+Zn+Sn)＝0.00～0.15
And contain the transparent conductive material of 0.5～20 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in iridium oxide, rhenium oxide and the palladous oxide.
In the transparent conductive material of the present invention, as Indium sesquioxide, zinc oxide and the stannic oxide of basic comprising composition or the mixture of these metal oxides, as mentioned above, can use Indium sesquioxide, zinc oxide or stannic oxide separately, maybe can use the mixture of Indium sesquioxide and small amounts of zinc, or use the mixture of Indium sesquioxide and stannic oxide, maybe can use the mixture of Indium sesquioxide and zinc oxide and stannic oxide.
About the blended ratio of these basic comprising compositions, Indium sesquioxide is not often to need here.But in order to make this material can form the nesa coating of low surface resistivity, the atomic ratio of wishing iridium oxide is more than 0.5.Zinc oxide is not often to need here.But but, just in this material prescription, add small amounts of zinc in order to make this material can form the nesa coating of higher etching.For this reason, for example the atomic ratio of zinc oxide can be more than 0.05.When if the etching of the nesa coating that forms of material is not good thus, can be in making this material sintered product sputter add a spot of water or hydrogen in the film forming device with shape, thus but can improve the film forming etching of institute's shape.If the atomic ratio of zinc oxide surpasses at 0.25 o'clock, then the wearing quality of this nesa coating will be low.Stannic oxide is not often to need here.But for the electroconductibility that makes the target that this material forms in higher level, preferably contain stannic oxide in the material of the present invention.Yet when the nesa coating that is formed by this target when hope had low surface resistivity, the atomic ratio of stannic oxide was preferably in below 0.5 in this material.
In this material, its basic comprising composition should with any iridium oxide, rhenium oxide, and palladous oxide or with can wish that the mixture of this metal oxide of ratio combines in any.Desire adds this part the added metal oxide compound in this material, should account for 0.5～20 atom % of this material metal atom total amount of whole formations that comprises this added metal oxide compound.If when representing with atomic ratio, available following formula provides:
Ir/(In+Zn+Sn+Ir)＝0.005～0.20，
Re/(In+Zn+Sn+Re)＝0.005～0.20，
Pd/(In+Zn+Sn+Pd)＝0.005～0.20，
Preferably,
Ir/(In+Zn+Sn+Ir)＝0.01～0.10，
Re/(In+Zn+Sn+Re)＝0.01～0.10，
Pd/(In+Zn+Sn+Pd)＝0.01～0.10，
More preferably
Ir/(In+Zn+Sn+Ir)＝0.03～0.08，
Re/(In+Zn+Sn+Re)＝0.03～0.08，
Pd/(In+Zn+Sn+Pd)＝0.03～0.08。
If the content of these supplementary component iridium oxides, rhenium oxide and palladous oxide can't make the work function of nesa coating reach sufficient height when being lower than 0.5 atom %, when this content surpasses 20 atom %, then can cause the reduction of the transparency.
Comprise above-mentioned basic comprising composition, and contain the composition of metal oxide of iridium oxide, rhenium oxide and the palladous oxide of 0.5～20 atom % that accounts for whole atoms metal total amounts that can be sintered into sputtering target, this target forms nesa coating through sputter.The transmittance of this nesa coating be 70% with, the value of work function is more than 5.4 electron-volts.The numerical value of the work function of this nesa coating, with 5.5～5.6 electron-volts of the mean value of the ionization potential energy of the organic compound that uses as luminophore or cavity conveying material etc. in the organic electroluminescence device quite.Therefore, when using this nesa coating, the energy gap when injecting luminescent layer through anode injected hole transfer layer thus or with the hole is reduced as the anode of organic electroluminescence device, and a higher hole input rate.Therefore, can make the driving pressure drop of organic electroluminescence device low, also can suppress the heating phenomenon that produced because of each interlayer energy gap, and it is stable for a long time to guarantee that it has.
The manufacture method of relevant transparent conductive material of the present invention is for example the powder of above-mentioned each metal oxide to be mixed according to certain proportion, and it can use mixing and grinding machine, for example wet-type ball mill or ball mill, ultrasound etc. with uniform mixing, grinding and make.Herein with the raw material powder mixed grinding, be it is ground to fine as far as possible, but generally be mixed grinding handle to median size be below the 1 μ m.
In order to obtain sintered product with this transparent conductive material gained, for example can be after granulation, make desirable shape in the mode of extrusion forming, thereafter again with the molding sintering.In sintering step, be generally 1,200～1,500 ℃, be preferably 1,250～1,480 ℃ of sintering 10～72 hours, be preferably 24～48 hours.The temperature rise rate of this moment is 1～50 ℃/minute.
[IV] a fourth aspect of the present invention
Transparent conductive material of the present invention is by the metal oxide in the stannic oxide that comprises following atomic ratio, Indium sesquioxide and the zinc oxide
Sn/(Sn+In+Zn)＝0.55～1.00
In/(Sn+In+Zn)＝0.00～0.45
Zn/(Sn+In+Zn)＝0.00～0.25
And contain the transparent conductive material of 0.5～20 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in vanadium oxide, molybdenum oxide and the ruthenium oxide.
Preferably, this transparent conductive material is by the metal oxide in the stannic oxide that comprises following atomic ratio, Indium sesquioxide and the zinc oxide
Sn/(Sn+In+Zn)＝0.60～0.95
In/(Sn+In+Zn)＝0.00～0.35
Zn/(Sn+In+Zn)＝0.05～0.20
And contain the transparent conductive material of 0.5～10 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in vanadium oxide, molybdenum oxide and the ruthenium oxide.
More preferably, this transparent conductive material is by the metal oxide in the stannic oxide that comprises following atomic ratio, Indium sesquioxide and the zinc oxide
Sn/(Sn+In+Zn)＝0.55～0.95
In/(Sn+In+Zn)＝0.00～0.40
Zn/(Sn+In+Zn)＝0.05～0.25
And contain the transparent conductive material of 0.5～10 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in vanadium oxide, molybdenum oxide and the ruthenium oxide.
More preferably, this transparent conductive material is the metal oxide by the stannic oxide that comprises following atomic ratio, Indium sesquioxide and zinc oxide
Sn/(Sn+In+Zn)＝0.55～0.95
In/(Sn+In+Zn)＝0.00～0.40
Zn/(Sn+In+Zn)＝0.05～0.20
And contain the transparent conductive material of 0.5～10 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in vanadium oxide, molybdenum oxide and the ruthenium oxide.
Most preferably, this transparent conductive material is the metal oxide by the stannic oxide that comprises following atomic ratio, Indium sesquioxide and zinc oxide
Sn/(Sn+In+Zn)＝0.60～0.95
In/(Sn+In+Zn)＝0.00～0.35
Zn/(Sn+In+Zn)＝0.05～0.20
And contain the transparent conductive material of 0.5～10 atom % that accounts for whole atoms metal total amounts by the composition gained of selected one or more metal oxides in vanadium oxide, molybdenum oxide and the ruthenium oxide
In the transparent conductive material of the present invention, mixture as stannic oxide, Indium sesquioxide, zinc oxide or these metal oxides of basic comprising composition, as mentioned above, can use stannic oxide, Indium sesquioxide or zinc oxide separately, maybe can use the mixture of stannic oxide and small amounts indium, or the mixture of use stannic oxide and zinc oxide, maybe can use the mixture of stannic oxide and Indium sesquioxide and zinc oxide all can.
About the blended ratio of these basic comprising compositions, the content that it is desirable to stannic oxide is at least 0.55, so that it can inexpensively make and can be made into the nesa coating of tool excellent heat resistance.Indium sesquioxide is often inessential, but for making nesa coating maintain high electrical conductivity, its atomic ratio with 0.45 with interior be good.In the content ratio of this Indium sesquioxide,, the manufacturing expense of nesa coating is improved at 0.45 o'clock if its atomic ratio surpasses.Zinc oxide is often inessential, but for making the etching and processing raising of nesa coating, it can add composition.The atomic ratio of zinc oxide to be added is being good more than 0.05.For the nesa coating of keeping formation has good humidity resistance, the atomic ratio of zinc oxide is good with 0.25 following person.When if the etching and processing of nesa coating is not good, can when the spatter film forming of nesa coating, add a spot of water or hydrogen, so that its etching increases.
In this material, in above-mentioned basic comprising composition, can contain any vanadium oxide, molybdenum oxide and ruthenium oxide of wishing ratio, Individual existence or exist with the hybrid mode of its any blending ratio all can separately.Wherein, these additional metal oxide compounds comprise the atoms metal of additional metal oxide compound with respect to all atoms metals that constitute this material, are 0.5～10 atom %.If when it is represented with atomic ratio, then be
V/(In+Zn+Sn+V)＝0.005～0.10
Mo/(In+Zn+Sn+Mo)＝0.005～0.10
Ru/(In+Zn+Sn+Ru)＝0.005～0.10；
Be preferably
V/(In+Zn+Sn+V)＝0.01～0.08
Mo/(In+Zn+Sn+Mo)＝0.01～0.08
Ru/(In+Zn+Sn+Ru)＝0.01～0.08；
More preferably
V/(In+Zn+Sn+V)＝0.02～0.05
Mo/(In+Zn+Sn+Mo)＝0.02～0.05
Ru/(In+Zn+Sn+Ru)＝0.02～0.05
Arbitrary in these vanadium oxides, molybdenum oxide or the ruthenium oxide, or if the content of its mixture can't make the work function of nesa coating reach sufficient height when being lower than 0.5 atom %, when this content surpasses 10 atom %, then can cause the reduction of the transparency.
Contain above-mentioned basic comprising composition, and contain the composition of metal oxide of vanadium oxide, molybdenum oxide and the ruthenium oxide of 0.5～10 atom % that accounts for whole atoms metal total amounts, can be sintered into sputtering target, this target forms nesa coating through sputter.The transmittance of this nesa coating is more than 70%, and the value of work function is more than 5.4 electron-volts.The numerical value of the work function of this nesa coating, with 5.5～5.6 electron-volts of the mean value of the ionization potential energy of the organic compound that uses as luminophore or cavity conveying material etc. in the organic electroluminescence device quite.Therefore, when using this nesa coating, the energy gap when injecting luminescent layer through anode injected hole transfer layer thus or with the hole is reduced as the anode of organic electroluminescence device, and a higher hole input rate.Therefore, can make the driving pressure drop of organic electroluminescence device low, also can suppress the heating phenomenon that produced because of each interlayer energy gap, and can guarantee that it has long stabilized illumination.
The manufacture method of relevant transparent conductive material of the present invention, for example the powder with above-mentioned each metal oxide mixes according to certain proportion, and it can use mixing and grinding machine, for example wet-type ball mill or ball mill, ultrasound etc. with uniform mixing, grinding and make.Herein with the raw material powder mixed grinding, be it is ground to fine as far as possible, but generally be mixed grinding handle to median size be below the 1 μ m.
In order to obtain sintered product with this transparent conductive material gained, for example can be after granulation, make desirable shape in the mode of extrusion forming, thereafter again with the molding sintering.In sintering step, generally 1,200～1,500 ℃, be preferably 1,250～1,480 ℃ of sintering 10～72 hours, be preferably 24～48 hours.This moment, temperature rise rate was 1～50 ℃/minute.When adopting this sintering condition, can make resistivity is the following sintered product of 10m Ω cm.
The sintered product of gained like this is machined into the body of the sputter equipment of can packing into, the suitable device of attached cooperation after each body.Can make a sputtering target that has good electric conductivity and can stably carry out sputter like this.
The transparency electrode glass and the transparent conductive film of [V] first to fourth aspect of the present invention
Use above-mentioned gained target on transparent substrate, to carry out film forming.Transparent substrate can use present use glass substrate or, have the plastic film of high transparent or thin slice etc.Preferred synthetic resins for example can use polycarbonate resin, plexiglass, polyester resin, polyethersulfone resin, polyacrylate resin or the like.
Using above-mentioned target nesa coating being placed on the transparent substrate when carrying out film forming with sputtering method, is good to use magnetron formula sputter equipment.And use this device to carry out in the condition of spatter film forming, with the thickness of the surface-area of target or nesa coating to be formed, plasma body output can produce change, but the output of general plasma body is in target surface-area 1cm
2Be the scope of 0.3～4W, the film forming time is 5～120 minutes.The film thickness of this nesa coating has difference with the kind of display unit, generally with 2000～6000 dusts, is preferably 300～2000 dusts.
The electron bunch device of aforementioned sintered product write by the use dress or the target in the ion sputtering device carries out film forming.Can under filming condition same as described above, carry out the film forming step of nesa coating.
For the transparent conducting glass or the transparent film of the prepared a first aspect of the present invention of Using such method, these are formed transparency conducting layer on transparent substrate, has high transmittance and lower resistivity.This transparency conducting layer of etching obtains transparency electrode.Particularly, after hydrochloric acid or oxalic acid etching, etched part is very not level and smooth with the cross-sectional shape of the part of etched part boundary, and this etched part and etched part are not clearly distinguished.Thereby can form electrode cable circuit with even width and thickness.Therefore, the transparency conducting layer on transparent conducting glass of the present invention or the transparent conductive film, can any usual manner etching and processing in addition, obtain transparent good electricity level.When the nesa coating of electrode poor in processability was etched into electrode, the circuit resistance that comprises electrode partly increased or descends, and at this moment the insulation area in the circuit is with the unable to get up insulating effect, and circuit will damage.Comprise that to make the circuit of transparency electrode by the present invention then opposite, do not have these troubles.
In a first aspect of the present invention, by the metal oxide that comprises aforementioned 3 compositions system and contain positive 4 valencys and transparency conducting layer that above metal oxide gained sintered product forms, having transmittance is more than 75%, thereby has high transparent.Its resistivity of having is at most 5m Ω cm in addition, and work function is more than 5.45.Use this transparency conducting layer, transparent conducting glass of the present invention or transparent conductive film are suitable for making the organic electroluminescence device transparency electrode.In the present embodiment, if the content of positive 4 valencys and above metal oxide is too high, then the electric conductivity of conductive layer can reduce.Therefore, if when needing this conductive layer to keep higher electric conductivity, it should have a kind of laminate structures, this structure comprise with its on the laminated again upper strata of containing by positive 4 valencys or above metal oxide.This two-layer laminated thing of sintering then.Obtain having the transparency conducting layer of good electric conductivity.And its work function is close to identical with the organic compound that is applicable to organic electroluminescence device.This conductive layer is suitable for use in the electrode of organic electroluminescence device.
In the transparent conducting glass and transparent conductive film of a second aspect of the present invention of aforesaid way gained, it is identical with the sintered product of this conductive layer of formation that the metal oxide of transparency conducting layer is formed.The transparency of last transparency conducting layer is more than 75% to the transmittance of wavelength 500nm.With regard to the electroconductibility of this nesa coating, its resistivity is at most 5m Ω cm.As mentioned above, the work function of this conductive layer used common ITO film higher more in the past, was more than 5.45 electron-volts.
In the transparent conducting glass and transparent conductive film of a third aspect of the present invention of aforesaid way gained, it is identical with the sintered product of this conductive layer of formation that the metal oxide of transparency conducting layer is formed.The transparency of last transparency conducting layer is more than 70% to the transmittance of wavelength 500nm.With regard to the electroconductibility of this nesa coating, its resistivity is at most 5m Ω cm.Therefore, as mentioned above, the work function of this conductive layer used common ITO film higher more in the past, was more than 5.4 electron-volts.This value almost equates with the value of the ionization potential energy of the organic compound of luminescent layer that is formed with organic electroluminescence devices or hole transporting layer.
In the transparent conducting glass and transparent conductive film of a fourth aspect of the present invention of aforesaid way gained, it is identical with the sintered product of this conductive layer of formation that the metal oxide of transparency conducting layer is formed.The transparency of last transparency conducting layer is more than 70% to the transmittance of wavelength 500nm.Therefore, as mentioned above, the work function of this conductive layer used common ITO film higher more in the past, was more than 5.4 electron-volts.This value almost equates with the value of the ionization potential energy of the organic compound of luminescent layer that is formed with organic electroluminescence devices or hole transporting layer.
Therefore, transparent conducting glass of the present invention or transparent conductive film, in various display unit, in for example typical organic electroluminescence device, the utmost point is suitable as transparency electrode.
Embodiment
The present invention is described in more detail with reference to following embodiment, but the present invention is not subjected to the restriction of these examples.
[a first aspect of the present invention]
[example I-1]
(1) manufacturing of sintered sheets
The powder that uses Indium sesquioxide, stannic oxide and zinc oxide is as raw material, and mixed in the back feed-in wet-type ball mill with following atomic ratio, and through 72 hours mixed grindings.
In/(In+Sn+Zn)＝0.50
Sn/(In+Sn+Zn)＝0.25
Zn/(In+Sn+Zn)＝0.25
After the granulation of gained abrasive material, add the sheet that is pressed into 4 inches of diameters, thick 5mm again, again it is inserted in the sintering oven, carry out 1400 ℃, 36 hours pressure sintering.
The sintered sheets of Using such method gained, its density are 6.6g/cm
3, and body resistance is 0.95m Ω cm.
Secondly, the crystallinity of this sintered sheets confirms through X-ray analysis, the crystallization that forms Indium sesquioxide in the sintered sheets with, with In
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is main compound crystal with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned gained, be made into the sputtering target of 4 inches of diameters, thickness 5mm.It is loaded on the DC magnetic controlled tube sputtering apparatus, and on glass substrate film forming.
About sputtering condition, surrounding environment is to use the ar gas environment that is mixed with an amount of oxygen, and sputtering pressure is 3 * 10
-1Pa, final vacuum tightness is 5 * 10
-4Pa, substrate temperature are 25 ℃, and the importing energy is 100W, and the film forming deposition time is 14 minutes.
The nesa coating that forms on this transparent glass, its thickness are 1,200 dust, and are amorphous.And the transmittance of this nesa coating is with spectrophotometer measurement, and the light of 500nm is measured as 79%.The resistivity of the nesa coating of measuring with 4 probe methods is 0.36m Ω cm, so the electroconductibility of this film is high.Work function is measured with the ultraviolet electron spectroscopy for chemical analysis.
(3) processibility of nesa coating assessment
The nesa coating that will form on glass substrate in above-mentioned (2), via the mask with the penetrating hole of wire, coating is with protective layer, and video picture.And with this film of aqueous hydrochloric acid etching patterned protective layer on it.In the film of this etch processes, the boundary part of etching part and non-etching part, formation has level and smooth inclined surface.Thereafter the membrane portions that will contact with etching solution is removed, and not finding remainingly on this contact surface has a film.
Its assessment result is shown in Table I-2.
[example I-2]
Glass substrate temperature except that with the sputter of (2) part in the example I-1 time is adjusted into 215 ℃, and other all make transparent conducting glass with example I-1 same steps as.
The assessment result of the nesa coating on the gained transparent conducting glass is shown in Table I-2.
[example I-3]
Removing the used glass substrate of transparent substrate with (1) part in the example I-1, is that other all make transparent conducting glass with example I-1 same steps as beyond the polycarbonate substrate replacement of 0.1mm with thickness.
The assessment result of the transparent conductive film that forms on polycarbonate substrate is shown in Table I-2.
[example I-4]
(1) manufacturing of sintered sheets
The powder that remove to use Indium sesquioxide, stannic oxide and zinc oxide is as raw material, and beyond being mixed with following atomic ratio, other all according to example I-1 same steps as, make sintered sheets.
In/(In+Sn+Zn)＝0.50
Sn/(In+Sn+Zn)＝0.45
Zn/(In+Sn+Zn)＝0.05
The sintered sheets of Using such method gained, its density are 6.8g/cm
3, and body resistance is 0.98m Ω cm.The crystallinity of this sintered sheets is to form the crystallization that has by Indium sesquioxide through confirming it, with In
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms in above-mentioned (2), carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[example I-5]
(1) manufacturing of sintered sheets
The powder that removes the Indium sesquioxide, stannic oxide and the zinc oxide that use following atomic ratio is as raw material, and beyond being mixed, other all according to example I-1 same steps as, make sintered sheets.
In/(In+Sn+Zn)＝0.70
Sn/(In+Sn+Zn)＝0.25
Zn/(In+Sn+Zn)＝0.05
The sintered sheets of Using such method gained, its density are 6.8g/cm
3, and body resistance is 0.87m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide through confirming it, with In
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms in above-mentioned (2), carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[example I-6]
(1) manufacturing of sintered sheets
The powder that removes the Indium sesquioxide, stannic oxide and the zinc oxide that use following atomic ratio is as raw material, and beyond being mixed, other all according to example I-1 same steps as, make sintered sheets.
In/(In+Sn+Zn)＝0.60
Sn/(In+Sn+Zn)＝0.30
Zn/(In+Sn+Zn)＝0.10
The sintered sheets of Using such method gained, its density are 6.7g/cm
3, and body resistance is 0.82m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide through confirming it, with In
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide hexagonal crystal lamellar compound, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
The processibility of the nesa coating that forms on the transparent glass substrate in above-mentioned (2) is assessed according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[example I-7]
(1) manufacturing of sintered sheets
The powder of Indium sesquioxide, stannic oxide and zinc oxide that remove to use following atomic ratio is as raw material, and after being mixed,
In/(In+Sn+Zn)＝0.60
Sn/(In+Sn+Zn)＝0.30
Zn/(In+Sn+Zn)＝0.10
Adding atomic ratio again is
Ru/(In+Sn+Zn+Ru)＝0.02
The ruthenium oxide powder after again outside mixing, other all according to example I-1 same steps as, make sintered sheets.
The sintered sheets of Using such method gained, its density are 6.7g/cm
3, and body resistance is 0.80m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide through confirming it, with In
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.Metal oxide in the Table I-1 is formed in the hurdle, and Me represents Ru (back is applied to Mo etc. too).
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms in above-mentioned (2), carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[example I-8]
(1) manufacturing of sintered sheets
The powder of Indium sesquioxide, stannic oxide and zinc oxide that remove to use following atomic ratio is as raw material, and after being mixed,
In/(In+Sn+Zn)＝0.60
Sn/(In+Sn+Zn)＝0.30
Zn/(In+Sn+Zn)＝0.10
Adding atomic ratio again is
Mo/(In+Sn+Zn+Mo)＝0.02
Molybdenum oxide powder last again outside mixing, other all according to example I-1 same steps as, make sintered sheets.
The sintered sheets of Using such method gained, its density are 6.8g/cm
3, and body resistance is 0.94m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide, the In of gained through confirming it
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms in above-mentioned (2), carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[example I-8]
(1) manufacturing of sintered sheets
The powder of Indium sesquioxide, stannic oxide and zinc oxide that remove to use following atomic ratio is as raw material, and after being mixed,
In/(In+Sn+Zn)＝0.60
Sn/(In+Sn+Zn)＝0.30
Zn/(In+Sn+Zn)＝0.10
Adding atomic ratio again is
V/(In+Sn+Zn+V)＝0.02
Vanadium oxide powder last again outside mixing, other all according to example I-1 same steps as, make sintered sheets.
The sintered sheets of Using such method gained, its density are 6.8g/cm
3, and body resistance is 0.99m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide, the In of gained through confirming it
2O
3(ZnO) m represents and m is 4,5,7 the Indium sesquioxide and the crystallization of zinc oxide six side's lamellar compounds, and with Zn
2SnO
4It is the main crystallization that compound constituted with spinel structure.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms in above-mentioned (2), carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[Comparative Example I-1]
(1) manufacturing of sintered sheets
Remove the Indium sesquioxide of raw material and the powder of zinc oxide, beyond being mixed with following atomic ratio, other all according to example I-1 same steps as, make sintered sheets.
In/(In+Zn)＝0.85
Zn/(In+Zn)＝0.15
The sintered sheets of Using such method gained, its density are 6.75g/cm
3, and body resistance is 2.74m Ω cm.The crystallinity of this sintered sheets is to form the crystallization with Indium sesquioxide through confirming it, and the crystallization of six side's lamellar compounds of Indium sesquioxide-zinc oxide.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
Because of the resistivity of sintered sheets is bigger, so the poor stability when sputter, therefore arriving the required film formation time of predetermined film thickness needs 17 minutes.
(3) processibility of nesa coating assessment
With the nesa coating that on glass substrate, forms of above-mentioned (2) gained, carry out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[Comparative Example I-2]
(1) manufacturing of sintered sheets
Remove the Indium sesquioxide of raw material and the powder of stannic oxide, beyond being mixed with following atomic ratio, other all according to example I-1 same steps as, make sintered sheets.
In/(In+Sn)＝0.90
Sn/(In+Sn)＝0.10
The sintered sheets of Using such method gained, its density are 6.71g/cm
3, and body resistance is 0.69m Ω cm.The crystallinity of this sintered sheets is the crystallization for Indium sesquioxide through confirming it.
This result is shown in Table I-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (1) gained, make transparent conducting glass according to (2) same steps as of example I-1.
(3) processibility of nesa coating assessment
The nesa coating that forms on the glass substrate with above-mentioned (2) gained carries out the processibility assessment of nesa coating according to (3) same procedure of example I-1.
Its assessment result is shown in Table I-2.
[Comparative Example I-3]
Except that with in (2) of comparative example 2 during sputter the temperature of employed glass substrate be adjusted into 215 ℃, other all according to Comparative Example I-2 same steps as, make transparent conducting glass.
The assessment result of the nesa coating on the gained glass substrate is shown in Table I-2.
Table I-1 (1)
| Embodiment | ??I-1 | ??I-4 | ??I-5 | ??I-6 | |
| ??In/(In+Sn+Zn) | ??0.50 | ??0.50 | ??0.70 | ??0.60 | |
| ??Sn/(In+Sn+Zn) | ??0.25 | ??0.45 | ??0.25 | ??0.30 | |
| ??Zn/(In+Sn+Zn) | ??0.25 | ??0.05 | ??0.05 | ??0.10 | |
| Sintered sheets density (g/cm 3) | ??6.6 | ??6.8 | ??6.8 | ??6.7 | |
| Body resistance (m Ω cm) | ??0.95 | ??0.98 | ??0.87 | ??0.82 | |
| Crystallinity | Indium sesquioxide | Have | Have | Have | Have |
| Six side's lamellar compounds | Have | Have | Have | Have | |
| Spinel compound | Have | Have | Have | Have | |
Table I-1 (2)
| Embodiment | Comparative example | |||||
| Embodiment | ??I-7 | ??I-8 | ??I-9 | ??I-1 | ??I-2 | |
| ??In/(In+Sn+Zn) | ??0.60 | ??0.60 | ??0.60 | ??0.85 | ??0.90 | |
| ??Sn/(In+Sn+Zn) | ??0.30 | ??0.30 | ??0.30 | ??- | ??0.10 | |
| ??Zn/(In+Sn+Zn) | ??0.10 | ??0.10 | ??0.10 | ??0.15 | ??- | |
| ??Me/(In+Sn+Zn+Me) | ??0.02 | ??0.02 | ??0.02 | ??- | ??- | |
| Sintered sheets density (g/cm 3) | ??6.7 | ??6.8 | ??6.8 | ??6.75 | ??6.71 | |
| Body resistance (m Ω cm) | ??0.80 | ??0.94 | ??0.99 | ??2.74 | ??0.69 | |
| Crystallinity | Indium sesquioxide | Have | Have | Have | Have | Have |
| The hexagonal crystal lamellar compound | Have | Have | Have | Do not have | Do not have | |
| Spinel compound | Have | Have | Have | Do not have | Do not have | |
Table I-2 (1)
| Embodiment | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) | Electrode processibility (etching-film cross section) |
| ??I-1 | ??0.36 | ??79 | Amorphous | ??5.11 | Smoothly |
| ??I-2 | ??0.34 | ??79 | Amorphous | ??5.12 | Smoothly |
| ??I-3 | ??0.37 | ??78 | Amorphous | ??5.12 | Smoothly |
| ??I-4 | ??0.24 | ??80 | Amorphous | ??5.16 | Smoothly |
| ??I-5 | ??0.27 | ??81 | Amorphous | ??5.18 | Smoothly |
| ??I-6 | ??0.29 | ??80 | Amorphous | ??5.15 | Smoothly |
| ??I-7 | ??1.3 | ??79 | Amorphous | ??5.49 | Smoothly |
| ??I-8 | ??3.5 | ??78 | Amorphous | ??5.55 | Smoothly |
| ??I-9 | ??2.4 | ??78 | Amorphous | ??5.57 | Smoothly |
Table I-2 (2)
| Comparative example | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) | Electrode processibility (adding Ministry of worker cross section) |
| ??I-1 | ??0.34 | ??80 | Amorphous | ??5.18 | Smoothly |
| ??I-2 | ??0.42 | ??80 | Crystallite | ??4.97 | Coarse |
| ??I-3 | ??0.18 | ??82 | Crystalloid | ??4.95 | Coarse |
[a second aspect of the present invention]
[example II-1]
(1) manufacturing of sintered sheets
In indium oxide powder as raw material, will have after the ruthenium oxide powder mixes of following atomic ratio in the feed-in wet-type ball mill, and through 72 hours mixed grindings.
Ru/(In+Ru)＝0.03
Secondly, after the granulation of gained abrasive material, add the sheet that is pressed into 4 inches of diameters, thick 5mm again, sheet is inserted in the sintering oven, 1400 ℃ of pressure sinterings of carrying out 36 hours.
The sintered sheets of Using such method gained, its density are 6.8g/cm
3, and body resistance is 0.80m Ω cm.
This result is shown in Table II-1.
(2) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned gained, make the sputtering target of 4 inches of diameters, thickness 5mm.Target is loaded on the DC magnetic controlled tube sputtering apparatus, to the glass substrate sputter.
Its sputtering condition is that surrounding environment is to use the argon gas that is mixed with an amount of oxygen, and sputtering pressure is 3 * 10
-1Pa, final vacuum tightness is 5 * 10
-4Pa, substrate temperature are 25 ℃, and the adding electric energy is 100W, and film formation time is 14 minutes.
Nesa coating on the glass substrate of mode gained according to this, its thickness is 1,200 dust, and is amorphous.And this nesa coating is measured as 79% to the transmittance of the light of 500nm with spectrophotometric.The resistivity of the nesa coating of measuring with 4 probe methods is 0.84m Ω cm, and electroconductibility is higher.The result that work function is measured with ultraviolet electron spectroscopy for chemical analysis is 5.51 electron-volts.
The assessment result of this nesa coating is shown in Table II-2.
[example II-2]
(1) manufacturing of sintered sheets
Except that changing into the molybdenum oxide with following atomic ratio mixed as the ruthenium oxide of raw material in the example II-1, other all make sintered sheets according to (1) same steps as of example II-1.
Mo/(In+Mo)＝0.07
The rerum natura of gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-3]
(1) manufacturing of sintered sheets
Except that changing into the vanadium oxide with following atomic ratio mixed as the ruthenium oxide of raw material in the example II-1, other all make sintered sheets according to (1) same steps as of example II-1.
V/(In+V)＝0.07
The rerum natura of gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-4]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.83
Zn/(In+Zn)＝0.17
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Zn+Ru)＝0.020
The rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-5]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.85
Zn/(In+Zn)＝0.15
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Zn+Mo)＝0.020
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-6]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.85
Zn/(In+Zn)＝0.15
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Zn+V)＝0.020
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-7]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.93
Zn/(In+Zn)＝0.07
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Zn+Ru)＝0.015
The rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-8]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.90
Zn/(In+Zn)＝0.10
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Zn+Mo)＝0.050
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-9]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with Zinc oxide powder as the indium oxide powder of raw material,
In/(In+Zn)＝0.90
Zn/(In+Zn)＝0.10
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Zn+V)＝0.070
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-10]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)＝0.80
Sn/(In+Sn)＝0.20
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Sn+Ru)＝0.030
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-11]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)＝0.80
Sn/(In+Sn)＝0.20
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Sn+Mo)＝0.070
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-12]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)＝0.80
Sn/(In+Sn)＝0.20
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Sn+V)＝0.050
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-13]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)＝0.90
Sn/(In+Sn)＝0.10
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Sn+Ru)＝0.021
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-14]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)＝0.90
Sn/(In+Sn)＝0.10
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Sn+Mo)＝0.070
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-15]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio with stannic oxide powder as the indium oxide powder of raw material,
In/(In+Sn)0.90
Sn/(In+Sn)0.10
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Sn+V)＝0.020
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-16]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as indium oxide powder, Zinc oxide powder and the stannic oxide powder of raw material,
In/(In+Zn+Sn)0.80
Zn/(In+Zn+Sn)＝0.10
Sn/(In+Zn+Sn)＝0.10
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Zn+Sn+Ru)0.022
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-17]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as indium oxide powder, Zinc oxide powder and the stannic oxide powder of raw material,
In/(In+Zn+Sn)＝0.80
Zn/(In+Zn+Sn)＝0.10
Sn/(In+Zn+Sn)＝0.10
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Zn+Sn+Mo)＝0.050
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-18]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as the powder of indium oxide powder, Zinc oxide powder and the stannic oxide of raw material,
In/(In+Zn+Sn)＝0.80
Zn/(In+Zn+Sn)＝0.10
Sn/(In+Zn+Sn)0.10
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Zn+Sn+V)＝0.050
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-19]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as the powder of indium oxide powder, Zinc oxide powder and the stannic oxide of raw material,
In/(In+Zn+Sn)＝0.90
Zn/(In+Zn+Sn)＝0.07
Sn/(In+Zn+Sn)＝0.03
Thereafter, beyond the ruthenium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Ru/(In+Zn+Sn+Ru)＝0.025
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-20]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as the powder of indium oxide powder, Zinc oxide powder and the stannic oxide of raw material,
In/(In+Zn+Sn)＝0.90
Zn/(In+Zn+Sn)＝0.07
Sn/(In+Zn+Sn)＝0.03
Thereafter, beyond the molybdenum oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
Mo/(In+Zn+Sn+Mo)＝0.035
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-21]
(1) manufacturing of sintered sheets
Remove and will be mixed with following atomic ratio as the powder of indium oxide powder, Zinc oxide powder and the stannic oxide of raw material,
In/(In+Zn+Sn)＝0.90
Zn/(In+Zn+Sn)＝0.07
Sn/(In+Zn+Sn)＝0.03
Thereafter, beyond the vanadium oxide that wherein adds following atomic ratio was mixed, other all made sintered sheets according to (1) same steps as of example II-1 again.
V/(In+Zn+Sn+V)＝0.035
The measurement result of the rerum natura of its gained sintered sheets is shown in Table II-1.
(2) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (1) gained, other all make transparent conducting glass according to (2) same steps as of example II-1.The rerum natura assessment result of the nesa coating that forms on glass substrate is shown in Table II-2.
[example II-22]
The sintered sheets that will make by (1) same procedure of example II-4 is as target, and except that the glass substrate temperature with sputters in the example II-4 (2) is heated to 215 ℃ carrying out the sputter, other all make transparent conducting glass with example II-4 same steps as.
The rerum natura of the nesa coating that forms on glass substrate is assessed by (2) same procedure of example II-1, and its result is shown in Table II-2.
[example II-23]
The sintered sheets that will make by (1) same procedure of example II-10 is as target, and except that the glass substrate temperature with sputters in the example II-10 (2) is heated to 215 ℃ carrying out the sputter, other all make transparent conducting glass with example II-10 same steps as.
The rerum natura of the nesa coating that forms on glass substrate is assessed by (2) same procedure of example II-1, and its result is shown in Table II-2.
[example II-24]
The sintered sheets that will make by (1) same procedure of example II-10 is as target, and except that adding 2 weight % water in the example II-10 (2) during sputter carrying out the sputter, other all make transparent conducting glass with example II-10 same steps as.
The rerum natura of the nesa coating that forms on glass substrate is assessed by (2) same procedure of example II-1, and its result is shown in Table II-2.
With the nesa coating that mode like this makes, annealed 1 hour down in 215 ℃, and measure its rerum natura.Find that the rerum natura before and after the annealing does not change.
[example II-25]
The sintered sheets that will make by (1) same procedure of example II-4 is as target, except that with replacing with the transparent substrate of the polycarbonate substrate of 0.1mm as the glass substrate of transparent substrate in the example II-4 (2), other all make nesa coating with example II-4 same steps as.
The rerum natura of the nesa coating that forms on polycarbonate substrate is assessed by (2) same procedure of example II-1, and its result is shown in Table II-2.
[Comparative Example I I-1]
Remove the mixture that raw material only uses indium oxide powder with following atomic ratio and Zinc oxide powder mixing gained,
In/(In+Zn)＝0.85
Zn/(In+Zn)＝0.15
No longer add any supplementary component ruthenium oxide etc., make sintered product, produce target by sintered product again by (1) same steps as of example II-1.And (2) same steps as of pressing example II-1 forms nesa coating.
The physical property measurement result who is formed at the nesa coating on the glass substrate is shown in Table II-2.
[Comparative Example I I-2]
Remove the raw material use and have the indium oxide powder of following atomic ratio and the mixture of stannic oxide powder mixing gained,
In/(In+Sn)＝0.90
Sn/(In+Sn)＝0.10
No longer add any supplementary component ruthenium oxide etc., make sintered sheets, form sputtering target by sintered sheets again by (1) same steps as of example II-1.Use the target of producing like this, and the temperature of glass substrate is heated to 215 ℃ when sputter carrying out beyond the sputter, other all make transparent conducting glass according to (2) same steps as of example II-1.
The physical property measurement result who is formed at the nesa coating on the glass substrate is shown in Table II-2.
Table II-1 (1)
| Embodiment | ??II-1 | ??II-2 | ??II-3 | ??II-4 | ??II-5 | ??II-6 | ??II-7 |
| ??In/(In+Zn+Sn) | ??1.00 | ??1.00 | ??1.00 | ??0.83 | ??0.85 | ??0.85 | ??0.93 |
| ??Zn/(In+Zn+Sn) | ??- | ??- | ??- | ??0.17 | ??0.15 | ??0.15 | ??0.07 |
| ??Sn/(In+Zn+Sn) | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| ??Ru/(In+Zn+Sn+Ru) | ??0.030 | ??- | ??- | ??0.020 | ??- | ??- | ??0.015 |
| ??Mo/(In+Zn+Sn+Mo) | ??- | ??0.070 | ??- | ??- | ??0.020 | ??- | ??- |
| ??V/(In+Zn+Sn+V) | ??- | ??- | ??0.050 | ??- | ??- | ??0.020 | ??- |
| Sintered sheets density (g/cm 3) | ??6.81 | ??6.78 | ??6.76 | ??6.81 | ??6.90 | ??6.70 | ??6.75 |
| Body resistance (m Ω cm) | ??0.80 | ??0.88 | ??0.95 | ??0.95 | ??2.74 | ??1.72 | ??0.95 |
Table II-1 (2)
| Embodiment | ??II-8 | ??II-9 | ??II-10 | ??II-11 | ??II-12 | ??II-13 | ??II-14 |
| ??In/(In+Zn+Sn) | ??0.90 | ??0.90 | ??0.80 | ??0.80 | ??0.80 | ??0.90 | ??0.90 |
| ??Zn/(In+Zn+Sn) | ??0.10 | ??0.10 | ??- | ??- | ??- | ??- | ??- |
| ??Sn/(In+Zn+Sn) | ??- | ??- | ??0.20 | ??0.20 | ??0.20 | ??0.20 | ??0.20 |
| ??Ru/(In+Zn+Sn+Ru) | ??- | ??- | ??0.030 | ??- | ??- | ??0.021 | ??- |
| ??Mo/(In+Zn+Sn+Mo) | ??0.050 | ??- | ??- | ??0.070 | ??- | ??- | ??0.020 |
| ??V/(In+Zn+Sn+V) | ??- | ??0.070 | ??- | ??- | ??0.050 | ??- | ??- |
| Sintered sheets density (g/cm 3) | ??6.85 | ??6.68 | ??6.72 | ??6.76 | ??6.56 | ??6.81 | ??6.85 |
| Body resistance (m Ω cm) | ??1.85 | ??4.85 | ??0.74 | ??0.92 | ??1.92 | ??0.79 | ??0.93 |
Table II-1 (3)
| Embodiment | ??II-15 | ??II-16 | ??II-17 | ??II-18 | ??II-19 | ??II-20 | ??II-21 |
| ??In/(In+Zn+Sn) | ??0.90 | ??0.80 | ??0.80 | ??0.80 | ??0.80 | ??0.90 | ??0.90 |
| ??Zn/(In+Zn+Sn) | ??- | ??0.10 | ??0.10 | ??0.10 | ??0.07 | ??0.07 | ??0.07 |
| ??Sn/(In+Zn+Sn) | ??0.10 | ??0.10 | ??0.10 | ??0.10 | ??0.03 | ??0.03 | ??0.03 |
| ??Ru/(In+Zn+Sn+Ru) | ??- | ??0.022 | ??- | ??- | ??0.025 | ??- | ??- |
| ??Mo/(In+Zn+Sn+Mo) | ??- | ??- | ??0.050 | ??- | ??- | ??0.035 | ??- |
| ??V/(In+Zn+Sn+V) | ??0.020 | ??- | ??- | ??0.050 | ??- | ??- | ??0.035 |
| Sintered sheets density (g/cm 3) | ??6.55 | ??6.74 | ??6.78 | ??6.57 | ??6.71 | ??6.78 | ??6.58 |
| Body resistance (m Ω cm) | ??1.93 | ??0.92 | ??1.85 | ??1.85 | ??0.98 | ??1.98 | ??1.98 |
Table II-2 (1)
| Embodiment | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??II-1 | ??0.84 | ??79 | Crystallite | ??5.51 |
| ??II-2 | ??1.51 | ??80 | Crystallite | ??5.48 |
| ??II-3 | ??4.10 | ??79 | Crystallite | ??5.49 |
| ??II-4 | ??1.70 | ??79 | Amorphous | ??5.52 |
| ??II-5 | ??2.80 | ??76 | Amorphous | ??5.46 |
| ??II-6 | ??3.70 | ??79 | Amorphous | ??5.47 |
| ??II-7 | ??1.20 | ??79 | Amorphous | ??5.45 |
| ??II-8 | ??2.10 | ??77 | Amorphous | ??5.48 |
| ??II-9 | ??3.12 | ??80 | Amorphous | ??5.50 |
| ??II-10 | ??0.70 | ??81 | Crystallite | ??5.52 |
Table II-2 (2)
| Embodiment | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??II-11 | ??1.47 | ??78 | Crystallite | ??5.50 |
| ??II-12 | ??3.74 | ??80 | Crystallite | ??5.48 |
| ??II-13 | ??0.71 | ??80 | Crystallite | ??5.47 |
| ??II-14 | ??1.56 | ??76 | Crystallite | ??5.46 |
| ??II-15 | ??2.65 | ??78 | Crystallite | ??5.47 |
| ??II-16 | ??0.65 | ??78 | Amorphous | ??5.54 |
| ??II-17 | ??2.56 | ??74 | Amorphous | ??5.48 |
| ??II-18 | ??3.62 | ??76 | Amorphous | ??5.49 |
| ??II-19 | ??0.72 | ??79 | Amorphous | ??5.55 |
| ??II-20 | ??1.27 | ??76 | Amorphous | ??5.50 |
Table II-2 (3)
| Embodiment (comparative example) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??II-21 | ??4.27 | ??75 | Amorphous | ??5.51 |
| ??II-22 | ??1.40 | ??80 | Amorphous | ??5.53 |
| ??II-23 | ??0.71 | ??81 | Crystallization | ??5.52 |
| ??II-24 | ??0.84 | ??80 | Amorphous | ??5.51 |
| ??II-25 | ??1.70 | ??78 | Amorphous | ??5.51 |
| ??(II-1) | ??0.34 | ??80 | Amorphous | ??5.18 |
| ??(II-2) | ??0.18 | ??82 | Crystallization | ??4.97 |
[a third aspect of the present invention]
[EXAMPLE III-1]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.90
Zn/(In+Zn+Sn)＝0.00
Sn/(In+Zn+Sn)＝0.10
And,
Ir/(In+Zn+Sn+Ir)＝0.04
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
After the powder granulation with above-mentioned (1) gained transparent conductive material, its press molding is become the sheet of 4 inches of diameters, thick 5mm.Sintered sheets is placed firing furnace, under 1400 ℃, carry out 36 hours pressure sintering.
The Using such method gained sintered sheets, its density is 6.8g/cm
3, and body resistance is 0.98m Ω cm.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (2) gained, make the sputtering target of 4 inches of diameters, thickness 5mm.This target is loaded on the DC magnetic controlled tube sputtering apparatus, is splashed to and makes film on the glass substrate.
In its sputtering condition, surrounding environment is to use the ar gas environment that is mixed with an amount of oxygen, and sputtering pressure is 3 * 10
-1Pa, final vacuum tightness is 5 * 10
-4Pa, substrate temperature is 25 ℃, and applying energy is 80W, and film formation time is 14 minutes.
Nesa coating on the transparent conducting glass of mode gained according to this, its thickness is 1,200 dust, and is amorphous.And the transmittance of this nesa coating is measured the gained result with spectrophotometer to the light of 500nm, is 81%.The resistivity of measuring this nesa coating with 4 probe methods is 1.2m Ω cm, and electroconductibility is higher.The result that work function is measured with ultraviolet electronics optical spectroscopy is 5.46 electron-volts.
The assessment result of this nesa coating is shown in Table III-2.
[EXAMPLE III-2]
(1) manufacturing of transparent conducting glass
Use the sputtering target identical with EXAMPLE III-1, except that the glass substrate temperature in the sputtering condition is adjusted into 215 ℃, other all make transparent conducting glass with (3) the same terms of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on this glass substrate is shown in Table III-2.
[EXAMPLE III-3]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.70
Zn/(In+Zn+Sn)＝0.00
Sn/(In+Zn+Sn)＝0.30
And,
Ir/(In+Zn+Sn+Ir)＝0.08
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-4]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.25
Zn/(In+Zn+Sn)＝0.00
Sn/(In+Zn+Sn)＝0.75
And,
Ir/(In+Zn+Sn+Ir)＝0.05
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The former of gained transparent conductive material gives such as shown in the Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-5]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝1.00
Zn/(In+Zn+Sn)＝0.00
Sn/(In+Zn+Sn)＝0.00
And,
Ir/(In+Zn+Sn+Ir)＝0.04
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-6]
(1) manufacturing of transparent conductive material
Will be as Zinc oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.00
Zn/(In+Zn+Sn)＝0.20
Sn/(In+Zn+Sn)＝0.80
And,
Ir/(In+Zn+Sn+Ir)＝0.05
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-7]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.80
Zn/(In+Zn+Sn)＝0.10
Sn/(In+Zn+Sn)＝0.10
And,
Ir/(In+Zn+Sn+Ir)＝0.06
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-8]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder, stannic oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.05
Zn/(In+Zn+Sn)＝0.90
Sn/(In+Zn+Sn)＝0.05
And,
Ir/(In+Zn+Sn+Ir)＝0.06
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-9]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder and the iridium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.85
Zn/(In+Zn+Sn)＝0.15
Sn/(In+Zn+Sn)＝0.00
And,
Ir/(In+Zn+Sn+Ir)＝0.06
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-10]
(1) manufacturing of transparent conducting glass
Use the sputtering target identical with EXAMPLE III-9, except that the glass substrate temperature in the sputtering condition is adjusted into 215 ℃, other all make transparent conducting glass with (3) the same terms of EXAMPLE III-1.
The assessment result of the nesa coating of gained transparent conducting glass is shown in Table III-2.
[EXAMPLE III-11]
(1) manufacturing of transparent conductive film
Use the sputtering target identical with EXAMPLE III-10, except that will replacing with the transparent resin film of polycarbonate resin as the glass substrate of substrate, other all make transparent conducting glass with (3) the same terms of EXAMPLE III-1.
The assessment result of the nesa coating on the gained transparent conductive film is shown in Table III-2.
[EXAMPLE III-12]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, stannic oxide powder and the rhenium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.90
Zn/(In+Zn+Sn)＝0.00
Sn/(In+Zn+Sn)＝0.10
And,
Re/(In+Zn+Sn+Re)＝0.04
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-13]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder and the rhenium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.85
Zn/(In+Zn+Sn)＝0.15
Sn/(In+Zn+Sn)＝0.00
And,
Re/(In+Zn+Sn+Re)＝0.06
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-14]
(2) manufacturing of transparent conductive film
Use the sputtering target identical with EXAMPLE III-13, except that will replacing with the transparent resin film of polycarbonate resin as the glass substrate of substrate, other all make transparent conducting glass with (3) the same terms of EXAMPLE III-1.
The assessment result of the nesa coating on the gained transparent conductive film is shown in Table III-2.
[EXAMPLE III-15]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder, stannic oxide powder and the rhenium oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.80
Zn/(In+Zn+Sn)＝0.10
Sn/(In+Zn+Sn)0.10
And,
Re/(In+Zn+Sn+Re)＝0.05
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[EXAMPLE III-16]
(1) manufacturing of transparent conductive material
Will be as indium oxide powder, Zinc oxide powder and the palladous oxide powder of raw material, after being mixed with following atomic ratio,
In/(In+Zn+Sn)＝0.80
Zn/(In+Zn+Sn)＝0.20
Sn/(In+Zn+Sn)＝0.00
And,
Pd/(In+Zn+Sn+Pd)＝0.05
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table III-1.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
The physical property measurement result of gained sintered sheets is shown in Table III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[Comparative Example I II-1]
(1) manufacturing of transparent conductive material
After will being mixed with following atomic ratio as indium oxide powder, the Zinc oxide powder of raw material,
In/(In+Zn)＝0.85
Zn/(In+Zn)＝0.15
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
(3) manufacturing of transparent conducting glass
Except that the sintered sheets of using above-mentioned (2) gained, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
[Comparative Example I II-2]
(1) manufacturing of transparent conductive material
After will being mixed with following atomic ratio as indium oxide powder, the stannic oxide powder of raw material,
In/(In+Sn)＝0.90
Sn/(In+Sn)＝0.10
In its feed-in wet-type ball mill, and, make the powder of transparent conductive material through 72 hours mixed grindings.
(2) manufacturing of sintered sheets
Use the powder of above-mentioned (1) gained transparent conductive material, make sintered sheets according to (2) same steps as of EXAMPLE III-1.
(3) manufacturing of transparent conducting glass
Remove to use the sintered sheets of above-mentioned (2) gained, and the glass substrate temperature is adjusted into beyond 215 ℃, other all make transparent conducting glass according to (3) same steps as of EXAMPLE III-1.
The assessment result of the rerum natura of the nesa coating that forms on glass substrate is shown in Table III-2.
Table III-1 (1)
| Embodiment | ??III-1 | ??III-3 | ??III-4 | ??III-5 | ??III-6 | ??III-7 | ??III-8 |
| ??In/(In+Zn+Sn) | ??0.90 | ??0.70 | ??0.25 | ??1.0 | ??- | ??0.80 | ??0.05 |
| ??Zn/(In+Zn+Sn) | ??- | ??- | ??- | ??- | ??0.20 | ??0.10 | ??0.90 |
| ??Sn/(In+Zn+Sn) | ??0.10 | ??0.30 | ??0.75 | ??- | ??0.80 | ??0.10 | ??0.05 |
| ??Ir/(In+Zn+Sn+Ir) | ??0.04 | ??0.08 | ??0.05 | ??0.04 | ??0.05 | ??0.06 | ??0.06 |
| ??Re/(In+Zn+Sn+Re) | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| ??Pd/(In+Zn+Sn+Pd) | ??- | ??- | ??- | ??- | ??- | ??- | ??- |
| Sintered sheets density (g/cm 3) | ??6.8 | ??6.6 | ??6.3 | ??6.7 | ??6.62 | ??6.8 | ??5.8 |
| Body resistance (m Ω cm) | ??0.98 | ??1.4 | ??4.7 | ??0.92 | ??8.9 | ??0.95 | ??8.9 |
Table III-1 (2)
| Embodiment/comparative example | ??III-9 | ??III-11 | ??III-12 | ??III-13 | ??III-16 | ??(III-1) | ??(III-2) |
| ??In/(In+Zn+Sn) | ??0.85 | ??0.90 | ??0.85 | ??0.80 | ??0.80 | ??0.85 | ??0.90 |
| ??Zn/(In+Zn+Sn) | ??0.15 | ??- | ??0.15 | ??0.10 | ??0.20 | ??0.15 | ??- |
| ??Sn/(In+Zn+Sn) | ??- | ??0.10 | ??- | ??0.10 | ??- | ??- | ??0.10 |
| ??Ir/(In+Zn+Sn+Ir) | ??0.06 | ??- | ??- | ??- | ??- | ??- | ??- |
| ??Re/(In+Zn+Sn+Re) | ??- | ??0.04 | ??0.06 | ??0.05 | ??- | ??- | ??- |
| ??Pd/(In+Zn+Sn+Pd) | ??- | ??- | ??- | ??- | ??0.05 | ??- | ??- |
| Sintered sheets density (g/cm 3) | ??6.8 | ??6.7 | ??6.8 | ??6.3 | ??6.48 | ??6.9 | ??6.71 |
| Body resistance (m Ω cm) | ??1.0 | ??0.85 | ??0.94 | ??0.73 | ??3.4 | ??2.4 | ??0.69 |
Table III-2 (1)
| Embodiment | Substrate temperature (℃) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??III-1 | ??25 | ??1.2 | ??81 | Amorphous | ??5.46 |
| ??III-2 | ??215 | ??0.52 | ??82 | Crystallite | ??5.45 |
| ??III-3 | ??25 | ??1.7 | ??82 | Amorphous | ??5.47 |
| ??III-4 | ??25 | ??3.8 | ??81 | Amorphous | ??5.48 |
| ??III-5 | ??25 | ??0.80 | ??80 | Amorphous | ??5.45 |
| ??III-6 | ??25 | ??450 | ??80 | Amorphous | ??5.46 |
| ??III-7 | ??25 | ??1.1 | ??81 | Amorphous | ??5.54 |
| ??III-8 | ??25 | ??8.8 | ??78 | Amorphous | ??5.48 |
| ??III-9 | ??25 | ??1.3 | ??82 | Amorphous | ??5.54 |
Table III-2 (2)
| Embodiment/comparative example | Substrate temperature (℃) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??III-10 | ??215 | ??0.56 | ??80 | Amorphous | ??5.49 |
| ??III-11 | ??25 | ??0.45 | ??82 | Amorphous | ??5.45 |
| ??III-12 | ??25 | ??0.64 | ??81 | Amorphous | ??5.48 |
| ??III-13 | ??25 | ??0.55 | ??82 | Amorphous | ??5.47 |
| ??III-14 | ??25 | ??1.3 | ??82 | Amorphous | ??5.54 |
| ??III-15 | ??25 | ??0.64 | ??81 | Amorphous | ??5.48 |
| ??III-16 | ??25 | ??360 | ??76 | Amorphous | ??5.61 |
| ??(III-1) | ??25 | ??0.32 | ??80 | Amorphous | ??5.18 |
| ??(III-2) | ??215 | ??0.18 | ??82 | Crystallization | ??4.95 |
[a fourth aspect of the present invention]
[EXAMPLE IV-1]
(1) manufacturing of the raw material powder of transparent conductive material
Will be as the powder of stannic oxide, zinc oxide and the vanadium oxide of raw material, after being mixed with following atomic ratio,
Sn/(Sn+In+Zn)＝0.80
In/(Sn+In+Zn)＝0.00
Zn/(Sn+In+Zn)＝0.20
And,
V/(Sn+In+Zn+V)＝0.04
In its feed-in wet-type ball mill, and, make the raw material powder of transparent conductive material through 72 hours mixed grindings.
The atomic ratio of gained transparent conductive material is shown in Table IV-1.
(2) manufacturing of sintered sheets
After the raw material powder granulation with above-mentioned (1) gained transparent conductive material, its press molding is become the sheet of 4 inches of diameters, thick 5mm.It is inserted in the firing furnace, under 1400 ℃, carry out 36 hours pressure sintering.
The Using such method gained sintered sheets, its density is 6.8g/cm
3, and body resistance is 6.5m Ω cm.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
With the sintered sheets of above-mentioned (2) gained, make the sputtering target [A] of 4 inches of diameters, thickness 5mm.This target is loaded on the DC magnetic controlled tube sputtering apparatus, is splashed to and makes film on the glass substrate.
In its sputtering condition, surrounding environment is to use the ar gas environment that is mixed with an amount of oxygen, and sputtering pressure is 3 * 10
-1Pa, final vacuum tightness is 5 * 10
-4Pa, substrate temperature is 25 ℃, and applying energy is 100W, and film formation time is 14 minutes.
Nesa coating on the transparent conducting glass of mode gained according to this, its thickness is 1,200 dust, and is amorphous.And the transmittance of this nesa coating is measured the gained result with spectrophotometer to the light of 500nm, is 80%.The resistivity of measuring this nesa coating with 4 probe methods is 1,000m Ω cm, and electroconductibility is higher.The result that work function is measured with ultraviolet electronics optical spectroscopy is 5.50 electron-volts.
The assessment result of this nesa coating is shown in Table IV-2.
[EXAMPLE IV-2]
(1) manufacturing of transparent conducting glass
Use the sputtering target [A] identical with EXAMPLE IV-1, except that the glass substrate temperature in the sputtering condition is adjusted into 215 ℃, other all make transparent conducting glass with (3) the same terms of EXAMPLE IV-1.
The assessment result of the rerum natura of the nesa coating that forms on this glass substrate is shown in Table IV-2.
[EXAMPLE IV-3]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of stannic oxide, zinc oxide and the vanadium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [B] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-4]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of stannic oxide, zinc oxide and the vanadium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [C] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-5]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of stannic oxide, Indium sesquioxide and the vanadium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [D] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-6]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of the stannic oxide of raw material and vanadium oxide, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [E] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-7]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the vanadium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [F] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-8]
(1) manufacturing of transparent conductive film
To replace with transparency polycarbonate film as the glass of base material, and use the sputtering target [F] of EXAMPLE IV-7 gained to make transparent conductive film.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[EXAMPLE IV-9]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-1 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the vanadium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [G] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of formed nesa coating is shown in Table IV-2.
[Comparative Example I V-1]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will be as the Indium sesquioxide of raw material with the powder of zinc oxide is mixed with atomic ratio shown in the Table IV-1, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [H] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[Comparative Example I V-2]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will be as the stannic oxide of raw material with the powder of Indium sesquioxide is mixed with atomic ratio shown in the Table IV-1, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-1.
(2) manufacturing of transparent conducting glass
Except that the sputtering target [I] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of formed nesa coating is shown in Table IV-2.
[Comparative Example I V-3]
(1) manufacturing of transparent conducting glass
Remove to use the prepared sputtering target of Comparative Example I V-1 [H], and the temperature of glass substrate is adjusted to beyond 215 ℃ during with sputter, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
[Comparative Example I V-4]
(1) manufacturing of transparent conducting glass
Remove to use the prepared sputtering target of Comparative Example I V-2 [I], and the temperature of glass substrate is adjusted to beyond 215 ℃ during with sputter, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-2.
Table IV-1
| Embodiment/comparative example | ??IV-1 | ??IV-3 | ??IV-4 | ??IV-5 | ??IV-6 | ??IV-7 | ??IV-9 | ??(IV-1) | ??IV-2 |
| ??Sn/(Sn+In+Zn) | ??0.80 | ??0.95 | ??0.55 | ??0.80 | ??1.00 | ??0.80 | ??0.80 | ??- | ??0.10 |
| ??In/(Sn+In+Zn) | ??- | ??- | ??0.45 | ??0.20 | ??- | ??0.10 | ??0.15 | ??0.85 | ??0.90 |
| ??Zn/(Sn+In+Zn) | ??0.20 | ??0.05 | ??- | ??- | ??- | ??0.10 | ??0.05 | ??0.15 | ??- |
| ??V/(Sn+In+Zn+V) | ??0.04 | ??0.032 | ??0.035 | ??0.03 | ??0.02 | ??0.02 | ??0.035 | ??- | ??- |
| Sintered sheets density (g/cm 3) | ??6.8 | ??6.6 | ??6.5 | ??6.6 | ??6.5 | ??6.7 | ??6.6 | ??6.75 | ??6.71 |
| Body resistance (m Ω cm) | ??6.5 | ??5.8 | ??8.3 | ??6.8 | ??8.1 | ??3.8 | ??4.2 | ??2.74 | ??0.69 |
| The target number | ??[A] | ??[B] | ??[C] | ??[D] | ??[E] | ??[F] | ??[G] | ??[H] | ??[I] |
Table IV-2
| Embodiment/comparative example | The target number | Substrate temperature (℃) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??IV-1 | ??[A] | ??25 | ??1000 | ??80 | Amorphous | ??5.50 |
| ??IV-2 | ??[A] | ??215 | ??1000 | ??81 | Crystallization | ??5.51 |
| ??IV-3 | ??[B] | ??25 | ??700 | ??80 | Amorphous | ??5.49 |
| ??IV-4 | ??[C] | ??25 | ??3 | ??81 | Amorphous | ??5.48 |
| ??IV-5 | ??[D] | ??25 | ??5 | ??80 | Amorphous | ??5.47 |
| ??IV-6 | ??[E] | ??25 | ??4 | ??81 | Amorphous | ??5.46 |
| ??IV-7 | ??[F] | ??25 | ??1 | ??82 | Amorphous | ??5.48 |
| ??IV-8 | ??[F] | ??25 | ??1 | ??82 | Amorphous | ??5.48 |
| ??IV-9 | ??[G] | ??25 | ??2 | ??81 | Amorphous | ??5.48 |
| ??(Iv-1) | ??[H] | ??25 | ??0.34 | ??80 | Amorphous | ??5.18 |
| ??(IV-2) | ??[I] | ??25 | ??0.42 | ??80 | Crystallite | ??4.97 |
| ??(IV-3) | ??[H] | ??215 | ??0.32 | ??80 | Amorphous | ??5.18 |
| ??(IV-4) | ??[I] | ??215 | ??0.18 | ??82 | Crystallization | ??4.95 |
[EXAMPLE IV-10]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-3 as the powder of stannic oxide, zinc oxide and the molybdenum oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-3.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [J] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-11]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-3 as the powder of stannic oxide, zinc oxide and the molybdenum oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-3.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [K] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-12]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-3 as the powder of stannic oxide, Indium sesquioxide and the molybdenum oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-3.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [L] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-13]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-3 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the molybdenum oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-3.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [M] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-14]
(1) manufacturing of transparent conducting glass
Use EXAMPLE IV-13 to make the sputtering target [M] of gained, except that the glass substrate temperature in the sputtering condition is adjusted into 215 ℃, other all make transparent conducting glass with (3) the same terms of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-15]
(1) manufacturing of transparent conductive film
Remove and will replace with transparency polycarbonate film as the glass substrate of substrate, and the sputtering target [M] of use EXAMPLE IV-13 making gained in addition, other all make transparent conductive film with (3) the same terms of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
[EXAMPLE IV-16]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-3 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the molybdenum oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-3.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [N] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-4.
Table IV-3
| Embodiment | ??IV-10 | ??IV-11 | ??IV-12 | ??IV-13 | ??IV-16 |
| ??Sn/(Sn+In+Zn) | ??0.80 | ??0.95 | ??0.80 | ??0.80 | ??0.80 |
| ??In/(Sn+In+Zn) | ??- | ??- | ??0.20 | ??0.10 | ??0.15 |
| ??Zn/(Sn+In+Zn) | ??0.20 | ??0.05 | ??- | ??0.10 | ??0.05 |
| ??Mo/(Sn+In+Zn+Mo) | ??0.04 | ??0.032 | ??0.03 | ??0.05 | ??0.04 |
| Sintered sheets density (g/cm 3) | ??6.7 | ??6.5 | ??6.7 | ??6.8 | ??6.7 |
| Body resistance (m Ω cm) | ??5.3 | ??4.9 | ??5.2 | ??3.6 | ??3.8 |
| The target number | ??[J] | ??[K] | ??[L] | ??[M] | ??[N] |
Table IV-4
| Embodiment | The target number | Substrate temperature (℃) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??IV-10 | ??[J] | ??25 | ??850 | ??80 | Amorphous | ??5.47 |
| ??IV-11 | ??[K] | ??25 | ??650 | ??81 | Crystallization | ??5.49 |
| ??IV-12 | ??[L] | ??25 | ??8 | ??80 | Amorphous | ??5.49 |
| ??IV-13 | ??[M] | ??25 | ??1 | ??81 | Amorphous | ??5.48 |
| ??IV-14 | ??[M] | ??215 | ??0.8 | ??80 | Amorphous | ??5.47 |
| ??IV-15 | ??[M] | ??25 | ??1 | ??81 | Amorphous | ??5.48 |
| ??IV-16 | ??[N] | ??25 | ??2 | ??81 | Amorphous | ??5.46 |
[EXAMPLE IV-17]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-5 as the powder of stannic oxide, zinc oxide and the ruthenium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-5.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [O] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-18]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-5 as the powder of stannic oxide, zinc oxide and the ruthenium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-5.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [P] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-19]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-5 as the powder of stannic oxide, Indium sesquioxide and the ruthenium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-5.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [Q] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-20]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-5 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the ruthenium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-5.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [R] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-21]
(1) manufacturing of transparent conducting glass
Use EXAMPLE IV-20 to make the sputtering target [R] of gained, except that the glass substrate temperature in the sputtering condition is adjusted into 215 ℃, other all make transparent conducting glass with (3) the same terms of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-22]
(1) manufacturing of transparent conductive film
Remove and will replace with transparency polycarbonate film as the glass substrate of substrate, and the sputtering target [R] of use EXAMPLE IV-20 making gained in addition, other all make transparent conductive film with (3) the same terms of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
[EXAMPLE IV-23]
(1) manufacturing of the raw material powder of transparent conductive material
Except that will being mixed with atomic ratio shown in the Table IV-5 as the powder of stannic oxide, Indium sesquioxide, zinc oxide and the ruthenium oxide of raw material, other all make the raw material powder of transparent conductive material according to (1) same steps as of EXAMPLE IV-1.
(2) manufacturing of sintered sheets
Except that the raw material powder that uses above-mentioned (1) gained transparent conductive material, other all make sintered sheets according to (2) same steps as of EXAMPLE IV-1.
The physical property measurement result of gained sintered sheets is shown in Table IV-5.
(3) manufacturing of transparent conducting glass
Except that the sputtering target [S] that uses above-mentioned (2) gained sintered sheets made, other all make transparent conducting glass according to (3) same steps as of EXAMPLE IV-1.
The rerum natura assessment result of gained nesa coating is shown in Table IV-6.
Table IV-5
| Embodiment | ??IV-17 | ??IV-18 | ??IV-19 | ??IV-20 | ??IV-23 |
| ??Sn/(Sn+In+Zn) | ??0.80 | ??0.95 | ??0.80 | ??0.80 | ??0.80 |
| ??In/(Sn+In+Zn) | ??- | ??- | ??0.20 | ??0.10 | ??0.15 |
| ??Zn/(Sn+In+Zn) | ??0.20 | ??0.05 | ??- | ??0.10 | ??0.05 |
| ??Ru/(Sn+In+Zn+Ru) | ??0.04 | ??0.032 | ??0.03 | ??0.05 | ??0.04 |
| Sintered sheets density (g/cm 3) | ??6.5 | ??6.4 | ??6.6 | ??6.7 | ??6.7 |
| Body resistance (m Ω cm) | ??4.2 | ??5.6 | ??4.25 | ??3.4 | ??3.6 |
| The target number | ??[O] | ??[P] | ??[Q] | ??[R] | ??[S] |
Table IV-6
| Embodiment | The target number | Substrate temperature (℃) | The resistivity of film (m Ω cm) | Transmittance (%) | Crystallinity | Work function (eV) |
| ??IV-17 | ??[O] | ??25 | ??45 | ??81 | Amorphous | ??5.51 |
| ??IV-18 | ??[P] | ??25 | ??42 | ??82 | Crystallization | ??5.48 |
| ??IV-19 | ??[Q] | ??25 | ??6 | ??81 | Amorphous | ??5.47 |
| ??IV-20 | ??[R] | ??25 | ??2 | ??80 | Amorphous | ??5.52 |
| ??IV-21 | ??[R] | ??215 | ??1 | ??82 | Amorphous | ??5.49 |
| ??IV-22 | ??[R] | ??25 | ??2 | ??80 | Amorphous | ??5.52 |
| ??IV-23 | ??[S] | ??25 | ??2 | ??81 | Amorphous | ??5.51 |
[usability on the industry]
As mentioned above, the invention provides for effective means forms the sintered product of nesa coating, the sputtering target of this sintered product and transparent conducting glass and the conducting film of making from this class target to stablize. The electrode that this class electro-conductive glass and conducting film are made has good transparency, and therefore electric conductivity and processability are suitable for being used as transparency electrode in organic electroluminescence device, to realize good hole injection rate wherein.
Claims (13)
1. the sintered product of a composition, said composition contains Indium sesquioxide or Indium sesquioxide and zinc oxide and/or stannic oxide, and its atomic ratio is
In/(In+Zn+Sn)＝0.80～1.00，
Zn/(In+Zn+Sn)＝0.00～0.20，
Sn/(In+Zn+Sn)＝0.00～0.20，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by a kind of metal oxide selected in ruthenium oxide, molybdenum oxide and the vanadium oxide.
2. sputtering target, it comprises the sintered product of claim 1.
3. electron bunch target, it comprises the sintered product of claim 1.
4. ion plating target, it comprises the sintered product of claim 1.
5. the transparent conductive material of a composition, said composition contains by one or more selected in Indium sesquioxide, zinc oxide and stannic oxide metal oxides, and contain 0.5～20 atom % that accounts for whole atoms metal total amounts by one or more selected in iridium oxide, rhenium oxide and palladous oxide metal oxides.
6. the composition of a sintering claim 5 and the sintered product that makes.
7. sputtering target, it comprises the sintered product of claim 6.
8. the transparent conductive material of a composition, said composition contains one or more in stannic oxide, Indium sesquioxide and the zinc oxide, and its atomic ratio is
Sn/(Sn+In+Zn)＝0.55～1.00，
In/(Sn+In+Zn)＝0.00～0.45，
Zn/(Sn+In+Zn)＝0.00～0.25，
And contain 0.5～10 atom % that accounts for whole atoms metal total amounts by one or more selected in vanadium oxide, molybdenum oxide and ruthenium oxide metal oxides.
9. transparent conductive material as claimed in claim 8, wherein, the atomic ratio of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.55～0.95，
In/(Sn+In+Zn)＝0.00～0.40，
Zn/(Sn+In+Zn)＝0.05～0.25。
10. transparent conductive material as claimed in claim 8, wherein, the atomic ratio of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.55～0.95，
In/(Sn+In+Zn)＝0.00～0.40，
Zn/(Sn+In+Zn)＝0.05～0.20.
11. transparent conductive material as claimed in claim 8, wherein, the atomic ratio of stannic oxide, Indium sesquioxide and zinc oxide is
Sn/(Sn+In+Zn)＝0.60～0.95，
In/(Sn+In+Zn)＝0.00～0.35，
Zn/(Sn+In+Zn)＝0.05～0.20。
12. sintered product that each composition in 8 to 11 of the claims the is made in the sintering temperature that is not less than 1200 ℃.
13. a sputtering target, it comprises the sintered product of claim 12, and its resistivity is at most 10m Ω cm.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24532298A JP4233641B2 (en) | 1998-08-31 | 1998-08-31 | Target for transparent conductive film, transparent conductive glass and transparent conductive film |
| JP245322/98 | 1998-08-31 | ||
| JP251200/98 | 1998-09-04 | ||
| JP5046/99 | 1999-01-12 | ||
| JP58384/99 | 1999-03-05 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998019828A Division CN1281544C (en) | 1998-08-31 | 1999-08-19 | Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1699262A true CN1699262A (en) | 2005-11-23 |
| CN100513353C CN100513353C (en) | 2009-07-15 |
Family
ID=17131946
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101219187A Expired - Fee Related CN100480210C (en) | 1998-08-31 | 1999-08-19 | Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film |
| CNB2005100791831A Expired - Fee Related CN100513353C (en) | 1998-08-31 | 1999-08-19 | Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101219187A Expired - Fee Related CN100480210C (en) | 1998-08-31 | 1999-08-19 | Target for transparent conductive film, transparent conductive material, transparent conductive glass, and transparent conductive film |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4233641B2 (en) |
| CN (2) | CN100480210C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102543250A (en) * | 2006-03-15 | 2012-07-04 | 住友金属矿山株式会社 | Oxide sintered body, manufacturing method therefor, manufacturing method for transparent conductive film using the same, and resultant transparent conductive film |
| CN102803547A (en) * | 2009-06-30 | 2012-11-28 | 出光兴产株式会社 | Transparent conductive film |
| CN103038834A (en) * | 2010-06-04 | 2013-04-10 | 奈米新素材株式会社 | Transparent conductive layer, target for transparent conductive layer and a process for producing the target for transparent conductive layer |
| CN102216237B (en) * | 2008-11-20 | 2015-05-13 | 出光兴产株式会社 | ZnO-SnO2-In2O3Oxide-like sintered body and amorphous transparent conductive film |
| CN104649664A (en) * | 2013-11-21 | 2015-05-27 | 青岛润鑫伟业科贸有限公司 | Molybdenum dioxide conductive ceramic material |
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| DE60041353D1 (en) * | 1999-11-25 | 2009-02-26 | Idemitsu Kosan Co | SPUTTERTARGET, TRANSPARENT CONDUCTIVE OXID AND PREPARATION PROCESS FOR SPUTTERTARGET |
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| JP4933756B2 (en) * | 2005-09-01 | 2012-05-16 | 出光興産株式会社 | Sputtering target |
| JP4804867B2 (en) * | 2005-10-18 | 2011-11-02 | 出光興産株式会社 | Transparent conductive film, transparent electrode, electrode substrate and manufacturing method thereof |
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| JP4947942B2 (en) * | 2005-09-20 | 2012-06-06 | 出光興産株式会社 | Sputtering target |
| KR101080527B1 (en) * | 2005-09-20 | 2011-11-04 | 이데미쓰 고산 가부시키가이샤 | Sputtering target, transparent conductive film and transparent electrode |
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Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029655C (en) * | 1992-07-31 | 1995-08-30 | 中国科学院上海硅酸盐研究所 | Electric heater of transparent conductive membrance working in high temp. and its application |
| US5763091A (en) * | 1994-10-27 | 1998-06-09 | Sumitomo Metal Mining Co., Ltd. | Electroconductive substrate and method for forming the same |
| WO1997001853A1 (en) * | 1995-06-28 | 1997-01-16 | Idemitsu Kosan Co., Ltd. | Transparent conductive laminate and touch panel made by using the same |
| CN1174487A (en) * | 1996-08-21 | 1998-02-25 | 无锡市现代技术发展公司 | Production process of transparent electrothermic film element |
-
1998
- 1998-08-31 JP JP24532298A patent/JP4233641B2/en not_active Expired - Fee Related
-
1999
- 1999-08-19 CN CNB2006101219187A patent/CN100480210C/en not_active Expired - Fee Related
- 1999-08-19 CN CNB2005100791831A patent/CN100513353C/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| CN100513353C (en) | 2009-07-15 |
| JP4233641B2 (en) | 2009-03-04 |
| CN100480210C (en) | 2009-04-22 |
| CN1915898A (en) | 2007-02-21 |
| JP2000072537A (en) | 2000-03-07 |
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