TWI394872B - Indium oxide-zinc oxide-magnesium oxide based sputtering target and transparent conductive film - Google Patents
Indium oxide-zinc oxide-magnesium oxide based sputtering target and transparent conductive film Download PDFInfo
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- TWI394872B TWI394872B TW094109151A TW94109151A TWI394872B TW I394872 B TWI394872 B TW I394872B TW 094109151 A TW094109151 A TW 094109151A TW 94109151 A TW94109151 A TW 94109151A TW I394872 B TWI394872 B TW I394872B
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- 238000005477 sputtering target Methods 0.000 title claims description 63
- XBJOBWPPZLJOLG-UHFFFAOYSA-N [O-2].[Mg+2].[O-2].[In+3].[O-2].[Zn+2] Chemical compound [O-2].[Mg+2].[O-2].[In+3].[O-2].[Zn+2] XBJOBWPPZLJOLG-UHFFFAOYSA-N 0.000 title 1
- 239000011701 zinc Substances 0.000 claims description 89
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 87
- 239000011777 magnesium Substances 0.000 claims description 67
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 57
- 239000011787 zinc oxide Substances 0.000 claims description 43
- 229910003437 indium oxide Inorganic materials 0.000 claims description 38
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 38
- 239000000395 magnesium oxide Substances 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 29
- 239000002184 metal Substances 0.000 claims description 29
- 229910044991 metal oxide Inorganic materials 0.000 claims description 29
- 150000004706 metal oxides Chemical class 0.000 claims description 29
- 229910052725 zinc Inorganic materials 0.000 claims description 25
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052749 magnesium Inorganic materials 0.000 claims description 19
- 229910017976 MgO 4 Inorganic materials 0.000 claims description 16
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 15
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 11
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical group [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 239000010408 film Substances 0.000 description 139
- 238000002834 transmittance Methods 0.000 description 46
- 239000000843 powder Substances 0.000 description 42
- 238000004544 sputter deposition Methods 0.000 description 36
- 239000000203 mixture Substances 0.000 description 32
- 239000002245 particle Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 17
- 238000005054 agglomeration Methods 0.000 description 15
- 230000002776 aggregation Effects 0.000 description 15
- 239000011521 glass Substances 0.000 description 11
- 239000011135 tin Substances 0.000 description 11
- 238000005530 etching Methods 0.000 description 10
- 238000009616 inductively coupled plasma Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 9
- 238000004993 emission spectroscopy Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052732 germanium Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 229910020203 CeO Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- OYQCBJZGELKKPM-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O-2].[Zn+2].[O-2].[In+3] OYQCBJZGELKKPM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/08—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—Electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
Description
本發明係有關液晶驅動用電極基板、電致發光(EL，ElectroLuminescent)用電極基板，特別是有關構成上述電極基板用之透明電極的透明導電膜。又，本發明係有關製造該透明導電膜用之濺鍍靶。 The present invention relates to an electrode substrate for liquid crystal driving, an electrode substrate for electroluminescence (EL), and particularly to a transparent conductive film constituting a transparent electrode for the electrode substrate. Further, the present invention relates to a sputtering target for producing the transparent conductive film.
以往即研究以摻雜錫之材料作為透明導電膜用濺鍍靶。特別是ITO(銦錫氧化物：Indium Tin Oxide)廣為使用。 In the past, a material doped with tin was investigated as a sputtering target for a transparent conductive film. In particular, ITO (Indium Tin Oxide) is widely used.
然而，使用ITO之情況，為降低其電阻率(specific resistance)而有結晶化之必要。因而，必須以高溫成膜，或於成膜後必須進行規定之加熱處理。 However, in the case of using ITO, it is necessary to crystallize in order to lower its specific resistance. Therefore, it is necessary to form a film at a high temperature or to perform a predetermined heat treatment after film formation.
又，於結晶化之ITO膜進行蝕刻加工時，使用王水(硝酸‧鹽酸之混合液)等強酸作為蝕刻液，而產生由於使用強酸所引起之不便且成為問題。亦即，作為構成薄膜電晶體(TFT：Thin Film Transistor)等構成要素使用之液晶顯示裝置，有使用金屬細線作為柵線(gate line)、源極‧漏極線(source-drain line)(或電極)。此種情況，於ITO膜之蝕刻加工時，由於王水而發生該等配線材料斷線或線變細之問題。 Further, when the crystallization of the crystallized ITO film is performed, a strong acid such as aqua regia (a mixed solution of nitric acid or hydrochloric acid) is used as an etching liquid, which causes inconvenience due to the use of a strong acid and becomes a problem. In other words, as a liquid crystal display device which is used as a constituent element such as a thin film transistor (TFT), a metal thin wire is used as a gate line or a source-drain line (or electrode). In this case, when the ITO film is etched, the wiring material is broken or the line is thinned due to the aqua regia.
因而，建議於成膜時，藉由使氫或水存在於濺射氣體中，使非晶質ITO成膜，並以弱酸對非晶質ITO進行蝕 刻之方法。然而，由於ITO本身具結晶性，以弱酸進行蝕刻時，會有產生蝕刻殘渣問題之情況。又，當氫或水分布於濺射氣體中時，則成膜時，於ITO濺鍍靶上會產生稱為結粒之突起，而可能成為異常放電之原因。 Therefore, it is recommended that amorphous ITO be formed into a film by forming hydrogen or water in a sputtering gas during film formation, and the amorphous ITO is etched with a weak acid. The method of engraving. However, since ITO itself has crystallinity and is etched with a weak acid, there is a problem that etching residue occurs. Further, when hydrogen or water is distributed in the sputtering gas, a protrusion called agglomeration is formed on the ITO sputtering target at the time of film formation, which may cause abnormal discharge.
一方面，下列專利文獻揭示有關添加鋅作為一般透明導電膜所添加之Sn以外之添加金屬的濺鍍靶或導電材料、透明導電膜之專利之一例。 On the one hand, the following patent documents disclose an example of a patent relating to the addition of zinc as a sputtering target or a conductive material or a transparent conductive film to which a metal other than Sn added to a general transparent conductive film is added.
例如，下列專利文獻1揭示以In及Zn為主成分，含通式In2O3(ZnO)m(m=2至20)所示六方晶層狀化合物之標靶。若藉由該標靶即可獲得耐濕性較ITO膜更優越，且具有與ITO膜同等導電性及光透過率之透明導電膜。 For example, the following Patent Document 1 discloses a target containing a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m (m = 2 to 20) containing In and Zn as main components. When the target is used, a transparent conductive film which is superior in moisture resistance to the ITO film and has the same conductivity and light transmittance as the ITO film can be obtained.
下列專利文獻2揭示具備有非晶質氧化物之鋅元素與銦元素之原子比Zn/(Zn+In)之值為0.2至0.9以下之液晶驅動用透明電極之液晶顯示器用彩色濾光片(color filter)，而上述液晶驅動用透明電極不易發生龜裂或剝離之液晶顯示器用彩色濾光片。 In the following Patent Document 2, a color filter for a liquid crystal display having a transparent electrode for liquid crystal driving having an atomic ratio of zinc element to indium element of an amorphous oxide of Zn/(Zn+In) of 0.2 to 0.9 or less is disclosed ( The color filter) is a color filter for a liquid crystal display in which the transparent electrode for liquid crystal driving is less likely to be cracked or peeled off.
下列專利文獻3揭示含有In與Zn，而In/(In+Zn)之值為0.8至0.9之導電性透明基材，且其蝕刻特性、電阻率之熱安定性優越之導電性透明基材。 Patent Document 3 listed below discloses a conductive transparent substrate containing a conductive transparent substrate having In and Zn and having an In/(In+Zn) value of 0.8 to 0.9, and having excellent thermal stability in etching characteristics and electrical resistivity.
此外，上述揭示之專利文獻1至3中，亦有揭示獲得不產生結粒之標靶、獲得蝕刻性優越、且具有與ITO膜同等電阻率之透明導電膜之專利文獻。 Further, in Patent Documents 1 to 3 disclosed above, there is also disclosed a patent document which obtains a target which does not cause agglomeration, and which has a transparent conductive film which is excellent in etching property and has the same electrical resistivity as that of the ITO film.
專利文獻1：日本特開平06-234565號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. 06-234565
專利文獻2：日本特開平07-120612號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 07-120612
專利文獻3：日本特開平07-235219號公報 Patent Document 3: Japanese Laid-Open Patent Publication No. 07-235219
專利文獻4：日本特開平08-264022號公報 Patent Document 4: Japanese Laid-Open Patent Publication No. 08-264022
然而，非晶質透明導電膜之帶隙(band gap)並不明確，亦即由於帶隙不甚大，因而可能產生短波長側，特別是400至450 nm區域之光線透過率降低之問題。 However, the band gap of the amorphous transparent conductive film is not clear, that is, since the band gap is not so large, there is a possibility that the light transmittance of the short-wavelength side, particularly the region of 400 to 450 nm, is lowered.
相對於此，上述專利文獻4係藉由調整擬3元系氧化物之組成而製造可控制折射率且透明性高之透明導電膜。然而該透明導電膜成膜所用之濺鍍靶之導電率低而不易進行濺鍍，且成膜之透明導電膜為結晶性，而有蝕刻性不太高之問題。 On the other hand, in the above-mentioned Patent Document 4, a transparent conductive film having a controllable refractive index and high transparency is produced by adjusting the composition of the pseudo-ternary oxide. However, the sputtering target used for film formation of the transparent conductive film has low conductivity and is not easily sputtered, and the film-formed transparent conductive film is crystalline and has a problem that etching property is not so high.
本發明為了解決上述課題，其目的係提供濺鍍時不產生結粒(Nodule)之標靶。本發明之另一目的係提供蝕刻性優越，且特別是400至450 nm區域之透明性優越(於400至450 nm區域具有高光線透過率)之非晶質透明導電膜。 In order to solve the above problems, the present invention has an object of providing a target which does not cause agglomeration during sputtering. Another object of the present invention is to provide an amorphous transparent conductive film which is excellent in etching property, and particularly excellent in transparency in a region of 400 to 450 nm (having high light transmittance in a region of 400 to 450 nm).
(1)因而為了解決上述課題，本發明之濺鍍靶其特徵係含氧化銦、氧化鋅、氧化鎂。 (1) Therefore, in order to solve the above problems, the sputtering target of the present invention is characterized by containing indium oxide, zinc oxide, and magnesium oxide.
於氧化銦與氧化鋅所成之濺鍍靶中，藉由另外添加氧 化鎂可更有效的抑制濺鍍時產生結粒，而獲得異常放電少之標靶。 In the sputtering target formed by indium oxide and zinc oxide, by additionally adding oxygen Magnesium is more effective in suppressing the formation of agglomerates during sputtering, and obtaining a target with less abnormal discharge.
(2)本發明之濺鍍靶，係含氧化銦、氧化鋅、氧化鎂之濺鍍靶，其特徵係以X射線繞射觀察所得結晶之波峰時，前述結晶波峰含有源自氧化銦與氧化鋅所成之通式In2O3(ZnO)m所示六方晶層狀化合物之波峰，以及源自氧化銦與氧化鎂所成之In2MgO4之波峰，此處，m為3至20。 (2) The sputtering target of the present invention is a sputtering target containing indium oxide, zinc oxide or magnesium oxide, characterized in that the peak of the crystal obtained by X-ray diffraction is derived from indium oxide and oxidation. a peak of a hexagonal layered compound represented by the formula of In 2 O 3 (ZnO) m and a peak of In 2 MgO 4 derived from indium oxide and magnesium oxide, where m is 3 to 20 .
以X射線繞射測定濺鍍靶表面之結果，觀察所得結晶之波峰時，該結晶波峰必須含有源自規定之六方晶層狀化合物以及In2MgO4之波峰。此處，規定之六方晶層狀化合物係指由氧化銦與氧化鋅所成之通式In2O3(ZnO)m(m為3至20之整數)所示之六方晶層狀化合物。又，上述In2MgO4係由氧化銦與氧化鎂構成。 As a result of measuring the surface of the sputtering target by X-ray diffraction, when the peak of the obtained crystal is observed, the crystal peak must contain a peak derived from a predetermined hexagonal layered compound and In 2 MgO 4 . Here, the predetermined hexagonal layered compound means a hexagonal layered compound represented by the general formula In 2 O 3 (ZnO) m (m is an integer of 3 to 20) formed of indium oxide and zinc oxide. Further, the above In 2 MgO 4 is composed of indium oxide and magnesium oxide.
由氧化銦與氧化鋅所成之六方晶層狀化合物其具體例為例如In2Zn3O6、In2Zn4O7、In2Zn5O8等，其通式係以In2O3(ZnO)m(m為3至20之整數)表示。由EPMA(電子微探分析(Electron Probe Microanalysis：X射線微分析儀)測繪圖(mapping)所測得該等複合氧化物之結晶粒大小以10μm以下為佳，較好為5μm以下，更好為3μm以下。 Specific examples of the hexagonal layered compound formed of indium oxide and zinc oxide are, for example, In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 , etc., and the general formula is In 2 O 3 . (ZnO) m (m is an integer from 3 to 20). The crystal grain size of the composite oxides measured by EPMA (Electron Probe Microanalysis) is preferably 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less.
濺鍍靶不含氧化銦與氧化鋅所成之上述六方晶層狀化合物及In2MgO4等時，濺鍍靶之整體電阻(bulk resistance)會超過10m Ω cm。而如整體電阻超過10 m Ω cm，則濺鍍靶中產生異常放電，且濺鍍靶會破裂。 When the sputtering target does not contain the above hexagonal layered compound and In 2 MgO 4 formed by indium oxide and zinc oxide, the bulk resistance of the sputtering target exceeds 10 m Ω cm. If the overall resistance exceeds 10 m Ω cm, an abnormal discharge occurs in the sputtering target, and the sputtering target may be broken.
(3)本發明係上述(1)項記載之濺鍍靶，其特徵為含氧化銦與氧化鋅所成之六方晶層狀化合物及氧化銦與氧化鎂所成之In2MgO4者 (3) The sputtering target according to (1) above, characterized in that the hexagonal layered compound containing indium oxide and zinc oxide and In 2 MgO 4 formed by indium oxide and magnesium oxide are used.
(4)本發明係上述(1)至(3)項中任一項記載之濺鍍靶，其特徵為[In]/([In]+[Zn]+[Mg])=0.74至0.94，[Zn]/([In]+[Zn]+[Mg])=0.05至0.25，[Mg]/([In]+[Zn]+[Mg])=0.01至0.20。此處，[In]表示毎單位體積之銦原子數目，[Zn]表示毎單位體積之鋅原子數目，[Mg]表示毎單位體積之鎂原子數目。 (4) The sputtering target according to any one of the above (1) to (3), wherein [In] / ([In] + [Zn] + [Mg]) = 0.74 to 0.94, [Zn] / ([In] + [Zn] + [Mg]) = 0.05 to 0.25, [Mg] / ([In] + [Zn] + [Mg]) = 0.01 to 0.20. Here, [In] represents the number of indium atoms per unit volume, [Zn] represents the number of zinc atoms per unit volume, and [Mg] represents the number of magnesium atoms per unit volume.
本發明之濺鍍靶中，[In]/([In]+[Zn]+[Mg])=0.74至0.94。[In]/([In]+[Zn]+[Mg])之值小於0.74時，濺鍍靶之整體電阻過高，經成膜之透明導電膜之電阻率會增大。另一方面，若[In]/([In]+[Zn]+[Mg])之值超過0.94時，經成膜之透明導電膜之電阻率增大，且透明導電膜結晶化，於蝕刻時會產生殘渣。 In the sputtering target of the present invention, [In] / ([In] + [Zn] + [Mg]) = 0.74 to 0.94. When the value of [In]/([In]+[Zn]+[Mg]) is less than 0.74, the overall resistance of the sputtering target is too high, and the resistivity of the film-formed transparent conductive film increases. On the other hand, when the value of [In]/([In]+[Zn]+[Mg]) exceeds 0.94, the resistivity of the film-formed transparent conductive film increases, and the transparent conductive film crystallizes and is etched. Residues are produced.
本發明之濺鍍靶中，[Zn]/([In]+[Zn]+[Mg])=0.05至0.25。[Zn]/([In]+[Zn]+[Mg])之值小於0.05時，經成膜之透明導電膜之電阻率過度增高，而會結晶化。另一方面，若[Zn]/([In]+[Zn]+[Mg])之值超過 0.25時，經成膜之透明導電膜之電阻率會過度增高。 In the sputtering target of the present invention, [Zn] / ([In] + [Zn] + [Mg]) = 0.05 to 0.25. When the value of [Zn]/([In]+[Zn]+[Mg]) is less than 0.05, the resistivity of the film-formed transparent conductive film is excessively increased, and crystallizes. On the other hand, if the value of [Zn]/([In]+[Zn]+[Mg]) exceeds At 0.25, the resistivity of the film-formed transparent conductive film is excessively increased.
本發明之濺鍍靶中，[Mg]/([In]+[Zn]+[Mg])=0.01至0.20。[Mg]/([In]+[Zn]+[Mg])之值小於0.01時，經成膜之透明導電膜之電阻率過度增高，而會結晶化，且透明導電膜之透過率不會增高。另一方面，若[Mg]/([In]+[Zn]+[Mg])之值超過0.25時，經成膜之透明導電膜之電阻率會過度增高。 In the sputtering target of the present invention, [Mg] / ([In] + [Zn] + [Mg]) = 0.01 to 0.20. When the value of [Mg]/([In]+[Zn]+[Mg]) is less than 0.01, the resistivity of the film-formed transparent conductive film is excessively increased, and crystallization occurs, and the transmittance of the transparent conductive film does not occur. Increase. On the other hand, when the value of [Mg] / ([In] + [Zn] + [Mg]) exceeds 0.25, the resistivity of the film-formed transparent conductive film is excessively increased.
(5)本發明係上述(1)至(4)項中任一項記載之濺鍍靶，其特徵為另含正四價之金屬氧化物。 The sputtering target according to any one of the items (1) to (4) above, characterized in that it further contains a tetravalent metal oxide.
正四價係指金屬氧化物中金屬原子之原子價為+4者。藉由含正四價之金屬氧化物，濺鍍靶之整體電阻下降，而可防止異常放電。 Positive tetravalent means that the atomic valence of a metal atom in a metal oxide is +4. By containing a tetravalent metal oxide, the overall resistance of the sputtering target is lowered, and abnormal discharge can be prevented.
(6)本發明係上述(5)項記載之濺鍍靶，其特徵為，正四價之上述金屬氧化物為SnO2、ZrO2、GeO2、CeO2者。 (6) The sputtering target according to the above (5), wherein the tetravalent metal oxide is SnO 2 , ZrO 2 , GeO 2 or CeO 2 .
正四價之上述金屬氧化物可適當使用SnO2、ZrO2、GeO2、CeO2。 As the tetravalent metal oxide, SnO 2 , ZrO 2 , GeO 2 or CeO 2 can be suitably used.
(7)本發明係上述(6)項記載之濺鍍靶，其特徵為含有1種或2種以上選自SnO2、ZrO2、GeO2、CeO2及Ga2O3所成組群M之金屬氧化物者。 (7) The sputtering target according to the above (6), which is characterized in that it contains one or more selected from the group consisting of SnO 2 , ZrO 2 , GeO 2 , CeO 2 and Ga 2 O 3 . The metal oxides.
(8)本發明係上述(7)項記載之濺鍍靶，其特徵為選自前述組群M之1種或2種以上之前述金屬氧化物之 添加量為：[M]/[全部金屬]=0.0001至0.15。此處[M]表示毎單位體積之選自前述組群M之1種或2種以上之金屬氧化物中金屬原子之數目，亦即毎單位體積之Sn、Zr、Ge、Ce、Ga之任1種或2種以上之原子數目，[全部金屬]表示毎單位體積之全部金屬，亦即毎單位體積之In、Zn、Mg以及選自前述組群M之1種或2種以上之金屬氧化物中之金屬之原子總數。 (8) The sputtering target according to the above (7), which is characterized by being selected from one or more of the group M of the group M The amount added is: [M] / [all metals] = 0.0001 to 0.15. Here, [M] represents the number of metal atoms in one or more metal oxides selected from the group M of the unit volume, that is, the unit volume of Sn, Zr, Ge, Ce, Ga. One or two or more atomic numbers, [all metals] means all metals per unit volume, that is, in units of In, Zn, Mg, and one or more metal oxides selected from the group M described above. The total number of atoms in the metal.
濺鍍靶中，[M]/[全部金屬]之值為0.0001至0.15，以0.0003至0.12為佳，0.0005至0.1更佳。[M]/[全部金屬]之值小於0.0001時，未能顯出添加效果，而若[M]/[全部金屬]之值超過0.15時，經成膜之透明導電膜之蝕刻性幾乎不提升。 In the sputtering target, the value of [M] / [all metal] is 0.0001 to 0.15, preferably 0.0003 to 0.12, more preferably 0.0005 to 0.1. When the value of [M]/[all metals] is less than 0.0001, the additive effect is not exhibited, and if the value of [M]/[all metals] exceeds 0.15, the etching property of the transparent conductive film formed is hardly improved. .
(9)本發明係一種非晶質透明導電膜，其特徵為含氧化銦、氧化鋅及氧化鎂。 (9) The present invention is an amorphous transparent conductive film characterized by containing indium oxide, zinc oxide and magnesium oxide.
透明導電膜係藉由含氧化銦、氧化鋅以及氧化鎂而獲得之完全非晶質之透明導電膜。藉由使此種透明導電膜成為非晶質，而於蝕刻時幾乎不會產生殘渣。又，透明導電膜藉含氧化鎂而可有效的防止400至450 nm區域之光線透過率降低。 The transparent conductive film is a completely amorphous transparent conductive film obtained by containing indium oxide, zinc oxide, and magnesium oxide. By making such a transparent conductive film amorphous, almost no residue is generated during etching. Further, the transparent conductive film can effectively prevent the light transmittance in the region of 400 to 450 nm from being lowered by containing magnesium oxide.
(10)本發明係上述(9)項記載之非晶質透明導電膜，其特徵為[In]/([In]+[Zn]+[Mg])=0.74至0.94、[Zn]/([In]+[Zn]+[Mg])=0.05至0.25、[Mg]/( [In]+[Zn]+[Mg])=0.01至0.20。此處，[In]表示毎單位體積之銦原子數目，[Zn]表示毎單位體積之鋅原子數目，[Mg]表示毎單位體積之鎂原子數目。 (10) The amorphous transparent conductive film according to (9) above, which is characterized by [In]/([In]+[Zn]+[Mg])=0.74 to 0.94, [Zn]/( [In]+[Zn]+[Mg])=0.05 to 0.25, [Mg]/( [In]+[Zn]+[Mg])=0.01 to 0.20. Here, [In] represents the number of indium atoms per unit volume, [Zn] represents the number of zinc atoms per unit volume, and [Mg] represents the number of magnesium atoms per unit volume.
本發明之透明導電膜中，[In]/([In]+[Zn]+[Mg])之值為0.74至0.94，以0.74至0.92為佳，0.75至0.9更佳。[In]/([In]+[Zn]+[Mg])之值小於0.74時，透明導電膜之電阻率會過高，而若[In]/([In]+[Zn]+[Mg])之值超過0.94時，透明導電膜易結晶化，且電阻率會增大。 In the transparent conductive film of the present invention, the value of [In] / ([In] + [Zn] + [Mg]) is from 0.74 to 0.94, preferably from 0.74 to 0.92, more preferably from 0.75 to 0.9. When the value of [In]/([In]+[Zn]+[Mg]) is less than 0.74, the resistivity of the transparent conductive film may be too high, and if [In]/([In]+[Zn]+[Mg When the value of ]) exceeds 0.94, the transparent conductive film is easily crystallized and the resistivity is increased.
本發明之透明導電膜中，[Zn]/([In]+[Zn]+[Mg])為0.05至0.25，以0.07至0.25為佳，0.08至0.22更佳。[Zn]/([In]+[Zn]+[Mg])之值小於0.05時，透明導電膜易結晶化，且電阻率會增大。另一方面，若[Zn]/([In]+[Zn]+[Mg])之值超過0.25時，透明導電膜之電阻率有過度增高之情況。 In the transparent conductive film of the present invention, [Zn] / ([In] + [Zn] + [Mg]) is 0.05 to 0.25, preferably 0.07 to 0.25, more preferably 0.08 to 0.22. When the value of [Zn]/([In]+[Zn]+[Mg]) is less than 0.05, the transparent conductive film is easily crystallized, and the specific resistance is increased. On the other hand, when the value of [Zn]/([In]+[Zn]+[Mg]) exceeds 0.25, the resistivity of the transparent conductive film may excessively increase.
本發明之透明導電膜中，[Mg]/([In]+[Zn]+[Mg])為0.01至0.20，以0.01至0.15為佳，0.02至0.1更佳。[Mg]/([In]+[Zn]+[Mg])之值小於0.01時，透明導 電膜之透過率不會增高，且易結晶化，電阻率亦會增高。另一方面，若[Mg]/([In]+[Zn]+[Mg])之值超過0.20時，經成膜之透明導電膜之電阻率會過度增高。 In the transparent conductive film of the present invention, [Mg] / ([In] + [Zn] + [Mg]) is from 0.01 to 0.20, preferably from 0.01 to 0.15, more preferably from 0.02 to 0.1. Transparent guide when the value of [Mg]/([In]+[Zn]+[Mg]) is less than 0.01 The transmittance of the electric film does not increase, and it is easy to crystallize, and the electrical resistivity is also increased. On the other hand, when the value of [Mg] / ([In] + [Zn] + [Mg]) exceeds 0.20, the resistivity of the film-formed transparent conductive film is excessively increased.
透明導電膜中In、Zn、Mg之含量不在上述範圍內時，透明導電膜有不能獲得較佳透明性、電阻率、蝕刻性等之情況。 When the content of In, Zn, and Mg in the transparent conductive film is out of the above range, the transparent conductive film may not have good transparency, electrical resistivity, etching property, or the like.
(11)本發明係上述(9)或(10)項記載之非晶質透明導電膜，其特徵為另含正四價之金屬氧化物。 (11) The amorphous transparent conductive film according to the above (9) or (10), which further comprises a tetravalent metal oxide.
於透明導電膜中藉由含正四價之金屬氧化物，而標靶之整體電阻降低，可於安定之放電狀態下使透明導電膜成膜。因而可獲得更安定之透明導電膜。 In the transparent conductive film, by the metal oxide containing a positive tetravalent, the overall electrical resistance of the target is lowered, and the transparent conductive film can be formed into a film in a stable discharge state. Thus, a more stable transparent conductive film can be obtained.
(12)本發明係上述(11)項記載之非晶質透明導電膜，其特徵為，正四價之上述金屬氧化物為SnO2、ZrO2、GeO2、CeO2者。 (12) The amorphous transparent conductive film according to the above aspect (11), wherein the tetravalent metal oxide is SnO 2 , ZrO 2 , GeO 2 or CeO 2 .
正四價之金屬氧化物可適當使用SnO2、ZrO2、GeO2、CeO2。 As the tetravalent metal oxide, SnO 2 , ZrO 2 , GeO 2 , or CeO 2 can be suitably used.
(13)本發明係上述(9)或(10)項記載之非晶質透明導電膜，其特徵為含有1種或2種以上選自SnO2、ZrO2、GeO2、CeO2及Ga2O3所成組群M之金屬氧化物者。 (13) The amorphous transparent conductive film according to the above (9) or (10), which is characterized by containing one or more selected from the group consisting of SnO 2 , ZrO 2 , GeO 2 , CeO 2 and Ga 2 . O 3 is a group of metal oxides of group M.
(14)本發明係上述(13)項記載之非晶質透明導電膜，其特徵為選自前述組群M之1種或2種以上之前述金屬氧化物之添加量為：[M]/[全部金屬]=0.0001至0.15者。此處[M]表示毎單位體積之選自前述組群M之1 種或2種以上之金屬氧化物中金屬原子之數目，亦即毎單位體積之Sn、Zr、Ge、Ce、Ga任1種或2種以上之原子數目，[全部金屬]表示毎單位體積之全部金屬，亦即毎單位體積之In、Zn、Mg以及選自前述組群M之1種或2種以上之金屬氧化物中之金屬的原子總數。 (14) The amorphous transparent conductive film according to the above (13), wherein the amount of the metal oxide selected from one or more of the group M is: [M]/ [All metals] = 0.0001 to 0.15. Here [M] represents the unit volume of 毎 selected from the aforementioned group M 1 The number of metal atoms in the metal oxide of two or more kinds, that is, the number of atoms of one or more of Sn, Zr, Ge, Ce, and Ga per unit volume, and [all metals] means unit volume of yttrium. The total number of atoms of the metal, that is, the unit volume of In, Zn, Mg, and the metal selected from the metal oxides of one or more of the above-mentioned group M.
透明導電膜中，[M]/[全部金屬]之值為0.0001至0.15，以0.0003至0.12為佳，0.0005至0.1更佳。[M]/[全部金屬]之值小於0.0001時，未能顯出添加效果，而若[M]/[全部金屬]之值超過0.15時，透明導電膜之蝕刻性幾乎不提升。 In the transparent conductive film, the value of [M] / [all metal] is 0.0001 to 0.15, preferably 0.0003 to 0.12, more preferably 0.0005 to 0.1. When the value of [M]/[all metals] is less than 0.0001, the effect of addition is not exhibited, and when the value of [M]/[all metals] exceeds 0.15, the etching property of the transparent conductive film hardly increases.
如上述，本發明之濺鍍靶於濺鍍時幾乎不產生結粒。 As described above, the sputtering target of the present invention hardly causes agglomeration during sputtering.
又，本發明之非晶質透明導電膜以弱酸(有機酸)進行蝕刻時幾乎不產生殘渣，且400至450 nm區域之透明性(光線透過性)優越。 Further, the amorphous transparent conductive film of the present invention hardly generates residue when it is etched with a weak acid (organic acid), and has excellent transparency (light transmittance) in a region of 400 to 450 nm.
下文說明本發明之較佳實施型態。 Preferred embodiments of the invention are described below.
依規定之比例秤量平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1 μm以下之MgO粉末，混合後，裝入樹脂製容器內，再添加水，以使用硬質ZrO2球之濕式球磨機進行混合。此時混合時間設為20小時。經由該混合後，取出所得之混合淤漿，過濾、乾燥並造粒。將所得之造粒物裝入成形模型中，以3噸/cm2之壓力施予冷間淨水壓壓縮使成形，而得成形體。 In 2 O 3 powder having an average particle diameter of 1 μm or less, ZnO powder having an average particle diameter of 1 μm or less, and MgO powder having an average particle diameter of 1 μm or less are weighed according to a predetermined ratio, and mixed, and then placed in a resin container, and then placed in a resin container. Water was added and mixed by a wet ball mill using a hard ZrO 2 ball. At this time, the mixing time was set to 20 hours. After the mixing, the resulting mixed slurry was taken out, filtered, dried and granulated. The obtained granules were placed in a molding mold, and subjected to cold water pressure compression molding at a pressure of 3 ton / cm 2 to form a molded body.
繼之，將所得成形體以如下之方法進行燒結。首先，將成形體載置於燒結爐內，對該燒結爐內容積每0.1 m3，以5公升/分鐘之比例通入氧氣。於該氛圍中，以1470℃燒結上述成形體5小時。此時，將燒結爐內之溫度以1℃/分鐘之速度升溫至1000℃，1000℃至1470℃間則以3℃/分鐘之速度升溫。 Next, the obtained shaped body was sintered in the following manner. First, the formed body was placed in a sintering furnace, and the inner volume of the sintering furnace was introduced into oxygen at a ratio of 5 liters per minute per 0.1 m 3 . The molded body was sintered at 1470 ° C for 5 hours in this atmosphere. At this time, the temperature in the sintering furnace was raised to 1000 ° C at a rate of 1 ° C / minute, and the temperature was raised at a rate of 3 ° C / minute between 1000 ° C and 1470 ° C.
然後停止通入氧氣，將上述燒結爐內之溫度以10℃/分鐘之速度自1470℃降溫至1300℃。然後，對該燒結爐內容積每0.1m3，以10公升/分鐘之比例通入Ar，於該氛圍中，將上述成形體於1300℃保持3小時後，放冷而獲得燒結體。 Then, oxygen gas was stopped, and the temperature in the above sintering furnace was lowered from 1,470 ° C to 1,300 ° C at a rate of 10 ° C / minute. Then, each of the sintering furnace capacity 0.1m 3, at a ratio of 10 liters / minute into Ar, in this atmosphere, the shaped body will be maintained after 3 hours at 1300 ℃, allowed to cool to obtain a sintered body.
所得燒結體之相對密度以如下方法而求得。首先，使用水以阿基米得法測定，自理論密度算出相對密度，其值為97%。該相對密度示於表1。該理論密度係由不缺氧之In2O3結晶(綠柱石型(Bixbite)構造)與Zn、Mg之氧化物重量分率算出。 The relative density of the obtained sintered body was determined by the following method. First, water was measured by the Archimedes method, and the relative density was calculated from the theoretical density, and its value was 97%. The relative density is shown in Table 1. The theoretical density was calculated from the weight fraction of the oxide of Zn and Mg which is not deficient in In 2 O 3 crystal (Bixbite structure).
又，燒結體中Zn與Mg之含有量係以感應偶合電漿(ICP，Inductively coupled plasma)發光分析法進行定 量分析，結果可確認燒結體中仍然維持與原料粉末混合時所裝入之相同組成。此時，經確認之燒結體中之具體原子組成比率[In]/([In]+[Zn]+[Mg])之值、[Zn]/([In]+[Zn]+[Mg])之值、[Mg]/([In]+[Zn]+[Mg])之值示於表1。 In addition, the content of Zn and Mg in the sintered body is determined by ICP (Inductively coupled plasma) luminescence analysis. As a result of the analysis, it was confirmed that the same composition which was charged while mixing with the raw material powder was maintained in the sintered body. At this time, the specific atomic composition ratio [In] / ([In] + [Zn] + [Mg]) in the confirmed sintered body, [Zn] / ([In] + [Zn] + [Mg] The value of [), [Mg] / ([In] + [Zn] + [Mg]) is shown in Table 1.
表1中，[In]表示燒結體中毎單位體積之銦原子數目，[Zn]表示燒結體中毎單位體積之鋅原子數目，[Mg]表示燒結體中毎單位體積之鎂原子數目。 In Table 1, [In] represents the number of indium atoms per unit volume of the sintered body, [Zn] represents the number of zinc atoms per unit volume of the sintered body, and [Mg] represents the number of magnesium atoms per unit volume of the sintered body.
繼之，以杯模式(cup)磨刀石研磨上述燒結體之濺鍍面，加工成為直徑100 mm、厚度5 mm，並使用In系合金與靶座(backing plate)貼合，而製造濺鍍用標靶1。該濺鍍用標靶1之整體電阻，係先使用羅雷斯塔(三菱油化製)，以4探針法計測標靶1之電阻率，再依據計測之電阻率值計算而求得。算出之整體電阻值示於表1。 Then, the sputtered surface of the sintered body was ground in a cup-type whetstone, processed to have a diameter of 100 mm, a thickness of 5 mm, and bonded with a backing plate using an In-based alloy to produce a sputtering. Use target 1. The overall resistance of the target 1 for sputtering is determined by using the Rayresta (manufactured by Mitsubishi Petrochemical Co., Ltd.), and the resistivity of the target 1 is measured by a 4-probe method, and then calculated based on the calculated resistivity value. The calculated overall resistance values are shown in Table 1.
標靶1內所含之鋅或鎂之形態係以氧化銦-氧化鋅之複合氧化物(例如，In2Zn5O8、In2Zn7O10、In2Zn3O6、In2Zn4O7等)形態分散者，較以氧化鋅(ZnO)或氧化鎂(MgO)分散者為佳。第1圖係示標靶1之X射線曲線圖。第1圖中，縱軸表示繞射X射線之強度，橫軸表示繞射X射線之角度。由氧化銦與氧化鋅所構成之上述六方晶層狀化合物為例如In2Zn3O6、In2Zn4O7、In2Zn5O8等，以通式In2O3(ZnO)m(m為3至20之整數)表示者為佳。 The form of zinc or magnesium contained in the target 1 is a composite oxide of indium oxide-zinc oxide (for example, In 2 Zn 5 O 8 , In 2 Zn 7 O 10 , In 2 Zn 3 O 6 , In 2 Zn). 4 O 7 and the like) are more dispersed than zinc oxide (ZnO) or magnesium oxide (MgO). Figure 1 is an X-ray plot of the target 1. In Fig. 1, the vertical axis represents the intensity of the diffracted X-rays, and the horizontal axis represents the angle of the diffracted X-rays. The above hexagonal layered compound composed of indium oxide and zinc oxide is, for example, In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 or the like, and has the general formula In 2 O 3 (ZnO) m (m is an integer from 3 to 20) is preferred.
鋅原子或鎂原子於氧化銦之銦部位置換固溶，而於氧化銦燒結體中以原子層次分散時，標靶1之整體電阻變得 過大，濺鍍時放電不安定，而可能引發異常放電。 The zinc atom or the magnesium atom is replaced by a solid solution in the indium portion of the indium oxide, and when the indium oxide sintered body is dispersed in an atomic layer, the overall resistance of the target 1 becomes Too large, the discharge is not stable during sputtering, and may cause abnormal discharge.
標靶1中之氧化銦、氧化鋅及氧化鎂係以例如由氧化銦與氧化鋅所構成之六方晶層狀化合物之形態、氧化銦與氧化鎂所構成之In2MgO4之形態分散為佳。藉以此種形態分散，標靶1之整體電阻不會過大，濺鍍時放電安定。 Indium oxide, zinc oxide, and magnesium oxide in the target 1 are preferably dispersed in the form of a hexagonal layered compound composed of indium oxide and zinc oxide, and in the form of In 2 MgO 4 composed of indium oxide and magnesium oxide. . By dispersing in this form, the overall resistance of the target 1 is not excessively large, and the discharge is stable at the time of sputtering.
以X射線繞射確認，本實施例1之標靶1中，氧化銦、氧化鋅及氧化鎂係以上述六方晶層狀化合物及In2MgO4之形態分散。又，濺鍍用標靶1中氧化銦、氧化鋅及氧化鎂係以上述之形態分散，係依據X射線繞射所得之結晶波峰加以確認。 It was confirmed by X-ray diffraction that in the target 1 of the first embodiment, indium oxide, zinc oxide, and magnesium oxide were dispersed in the form of the above hexagonal layered compound and In 2 MgO 4 . Further, in the sputtering target 1, the indium oxide, the zinc oxide, and the magnesium oxide are dispersed in the above-described form, and are confirmed by the crystallization peak obtained by the X-ray diffraction.
由氧化銦與氧化鋅所構成之六方晶層狀化合物為例如In2Zn3O6、In2Zn4O7、In2Zn5O8等，以通式In2O3(ZnO)m(m為3至20之整數)表示者為佳。 The hexagonal layered compound composed of indium oxide and zinc oxide is, for example, In 2 Zn 3 O 6 , In 2 Zn 4 O 7 , In 2 Zn 5 O 8 or the like, and has the general formula In 2 O 3 (ZnO) m ( m is an integer from 3 to 20) is preferred.
藉以此種形態分散，標靶1之整體電阻小於10m Ω cm，而可能安定地濺鍍。使用該標靶1進行濺鍍不會產生結粒(表1)。 By dispersing in this form, the overall resistance of the target 1 is less than 10 m Ω cm, and it is possible to stably deposit. Sputtering using this target 1 did not cause agglomeration (Table 1).
將所得之標靶1安裝於直流(DC(Direct Current))濺鍍裝置後，以200℃，於玻片上形成膜厚130 nm之透明導電膜1a。測定經成膜之透明導電膜1a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜1a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸 對該透明導電膜1a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 1 was mounted on a direct current (DC) sputtering apparatus, a transparent conductive film 1a having a film thickness of 130 nm was formed on the glass slide at 200 °C. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 1a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 1a, no peak was observed, and it was found to be amorphous. Use weak acid When the transparent conductive film 1a was etched, no residue was generated (Table 1).
如上之本實施例1係獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜1a。 As in the first embodiment as described above, the transparent conductive film 1a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
除了改變平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1μm以下之MgO粉末之混合比例之外，以與上述實施例1相同之方法將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1相同之方法求得。所求得之相對密度示於表1。 In the same manner as in the above Example 1, except that the In 2 O 3 powder having an average particle diameter of 1 μm or less, the ZnO powder having an average particle diameter of 1 μm or less, and the mixing ratio of MgO powder having an average particle diameter of 1 μm or less were changed. The above powder is mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered body was determined in the same manner as in the above Example 1. The relative densities obtained are shown in Table 1.
與上述實施例1同樣，以ICP發光分析法定量分析所得燒結體中Zn與Mg之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍維持相同。此時，經確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above-mentioned Example 1, the content of Zn and Mg in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed remained the same in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1相同之方法，將該燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶2。再以與上述實施例1相同之方法求得該標靶2之整體電阻。求得之整體電阻值示於表1。又，使用該標靶2進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described first embodiment, the sputtered surface of the sintered body was bonded to the target holder to produce a target 2 for sputtering. Further, the overall resistance of the target 2 was obtained in the same manner as in the above-described first embodiment. The overall resistance values obtained are shown in Table 1. Further, sputtering using the target 2 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例2之濺鍍用標靶2中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 In the sputtering target 2 of the second embodiment, indium oxide, zinc oxide, and magnesium oxide were in the form of a hexagonal layered compound and In 2 MgO 4 in the same manner as in the above-described first embodiment. presence.
將所得之標靶2安裝於直流濺鍍裝置後，以與上述實施例1相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜2a。測定經成膜之透明導電膜2a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜2a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜2a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 2 was attached to a DC sputtering apparatus, a transparent conductive film 2a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in the above Example 1. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 2a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 2a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 2a was etched using a weak acid, no residue was generated (Table 1).
如上於本實施例2中亦與上述實施例1同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜2a。 Also in the second embodiment, as in the above-described first embodiment, the transparent conductive film 2a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
除了改變平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1μm以下之MgO粉末之混合比例之外，以與上述實施例1及2相同之方法將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1及2相同之方法求得。所求得之相對密度示於表1。 The same as the above-described Examples 1 and 2 except that the In 2 O 3 powder having an average particle diameter of 1 μm or less, the ZnO powder having an average particle diameter of 1 μm or less, and the MgO powder having an average particle diameter of 1 μm or less were changed. Method The above powder was mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered body was determined in the same manner as in the above Examples 1 and 2. The relative densities obtained are shown in Table 1.
與上述實施例1及2同樣，以ICP發光分析法定量分析所得燒結體中Zn與Mg之含有量，結果可確認原料粉 末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above Examples 1 and 2, the content of Zn and Mg in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry, and as a result, the raw material powder was confirmed. The composition charged at the time of the final mixing is also maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1及2相同之方法，將該燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶3。再以與上述實施例1及2相同之方法求得該標靶3之整體電阻。求得之整體電阻值示於表1。又，使用該標靶3進行濺鍍不會產生結粒(表1)。 Then, the sputtering target of the sintered body was bonded to the target holder in the same manner as in the above Examples 1 and 2 to produce a sputtering target 3. Further, the overall resistance of the target 3 was obtained in the same manner as in the above Examples 1 and 2. The overall resistance values obtained are shown in Table 1. Further, sputtering using the target 3 did not cause agglomeration (Table 1).
本實施例3之濺鍍用標靶3中，以X射線繞射確認，氧化銦、氧化鋅及氧化鎂係以與上述實施例1及2同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 In the sputtering target 3 of the third embodiment, X-ray diffraction was confirmed, and indium oxide, zinc oxide, and magnesium oxide were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 and 2. The form exists.
將所得之標靶3安裝於直流濺鍍裝置後，以與實施例1及2相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜3a。測定經成膜之透明導電膜3a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜3a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜3a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 3 was attached to a DC sputtering apparatus, a transparent conductive film 3a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 and 2. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 3a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 3a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 3a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例3中亦與實施例1及2同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜3a。 Also in the above-described Example 3, as in the first and second embodiments, the transparent conductive film 3a having an amorphous light transmittance improved in the region of 400 to 450 nm was obtained.
除了改變平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1μm以下之MgO粉末之混合比例之外，以與上述實施例1至3相同之方法將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至3相同之方法求得。所求得之相對密度示於表1。 The same as the above-described Examples 1 to 3 except that the In 2 O 3 powder having an average particle diameter of 1 μm or less, the ZnO powder having an average particle diameter of 1 μm or less, and the mixing ratio of MgO powder having an average particle diameter of 1 μm or less were changed. Method The above powder was mixed, shaped and sintered to obtain a sintered body. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 3. The relative densities obtained are shown in Table 1.
與上述實施例1至3同樣，以ICP發光分析法定量分析所得燒結體中Zn與Mg之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above Examples 1 to 3, the content of Zn and Mg in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1至3相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶4。再以與上述實施例1至3相同之方法求得該標靶4之整體電阻。求得之整體電阻值示於表1。又，使用該標靶4進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 3, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 4. Further, the overall resistance of the target 4 was obtained in the same manner as in the above Examples 1 to 3. The overall resistance values obtained are shown in Table 1. Further, sputtering using the target 4 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例4之濺鍍用標靶4中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至3同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It was confirmed by X-ray diffraction that in the sputtering target 4 of the fourth embodiment, indium oxide, zinc oxide, and magnesium oxide were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 3. The form exists.
將所得之標靶4安裝於直流濺鍍裝置後，以與實施例1相同之方法，以200℃，於玻片上形成膜厚130 nm之透 明導電膜4a。測定經成膜之透明導電膜4a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜4a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜4a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 4 was mounted on a DC sputtering apparatus, a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Example 1. The conductive film 4a is shown. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 4a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 4a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 4a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例4中亦與上述實施例1至3同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜4a。 Also in the above-described Example 4, as in the above-described Embodiments 1 to 3, the transparent conductive film 4a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
再者，除了以規定比例混合SnO2粉末以外，以與上述實施例1同樣之組成比例將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至4相同之方法求得。所求得之相對密度示於表1。 In addition, the powder was mixed, molded, and sintered at a composition ratio similar to that of the above Example 1 except that the SnO 2 powder was mixed in a predetermined ratio to obtain a sintered body. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 4. The relative densities obtained are shown in Table 1.
與上述實施例1至4同樣之方法，以ICP發光分析法定量分析所得燒結體中Zn、Mg及Sn之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above-mentioned Examples 1 to 4, the content of Zn, Mg, and Sn in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
又，本專利中，[M]係指Sn、Zr、Ge所成之組群，特別是表1中，M表示Sn、Zr、Ge之任一者。[M]表示燒結體中毎單位體積之Sn、Zr及Ge之原子數目。 Further, in the present patent, [M] means a group formed of Sn, Zr, and Ge, and particularly in Table 1, M represents any one of Sn, Zr, and Ge. [M] represents the number of atoms of Sn, Zr, and Ge per unit volume of the sintered body.
繼之，以與上述實施例1至4相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶5。再以與上述實 施例1至4相同之方法求得該標靶5之整體電阻。求得之整體電阻值示於表1。使用該標靶5進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 4, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 5. And with the above The overall resistance of the target 5 was determined in the same manner as in the first to fourth embodiments. The overall resistance values obtained are shown in Table 1. Sputtering using this target 5 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例5之濺鍍用標靶5中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至4同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It is confirmed by X-ray diffraction that in the sputtering target 5 of the fifth embodiment, indium oxide, zinc oxide, and magnesium oxide are hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 4. The form exists.
將所得之標靶5安裝於直流濺鍍裝置後，以與實施例1至4相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜5a。測定經成膜之透明導電膜5a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜5a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜5a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 5 was mounted on a DC sputtering apparatus, a transparent conductive film 5a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 4. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 5a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 5a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 5a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例5中亦與上述實施例1至4同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜5a。 Also in the above-described Example 5, as in the above-described Embodiments 1 to 4, the transparent conductive film 5a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
除了改變平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1μm以下之 MgO粉末與SnO2粉末之混合比例之外，以與上述實施例5相同之方法將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至5相同之方法求得。所求得之相對密度示於表1。 In addition to changing the mixing ratio of the In 2 O 3 powder having an average particle diameter of 1 μm or less, the ZnO powder having an average particle diameter of 1 μm or less, and the MgO powder having an average particle diameter of 1 μm or less and the SnO 2 powder, In the same manner, the above powder was mixed, shaped, and sintered to obtain a sintered body. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 5. The relative densities obtained are shown in Table 1.
與上述實施例5同樣，以ICP發光分析法定量分析所得燒結體中Zn、Mg及Sn之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above-mentioned Example 5, the content of Zn, Mg, and Sn in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1至5相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶6。再以與上述實施例1至5相同之方法求得該標靶6之整體電阻。求得之整體電阻值示於表1。又，使用該標靶6進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 5, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 6. Further, the overall resistance of the target 6 was obtained in the same manner as in the above Examples 1 to 5. The overall resistance values obtained are shown in Table 1. Further, sputtering using the target 6 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例6之濺鍍用標靶6中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至5同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It was confirmed by X-ray diffraction that in the sputtering target 6 of the sixth embodiment, indium oxide, zinc oxide, and magnesium oxide were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 5. The form exists.
將所得之標靶6安裝於直流濺鍍裝置後，以與實施例1至5相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜6a。測定經成膜之透明導電膜6a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜6a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱 酸對該透明導電膜6a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 6 was mounted on a DC sputtering apparatus, a transparent conductive film 6a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 5. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 6a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 6a, no peak was observed, and it was found to be amorphous. Use weak When the transparent conductive film 6a was etched with an acid, no residue was generated (Table 1).
如上之本實施例6中亦與上述實施例1至5同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜6a。 Also in the above-described Example 6, as in the above-described Embodiments 1 to 5, the transparent conductive film 6a having an amorphous light transmittance improved in the region of 400 to 450 nm was obtained.
除了改變平均粒徑為1μm以下之In2O3粉末、平均粒徑為1μm以下之ZnO粉末、平均粒徑為1μm以下之MgO粉末與SnO2粉末之混合比例之外，以與上述實施例5及6相同之方法將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至6相同之方法求得。所求得之相對密度示於表1。 In addition to changing the mixing ratio of the In 2 O 3 powder having an average particle diameter of 1 μm or less, the ZnO powder having an average particle diameter of 1 μm or less, and the MgO powder having an average particle diameter of 1 μm or less and the SnO 2 powder, The powder was mixed, shaped, and sintered in the same manner as in 6 to obtain a sintered body. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 6. The relative densities obtained are shown in Table 1.
與上述實施例5及6同樣，以ICP發光分析法定量分析所得燒結體中Zn、Mg及Sn之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above-mentioned Examples 5 and 6, the content of Zn, Mg, and Sn in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1至6相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶7。再以與上述實施例1至6相同之方法求得該標靶7之整體電阻。求得之整體電阻值示於表1。又，使用該標靶7進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 6, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 7. The overall resistance of the target 7 was determined in the same manner as in the above Examples 1 to 6. The overall resistance values obtained are shown in Table 1. Further, sputtering using the target 7 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例7之濺鍍用標靶7中 ，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至6同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It was confirmed by X-ray diffraction that the indium oxide, zinc oxide, and magnesium oxide in the sputtering target No. 7 of the seventh embodiment were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 6. The form exists.
將所得之標靶7安裝於直流濺鍍裝置後，以與實施例1至6相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜7a。測定經成膜之透明導電膜7a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜7a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜6a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 7 was mounted on a DC sputtering apparatus, a transparent conductive film 7a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 6. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 7a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 7a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 6a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例7中亦與實施例1至6同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜7a。 Also in the above-described Example 7, as in the first to sixth embodiments, the transparent conductive film 7a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
再者，除了以規定比例混合ZrO2粉末以外，以與上述實施例4同樣之組成比例將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至7相同之方法求得。所求得之相對密度示於表1。 In addition, the powder was mixed, molded, and sintered at a composition ratio similar to that of the above-described Example 4 except that the ZrO 2 powder was mixed in a predetermined ratio to obtain a sintered body. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 7. The relative densities obtained are shown in Table 1.
與上述實施例1至7同樣之方法，以ICP發光分析法定量分析所得燒結體中Zn、Mg及Zr之含有量，結果可 確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above Examples 1 to 7, the content of Zn, Mg and Zr in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry, and the result was It was confirmed that the composition charged when the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1至7相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶8。再以與上述實施例1至7相同之方法求得該標靶8之整體電阻。求得之整體電阻值示於表1。使用該標靶8進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 7, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 8. The overall resistance of the target 8 was determined in the same manner as in the above Examples 1 to 7. The overall resistance values obtained are shown in Table 1. Sputtering using this target 8 did not result in agglomeration (Table 1).
以X射線繞射確認，本實施例8之濺鍍用標靶8中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至7同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It was confirmed by X-ray diffraction that in the sputtering target 8 of the eighth embodiment, indium oxide, zinc oxide, and magnesium oxide were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 7. The form exists.
將所得之標靶8安裝於直流濺鍍裝置後，以與實施例1至7相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜8a。測定經成膜之透明導電膜8a之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜8a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜8a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 8 was mounted on a DC sputtering apparatus, a transparent conductive film 8a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 7. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film 8a were measured. The values of the measured resistivity and light transmittance are shown in Table 1. As a result of the X-ray diffraction measurement of the transparent conductive film 8a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 8a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例8中亦與上述實施例1至7同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜8a。 Also in the above-described Example 8, as in the above-described Embodiments 1 to 7, the transparent conductive film 8a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
再者，除了以GeO2粉末替代ZrO2粉末進行混合以外，以與上述實施例8同樣之組成比例將上述粉末混合、成形並燒結而獲得燒結體。所得燒結體之相對密度以與上述實施例1至8相同之方法求得。所求得之相對密度示於表1。 In addition, the powder was mixed, molded, and sintered at a composition ratio similar to that of the above Example 8 except that the GeO 2 powder was used instead of the ZrO 2 powder, and a sintered body was obtained. The relative density of the obtained sintered bodies was determined in the same manner as in the above Examples 1 to 8. The relative densities obtained are shown in Table 1.
與上述實施例1至8同樣之方法，以ICP發光分析法定量分析所得燒結體中Zn、Mg及Ge之含有量，結果可確認原料粉末混合時裝入之組成在燒結體中仍同樣維持。此時，所確認之燒結體中之具體組成比率之值示於表1。 In the same manner as in the above-mentioned Examples 1 to 8, the content of Zn, Mg, and Ge in the obtained sintered body was quantitatively analyzed by ICP emission spectrometry. As a result, it was confirmed that the composition charged in the case where the raw material powder was mixed was maintained in the sintered body. At this time, the values of the specific composition ratios in the confirmed sintered bodies are shown in Table 1.
繼之，以與上述實施例1至8相同之方法，將燒結體之濺鍍面與靶座貼合，製造濺鍍用標靶9。再以與上述實施例1至8相同之方法求得該標靶9之整體電阻。求得之整體電阻值示於表1。使用該標靶9進行濺鍍不會產生結粒(表1)。 Then, in the same manner as in the above-described Examples 1 to 8, the sputtering target of the sintered body was bonded to the target holder to produce a sputtering target 9. Further, the overall resistance of the target 9 was obtained in the same manner as in the above-described Embodiments 1 to 8. The overall resistance values obtained are shown in Table 1. Sputtering using this target 9 did not cause agglomeration (Table 1).
以X射線繞射確認，本實施例9之濺鍍用標靶9中，氧化銦、氧化鋅及氧化鎂係以與上述實施例1至8同樣形態之六方晶層狀化合物及In2MgO4之形態存在。 It was confirmed by X-ray diffraction that in the sputtering target No. 9 of the ninth embodiment, indium oxide, zinc oxide, and magnesium oxide were hexagonal layered compounds and In 2 MgO 4 in the same manner as in the above Examples 1 to 8. The form exists.
將所得之標靶9安裝於直流濺鍍裝置後，以與實施例1至8相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜9a。測定經成膜之透明導電膜9a之電阻率 及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。有關該透明導電膜9a以X射線繞射測定之結果，未觀測到波峰，而判明為非晶質。使用弱酸對該透明導電膜9a進行蝕刻時，不產生殘渣(表1)。 After the obtained target 9 was mounted on a DC sputtering apparatus, a transparent conductive film 9a having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 8. The resistivity of the film-formed transparent conductive film 9a is measured And light transmittance (400 nm, 450 nm). The values of the measured resistivity and light transmittance are shown in Table 1. As a result of measuring the X-ray diffraction of the transparent conductive film 9a, no peak was observed, and it was found to be amorphous. When the transparent conductive film 9a was etched using a weak acid, no residue was generated (Table 1).
如上之本實施例9中亦與實施例1至8同樣獲得非晶質且400至450 nm區域之光線透過率改善之透明導電膜9a。 Also in the above-described Example 9, as in the first to eighth embodiments, the transparent conductive film 9a having an amorphous light transmittance and improved light transmittance in the region of 400 to 450 nm was obtained.
本發明之濺鍍用標靶除了含有規定比例之氧化銦、氧化鋅及氧化鎂3成分以外，並無特別限制。因此例如可使用週知方法將由上述3成分所成之粉末加以混合、成形並燒結即可製造。 The target for sputtering of the present invention is not particularly limited, except that it contains a predetermined ratio of indium oxide, zinc oxide, and magnesium oxide. Therefore, for example, a powder obtained from the above three components can be mixed, formed, and sintered by a known method.
又，在不損及本發明效果之範圍內，含有上述3成分以外之成份亦佳。例如，於上述實施例5至9中，濺鍍用標靶除上述3成分以外，另含有規定比例之SnO2、ZrO2或GeO2亦佳。又，除上述3成分以外，另含有Ga2O3或CeO2等亦佳。除上述3成分以外，同時另含有選自SnO2、ZrO2、GeO2、Ga2O3及CeO2等之2種以上成分亦佳。 Further, it is also preferable to contain components other than the above three components within the range which does not impair the effects of the present invention. For example, in the above-described Examples 5 to 9, the sputtering target is preferably contained in a predetermined ratio of SnO 2 , ZrO 2 or GeO 2 in addition to the above three components. Further, in addition to the above three components, it is also preferable to further contain Ga 2 O 3 or CeO 2 . In addition to the above three components, two or more components selected from the group consisting of SnO 2 , ZrO 2 , GeO 2 , Ga 2 O 3 , and CeO 2 are also preferable.
於標靶中添加Ga2O3時，係以InGaMgO4、InGaMg2O5或InGaMgZnO5、InGaMgZn2O6、In2Ga2ZnO7、InGaZnO4、InGaZn2O5、InGaZn3O6、InGaZn4O7、InGaZn5O8、InGaZn6O9、InGaZn7O10等複合氧化物之形態 分散為佳。 When Ga 2 O 3 is added to the target, InGaMgO 4 , InGaMg 2 O 5 or InGaMgZnO 5 , InGaMgZn 2 O 6 , In 2 Ga 2 ZnO 7 , InGaZnO 4 , InGaZn 2 O 5 , InGaZn 3 O 6 , InGaZn The form of the composite oxide such as 4 O 7 , InGaZn 5 O 8 , InGaZn 6 O 9 or InGaZn 7 O 10 is preferably dispersed.
本實施例10之濺鍍用標靶，除了含有氧化銦、氧化鋅及氧化鎂3成分以外，即使含有上述SnO2、ZrO2、GeO2、Ga2O3、CeO2等成分，該實施例10之濺鍍用標靶亦發揮與上述實施例1至9之濺鍍用標靶同樣之作用效果。又，使用此種濺鍍用標靶所成膜之透明導電膜亦同樣發揮與上述實施例1至9之透明導電膜同樣之作用效果。 The sputtering target of the tenth embodiment contains components such as SnO 2 , ZrO 2 , GeO 2 , Ga 2 O 3 , and CeO 2 in addition to the components of indium oxide, zinc oxide, and magnesium oxide. The sputtering target of 10 also exerted the same effects as those of the sputtering targets of the above-described Examples 1 to 9. Moreover, the transparent conductive film formed by using such a target for sputtering also exhibits the same effects as those of the transparent conductive films of the above-described first to ninth embodiments.
使用市售之ITO標靶，亦即由氧化銦與氧化錫構成之濺鍍用標靶，進行與上述實施例1至9同樣之處理與操作。 The same treatments and operations as in the above Examples 1 to 9 were carried out using a commercially available ITO target, that is, a target for sputtering composed of indium oxide and tin oxide.
以與上述實施例1至9同樣之方法求得ITO標靶之相對密度、組成比率及整體電阻。所求得相對密度、組成比率及整體電阻之值示於表1。表1中之[X]表示標靶中毎單位體積之Sn、Zn原子之數目。使用該ITO標靶進行濺鍍時產生結粒(表1)。 The relative density, composition ratio, and overall electrical resistance of the ITO target were determined in the same manner as in the above Examples 1 to 9. The values obtained for the relative density, composition ratio, and overall resistance are shown in Table 1. [X] in Table 1 indicates the number of Sn and Zn atoms per unit volume of the target. Agglomeration occurred during sputtering using the ITO target (Table 1).
將該ITO標靶安裝於直流濺鍍裝置後，以與實施例1至9相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜。測定經成膜之透明導電膜之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率 之值示於表1。使用弱酸對該透明導電膜進行蝕刻時產生殘渣(表1)。 After the ITO target was mounted on a DC sputtering apparatus, a transparent conductive film having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 9. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film were measured. Determination of resistivity and light transmittance The values are shown in Table 1. Residue was generated when the transparent conductive film was etched using a weak acid (Table 1).
如上述，比較例1之透明導電膜以弱酸進行蝕刻時產生殘渣(表1)。 As described above, the transparent conductive film of Comparative Example 1 produced a residue when it was etched with a weak acid (Table 1).
使用市售之IZO(銦-鋅氧化物：登錄商標為[IZO])標靶，亦即由氧化銦與氧化鋅構成之濺鍍用標靶，進行與上述實施例1至9同樣之處理與操作。 The same treatment as in the above Examples 1 to 9 was carried out using a commercially available IZO (indium-zinc oxide: registered trademark [IZO]) target, that is, a target for sputtering composed of indium oxide and zinc oxide. operating.
以與上述實施例1至9同樣之方法求得IZO標靶之相對密度、組成比率及整體電阻。所求得相對密度、組成比率及整體電阻之值示於表1。使用IZO標靶進行濺鍍時產生結粒(表1)。 The relative density, composition ratio, and overall resistance of the IZO target were determined in the same manner as in the above Examples 1 to 9. The values obtained for the relative density, composition ratio, and overall resistance are shown in Table 1. Agglomeration occurred during sputtering using the IZO target (Table 1).
將該IZO標靶安裝於直流濺鍍裝置後，以與實施例1至9相同之方法，以200℃，於玻片上形成膜厚130 nm之透明導電膜。測定經成膜之透明導電膜之電阻率及光線透過率(400 nm、450 nm)。測定之電阻率及光線透過率之值示於表1。使用弱酸對該透明導電膜進行蝕刻時不產生殘渣(表1)。 After the IZO target was mounted on a DC sputtering apparatus, a transparent conductive film having a film thickness of 130 nm was formed on the glass slide at 200 ° C in the same manner as in Examples 1 to 9. The resistivity and light transmittance (400 nm, 450 nm) of the film-formed transparent conductive film were measured. The values of the measured resistivity and light transmittance are shown in Table 1. No residue was generated when the transparent conductive film was etched using a weak acid (Table 1).
如上述，比較例2之透明導電膜於400 nm至450 nm中之光線透過率不太高。 As described above, the light transmittance of the transparent conductive film of Comparative Example 2 at 400 nm to 450 nm was not so high.
表1係示本發明實施例1至9及比較例1、2中濺鍍用標靶及透明導電膜之物性參數之表。 Table 1 shows the physical property parameters of the sputtering target and the transparent conductive film in Examples 1 to 9 and Comparative Examples 1 and 2 of the present invention.
第1圖係示本發明實施例1中標靶1之X射線圖譜之圖。 Fig. 1 is a view showing an X-ray spectrum of a target 1 in Example 1 of the present invention.
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| JP5494082B2 (en) * | 2010-03-23 | 2014-05-14 | 住友電気工業株式会社 | Conductive oxide and method for producing the same |
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