WO2015178429A1 - 酸化物焼結体、スパッタリング用ターゲット、及びそれを用いて得られる酸化物半導体薄膜 - Google Patents
酸化物焼結体、スパッタリング用ターゲット、及びそれを用いて得られる酸化物半導体薄膜 Download PDFInfo
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- WO2015178429A1 WO2015178429A1 PCT/JP2015/064527 JP2015064527W WO2015178429A1 WO 2015178429 A1 WO2015178429 A1 WO 2015178429A1 JP 2015064527 W JP2015064527 W JP 2015064527W WO 2015178429 A1 WO2015178429 A1 WO 2015178429A1
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- Prior art keywords
- phase
- oxide
- sintered body
- thin film
- less
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- 239000010409 thin film Substances 0.000 title claims abstract description 75
- 239000004065 semiconductor Substances 0.000 title claims abstract description 49
- 238000005477 sputtering target Methods 0.000 title claims abstract description 22
- 239000011777 magnesium Substances 0.000 claims abstract description 71
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 57
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052738 indium Inorganic materials 0.000 claims abstract description 39
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000004544 sputter deposition Methods 0.000 claims abstract description 29
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 38
- 239000000758 substrate Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002441 X-ray diffraction Methods 0.000 claims description 8
- 229910017857 MgGa Inorganic materials 0.000 claims description 7
- 229910017976 MgO 4 Inorganic materials 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 32
- 239000012071 phase Substances 0.000 description 119
- 239000010408 film Substances 0.000 description 32
- 239000000843 powder Substances 0.000 description 31
- 229910052760 oxygen Inorganic materials 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 230000015572 biosynthetic process Effects 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910003437 indium oxide Inorganic materials 0.000 description 9
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000004973 liquid crystal related substance Substances 0.000 description 6
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 5
- 229910001195 gallium oxide Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000005355 Hall effect Effects 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
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013081 microcrystal Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000002250 progressing effect Effects 0.000 description 2
- 238000004151 rapid thermal annealing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- 229910017902 MgIn2O4 Inorganic materials 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 argon and oxygen Chemical compound 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
- H01L29/78693—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate the semiconducting oxide being amorphous
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- 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
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- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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Definitions
- the present invention relates to an oxide sintered body, a target, and an oxide semiconductor thin film obtained using the oxide sintered body, and more specifically, contains amorphous indium, gallium, and magnesium exhibiting a low carrier concentration and a high carrier mobility.
- the present invention relates to an oxide semiconductor thin film, a sputtering target containing indium, gallium and magnesium suitable for forming the oxide semiconductor thin film, and an oxide sintered body containing indium, gallium and magnesium suitable for obtaining the target.
- a thin film transistor is one type of a field effect transistor (hereinafter referred to as FET).
- a TFT is a three-terminal element having a gate terminal, a source terminal, and a drain terminal as a basic structure, and a semiconductor thin film formed on a substrate is used as a channel layer in which electrons or holes move and is used as a gate terminal.
- the active element has a function of switching a current between a source terminal and a drain terminal by applying a voltage to control a current flowing in a channel layer.
- a TFT is an electronic device that is most frequently put into practical use, and a typical application is a liquid crystal driving element.
- the most widely used TFT is a metal-insulator-semiconductor-FET (MIS-FET) using a polycrystalline silicon film or an amorphous silicon film as a channel layer material. Since the MIS-FET using silicon is opaque to visible light, a transparent circuit cannot be formed. For this reason, when the MIS-FET is applied as a switching element for liquid crystal driving of a liquid crystal display, the device has a small aperture ratio of display pixels.
- MIS-FET metal-insulator-semiconductor-FET
- Patent Document 1 discloses a transparent amorphous oxide thin film formed by vapor phase film formation and composed of elements of In, Ga, Zn, and O, and the oxide
- the composition of the composition is InGaO 3 (ZnO) m (m is a natural number of less than 6) when crystallized, and the carrier mobility (also referred to as carrier electron mobility) is 1 cm without adding impurity ions.
- a thin film (a-IGZO film) has an electron carrier mobility in the range of approximately 1 to 10 cm 2 V ⁇ 1 sec ⁇ 1 , so that the mobility is insufficient when formed as a TFT channel layer. It was.
- Patent Document 2 a compound represented by In (GaMg) O 4 containing In, Ga and Mg and represented by In 2 O 3 , a compound represented by MgGa 2 O 4 , and In 2 MgO 4 is disclosed.
- a sputtering target including a sintered body containing one or more compounds selected from the compounds represented by:
- Patent Document 2 since the target of Patent Document 2 includes a phase such as Ga 2 MgO 4 having poor conductivity that causes arcing, there is a problem that abnormal discharge occurs.
- An object of the present invention is to provide a sputtering target that enables reduction of the carrier concentration of an amorphous oxide semiconductor thin film, an oxide sintered body that is optimal for obtaining the sputtering target, and a low carrier concentration obtained by using the target.
- An object is to provide an oxide semiconductor thin film exhibiting high carrier mobility.
- the present inventors have made a small amount of magnesium, specifically, an oxide sintered body containing gallium as an oxide with a Ga / (In + Ga) ratio of indium to gallium of 0.20 to 0.45.
- the sintered oxide sintered body is substantially made of an In 2 O 3 phase having a bixbite structure, and In 2 O A generation phase other than the three phases includes a ⁇ -Ga 2 O 3 type GaInO 3 phase, or a ⁇ -Ga 2 O 3 type GaInO 3 phase and a (Ga, In) 2 O 3 phase, and the oxide
- an oxide semiconductor thin film manufactured using a sintered body has a carrier mobility of 10 cm 2 V ⁇ 1 sec ⁇ 1 or higher.
- the first invention contains indium, gallium, and magnesium as oxides, and the gallium content is in a Ga / (In + Ga) atomic ratio of 0.20 or more and 0.45 or less, and the magnesium content
- the Mg / (In + Ga + Mg) atomic ratio is 0.0001 or more and less than 0.05, and the In 2 O 3 phase having a bixbite structure and ⁇ -Ga 2 O 3 as a generation phase other than the In 2 O 3 phase Type structure GaInO 3 phase, or ⁇ -Ga 2 O 3 type GaInO 3 phase and (Ga, In) 2 O 3 phase, In (GaMg) O 4 phase, MgGa 2 O 4 phase, In 2
- the oxide sintered body is characterized by being substantially free of MgO 4 phase and Ga 2 O 3 phase.
- the second invention is the oxide sintered body according to the first invention, wherein the magnesium content is 0.01 to 0.03 in terms of Mg / (In + Ga + Mg) atomic ratio.
- the third invention is the oxide sintered body according to the first or second invention, wherein the gallium content is in a Ga / (In + Ga) atomic ratio of 0.20 or more and 0.30 or less.
- an oxide firing according to any one of the first to third aspects of the present invention which does not substantially contain a positive divalent element other than magnesium and a positive trivalent to positive hexavalent element other than indium and gallium. It is a ligation.
- the X-ray diffraction peak intensity ratio of the GaInO 3 phase having a ⁇ -Ga 2 O 3 type structure defined by the following formula 1 is in the range of 2% to 80%.
- the sixth invention is a sputtering target obtained by processing the oxide sintered body according to any one of the first to fifth inventions.
- the seventh invention is an amorphous oxide semiconductor thin film formed on a substrate by a sputtering method using the sputtering target described in the sixth invention and then heat-treated.
- An eighth invention is the oxide semiconductor thin film according to the seventh invention, wherein the carrier mobility is 10 cm 2 V ⁇ 1 sec ⁇ 1 or more.
- a ninth invention is the oxide semiconductor thin film according to the seventh or eighth invention, wherein the carrier concentration is less than 3.0 ⁇ 10 18 cm ⁇ 3 .
- the oxide sintered body containing indium and gallium as an oxide and containing magnesium in an Mg / (In + Ga + Mg) atomic ratio of 0.0001 or more and less than 0.05 is used as, for example, a sputtering target.
- the amorphous oxide semiconductor thin film of the present invention formed by sputtering film formation and then obtained by heat treatment can be obtained.
- the amorphous oxide semiconductor thin film has sufficient amorphous properties because it does not generate microcrystals due to the effect of a predetermined amount of gallium and magnesium, and has a desired shape by wet etching. Can be patterned.
- the amorphous oxide semiconductor thin film of the present invention exhibits low carrier concentration and high carrier mobility. Therefore, the amorphous oxide semiconductor thin film of the present invention can be applied as a channel layer of a TFT. Therefore, the oxide sintered body, the target, and the oxide semiconductor thin film obtained using the oxide sintered body of the present invention are extremely useful industrially.
- the oxide sintered body of the present invention the sputtering target, and the oxide thin film obtained using the same will be described in detail.
- the oxide sintered body of the present invention contains indium, gallium and magnesium as oxides, and gallium is in a Ga / (In + Ga) atomic ratio of 0.20 or more and 0.45 or less, and magnesium is Mg / (In + Ga + Mg). ) A sintered oxide containing 0.0001 or more and less than 0.05 in atomic ratio.
- the gallium content is Ga0 (In + Ga) atomic ratio of 0.20 or more and 0.45 or less, and more preferably 0.20 or more and 0.30 or less.
- Gallium has a strong bonding force with oxygen and has an effect of reducing the amount of oxygen vacancies in the amorphous oxide semiconductor thin film of the present invention.
- the gallium content is less than 0.20 in terms of the Ga / (In + Ga) atomic ratio, this effect cannot be obtained sufficiently.
- it exceeds 0.45 carrier mobility sufficiently high as an oxide semiconductor thin film cannot be obtained.
- the oxide sintered body of the present invention contains magnesium in addition to indium and gallium in the composition range specified as described above.
- the magnesium concentration is 0.0001 or more and less than 0.05, and preferably 0.01 or more and 0.03 or less in terms of the atomic ratio of Mg / (In + Ga + Mg).
- the carrier concentration is suppressed mainly by the action of neutralizing electrons generated by oxygen vacancies, and the amorphous oxide of the present invention.
- the on / off of the TFT can be increased.
- the oxide sintered body of the present invention does not substantially contain an element M which is a positive divalent element other than magnesium and a positive trivalent to positive hexavalent element other than indium and gallium.
- element M which is a positive divalent element other than magnesium and a positive trivalent to positive hexavalent element other than indium and gallium.
- substantially not contained means that each single M is 500 ppm or less, preferably 200 ppm or less, more preferably 100 ppm or less in terms of the atomic ratio of M / (In + Ga + M).
- M include Cu, Ni, Co, Zn, Ca, Sr, and Pb as positive divalent elements, and Al, Y, Sc, B, and lanthanoids as positive trivalent elements.
- Sn, Ge, Ti, Si, Zr, Hf, C, and Ce can be exemplified as positive tetravalent elements
- Nb and Ta can be exemplified as positive pentavalent elements
- W and Mo can be exemplified as positive hexavalent elements. It can be illustrated.
- the oxide sintered body of the oxide sintered body tissue present invention the In 2 O 3 phase bixbyite structure, GaInO 3-phase ⁇ -Ga 2 O 3 -type structure as a product phases other than the In 2 O 3 phase Or a ⁇ -Ga 2 O 3 type GaInO 3 phase and a (Ga, In) 2 O 3 phase.
- the oxide sintered body is composed of only the In 2 O 3 phase, nodules are generated in the same manner as in Comparative Example 11 of Patent Document 3 (WO2003 / 014409), regardless of the Mg content.
- the In (GaMg) O 4 phase, the MgGa 2 O 4 phase, and the In 2 MgO 4 phase are all high resistance phases, and therefore cause arcing and nodules.
- the In 2 MgO 4 phase has a specific resistance of about 10 ⁇ 2 ⁇ ⁇ cm (Non-patent Document 1) and has an electrical resistance that is about 1 to 2 digits higher than that of the In 2 O 3 phase or GaInO 3 phase. Nodules are likely to be dug easily in the film.
- the In (GaMg) O 4 phase has a higher specific resistance of about 10 0 ⁇ ⁇ cm (Non-patent Document 2), and causes nodules. Since the MgGa 2 O 4 phase does not contain In, it has a higher specific resistance and causes arcing.
- an oxide semiconductor thin film formed by sputtering using an oxide sintered body in which these phases are generated tends to have low carrier mobility.
- Gallium and magnesium are dissolved in the In 2 O 3 phase. Further, gallium constitutes a GaInO 3 phase or a (Ga, In) 2 O 3 phase. In the case of solid solution in the In 2 O 3 phase, gallium and magnesium substitute for lattice positions of indium which is a positive trivalent ion. For reasons such as the sintering not progressing, it is not preferable to form a Ga 2 O 3 phase of ⁇ -Ga 2 O 3 type structure without causing gallium to dissolve in the In 2 O 3 phase. Since the Ga 2 O 3 phase has poor conductivity, it causes abnormal discharge.
- the oxide sintered body of the present invention includes not only a bixbite type In 2 O 3 phase but also a ⁇ -Ga 2 O 3 type GaInO 3 phase or a ⁇ -Ga 2 O 3 type GaInO 3 phase. It is preferable that the (Ga, In) 2 O 3 phase is contained in the range where the X-ray diffraction peak intensity ratio defined by the following formula 1 is 2% or more and 80% or less.
- the oxide sintered body of the present invention uses oxide powder composed of indium oxide powder and gallium oxide powder, and magnesium oxide powder as raw material powder.
- the oxide sintered body of the present invention In the manufacturing process of the oxide sintered body of the present invention, these raw material powders are mixed and then molded, and the molded product is sintered by a normal pressure sintering method.
- the formation phase of the oxide sintered body structure of the present invention strongly depends on the production conditions in each step of the oxide sintered body, for example, the particle diameter of the raw material powder, the mixing conditions, and the sintering conditions.
- GaInO 3-phase ⁇ -Ga 2 O 3 -type structure as a product phases other than the In 2 O 3 phase or ⁇ - It is preferable that the GaInO 3 phase and the (Ga, In) 2 O 3 phase having a Ga 2 O 3 type structure are configured in a desired ratio, and for this purpose, the average particle diameter of each raw material powder is set to 3 ⁇ m or less. It is preferable that the thickness is 1.5 ⁇ m or less.
- the average particle diameter of each raw material powder is 1.5 ⁇ m or less.
- Indium oxide powder is a raw material of ITO (indium-tin oxide), and the development of fine indium oxide powder excellent in sinterability has been promoted along with the improvement of ITO. Since indium oxide powder is continuously used in large quantities as a raw material for ITO, it is possible to obtain a raw material powder having an average particle size of 0.8 ⁇ m or less recently.
- ITO indium-tin oxide
- gallium oxide powder or magnesium oxide powder since the amount used is still smaller than that of indium oxide powder, it is difficult to obtain a raw material powder having an average particle size of 1.5 ⁇ m or less. Therefore, when only coarse gallium oxide powder is available, it is necessary to grind to an average particle size of 1.5 ⁇ m or less.
- the atmospheric pressure sintering method is a simple and industrially advantageous method, and is also a preferable means from the viewpoint of low cost.
- a molded body is first prepared as described above.
- the raw material powder is put in a resin pot and mixed with a binder (for example, PVA) by a wet ball mill or the like.
- a binder for example, PVA
- a wet ball mill or the like In the production of the oxide sintered body of the present invention, in addition to the In 2 O 3 phase, a ⁇ -Ga 2 O 3 type GaInO 3 phase, or a ⁇ -Ga 2 O 3 type GaInO 3 phase and (Ga, In order to suppress excessive formation of the In) 2 O 3 phase or not to form a ⁇ 2 -Ga 2 O 3 type Ga 2 O 3 phase, it is preferable to carry out the ball mill mixing for 18 hours or more.
- a hard ZrO 2 ball may be used as the mixing ball.
- the slurry is taken out, filtered, dried and granulated. Thereafter, the granulated product obtained was molded by applying a pressure of about 9.8MPa (0.1ton / cm 2) ⁇ 294MPa (3ton / cm 2) cold isostatic pressing, the molded body.
- an atmosphere in which oxygen is present is preferable, and the oxygen volume fraction in the atmosphere is more preferably more than 20%.
- the oxygen volume fraction exceeds 20%, the oxide sintered body is further densified. Due to the excessive oxygen in the atmosphere, the sintering of the surface of the compact proceeds first in the early stage of sintering. Subsequently, sintering in a reduced state inside the molded body proceeds, and finally a high-density oxide sintered body is obtained.
- the temperature range of atmospheric pressure sintering is preferably 1200 ° C. or more and 1550 ° C. or less, and more preferably, sintering is performed at 1350 ° C. or more and 1450 ° C. or less in an atmosphere in which oxygen gas is introduced into the atmosphere in the sintering furnace.
- the sintering time is preferably 10 to 30 hours, more preferably 15 to 25 hours.
- the oxide powder composed of indium oxide powder and gallium oxide powder adjusted to the average particle size of 1.5 ⁇ m or less, and magnesium oxide powder as raw material powder the bixbite structure
- the In 2 O 3 phase and the ⁇ -Ga 2 O 3 type GaInO 3 phase or the ⁇ -Ga 2 O 3 type GaInO 3 phase and the (Ga, In) 2 as a generation phase other than the In 2 O 3 phase An oxide sintered body constituted by the O 3 phase is obtained.
- the sintering temperature is less than 1200 ° C., the sintering reaction does not proceed sufficiently, and the density of the oxide sintered body becomes less than 6.4 g / cm 3 .
- the sintering temperature exceeds 1550 ° C., the formation of the (Ga, In) 2 O 3 phase becomes significant.
- the (Ga, In) 2 O 3 phase has a higher electrical resistance than the GaInO 3 phase, and therefore causes a decrease in the deposition rate.
- a sintering temperature of 1550 ° C. or lower, that is, a small amount of (Ga, In) 2 O 3 phase is not a problem. From such a viewpoint, the sintering temperature is preferably 1200 ° C. or higher and 1550 ° C. or lower, and more preferably 1350 ° C. or higher and 1450 ° C. or lower.
- the heating rate up to the sintering temperature is preferably in the range of 0.2 to 5 ° C./min in order to prevent cracking of the sintered body and to proceed with debinding. If it is this range, you may heat up to sintering temperature combining a different temperature increase rate as needed.
- it in order to promote the solid solution of magnesium in the In 2 O 3 phase, it is effective to hold at a temperature of 1100 ° C. or lower for a certain period of time.
- the binder may be held for a certain time at a specific temperature for the purpose of progressing debinding and sintering.
- the holding time is not particularly limited, but is preferably 1 hour or more and 10 hours or less.
- the introduction of oxygen is stopped, and the temperature can be lowered to 1000 ° C. at a rate of 0.2 to 5 ° C./min, particularly 0.2 ° C./min or more and less than 1 ° C./min. preferable.
- Target The target of the present invention can be obtained by cutting the oxide sintered body into a predetermined size, polishing the surface, and adhering it to a backing plate.
- the target shape is preferably a flat plate shape, but may be a cylindrical shape. When a cylindrical target is used, it is preferable to suppress particle generation due to target rotation.
- the density of the oxide sintered body of the present invention is preferably 6.4 g / cm 3 or more.
- the density is less than 6.4 g / cm 3 , it causes nodules during mass production and is not preferable.
- the amorphous oxide semiconductor thin film of the present invention is formed by forming an amorphous thin film once on a substrate by sputtering using the sputtering target and then subjecting it to a heat treatment. It is obtained by applying.
- the sputtering target is obtained from an oxide sintered body, and is basically formed by the oxide sintered body structure, that is, the In 2 O 3 phase having a bixbite type structure and the GaInO 3 phase having a ⁇ -Ga 2 O 3 type structure.
- the organized organization is important.
- it is important that the amorphous oxide thin film has a high crystallization temperature, which is related to the oxide sintered body structure. . That is, when the oxide sintered body used in the present invention includes not only the In 2 O 3 phase of the bixbite type structure but also the GaInO 3 phase of the ⁇ -Ga 2 O 3 type structure, it is obtained from this.
- the formed oxide thin film has a high crystallization temperature, that is, preferably a crystallization temperature of 250 ° C. or higher, more preferably 300 ° C. or higher, and further preferably 350 ° C. or higher, and becomes a stable amorphous state.
- the oxide sintered body is constituted only by the In 2 O 3 phase having a bixbite structure
- the oxide thin film after film formation has a low crystallization temperature of about 190 to 230 ° C., It is no longer stable amorphous. For this reason, when it heat-processes at about 250 degreeC, it may crystallize. In this case, microcrystals are already generated after film formation, and the amorphous state is not maintained, and patterning processing by wet etching becomes difficult. This is well known in general ITO (tin-added indium oxide) transparent conductive films.
- a general sputtering method is used.
- the direct current (DC) sputtering method is industrial because it is less affected by heat during film formation and enables high-speed film formation. Is advantageous.
- a mixed gas composed of an inert gas and oxygen, particularly argon and oxygen as a sputtering gas.
- the substrate is typically a glass substrate and is preferably alkali-free glass, but any resin plate or resin film that can withstand the temperature of the above process can be used.
- the target Pre-sputtering can be carried out by generating direct current plasma by applying direct current power so that the direct current power with respect to the area, that is, the direct current power density is in the range of about 1 to 7 W / cm 2 .
- the direct current power input within an allowable range is increased.
- the amorphous oxide semiconductor thin film of the present invention can be obtained by heat-treating the amorphous thin film after the formation.
- the heat treatment condition is a temperature lower than the crystallization temperature in an oxidizing atmosphere.
- an atmosphere containing oxygen, ozone, water vapor, nitrogen oxide, or the like is preferable.
- the heat treatment temperature is preferably 250 to 600 ° C, more preferably 300 to 550 ° C, and further preferably 350 to 500 ° C.
- the heat treatment time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes, which is maintained at the heat treatment temperature.
- an amorphous film is formed at a low temperature such as near room temperature, and then heat-treated in the above temperature range below the crystallization temperature to maintain the amorphous semiconductor thin film Get.
- the substrate is heated to a temperature lower than the crystallization temperature of the oxide thin film, preferably 100 to 300 ° C., to form an amorphous oxide semiconductor thin film. This may be followed by further heat treatment.
- the composition of indium, gallium, and magnesium of the thin film before the heat treatment and the amorphous oxide semiconductor thin film after the heat treatment is almost the same as the composition of the oxide sintered body of the present invention. That is, it is an amorphous oxide-baked semiconductor thin film containing indium and gallium as oxides and containing magnesium.
- Gallium content is 0.20 or more and 0.45 or less in Ga / (In + Ga) atomic ratio
- magnesium content is 0.0001 or more and less than 0.05 in Mg / (In + Ga + Mg) atomic ratio.
- the gallium content is more preferably 0.20 or more and 0.30 or less, and further preferably 0.25 or more and 0.30 or less in terms of Ga / (In + Ga) atomic ratio.
- the magnesium content is more preferably 0.01 or more and 0.03 or less in terms of the Mg / (In + Ga + Mg) atomic ratio.
- the amorphous oxide semiconductor thin film of the present invention is formed by using an oxide sintered body having a controlled composition and structure as described above as a sputtering target and heat-treating it under the appropriate conditions described above.
- the carrier concentration is reduced to 3 ⁇ 10 18 cm ⁇ 3 or less, more preferably a carrier concentration of 1 ⁇ 10 18 cm ⁇ 3 or less, and particularly preferably 8 ⁇ 10 17 cm ⁇ 3 or less.
- the amorphous oxide semiconductor thin film composed of indium, gallium, and zinc described in Non-Patent Document 3 the amorphous oxide semiconductor thin film containing a large amount of indium has a carrier concentration of 4 ⁇ 10 6.
- the amorphous oxide semiconductor thin film according to the present invention is convenient because the carrier concentration is controlled in a range in which the above TFT shows normally-off.
- the carrier mobility is 10 cm 2 V ⁇ 1 sec ⁇ 1 or more, and more preferably the carrier mobility is 15 cm 2 V ⁇ 1 sec ⁇ 1 or more.
- the amorphous oxide semiconductor thin film of the present invention is subjected to fine processing necessary for applications such as TFT by wet etching or dry etching.
- fine processing by wet etching can be performed.
- the etchant any weak acid can be used, but a weak acid mainly composed of oxalic acid or hydrochloric acid is preferred.
- commercially available products such as ITO-06N manufactured by Kanto Chemical Co., Ltd. can be used.
- dry etching may be selected.
- the thickness of the amorphous oxide semiconductor thin film of the present invention is not limited, but is 10 to 500 nm, preferably 20 to 300 nm, and more preferably 30 to 100 nm. If the thickness is less than 10 nm, high carrier mobility cannot be realized. On the other hand, if it exceeds 500 nm, a problem of productivity occurs, which is not preferable.
- the average transmittance in the visible region (400 to 800 nm) is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more. It is.
- the average transmittance is less than 80%, the light extraction efficiency of a liquid crystal element or an organic EL element as a transparent display device is lowered.
- the composition of the obtained oxide thin film was examined by ICP emission spectroscopy.
- the film thickness of the oxide thin film was measured with a surface roughness meter (manufactured by Tencor).
- the film formation rate was calculated from the film thickness and the film formation time.
- the carrier concentration and carrier mobility of the oxide thin film were determined by a Hall effect measuring device (manufactured by Toyo Technica).
- the formation phase of the film was identified by X-ray diffraction measurement.
- Indium oxide powder, gallium oxide powder, and magnesium oxide powder were adjusted to have an average particle size of 1.5 ⁇ m or less to obtain raw material powder. These raw material powders were prepared so that the Ga / (In + Ga) atomic number ratio and Mg / (In + Ga + Mg) atomic ratio in the examples and comparative examples in Tables 1 and 2 were as shown in FIG. And mixed with a wet ball mill. At this time, hard ZrO 2 balls were used and the mixing time was 18 hours. After mixing, the slurry was taken out, filtered, dried and granulated. The granulated product was molded by applying a pressure of 3 ton / cm 2 with a cold isostatic press.
- the compact was sintered as follows. Sintering was performed at a sintering temperature of 1000 to 1550 ° C. for 20 hours in an atmosphere in which oxygen was introduced into the atmosphere in the sintering furnace at a rate of 5 liters / minute per 0.1 m 3 of the furnace volume. At this time, the temperature was raised at 1 ° C./min. When cooling after sintering, the introduction of oxygen was stopped, and the temperature was lowered to 1000 ° C. at 10 ° C./min.
- the oxide sintered body was processed into a size of 152 mm in diameter and 5 mm in thickness, and the sputtering surface was polished with a cup grindstone so that the maximum height Rz was 3.0 ⁇ m or less.
- the processed oxide sintered body was bonded to a backing plate made of oxygen-free copper using metallic indium to obtain a sputtering target.
- a mixed gas of argon and oxygen was introduced so as to have an appropriate oxygen ratio according to the amount of gallium in each target, and the gas pressure was adjusted to 0.6 Pa.
- a DC plasma was generated by applying a DC power of 300 W (1.64 W / cm 2 ).
- an oxide thin film having a thickness of 50 nm was formed by placing the substrate directly above the sputtering target, that is, at a stationary facing position. It was confirmed that the composition of the obtained oxide thin film was almost the same as that of the target. Further, as a result of X-ray diffraction measurement, it was confirmed to be amorphous.
- the obtained amorphous oxide thin film was heat-treated at 250 to 400 ° C. for 30 minutes or less in the atmosphere using a RTA (Rapid Thermal Annealing) apparatus.
- the oxide thin film after the heat treatment was confirmed to be amorphous as a result of X-ray diffraction measurement, and had In 2 O 3 (111) as the main peak.
- the Hall effect of the obtained amorphous oxide semiconductor thin film was measured to determine the carrier concentration and carrier mobility. The evaluation results obtained are summarized in Table 2.
- Nodule generation evaluation The sputtering targets of Examples 2 and 10 and Comparative Example 2 were evaluated for nodule generation by sputtering film formation simulating mass production.
- a load lock type pass magnetron sputtering apparatus manufactured by ULVAC
- the target was a square target having a length of 5 inches and a width of 15 inches.
- Sputtering film formation evaluation After evacuating the sputtering chamber to 7 ⁇ 10 ⁇ 5 Pa or less, a mixed gas of argon and oxygen was introduced so as to have an appropriate oxygen ratio according to the amount of gallium in each target, and the gas pressure was reduced to 0.
- the reason why the sputtering gas under such conditions is selected is that when the degree of vacuum in the sputtering chamber exceeds 1 ⁇ 10 ⁇ 4 Pa and the moisture pressure in the chamber is high, or hydrogen gas is added, a legitimate evaluation is made. It is because it becomes impossible.
- ITO or the like when H + derived from moisture or hydrogen gas is taken into the film, the crystallization temperature of the film becomes high, and the film adhering to the target non-erosion part is likely to become amorphous. As a result, since the film stress is lowered, it is difficult to peel off from the non-erosion portion, and nodules are hardly generated.
- the DC power is set to 2500 W (DC power density 5.17 W / cm 2 ) considering that the DC power density generally used in mass production is about 3 to 6 W / cm 2 .
- the target surface was observed after the continuous sputtering discharge of 50 kWh under the above conditions, and the presence or absence of nodule generation was evaluated.
- the gallium content in Examples 1 to 11 is 0.20 or more and 0.45 or less in the Ga / (In + Ga) atomic ratio, and the magnesium content is in the Mg / (In + Ga + Mg) atomic ratio. If it is less than 0.0001 or more 0.05, and in 2 O 3 phase bixbyite structure, GaInO 3-phase ⁇ -Ga 2 O 3 -type structure as a product phases other than the in 2 O 3 phase or beta It was constituted by a GaInO 3 phase and a (Ga, In) 2 O 3 phase having a —Ga 2 O 3 type structure.
- the magnesium content is 0.05 or more in terms of Mg / (In + Ga + Mg) atomic weight ratio
- the In 2 O 3 phase having a bixbite structure
- it includes Ga 2 O 3 phase not the oxide sintered body for the purpose of the present invention can be obtained.
- Table 2 shows an amorphous oxide semiconductor thin film containing indium, gallium, and magnesium as oxides, and the gallium content is in a Ga / (In + Ga) atomic ratio of 0.20 or more and 0.45.
- characteristics of the oxide semiconductor thin film in which the magnesium content is controlled to be 0.0001 or more and less than 0.05 in terms of the Mg / (In + Ga + Mg) atomic weight ratio are shown.
- the oxide semiconductor thin film of the example has a carrier concentration of less than 3.0 ⁇ 10 18 cm ⁇ 3 and a carrier mobility of 10 cm 2 V ⁇ 1 sec ⁇ 1 or more.
- Examples 2 to 6 having a gallium content of Ga / (In + Ga) atomic weight ratio of 0.20 to 0.30 and a magnesium content of Mg / (In + Ga + Mg) atomic weight ratio of 0.01 to 0.03.
- the oxide semiconductor thin films of No. 8 and No. 8 exhibit excellent characteristics with a carrier concentration of 1.0 ⁇ 10 18 cm ⁇ 3 or less and a carrier mobility of 20 cm 2 V ⁇ 1 sec ⁇ 1 or more.
- the magnesium content is 0.05 or more in terms of the Mg / (In + Ga + Mg) atomic weight ratio, and the carrier mobility is less than 10 cm 2 V ⁇ 1 sec ⁇ 1. Therefore, the oxide semiconductor thin film targeted by the present invention has not been obtained.
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Abstract
Description
100×I[GaInO3相(111)]/{I[In2O3相(400)]+I[GaInO3相(111)]} [%]・・・・式1
本発明の酸化物焼結体は、ビックスバイト型構造のIn2O3相と、In2O3相以外の生成相としてβ-Ga2O3型構造のGaInO3相、あるいはβ-Ga2O3型構造のGaInO3相と(Ga,In)2O3相によって構成される。酸化物焼結体がIn2O3相のみによって構成されると、Mgの含有に関係なく、例えば特許文献3(WO2003/014409号公報)の比較例11と同様にノジュールが発生する。一方、In(GaMg)O4相、MgGa2O4相およびIn2MgO4相は、いずれも高抵抗相であるため、アーキングやノジュールの発生原因となる。In2MgO4相は、比抵抗が10-2Ω・cm程度(非特許文献1)でIn2O3相やGaInO3相と比較して1~2桁程度電気抵抗が高いため、スパッタリング成膜で掘れ残りやすくノジュールが発生しやすい。In(GaMg)O4相は、比抵抗が100Ω・cm程度とより高く(非特許文献2)、ノジュール発生の原因となる。MgGa2O4相はInを含まないためさらに比抵抗が高く、アーキング発生の原因となる。また、これらの相が生成した酸化物焼結体を用いてスパッタリング成膜された酸化物半導体薄膜は、キャリア移動度が低くなる傾向にある。
(式中、I[In2O3相(400)]は、ビックスバイト型構造のIn2O3相の(400)ピーク強度であり、I[GaInO3相(111)]は、β-Ga2O3型構造の複合酸化物β-GaInO3相(111)ピーク強度を示す。)
本発明の酸化物焼結体は、酸化インジウム粉末と酸化ガリウム粉末からなる酸化物粉末、ならびに酸化マグネシウム粉末を原料粉末とする。
本発明のターゲットは、上記酸化物焼結体を所定の大きさに切断、表面を研磨加工し、バッキングプレートに接着して得ることができる。ターゲット形状は、平板形が好ましいが、円筒形でもよい。円筒形ターゲットを用いる場合には、ターゲット回転によるパーティクル発生を抑制することが好ましい。
本発明の非晶質の酸化物半導体薄膜は、前記のスパッタリング用ターゲットを用いて、スパッタリング法で基板上に一旦非晶質の薄膜を形成し、次いで熱処理を施すことによって得られる。
得られた酸化物焼結体の金属元素の組成をICP発光分光法によって調べた。得られた酸化物焼結体の端材を用いて、X線回折装置(フィリップス製)を用いて粉末法による生成相の同定を行った。
得られた酸化物薄膜の組成をICP発光分光法によって調べた。酸化物薄膜の膜厚は表面粗さ計(テンコール社製)で測定した。成膜速度は、膜厚と成膜時間から算出した。酸化物薄膜のキャリア濃度およびキャリア移動度は、ホール効果測定装置(東陽テクニカ製)によって求めた。膜の生成相はX線回折測定によって同定した。
酸化インジウム粉末と酸化ガリウム粉末、ならびに酸化マグネシウム粉末を平均粒径1.5μm以下となるよう調整して原料粉末とした。これらの原料粉末を、表1及び表2の実施例及び比較例のGa/(In+Ga)原子数比、Mg/(In+Ga+Mg)原子数比の通りになるように調合し、水とともに樹脂製ポットに入れ、湿式ボールミルで混合した。この際、硬質ZrO2ボールを用い、混合時間を18時間とした。混合後、スラリーを取り出し、濾過、乾燥、造粒した。造粒物を、冷間静水圧プレスで3ton/cm2の圧力をかけて成形した。
実施例及び比較例のスパッタリング用ターゲットならびに無アルカリのガラス基板(コーニング製EagleXG)を用いて、基板加熱せずに室温で直流スパッタリングによる成膜を行った。アーキング抑制機能のない直流電源を装備した直流マグネトロンスパッタリング装置(トッキ製)のカソードに、上記スパッタリングターゲットを取り付けた。このときターゲット-基板(ホルダー)間距離を60mmに固定した。1×10-4Pa以下まで真空排気後、アルゴンと酸素の混合ガスを各ターゲットのガリウム量に応じて適当な酸素の比率になるように導入し、ガス圧を0.6Paに調整した。直流電力300W(1.64W/cm2)を印加して直流プラズマを発生させた。10分間のプリスパッタリング後、スパッタリングターゲットの直上、すなわち静止対向位置に基板を配置して、膜厚50nmの酸化物薄膜を形成した。得られた酸化物薄膜の組成は、ターゲットとほぼ同じであることが確認された。また、X線回折測定の結果、非晶質であることが確認された。得られた非晶質の酸化物薄膜には、RTA(Rapid Thermal Annealing)装置を用いて、大気中、250~400℃において30分間以内の熱処理を施した。熱処理後の酸化物薄膜は、X線回折測定の結果、非晶質であることが確認され、In2O3(111)を主ピークとしていた。得られた非晶質の酸化物半導体薄膜のホール効果測定を行い、キャリア濃度およびキャリア移動度を求めた。得られた評価結果を、表2にまとめて記載した。
実施例2、10及び比較例2のスパッタリング用ターゲットについて、量産を模擬したスパッタリング成膜によるノジュール発生の評価を実施した。スパッタリング装置は、アーキング抑制機能のない直流電源を装備したロードロック式通過型マグネトロンスパッタリング装置(アルバック製)を用いた。ターゲットは、縦5インチ、横15インチの角型のターゲットを用いた。スパッタリング成膜評価スパッタ室を7×10-5Pa以下まで真空排気後、アルゴンと酸素の混合ガスを各ターゲットのガリウム量に応じて適当な酸素の比率になるように導入し、ガス圧を0.6Paに調整した。このような条件のスパッタリングガスを選択した理由は、スパッタ室の真空度が1×10-4Paを超えてチャンバー内の水分圧が高い、あるいは水素ガスが添加される場合には、正当な評価ができなくなるためである。ITOなどでよく知られるように膜中に水分や水素ガス由来のH+が取り込まれると膜の結晶化温度が高くなり、ターゲット非エロージョン部に付着する膜が非晶質化し易くなる。その結果、膜応力が低下するため非エロージョン部から剥がれにくくなり、ノジュールが発生し難くなる。直流電力は、一般に量産で採用される直流電力密度は3~6W/cm2程度であることを考慮し、2500W(直流電力密度5.17W/cm2)とした。
表1に示すように、実施例1~11のガリウム含有量がGa/(In+Ga)原子数比で0.20以上0.45以下であり、マグネシウムの含有量がMg/(In+Ga+Mg)原子量比で0.0001以上0.05未満の場合には、ビックスバイト型構造のIn2O3相と、In2O3相以外の生成相としてβ-Ga2O3型構造のGaInO3相、あるいはβ-Ga2O3型構造のGaInO3相と(Ga,In)2O3相によって構成されていた。
Claims (9)
- インジウム、ガリウム及びマグネシウムを酸化物として含有し、
前記ガリウムの含有量がGa/(In+Ga)原子数比で0.20以上0.45以下であり、
前記マグネシウムの含有量がMg/(In+Ga+Mg)原子数比で0.0001以上0.05未満であり、
ビックスバイト型構造のIn2O3相と、In2O3相以外の生成相としてβ-Ga2O3型構造のGaInO3相、あるいはβ-Ga2O3型構造のGaInO3相と(Ga,In)2O3相によって構成され、In(GaMg)O4相、MgGa2O4相、In2MgO4相、Ga2O3相を実質的に含まないことを特徴とする酸化物焼結体。 - 前記マグネシウムの含有量がMg/(In+Ga+Mg)原子数比で0.01以上0.03以下である請求項1に記載の酸化物焼結体。
- 前記ガリウムの含有量がGa/(In+Ga)原子数比で0.20以上0.30以下である請求項1又は2に記載の酸化物焼結体。
- マグネシウム以外の正二価元素、及び、インジウムとガリウム以外の正三価から正六価の元素、を実質的に含有しない請求項1から3のいずれかに記載の酸化物焼結体。
- 下記の式1で定義されるβ-Ga2O3型構造のGaInO3相のX線回折ピーク強度比が2%以上80%以下の範囲である請求項1から4のいずれかに記載の酸化物焼結体。
100×I[GaInO3相(111)]/{I[In2O3相(400)]+I[GaInO3相(111)]} [%]・・・・式1 - 請求項1から5のいずれかに記載の酸化物焼結体を加工して得られるスパッタリング用ターゲット。
- 請求項6に記載のスパッタリング用ターゲットを用いてスパッタリング法によって基板上に形成された後、熱処理された非晶質の酸化物半導体薄膜。
- キャリア移動度が10cm2V-1sec-1以上である請求項7に記載の酸化物半導体薄膜。
- キャリア濃度が3.0×1018cm-3未満である請求項7又は8に記載の酸化物半導体薄膜。
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CN106103380A (zh) * | 2014-05-23 | 2016-11-09 | 住友金属矿山株式会社 | 氧化物烧结体、溅射用靶及使用该靶得到的氧化物半导体薄膜 |
JP2017154910A (ja) * | 2016-02-29 | 2017-09-07 | 住友金属鉱山株式会社 | 酸化物焼結体及びスパッタリング用ターゲット |
GB201705755D0 (en) | 2017-04-10 | 2017-05-24 | Norwegian Univ Of Science And Tech (Ntnu) | Nanostructure |
CN112512991B (zh) * | 2018-08-01 | 2023-04-07 | 出光兴产株式会社 | 晶体化合物、氧化物烧结体、溅射靶、晶质及无定形氧化物薄膜、薄膜晶体管及电子设备 |
TWI836206B (zh) * | 2020-04-06 | 2024-03-21 | 日商Jx金屬股份有限公司 | 靶及其製造方法、以及燒結體 |
KR20220094735A (ko) * | 2020-12-29 | 2022-07-06 | 에이디알씨 주식회사 | 결정성 산화물 반도체 박막 및 그 형성 방법, 박막 트랜지스터 및 그 제조 방법, 표시 패널 및 전자 장치 |
CN114361276A (zh) * | 2021-12-28 | 2022-04-15 | 仲恺农业工程学院 | 非晶MgGaO薄膜的光伏探测器及其制备方法和应用 |
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TWI613151B (zh) | 2018-02-01 |
US20170047206A1 (en) | 2017-02-16 |
KR20170008724A (ko) | 2017-01-24 |
CN106103380A (zh) | 2016-11-09 |
KR20170009819A (ko) | 2017-01-25 |
US20170092780A1 (en) | 2017-03-30 |
JP6414210B2 (ja) | 2018-10-31 |
TW201602004A (zh) | 2016-01-16 |
TWI613176B (zh) | 2018-02-01 |
US9941415B2 (en) | 2018-04-10 |
JPWO2015178429A1 (ja) | 2017-04-20 |
TW201602048A (zh) | 2016-01-16 |
WO2015178430A1 (ja) | 2015-11-26 |
JPWO2015178430A1 (ja) | 2017-04-27 |
JP6376215B2 (ja) | 2018-08-22 |
CN106132902A (zh) | 2016-11-16 |
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