WO2010070944A1 - 酸化インジウム系焼結体及びスパッタリングターゲット - Google Patents
酸化インジウム系焼結体及びスパッタリングターゲット Download PDFInfo
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- WO2010070944A1 WO2010070944A1 PCT/JP2009/059954 JP2009059954W WO2010070944A1 WO 2010070944 A1 WO2010070944 A1 WO 2010070944A1 JP 2009059954 W JP2009059954 W JP 2009059954W WO 2010070944 A1 WO2010070944 A1 WO 2010070944A1
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- Prior art keywords
- sintered body
- oxide
- indium oxide
- thin film
- metal
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- 229910003437 indium oxide Inorganic materials 0.000 title claims abstract description 75
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000005477 sputtering target Methods 0.000 title claims description 28
- 239000013078 crystal Substances 0.000 claims abstract description 39
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 17
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010408 film Substances 0.000 claims description 63
- 239000010409 thin film Substances 0.000 claims description 49
- 239000004065 semiconductor Substances 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 31
- 150000004706 metal oxides Chemical class 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 25
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- -1 cerium ions Chemical class 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910001432 tin ion Inorganic materials 0.000 claims description 3
- 238000002441 X-ray diffraction Methods 0.000 description 24
- 238000004544 sputter deposition Methods 0.000 description 17
- 238000005245 sintering Methods 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 230000002159 abnormal effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000011812 mixed powder Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000006104 solid solution Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- 238000003826 uniaxial pressing Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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Definitions
- the present invention relates to an indium oxide-based sintered body, in particular, a sintered body containing scandium oxide or aluminum oxide together with indium oxide, and a sputtering target using the same.
- TFTs thin film transistors
- This silicon-based thin film has good performance such as good stability and workability and high TFT switching speed.
- This silicon-based thin film is generally produced by a chemical vapor deposition method (CVD) method.
- the switching speed is relatively slow, and there is a problem that an image cannot be displayed when a high-speed moving image or the like is displayed.
- the switching speed is relatively fast, crystallization of the silicon-based thin film requires a high temperature of 800 ° C. or higher, heating with a laser, etc. There is a problem that it requires a lot of energy and processes.
- the silicon-based thin film has excellent performance as a voltage element, a change in characteristics over time is a problem when a current is passed.
- Patent Document 1 proposes an oxide semiconductor PN junction device and describes a transparent semiconductor thin film made of zinc oxide and magnesium oxide as one of semiconductor films constituting the device.
- a transparent semiconductor film made of zinc oxide and magnesium oxide is characterized by being etched with a weak acid and having a very high etching rate.
- etching is also performed by the etching solution used for the metal thin film, when the metal thin film on the transparent semiconductor film is etched, the metal thin film may be etched at the same time. Therefore, it is unsuitable when only the metal thin film on the transparent semiconductor film is selectively etched.
- T. T. O sintered bodies have been proposed. In this sintered body, 1 to 7 wt% of tin oxide is added, and in the crystallized film, carriers are generated from tin oxide, so that it becomes a conductive film instead of a semiconductor film.
- Patent Document 3 describes a thin film mainly composed of indium oxide, tin oxide and yttrium oxide, but relates to a transparent conductive film and does not describe an oxide semiconductor.
- the following sintered body, sputtering target and the like are provided.
- An oxide of one or more metals selected from the group consisting of aluminum and scandium is dissolved in the indium oxide crystal, and an atomic ratio of indium and one or more metals selected from the group consisting of aluminum and scandium ((1 A sintered body having a total of at least one kind of metal / (total of at least one kind of metal and In) ⁇ 100) is 0.001% or more and less than 45%.
- the sintered body according to 1, wherein the atomic ratio is 0.01 to 30 atomic%.
- the sintered body according to 1, wherein the atomic ratio is 0.5 to 15 atomic%. 4).
- the manufacturing method of the sintered compact of this. 12 One or more kinds of metal oxides selected from the group consisting of aluminum and scandium, indium oxide, and powders of positive tetravalent or higher metals are mixed and fired at a temperature of 1200 ° C. to 1600 ° C. for 2 to 200 hours.
- the method for producing a sintered body according to any one of 10. 13 The method for producing a sintered body according to 11 or 12, which is fired in an oxidizing atmosphere. 14.
- a semiconductor film comprising the metal oxide thin film according to 16.15.
- 20. A semiconductor device comprising the thin film transistor according to any one of 20.17 to
- the sintered body of the present invention has good film formation stability when used as a sputtering target. In addition, an excellent semiconductor film can be obtained using this sputtering target.
- FIG. 2 is an X-ray diffraction chart of a sintered body produced in Example 1.
- FIG. 3 is an X-ray diffraction chart of a sintered body produced in Example 2.
- FIG. 4 is an X-ray diffraction chart of a sintered body produced in Example 3.
- FIG. 6 is an X-ray diffraction chart of a sintered body produced in Example 4.
- FIG. 6 is an X-ray diffraction chart of a sintered body produced in Example 5.
- FIG. 3 is an X-ray diffraction chart of a sintered body produced in Comparative Example 1.
- 6 is an X-ray diffraction chart of a sintered body produced in Comparative Example 2.
- 6 is an X-ray diffraction chart of a sintered body produced in Comparative Example 3.
- FIG. 10 is an X-ray diffraction chart of a sintered body produced in Example 9.
- an oxide of at least one metal selected from the group consisting of aluminum and scandium (hereinafter also simply referred to as a specific positive trivalent metal) is dissolved in an indium oxide crystal.
- an atomic ratio of one or more metals selected from the group consisting of scandium ((total of one or more metals) / (total of one or more metals and In) ⁇ 100) is 0.001% or more and less than 45% It is.
- the atomic ratio is preferably 0.001 to 40 atomic%, more preferably 0.5 to 15 atomic%. This atomic ratio increases the mobility of the oxide semiconductor film obtained when the sintered body is used as a sputtering target, and a stable thin film transistor can be obtained using this oxide semiconductor film.
- the content (atomic ratio) of the metal element (ion) in the sintered body can be determined by ICP (Inductively Coupled Plasma) measurement.
- the metal oxide is in solid solution in indium oxide is a peak caused by the metal oxide (aluminum and scandium oxide) that is a raw material added to indium oxide in the X-ray diffraction measurement of the sintered body. Means the state is not observed.
- the lattice constant of an indium oxide crystal changes linearly toward the lattice constant of indium oxide or a specific positive trivalent metal oxide structure by the addition of the specific positive trivalent metal oxide.
- the fact that the lattice constant of the sintered body is between indium oxide and the specific positive trivalent metal oxide generally means that the specific positive trivalent metal oxide is sufficiently dissolved in indium oxide to cause abnormal discharge. It means that no amount of a single specific positive trivalent metal oxide is present in the sintered body. Therefore, the sputtering target obtained from this sintered body can perform stable sputtering and can provide an oxide semiconductor excellent in surface smoothness.
- the specific specific trivalent metal oxide of the quantity of the grade which does not produce abnormal discharge may be contained.
- the specific positive trivalent metal oxide is preferably completely dissolved in indium oxide.
- the specific positive trivalent metal oxide has high reduction resistance and suppresses reduction of indium oxide. For this reason, when using the sputtering target which consists of a sintered compact of this invention, generation
- the lattice constant of the crystalline thin film of indium oxide becomes small, so that the interatomic distance of the cation becomes small. Therefore, the mobility of the transistor using the obtained thin film is improved, and the S value and durability are improved.
- the indium oxide crystal contained in the sintered body of the present invention preferably has a bixbite structure.
- the bixbite structure can be confirmed by observing a peak by X-ray diffraction measurement.
- the crystal grain size of indium oxide is less than 10 ⁇ m. If the crystal becomes too large, it may cause abnormal discharge during sputtering or cause nodules on the sputtering target.
- the crystal grain size can be reduced by dissolving an oxide of one or more metals selected from the group consisting of aluminum and scandium in an indium oxide crystal.
- the crystal grain size is defined as the crystal grain size (major axis) as the average value of crystals in the entire field of view when observed with a scanning electron microscope in a field of 30 ⁇ m ⁇ 30 ⁇ m. Further, when observed with the above-mentioned visual field, the average particle diameter is less than 10 ⁇ m if there are no crystals of 10 ⁇ m or more.
- the bulk resistance of the sintered body of the present invention is preferably 1 ⁇ cm or less, and particularly preferably 0.5 ⁇ cm or less.
- the bulk resistance of the sintered body can be reduced to 1 ⁇ cm or less by sufficiently dispersing and dissolving one or more metal oxides.
- the lower limit of the bulk resistance of the sintered body is not particularly limited, but it is not necessary to make it lower than 0.001 ⁇ cm.
- the density of the sintered body of the present invention is preferably 5.5 g / cm 3 or more, more preferably 5.8 g / cm 3 or more, and particularly 6.0 g / cm 3 or more. preferable.
- the upper limit is the density of indium oxide.
- the density of a sintered compact can be 5.5 g / cm ⁇ 3 > or more by fully disperse
- the density of the sintered body is low, the target surface may be blackened during sputtering, and abnormal discharge may be induced. In addition, the sputtering rate may decrease.
- the relative density of the sintered body can be 90% or more by sufficiently dispersing and solid-solving one or more metal oxides. If the density is low, the target surface may be blackened, and abnormal discharge may be induced, or the sputtering rate may be reduced. Preferably, it is 95% or more, more preferably 97% or more. The upper limit relative density is 100% or less.
- a preferred embodiment of the present invention is a sintered body made of indium oxide and scandium oxide, wherein the lattice constant of the crystal of indium oxide is between InScO 3 and In 2 O 3 .
- Another preferred embodiment is a sintered body made of indium oxide and aluminum oxide and having a lattice constant of the crystal of indium oxide between InAlO 3 and In 2 O 3 .
- the sintered body of the present invention described above preferably contains 10 to 5000 atomic ppm of metal ions having a positive tetravalent or higher valence, and more preferably contains 100 to 2000 atomic ppm.
- the bulk resistance can be further reduced by containing a positive tetravalent or higher metal element. When it exceeds 5000 ppm, the obtained oxide semiconductor film may not exhibit normally-off semiconductor characteristics. It is preferable that positive tetravalent or higher metal oxide is also solid-solved in indium oxide, and the peak of positive tetravalent or higher metal oxide is not observed.
- the bulk resistance of the obtained sintered body is reduced, and the sputtering target using these can perform more stable sputtering, and has a stable surface smoothness.
- a high oxide semiconductor film can be obtained.
- Examples of the positive tetravalent or higher metal ions include Ti, Zr, Hf, Nb, Ta, W, Ge, Sn, and Ce. Among these, any one or both of a tin ion and a cerium ion is preferable. SnO 2 has a large amount of mining, supply stability is ensured, and there is no toxicity. Further, the cerium element has an effect of reducing the bulk resistance of the sintered body by being slightly (5000 atomic ppm or less) incorporated into the indium oxide crystal at a sintering temperature of 1200 ° C. or higher. On the other hand, at a temperature at which the thin film is crystallized (for example, about 250 ° C.
- the amount of cerium incorporated into indium oxide is reduced, and the effect of reducing resistance (the effect of generating carriers) is reduced.
- the carrier of the obtained crystalline indium oxide film can be controlled, a normally-off oxide semiconductor can be easily obtained.
- the sintered body according to the present invention has a low bulk resistance and can be suitably used as a target used in the sputtering method.
- the sputtering target using this sintered body has stable sputtering, and can produce a crystalline indium oxide film stably.
- a thin film having good semiconductor characteristics can be obtained.
- the sintered body of the present invention can be produced, for example, by sintering a powder obtained by mixing indium oxide and scandium oxide or aluminum oxide at a temperature of 1200 ° C. to 1600 ° C. for 2 to 200 hours.
- the raw material oxide is preferably a powder having a purity of 99.99% or more.
- a metal element having a positive tetravalent or higher value is added, for example, a compound such as an oxide of the metal element is added.
- the purity of this compound is also preferably 99.99% or higher.
- the amount of impurities is preferably less than 100 atomic ppm.
- the amount of each raw material is made to correspond to the amount of each metal element in the intended sintered body.
- the raw material mixture is mixed and pulverized by a general mill such as a bead mill, a ball mill, a planetary mill or the like. Then, granulate and shape
- the mixture is shaped into a suitable shape as a sputtering target or the like by molding.
- the molding process include press molding, cold isostatic pressing, uniaxial pressing, mold molding, cast molding, injection molding, and the like.
- molding aids such as polyvinyl alcohol, methylcellulose, polywax, and oleic acid may be used.
- the molded body is sintered at a temperature of 1200 ° C. to 1600 ° C. for 2 to 200 hours to obtain a sintered body. If the sintering temperature is less than 1200 ° C, a high-density sintered body may not be obtained. If the sintering temperature exceeds 1600 ° C, indium oxide and scandium oxide may be thermally decomposed. The temperature is preferably 1300 ° C to 1600 ° C, more preferably 1300 ° C to 1550 ° C.
- the sintering time is preferably 2 to 200 hours. If it is less than 2 hours, the sintering may not be completed, and a high-density sintered body may not be obtained. Moreover, when it is longer than 200 hours, the heating is too long, which may be disadvantageous economically. Preferably, it is 5 to 150 hours, more preferably 10 to 100 hours.
- Sintering is preferably performed in an oxidizing atmosphere.
- the oxidizing atmosphere may be in air, under an oxygen stream, or under oxygen pressure.
- the obtained sintered body is formed into a desired shape by cutting, polishing, or the like, and bonded to a backing plate to obtain a sputtering target.
- the metal oxide thin film of the present invention is formed using the above sputtering target. If necessary, an annealing process is performed after film formation.
- This metal oxide thin film is a semiconductor thin film, and can be used for a channel etch type, etch stopper type, etc. thin film transistor.
- Example 1 The following oxide powder was used as a mixed powder as a raw material.
- the specific surface area was measured by the BET method.
- Indium oxide powder specific surface area 6 m 2 / g
- Scandium oxide powder specific surface area 3 m 2 / g
- the specific surface area of the entire mixed powder was 6.0 m 2 / g.
- the above mixed powder of 990 g of indium oxide and 10 g of scandium oxide was mixed and ground using a wet medium stirring mill. As a grinding medium, 1 mm ⁇ zirconia beads were used. During the pulverization process, while confirming the specific surface area of the mixed powder, the specific surface area was increased by 2 m 2 / g from the specific surface area of the raw material mixed powder. After pulverization, the mixed powder dried with a spray dryer was filled in a mold (100 mm ⁇ 20 mm thickness) and pressure-molded with a cold press machine. After molding, the sintered body was manufactured by sintering at 1500 ° C. for 20 hours in an oxygen atmosphere while circulating oxygen.
- FIG. 1 shows an X-ray chart of the sintered body produced in Example 1.
- a bixbite structure of In 2 O 3 was observed in the sintered body.
- the lattice constant by X-ray diffraction it was 10.115 ⁇ .
- the measured value of the lattice constant almost coincides with the theoretical value of the lattice constant (see FIG. 9), and the peak due to the raw material Sc 2 O 3 is confirmed even when the X-ray diffraction chart is expanded 10 times.
- the above it was confirmed that scandium oxide was dissolved in the indium oxide crystal.
- the sintered body has a high density and is suitable for a sintered body for a sputtering target. Further, the bulk resistance of the sintered body was measured by a four-probe method using a resistivity meter (manufactured by Mitsubishi Oil Chemical Co., Ltd., Loresta) and found to be 0.9 ⁇ cm. From the ICP measurement, the atomic ratio [Sc / (In + Sc)] of the metal element in the sintered body was 0.02. The crystal grain size in the sintered body was 4.8 ⁇ m. The crystal grain size was defined as an average value of crystals in all fields when observed with a scanning electron microscope in a field of 30 ⁇ m ⁇ 30 ⁇ m.
- Table 1 shows the sintering conditions and the physical properties of the obtained sintered body.
- Table 1 shows the sintering conditions and the physical properties of the obtained sintered body.
- the presence or absence of nodules during sputtering was evaluated under the following conditions. Attach a 4-inch target to a sputtering device made by Shimadzu Corporation, visually observe the nodule formed on the target surface after applying 400 kW output, atmospheric gas 100% argon, and 10 kWhr electric power by DC magnetron sputtering. Confirmed with. Nodule generation was defined as a case where nodules generated in the inner and outer peripheral portions of erosion were continuously generated.
- Table 1 the presence or absence of abnormal discharge was evaluated under the following conditions.
- a 4 inch target is mounted on a sputtering device manufactured by Shimadzu Corporation, and the DC magnetron sputtering method is used to monitor the voltage during sputtering for 5 minutes after supplying 400 kW output, atmospheric gas at 100% argon, and 9 kWhr.
- the voltage decreased by 10% or more, abnormal discharge was determined, and when the number of times was 10 times or more, abnormal discharge was detected, and when the voltage was less than 10 times, abnormal discharge was not detected. Normally, when abnormal discharge starts to occur, 100 or more abnormal discharges are observed.
- Examples 2-5 A sintered body was produced in the same manner as in Example 1, except that the ratio of scandium element to indium element in the sintered body [Sc / (In + Sc)], sintering temperature and time were changed as shown in Table 1. ,evaluated. The results are shown in Table 1. 2 to 5 show X-ray charts of the sintered bodies obtained in the respective examples. As in Example 1, the measured value of the lattice constant almost coincides with the theoretical value of the lattice constant (see FIG. 9), and the peak caused by the raw material Sc 2 O 3 is an enlarged X-ray diffraction chart. Even it was not confirmed. From the above, it was confirmed that scandium oxide was dissolved in the indium oxide crystal.
- Example 6 To the indium oxide and scandium oxide weighed in Example 2, cerium oxide (CeO 2 ) was further added so that the Ce element would be 800 atomic ppm or 1200 atomic ppm with respect to all metal elements. A sintered body was produced in the same manner as in Example 2. Both the densities of the obtained sintered bodies were 6.5 g / cm 3 , and the bulk resistances were 0.015 ⁇ cm and 0.011 ⁇ cm, respectively. From this, it was confirmed that the bulk resistance of the sintered body can be lowered by adding a positive tetravalent metal element.
- the solid solution state was observed by X-ray diffraction to observe a peak of a bixbite structure caused by indium oxide, confirm that the lattice constants were 10.1015 ⁇ and 10.1019 ⁇ , and were Sc 2 O 3 as a raw material. , was confirmed by a peak due to the CeO 2 is not.
- Comparative Example 1 A sintered body was produced and evaluated in the same manner as in Example 1 except that 1000 g of only indium oxide was used without adding scandium oxide and the sintering temperature and time were changed as shown in Table 1. The results are shown in Table 1.
- FIG. 6 shows an X-ray chart of the sintered body obtained in Comparative Example 1. As a result, it was confirmed that the crystal grain size was larger than that of the example.
- Comparative Example 2 A sintered body was produced and evaluated in the same manner as in Example 3 except that the sintering temperature and time were changed as shown in Table 1. The results are shown in Table 1. As a result, it was confirmed that the crystal grain size was larger than that of the example. When the X-ray diffraction chart was enlarged, in addition to the solid solution peak of indium oxide / scandium oxide, a peak due to scandium oxide was observed, and it was confirmed that scandium oxide was not dissolved in the indium oxide crystal. .
- Comparative Example 3 Indium oxide and scandium oxide were weighed as shown in Table 1, mixed and pulverized, and after casting, the sintering temperature and time were changed as shown in Table 1, and sintering was performed in the same manner as in Example 1. The body was manufactured and evaluated. The results are shown in Table 1. As a result, it was confirmed that the density of the sintered body was lower than that of the example. The lattice constant obtained from X-ray diffraction is almost the same as the theoretical line of the solid solution state of indium oxide / scandium oxide, but when the X-ray diffraction chart is enlarged, the solid solution of indium oxide / scandium oxide is obtained.
- FIG. 9 shows the relationship between the lattice constant of In 2 O 3 bixbite and the amount of Sc 2 O 3 added in the sintered bodies produced in the examples and comparative examples.
- the straight line indicated by the dotted line is the theoretical value of the lattice constant.
- a channel etch type thin film transistor shown in FIG. 10 was produced by a photoresist method.
- a conductive silicon substrate 10 with a 200 nm thick thermal oxide film (SiO 2 film) was used.
- the thermal oxide film functions as the gate insulating film 30 and the conductive silicon portion functions as the gate electrode 20.
- sputtering target [Sc / (In + Sc) 0.06] made of the sintered body produced in Example 2 on the gate insulating film 30, a 40 nm oxide film (precursor of the semiconductor film 40) is formed by sputtering. ) was formed. Sputtering was carried out at room temperature with a sputtering power of 100 W while evacuating until the back pressure reached 5 ⁇ 10 ⁇ 4 Pa, adjusting the pressure to 0.2 Pa while flowing argon 9.5 sccm and oxygen 0.5 sccm. It was.
- a resist was applied to the substrate on which the oxide film was formed, and prebaked at 80 ° C. for 15 minutes to form a resist film. Thereafter, the resist film was irradiated with UV light (light intensity: 300 mJ / cm 2 ) through a mask, and then developed with 3 wt% tetramethylammonium hydroxide (TMAH). After washing with pure water, the resist film was post-baked at 130 ° C. for 15 minutes to form a resist pattern having a desired shape.
- the oxide film was etched by treating the substrate with a resist pattern with a mixed acid of phosphoric acid, acetic acid and nitric acid, the resist was peeled off, washed with pure water, air blown and dried.
- the substrate was heat-treated at 300 ° C. for 30 minutes in the air in a hot air heating furnace to convert the oxide film into a semiconductor, whereby the semiconductor film 40 was obtained. Thereafter, a molybdenum metal film was formed to 300 nm on the semiconductor film 40 and the gate insulating film 30.
- a resist was applied to the molybdenum metal film and pre-baked at 80 ° C. for 15 minutes to form a resist film. Thereafter, the resist film was irradiated with UV light (light intensity: 300 mJ / cm 2 ) through a mask, and then developed with 3 wt% tetramethylammonium hydroxide (TMAH). After washing with pure water, the resist film was post-baked at 130 ° C. for 15 minutes to form a resist pattern of source / drain electrodes.
- UV light light intensity: 300 mJ / cm 2
- TMAH 3 wt% tetramethylammonium hydroxide
- the substrate with a resist pattern was treated with a mixed acid of phosphoric acid / acetic acid / nitric acid to etch the molybdenum metal film, thereby forming the channel portion 60, the source electrode 50, and the drain electrode 52. Thereafter, it was washed with pure water, dried by air blowing, and a thin film transistor (the gap (L) between the source and drain electrodes of the channel portion 60 was 200 ⁇ m and the width (W) was 500 ⁇ m) was produced. At this time, it was confirmed that the semiconductor film 40 under the channel portion was not etched. The crystallized indium oxide film becomes resistant to a mixed acid of phosphoric acid / acetic acid / nitric acid and does not dissolve. Thus, a channel etch type TFT can be easily configured.
- Example 6 The following oxide powder was used and weighed as a mixed powder as a raw material. The specific surface area was measured by the BET method.
- Indium oxide powder specific surface area 6 m 2 / g
- B Aluminum oxide powder: specific surface area 6 m 2 / g
- the specific surface area of the whole mixed powder composed of (a) and (b) was 6.0 m 2 / g.
- the above mixed powder of 995 g of indium oxide and 5 g of aluminum oxide was mixed and ground using a wet medium stirring mill. As a grinding medium, 1 mm ⁇ zirconia beads were used. During the pulverization process, while confirming the specific surface area of the mixed powder, the specific surface area was increased by 2 m 2 / g from the specific surface area of the raw material mixed powder.
- the mixed powder obtained by drying with a spray dryer was filled into a mold (100 mm ⁇ 20 mm thickness) and pressure-molded with a cold press machine. After molding, the sintered body was manufactured by sintering at 1550 ° C. for 20 hours in an oxygen atmosphere while circulating oxygen.
- Example 7 to 10 Comparative Examples 4 and 5
- a sintered body was produced and evaluated in the same manner as in Example 6 except that indium oxide and aluminum oxide were mixed so as to have the mixing ratio shown in Table 2, and sintered at the sintering temperature shown in Table 2. The results are shown in Table 2.
- An X-ray chart of Example 9 is shown in FIG.
- Example 11 To the indium oxide and aluminum oxide weighed in Example 8, cerium oxide (CeO 2 ) was further added so that the Ce element was 800 atomic ppm or 1200 atomic ppm with respect to all the metal elements. A sintered body was produced in the same manner as in Example 8. Both the densities of the obtained sintered bodies were 6.56 g / cm 3 , and the bulk resistances were 0.017 ⁇ cm and 0.009 ⁇ cm, respectively. From this, it was confirmed that the bulk resistance of the sintered body can be lowered by adding a positive tetravalent metal element.
- the solid solution state was observed by X-ray diffraction by observing the peak of the bixbite structure caused by indium oxide, confirming that the lattice constants were 10.101510 and 10.1019Al, and the raw material Al 2 O 3 , was confirmed by a peak due to the CeO 2 is not.
- Evaluation example 2 Production of Thin Film Transistor A channel etch type thin film transistor shown in FIG. 10 was produced in the same manner as in Evaluation Example 1 (A) except that the sputtering target produced in Example 8 was used.
- Field effect mobility of the thin film transistor manufactured is 49.3cm 2 / V ⁇ sec, On -Off ratio 10 7, S value was a thin film transistor showing the characteristics of a small normally-off and 0.89. The output characteristics showed a clear pinch-off.
- the shift voltage (Vth) after applying 20V voltage to the gate electrode for 100 minutes was 0.2V.
- the sintered body of the present invention can be used as a sputtering target for forming an indium oxide-based semiconductor film. Moreover, the obtained film
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Abstract
Description
それら表示装置を駆動させるスイッチング素子、例えば、薄膜トランジスタ(TFT)では、現在、シリコン系の半導体膜を使用したものが主流を占めている。それは、シリコン系薄膜は安定性及び加工性が良く、また、TFTのスイッチング速度が速い等、良好な性能を有するためである。このシリコン系薄膜は、一般に化学蒸気析出法(CVD)法により作製されている。
また、優れた結晶質酸化物半導体膜を製造するためのスパッタリングターゲットを提供することである。
1.酸化インジウム結晶に、アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物が固溶し、インジウムと、アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の原子比((1種以上の金属の合計)/(1種以上の金属とInの合計)×100)が0.001%以上45%未満である焼結体。
2.前記原子比が0.01~30原子%である1に記載の焼結体。
3.前記原子比が0.5~15原子%である1に記載の焼結体。
4.前記酸化インジウム結晶がビックスバイト構造である1~3のいずれかに記載の焼結体。
5.前記酸化インジウムの結晶粒径が10μm未満である1~4のいずれかに記載の焼結体。
6.酸化インジウム及び酸化スカンジウムからなり、前記酸化インジウムの結晶の格子定数がInScO3とIn2O3の間にある1~5のいずれかに記載の焼結体。
7.酸化インジウム及び酸化アルミニウムからなり、前記酸化インジウムの結晶の格子定数がInAlO3とIn2O3の間にある1~5のいずれかに記載の焼結体。
8.さらに正4価以上の金属イオンを10~5000原子ppm含有する1~7のいずれかに記載の焼結体。
9.前記正4価以上の金属イオンを100~2000原子ppm含有する8に記載の焼結体。
10.前記正4価以上の金属イオンが、スズイオン又はセリウムイオンのいずれか一方又は両方である8又は9に記載の焼結体。
11.アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物及び酸化インジウムの粉末を混合し、1200℃~1600℃の温度にて、2~200時間焼成する1~7のいずれかに記載の焼結体の製造方法。
12.アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物、酸化インジウム並びに正四価以上の金属の粉末を混合し、1200℃~1600℃の温度にて、2~200時間焼成する8~10のいずれかに記載の焼結体の製造方法。
13.酸化雰囲気中で焼成する11又は12に記載の焼結体の製造方法。
14.1~10のいずれかに記載の焼結体を用いて作製されるスパッタリングターゲット。
15.14に記載のスパッタリングターゲットを用いて成膜される金属酸化物薄膜。
16.15に記載の金属酸化物薄膜からなる半導体膜。
17.16に記載の半導体膜を用いる薄膜トランジスタ。
18.チャンネルエッチ型である17に記載の薄膜トランジスタ。
19.エッチストッパー型である17に記載の薄膜トランジスタ。
20.17~19のいずれかに記載の薄膜トランジスタを備える半導体素子。
焼結体の格子定数が、酸化インジウムと特定正三価金属酸化物の間にあるということは、一般に、特定正三価金属酸化物が酸化インジウムに十分に固溶されていて、異状放電を生じさせる量の単独の特定正三価金属酸化物が焼結体中に存在しないことを意味する。従って、この焼結体から得られるスパッタリングターゲットは、安定したスパッタリングを行うことができ、かつ、表面平滑性に優れた酸化物半導体を与えることができる。尚、異状放電を生じさせない程度の量の単独の特定正三価金属酸化物は含まれていてもよい。
また、特定正三価金属酸化物は、酸素との結合力が高い。従って、本発明の焼結体からなるスパッタリングターゲットを用いて得られる結晶質薄膜内の酸素欠損が抑制され、薄膜が半導体化しやすい。
さらに、特定正三価金属酸化物は、それ自体が耐酸性・耐アルカリ性であるため、得られる薄膜の耐酸性・耐アルカリ性が向上する。
特定正三価金属酸化物を添加すると、酸化インジウムの結晶質薄膜の格子定数は小さくなるため、陽イオンの原子間距離が小さくなる。従って、得られる薄膜を用いたトランジスタの移動度が向上し、S値及び耐久性が向上する。
結晶粒径は、30μm×30μmの視野で走査型電子顕微鏡にて観察した場合の全視野での結晶の平均値を結晶粒径(長径)とする。また、上記視野で観察した場合に、10μm以上の結晶が存在しなければ、平均粒径は10μm未満になる。
原料である酸化物は、純度99.99%以上の粉体が好ましい。尚、正4価以上の金属元素を添加する場合、例えば、同金属元素の酸化物等の化合物を添加する。この化合物の純度も99.99%以上であることが好ましい。各原料の純度が99.99%以上であると、不純物量が100原子ppm未満となり好ましい。
各原料の配合量は目的とする焼結体の各金属元素の配合量に対応させる。
成形処理としては、例えば、プレス成形、冷間静水圧、一軸加圧、金型成形、鋳込み成形、射出成形等が挙げられる。尚、成形処理に際しては、ポリビニルアルコールやメチルセルロース、ポリワックス、オレイン酸等の成形助剤を用いてもよい。
焼結温度が1200℃未満では、高密度の焼結体が得られない場合があり、1600℃を超えると、酸化インジウム、酸化スカンジウムが熱分解する場合がある。好ましくは1300℃~1600℃、より好ましくは1300℃~1550℃である。
焼結時間は、2~200時間がよい。2時間未満では、焼結が完了しない場合があり、高密度の焼結体が得られなかったりする場合がある。また、200時間より長いと加熱が長すぎ、経済的に不利となる場合がある。好ましくは、5~150時間、より好ましくは10~100時間である。
得られた焼結体を、切削加工、研磨加工等により、所望の形状とし、バッキングプレートに接合することで、スパッタリングターゲットが得られる。
[実施例]
原料である混合粉体として、下記の酸化物粉を使用した。尚、比表面積はBET法で測定した。
(a)酸化インジウム粉:比表面積6m2/g
(b)酸化スカンジウム粉:比表面積3m2/g
尚、混合粉体全体の比表面積は6.0m2/gであった。
粉砕後、スプレードライヤーで乾燥させた混合粉を金型(100mmφ20mm厚)に充填し、コールドプレス機にて加圧成形した。
成形後、酸素を流通させながら酸素雰囲気中、1500℃で20時間焼結して、焼結体を製造した。
また、格子定数の測定値が格子定数の理論値とほぼ一致し(図9参照)、かつ原料であるSc2O3に起因するピークは、X線回折チャートを10倍に拡大しても確認されなかった。以上から、酸化スカンジウムは酸化インジウム結晶に固溶していることが確認できた。
また、焼結体のバルク抵抗を、抵抗率計(三菱油化製、ロレスタ)を使用し四探針法により測定したところ、0.9Ωcmであった。
ICP測定により、焼結体中の金属元素の原子比[Sc/(In+Sc)]は、0.02であった。
焼結体内の結晶粒径は、4.8μmであった。尚、結晶粒径は、30μm×30μmの視野で走査型電子顕微鏡にて観察した場合の全視野での結晶の平均値を結晶粒径とした。
表1中、スパッタ時のノジュール発生の有無は、以下の条件にて評価した。
島津製作所製スパッタ装置に、4インチターゲットを装着し、DCマグネトロンスパッタ法にて、400Wの出力、雰囲気ガスをアルゴン100%にて、10kWhrの電力を投入したあとの、ターゲット表面にできるノジュールを目視で確認した。エロージョンの内周部及び外周部に発生するノジュールが、連続して発生している場合をノジュール発生とした。
島津製作所製スパッタ装置に、4インチターゲットを装着し、DCマグネトロンスパッタ法にて、400Wの出力、雰囲気ガスをアルゴン100%にて、9kWhrの電力投入後、5分間、スパッタ中の電圧をモニターし、電圧が10%以上低下した場合を異常放電とし、その回数が10回以上の場合を異常放電ありとし、10回未満の場合を異常放電なしとした。通常、異常放電が発生し始めると100回以上の異常放電が観察される。
焼結体中のスカンジウム元素とインジウム元素の比[Sc/(In+Sc)]、焼結温度及び時間を表1に示すように変更した他は、実施例1と同様にして焼結体を製造し、評価した。結果を表1に示す。図2~5に各実施例で得られた焼結体のX線チャートを示す。
尚、実施例1と同様、格子定数の測定値が格子定数の理論値とほぼ一致し(図9参照)、かつ原料であるSc2O3に起因するピークは、X線回折チャートを拡大しても確認されなかった。以上から、酸化スカンジウムは酸化インジウム結晶に固溶していることが確認できた。
実施例2で秤量した酸化インジウム及び酸化スカンジウムに、更に、酸化セリウム(CeO2)を、Ce元素が全金属元素に対して、800原子ppm、又は1200原子ppmとなるように添加し、実施例2と同様にして焼結体を製造した。得られた焼結体の密度は、両方とも、6.5g/cm3であり、バルク抵抗は、それぞれ、0.015Ωcm、0.011Ωcmであった。これより、正4価の金属元素を添加することにより、焼結体のバルク抵抗を下げることができることが確認できた。また、固溶状態は、X線回折より、酸化インジウムに起因するビックスバイト構造のピークを観察し、格子定数が10.1015Å、10.1019Åであることを確認し、原料であるSc2O3、CeO2に起因するピークが無いことにより確認した。
酸化スカンジウムを配合せず、酸化インジウムのみ1000gを使用し、焼結温度及び時間を表1に示すように変更した他は、実施例1と同様にして焼結体を製造し、評価した。結果を表1に示す。また、図6に比較例1で得られた焼結体のX線チャートを示す。
この結果、実施例と比べて結晶粒径が大きいことが確認できた。
焼結温度及び時間を表1に示すように変更した他は、実施例3と同様にして焼結体を製造し、評価した。結果を表1に示す。
この結果、実施例と比べて実施例と比べて結晶粒径が大きいことが確認できた。X線回折チャートを拡大してみると、酸化インジウム・酸化スカンジウムの固溶体のピーク以外に、酸化スカンジウムに起因するピークが観察され、酸化スカンジウムは酸化インジウム結晶に固溶していないことが確認できた。
酸化インジウム、酸化スカンジウムを表1に示したように秤量し、混合・粉砕、造流後に、焼結温度及び時間を表1に示すように変更した他は、実施例1と同様にして焼結体を製造し、評価した。結果を表1に示す。
この結果、実施例と比べて焼結体の密度が低いことが確認できた。また、X線回折から求めた格子定数は、酸化インジウム・酸化スカンジウムの固溶状態の理論線にほぼ一致しているものの、X線回折チャートを拡大してみると、酸化インジウム・酸化スカンジウムの固溶体のピーク以外に、酸化スカンジウムに起因するピークが観察され、酸化スカンジウムは酸化インジウム結晶に固溶していないことが確認できた。また、密度が低く、また、結晶粒径も大きいことから、焼結体の強度が低く、ターゲットへの加工は行わなかった。
(A)薄膜トランジスタの作製
図10に示すチャンネルエッチ型の薄膜トランジスタをフォトレジスト法にて作製した。
200nm厚みの熱酸化膜(SiO2膜)付きの導電性シリコン基板10を使用した。熱酸化膜がゲート絶縁膜30として機能し、導電性シリコン部がゲート電極20として機能する。
レジストパターン付き基板を、燐酸・酢酸・硝酸の混合酸で処理することで、酸化物膜をエッチングし、レジストを剥離し、純水で洗浄しエアーブローして乾燥させた。
その後、半導体膜40及びゲート絶縁膜30上に、モリブデン金属膜を300nm成膜した。
石英ガラス基板上に、上記(A)のスパッタリングと同じ条件にて酸化スカンジウムを含む酸化インジウム膜を形成した。その後、熱風加熱炉内で、空気中、300℃で30分間熱処理した。得られた半導体膜のX線回折(XRD)を測定したところ、酸化インジウムに起因する構造のみのピークを示すX線回折パターンが得られた。これにより、半導体膜が結晶質であることが確認できた。この結晶質半導体膜の格子定数は、酸化インジウム単独の薄膜の場合より、小さな値を示すことから、大きな移動度が達成できていると考える。
また、ホール測定により求めたキャリヤー濃度は、5.7×10+16/cm3であった。
原料である混合粉体として、下記の酸化物粉を使用、秤量した。尚、比表面積はBET法で測定した。
(a)酸化インジウム粉:比表面積6m2/g
(b)酸化アルミニウム粉:比表面積6m2/g
(a)(b)からなる混合粉体全体の比表面積は6.0m2/gであった。
粉砕後、スプレードライヤーで乾燥させて得た混合粉を金型(100mmφ20mm厚)に充填し、コールドプレス機にて加圧成形した。成形後、酸素を流通させながら酸素雰囲気中、1550℃で20時間焼結して、焼結体を製造した。
表2に示す配合比となるように酸化インジウムと酸化アルミニウムを混合し、表2に示す焼結温度で焼結した他は実施例6と同様にして焼結体を製造し、評価した。結果を表2に示す。
実施例9のX線チャートを図11に示す。
実施例8で秤量した酸化インジウム及び酸化アルミニウムに、更に、酸化セリウム(CeO2)を、Ce元素が全金属元素に対して、800原子ppm、又は1200原子ppmとなるように添加し、実施例8と同様にして焼結体を製造した。得られた焼結体の密度は、両方とも、6.56g/cm3であり、バルク抵抗は、それぞれ、0.017Ωcm、0.009Ωcmであった。これより、正4価の金属元素を添加することにより、焼結体のバルク抵抗を下げることができることが確認できた。また、固溶状態は、X線回折より、酸化インジウムに起因するビックスバイト構造のピークを観察し、格子定数が10.1015Å、10.1019Åであることを確認し、原料であるAl2O3、CeO2に起因するピークが無いことにより確認した。
(A)薄膜トランジスタの作製
実施例8を製造したスパッタリングターゲットを用いた他は、評価例1(A)と同様にして、図10に示すチャンネルエッチ型の薄膜トランジスタを作製した。
実施例8を製造したスパッタリングターゲットを用いた他は、評価例1(B)と同様にして、半導体膜を形成し熱処理した。得られた半導体膜のX線回折(XRD)測定をしたところ、酸化インジウムに起因する構造のみのピークをしめすX線解説パターンが得られた。これにより、半導体膜が結晶質であることが確認できた。また、ホール測定により求めたキャリヤー濃度は、5.7×10+16/cm3であった。
Claims (20)
- 酸化インジウム結晶に、アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物が固溶し、インジウムと、アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の原子比((1種以上の金属の合計)/(1種以上の金属とInの合計)×100)が0.001%以上45%未満である焼結体。
- 前記原子比が0.01~30原子%である請求項1に記載の焼結体。
- 前記原子比が0.5~15原子%である請求項1に記載の焼結体。
- 前記酸化インジウム結晶がビックスバイト構造である請求項1~3のいずれかに記載の焼結体。
- 前記酸化インジウムの結晶粒径が10μm未満である請求項1~4のいずれかに記載の焼結体。
- 酸化インジウム及び酸化スカンジウムからなり、前記酸化インジウムの結晶の格子定数がInScO3とIn2O3の間にある請求項1~5のいずれかに記載の焼結体。
- 酸化インジウム及び酸化アルミニウムからなり、前記酸化インジウムの結晶の格子定数がInAlO3とIn2O3の間にある請求項1~5のいずれかに記載の焼結体。
- さらに正4価以上の金属イオンを10~5000原子ppm含有する請求項1~7のいずれかに記載の焼結体。
- 前記正4価以上の金属イオンを100~2000原子ppm含有する請求項8に記載の焼結体。
- 前記正4価以上の金属イオンが、スズイオン又はセリウムイオンのいずれか一方又は両方である請求項8又は9に記載の焼結体。
- アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物及び酸化インジウムの粉末を混合し、1200℃~1600℃の温度にて、2~200時間焼成する請求項1~7のいずれかに記載の焼結体の製造方法。
- アルミニウム及びスカンジウムからなる群から選ばれる1種以上の金属の酸化物、酸化インジウム並びに正四価以上の金属の粉末を混合し、1200℃~1600℃の温度にて、2~200時間焼成する請求項8~10のいずれかに記載の焼結体の製造方法。
- 酸化雰囲気中で焼成する請求項11又は12に記載の焼結体の製造方法。
- 請求項1~10のいずれかに記載の焼結体を用いて作製されるスパッタリングターゲット。
- 請求項14に記載のスパッタリングターゲットを用いて成膜される金属酸化物薄膜。
- 請求項15に記載の金属酸化物薄膜からなる半導体膜。
- 請求項16に記載の半導体膜を用いる薄膜トランジスタ。
- チャンネルエッチ型である請求項17に記載の薄膜トランジスタ。
- エッチストッパー型である請求項17に記載の薄膜トランジスタ。
- 請求項17~19のいずれかに記載の薄膜トランジスタを備える半導体素子。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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US13/139,563 US8664136B2 (en) | 2008-12-15 | 2009-06-01 | Indium oxide sintered compact and sputtering target |
CN2009801505180A CN102245533B (zh) | 2008-12-15 | 2009-06-01 | 氧化铟系烧结体及溅射靶 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011148614A1 (ja) * | 2010-05-27 | 2011-12-01 | 出光興産株式会社 | 酸化物焼結体、それからなるターゲット及び酸化物半導体薄膜 |
WO2013035335A1 (ja) * | 2011-09-06 | 2013-03-14 | 出光興産株式会社 | スパッタリングターゲット |
JP2016210679A (ja) * | 2013-12-27 | 2016-12-15 | 出光興産株式会社 | 酸化物焼結体、その製造方法及びスパッタリングターゲット |
TWI568703B (zh) * | 2011-08-22 | 2017-02-01 | Idemitsu Kosan Co | In-Ga-Sn-based oxide sintered body |
US10636914B2 (en) | 2015-07-30 | 2020-04-28 | Idemitsu Kosan Co., Ltd. | Crystalline oxide semiconductor thin film, method for producing crystalline oxide semiconductor thin film, and thin film transistor |
Families Citing this family (5)
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JP2013147738A (ja) * | 2011-12-22 | 2013-08-01 | Kobe Steel Ltd | Taを含有する酸化アルミニウム薄膜 |
US9577109B2 (en) * | 2012-09-18 | 2017-02-21 | Lg Chem, Ltd. | Transparent conducting film and preparation method thereof |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6288216A (ja) * | 1985-10-15 | 1987-04-22 | 住友電気工業株式会社 | 透明導電膜の製造方法 |
JP2000169220A (ja) * | 1998-12-09 | 2000-06-20 | Jiomatetsuku Kk | 金属酸化物焼結体およびその用途 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4962071A (en) * | 1989-05-01 | 1990-10-09 | Tektronix, Inc. | Method of fabricating a sintered body of indium tin oxide |
JP3781398B2 (ja) | 1998-11-09 | 2006-05-31 | キャノンオプトロン株式会社 | I.t.o焼結体、その製造方法及びi.t.o薄膜 |
JP2000169219A (ja) | 1998-12-09 | 2000-06-20 | Jiomatetsuku Kk | 金属酸化物焼結体およびその用途 |
US6940565B2 (en) * | 2000-08-26 | 2005-09-06 | Lg.Philips Lcd Co., Ltd. | Liquid crystal display device and fabricating method thereof |
JP4604440B2 (ja) * | 2002-02-22 | 2011-01-05 | 日本電気株式会社 | チャネルエッチ型薄膜トランジスタ |
KR100505536B1 (ko) * | 2002-03-27 | 2005-08-04 | 스미토모 긴조쿠 고잔 가부시키가이샤 | 투명한 도전성 박막, 그것의 제조방법, 그것의 제조를위한 소결 타겟, 디스플레이 패널용의 투명한 전기전도성기재, 및 유기 전기루미네선스 디바이스 |
JP4164563B2 (ja) | 2002-09-24 | 2008-10-15 | 独立行政法人科学技術振興機構 | 酸化物半導体pn接合デバイス及びその製造方法 |
TWI478347B (zh) | 2007-02-09 | 2015-03-21 | Idemitsu Kosan Co | A thin film transistor, a thin film transistor substrate, and an image display device, and an image display device, and a semiconductor device |
-
2009
- 2009-06-01 JP JP2010542894A patent/JPWO2010070944A1/ja active Pending
- 2009-06-01 US US13/139,563 patent/US8664136B2/en active Active
- 2009-06-01 CN CN2013101143667A patent/CN103204674A/zh active Pending
- 2009-06-01 KR KR1020117013692A patent/KR101565196B1/ko active IP Right Grant
- 2009-06-01 CN CN2009801505180A patent/CN102245533B/zh active Active
- 2009-06-01 WO PCT/JP2009/059954 patent/WO2010070944A1/ja active Application Filing
- 2009-06-02 TW TW098118184A patent/TWI436959B/zh active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6288216A (ja) * | 1985-10-15 | 1987-04-22 | 住友電気工業株式会社 | 透明導電膜の製造方法 |
JP2000169220A (ja) * | 1998-12-09 | 2000-06-20 | Jiomatetsuku Kk | 金属酸化物焼結体およびその用途 |
Non-Patent Citations (2)
Title |
---|
"Japan Society for the Promotion of Science Tomei Sankabutsu Hikari - Denshi Zairyo Dai 166 Iinkai", TOMEI DODEN MAKU NO GIJUTSU, 25 April 2000 (2000-04-25), pages 197 * |
SYED B. QADRI ET AL.: "Synthesis of bulk In203- Sc203 and their transparent conducting oxide films", JOURNAL OF APPLIED PHYSICS, vol. 92, no. 1, 1 July 2002 (2002-07-01), pages 227 - 229 * |
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JP2011249570A (ja) * | 2010-05-27 | 2011-12-08 | Idemitsu Kosan Co Ltd | 酸化物焼結体、それからなるターゲット及び酸化物半導体薄膜 |
WO2011148614A1 (ja) * | 2010-05-27 | 2011-12-01 | 出光興産株式会社 | 酸化物焼結体、それからなるターゲット及び酸化物半導体薄膜 |
TWI568703B (zh) * | 2011-08-22 | 2017-02-01 | Idemitsu Kosan Co | In-Ga-Sn-based oxide sintered body |
TWI567045B (zh) * | 2011-09-06 | 2017-01-21 | Idemitsu Kosan Co | Sputtering target |
KR20140057318A (ko) | 2011-09-06 | 2014-05-12 | 이데미쓰 고산 가부시키가이샤 | 스퍼터링 타겟 |
CN103732790A (zh) * | 2011-09-06 | 2014-04-16 | 出光兴产株式会社 | 溅射靶 |
JP2013067855A (ja) * | 2011-09-06 | 2013-04-18 | Idemitsu Kosan Co Ltd | スパッタリングターゲット |
WO2013035335A1 (ja) * | 2011-09-06 | 2013-03-14 | 出光興産株式会社 | スパッタリングターゲット |
CN103732790B (zh) * | 2011-09-06 | 2017-05-31 | 出光兴产株式会社 | 溅射靶 |
US9767998B2 (en) | 2011-09-06 | 2017-09-19 | Idemitsu Kosan Co., Ltd. | Sputtering target |
KR102075904B1 (ko) * | 2011-09-06 | 2020-02-11 | 이데미쓰 고산 가부시키가이샤 | 스퍼터링 타겟 |
JP2016210679A (ja) * | 2013-12-27 | 2016-12-15 | 出光興産株式会社 | 酸化物焼結体、その製造方法及びスパッタリングターゲット |
JP2018158880A (ja) * | 2013-12-27 | 2018-10-11 | 出光興産株式会社 | 酸化物焼結体、その製造方法及びスパッタリングターゲット |
TWI665173B (zh) * | 2013-12-27 | 2019-07-11 | Idemitsu Kosan Co., Ltd. | 氧化物燒結體、其製造方法及濺鍍靶 |
US10636914B2 (en) | 2015-07-30 | 2020-04-28 | Idemitsu Kosan Co., Ltd. | Crystalline oxide semiconductor thin film, method for producing crystalline oxide semiconductor thin film, and thin film transistor |
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CN103204674A (zh) | 2013-07-17 |
TWI436959B (zh) | 2014-05-11 |
CN102245533B (zh) | 2013-11-06 |
US20110243835A1 (en) | 2011-10-06 |
JPWO2010070944A1 (ja) | 2012-05-24 |
TW201022176A (en) | 2010-06-16 |
KR101565196B1 (ko) | 2015-11-02 |
CN102245533A (zh) | 2011-11-16 |
KR20110104496A (ko) | 2011-09-22 |
US8664136B2 (en) | 2014-03-04 |
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