WO2012029454A1 - Sintered oxide and oxide semiconductor thin film - Google Patents
Sintered oxide and oxide semiconductor thin film Download PDFInfo
- Publication number
- WO2012029454A1 WO2012029454A1 PCT/JP2011/067131 JP2011067131W WO2012029454A1 WO 2012029454 A1 WO2012029454 A1 WO 2012029454A1 JP 2011067131 W JP2011067131 W JP 2011067131W WO 2012029454 A1 WO2012029454 A1 WO 2012029454A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- thin film
- ions
- oxide semiconductor
- semiconductor thin
- Prior art date
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 32
- 239000004065 semiconductor Substances 0.000 title claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- -1 iron ions Chemical class 0.000 claims abstract description 20
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 229910001449 indium ion Inorganic materials 0.000 claims abstract description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 abstract description 24
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 41
- 238000004544 sputter deposition Methods 0.000 description 30
- 239000002245 particle Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 14
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000005477 sputtering target Methods 0.000 description 10
- 230000002159 abnormal effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- 238000009616 inductively coupled plasma Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052738 indium Inorganic materials 0.000 description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 229910003437 indium oxide Inorganic materials 0.000 description 3
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000036961 partial effect Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910007541 Zn O Inorganic materials 0.000 description 2
- 229910007604 Zn—Sn—O Inorganic materials 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 231100000989 no adverse effect Toxicity 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
Definitions
- the present invention relates to an oxide sintered body and an oxide semiconductor thin film useful for manufacturing a thin film transistor in a display device.
- Oxide semiconductors are used as active layers of thin film transistors in display devices such as liquid crystal display devices, plasma display devices, and organic EL display devices, as well as electrodes for solar cells and touch panels.
- display devices such as liquid crystal display devices, plasma display devices, and organic EL display devices, as well as electrodes for solar cells and touch panels.
- IGZO-based transparent In—Ga—Zn—O-based
- Patent Documents 1 and 2 There is also a report on a system to which Sn) is added (see Patent Documents 1 and 2).
- gallium (Ga) which is an essential component of these systems, is a rare element and has a large limitation in terms of industrial use because of its high price.
- Patent Document 3 As a transparent oxide semiconductor not using Ga, an In—Zn—O system (see Patent Document 3), an In—Zn—Sn—O system (see Patent Document 4), and a Zn—Sn—O system (Patent Document 5). Report).
- the IGZO-based alternative candidate materials described in Patent Documents 3 to 5 above have been limited to only the material system of elements that are transparent as oxides because the IGZO-based material is a transparent semiconductor.
- the IGZO system is used as a channel layer of a transistor, and in most cases, transparency is not necessarily required. Therefore, a material system that is not transparent but can be used as a channel layer of a transistor has not been studied as an alternative material for IGZO.
- an object of the present invention is to provide an oxide sintered body for manufacturing an oxide semiconductor film which is a scarce resource and does not contain expensive gallium (Ga).
- Another object of the present invention is to provide an oxide semiconductor thin film having the same composition as the oxide sintered body.
- trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and divalent X ions (X 2+ ) (where X is Cu, Zn, And an oxide sintered body composed of oxygen ions (O 2 ⁇ ) and trivalent indium ions (In 3+ ),
- the atomic ratio of iron ions (Fe 3+ ) and divalent X ions (X 2+ ) is 0.2 ⁇ (In 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2 + ) ⁇ ⁇ 0.8, 0.1 ⁇ (Fe 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ ⁇ 0.5, 0.1 ⁇ (X 2+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ ⁇ 0.5.
- the oxide sintered body according to the present invention has a relative density of 98% or more.
- the oxide sintered body according to the present invention has a bulk resistance of 3 m ⁇ or less.
- a trivalent indium ion (In 3+ ), a trivalent iron ion (Fe 3+ ), and a divalent X ion (X 2+ ) (where X is Cu,
- the atomic ratio of iron ions (Fe 3+ ) and divalent X ions (X 2+ ) is 0.2 ⁇ (In 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ ⁇ 0.8, 0.1 ⁇ (Fe 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ ⁇ 0.5, and 0.1 ⁇
- the oxide semiconductor thin film satisfies (X 2+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ ⁇ 0.5.
- the oxide semiconductor thin film according to the present invention is amorphous.
- the oxide semiconductor thin film according to the present invention has a carrier concentration of 10 16 to 10 18 cm ⁇ 3 .
- the oxide semiconductor thin film according to the present invention has a mobility of 1 cm 2 / Vs or more.
- the present invention is a thin film transistor including the oxide semiconductor thin film as an active layer.
- the present invention is an active matrix drive display panel including the thin film transistor.
- an oxide sintered body for producing an oxide semiconductor film that does not contain gallium (Ga) can be provided.
- This oxide sintered body is useful as a sputtering target.
- An oxide semiconductor film can be formed by sputtering using this target.
- the oxide sintered body according to the present invention includes a trivalent indium ion (In 3+ ), a trivalent iron ion (Fe 3+ ), and a divalent X ion (X 2+ ) (where X is It represents one or more elements selected from Cu, Zn, and Fe.) And oxygen ions (O 2 ⁇ ).
- X is It represents one or more elements selected from Cu, Zn, and Fe.
- oxygen ions O 2 ⁇
- elements that are inevitably included in the purification process of raw materials that are usually available, and impurity elements that are inevitably mixed in the oxide sintered body manufacturing process, are inevitably contained at a concentration, for example, each element. What contains about 10 ppm is included in the sintered compact which concerns on this invention.
- the number ratio (In 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is preferably 0.2 to 0.8. If (In 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is less than 0.2, the carrier concentration of the film becomes too small, and the relative value during target fabrication Density decreases, bulk resistance increases, and abnormal discharge during sputtering is likely to occur.
- the ratio of numbers (Fe 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is preferably 0.1 to 0.5 (Fe 3+ ) / ⁇ (In 3 + ) + (Fe 3+ ) + (X 2+ ) ⁇ is less than 0.1, the carrier concentration of the film obtained by sputtering the target having that composition becomes too high, and the channel layer of the transistor As a result, the on / off ratio becomes small.
- (Fe 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ exceeds 0.5, the carrier concentration of the film becomes too small, and the target is produced. The relative density of the metal becomes small, the bulk resistance becomes high, and abnormal discharge during sputtering is likely to occur.
- (Fe 3+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is more preferably in the range of 0.15 to 0.4, and more preferably 0.2 to 0. .35 range.
- Ratio of total number of atoms of metal element X to total number of trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and divalent X ions (X 2+ ) (X 2 + ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is preferably 0.1 to 0.5. If (X 2+ ) / ⁇ (In 3+ ) + (Fe 3+ ) + (X 2+ ) ⁇ is less than 0.1, the carrier concentration of the film becomes too large.
- iron ions Fe 2+
- the only types of metal ions are indium and iron.
- divalent and trivalent types of iron ions which are present in the oxide sintered body.
- Iron is a transition metal and can take a plurality of valences, and iron ions having different valences may exist in a certain compound.
- the compound is formed in advance by controlling the valence of iron ions. Thus, desired characteristics can be obtained more easily.
- the relative density of the oxide sintered body correlates with the generation of joules on the surface during sputtering. If the oxide sintered body has a low density, the oxide sintered body is processed into a target to form a sputter film. At the same time, a high-resistance portion called a protruding nodule, which is a lower oxide of indium, is generated on the surface as the film formation of the sputtering is performed, and it tends to be a starting point of abnormal discharge during the subsequent sputtering.
- a protruding nodule which is a lower oxide of indium
- the relative density of the oxide sintered body can be set to 98% or more by optimizing the appropriate range of the composition, and if this density is high, there is almost no adverse effect due to nodules during sputtering.
- the relative density is preferably 99% or more, more preferably 99.5% or more.
- the relative density of the oxide sintered body is obtained by dividing the density calculated from the weight and outer dimensions after processing the oxide sintered body into a predetermined shape by the theoretical density of the oxide sintered body. Can be sought.
- the bulk resistance of the oxide sintered body has a correlation with the ease of occurrence of abnormal discharge during sputtering, and when the bulk resistance is high, abnormal discharge is likely to occur during sputtering.
- the bulk resistance can be reduced to 3 m ⁇ cm or less by optimizing the appropriate range of the composition and the manufacturing conditions. With such a low bulk resistance, there is almost no adverse effect on the occurrence of abnormal discharge during sputtering.
- the bulk resistance is preferably 2.7 m ⁇ cm or less, more preferably 2.5 m ⁇ cm or less. Bulk resistance can be measured using a resistivity meter by the four-probe method.
- the oxide sintered body having various compositions according to the present invention includes, for example, raw materials such as indium oxide (In 2 O 3 ), iron oxide (Fe 2 O 3 as a supply source of trivalent iron, and a supply source of divalent iron. Conditions such as mixing ratio of raw material powders such as FeO), zinc oxide (ZnO), copper oxide (CuO), particle size of raw material powder, pulverization time, sintering temperature, sintering time, kind of sintering atmosphere gas, etc. Can be obtained by adjusting.
- raw materials such as indium oxide (In 2 O 3 ), iron oxide (Fe 2 O 3 as a supply source of trivalent iron, and a supply source of divalent iron.
- Conditions such as mixing ratio of raw material powders such as FeO), zinc oxide (ZnO), copper oxide (CuO), particle size of raw material powder, pulverization time, sintering temperature, sintering time, kind of sintering atmosphere gas, etc. Can be obtained by adjusting.
- the raw material powder preferably has an average particle size of 1 to 2 ⁇ m.
- the average particle diameter exceeds 2 ⁇ m, the density of the sintered body is difficult to improve. Therefore, wet pulverization or the like is performed as the raw material powder alone or as a mixed powder, and the average particle diameter is preferably reduced to about 1 ⁇ m.
- wet pulverization or the like is performed as the raw material powder alone or as a mixed powder, and the average particle diameter is preferably reduced to about 1 ⁇ m.
- it is also effective to perform calcination.
- raw materials having a particle size of less than 1 ⁇ m are difficult to obtain, and if the particle size is too small, agglomeration between particles tends to occur and handling becomes difficult.
- the average particle diameter of the raw material powder refers to the median diameter in the volume distribution measured by a laser diffraction particle size distribution measuring apparatus.
- the molded product is sintered to obtain a sintered body.
- the sintering is preferably performed at 1400 to 1600 ° C. for 2 to 20 hours. Thereby, a relative density can be 98% or more. If the sintering temperature is less than 1400 ° C., the density is difficult to improve. Conversely, if the sintering temperature exceeds 1600 ° C., the composition of the sintered body changes due to volatilization of the constituent elements, and voids are generated due to volatilization. May cause a decrease in density. Air can be used as the atmosphere gas during sintering, and the amount of oxygen vacancies in the sintered body can be increased to reduce the bulk resistance. However, depending on the composition of the sintered body, a sufficiently high density sintered body can be obtained even if the atmospheric gas is oxygen.
- the oxide sintered body obtained as described above can be used as a sputtering target by performing processing such as grinding and polishing, and by using this film, the same composition as that of the target can be obtained. It is possible to form an oxide film having At the time of processing, it is desirable that the surface roughness (Ra) be 5 ⁇ m or less by grinding the surface by a method such as surface grinding. By reducing the surface roughness, the starting point of nodule generation that causes abnormal discharge can be reduced.
- the sputtering target is affixed to a backing plate made of copper or the like, placed in a sputtering apparatus, and sputtered under appropriate conditions such as an appropriate degree of vacuum, atmospheric gas, and sputtering power, so that the film has almost the same composition as the target. Can be obtained.
- the degree of vacuum reached in the chamber before film formation is 2 ⁇ 10 ⁇ 4 Pa or less. If the pressure is too high, the mobility of the obtained film may decrease due to the influence of impurities in the residual atmospheric gas.
- a mixed gas of argon and oxygen can be used as the sputtering gas.
- a gas cylinder with 100% argon and a gas cylinder with 2% oxygen in argon are used, and the supply flow rate from each gas cylinder to the chamber is appropriately set by mass flow.
- the oxygen concentration in the mixed gas means oxygen partial pressure / (oxygen partial pressure + argon partial pressure), and is equal to the oxygen flow rate divided by the sum of oxygen and argon flow rates.
- the oxygen concentration may be appropriately changed according to the desired carrier concentration, but it can typically be 1 to 3%, more typically 1 to 2%.
- the total pressure of the sputtering gas is about 0.3 to 0.8 Pa. If the total pressure is lower than this, the plasma discharge is difficult to stand up, and even if it stands, the plasma becomes unstable. On the other hand, if the total pressure is higher than this, the film formation rate becomes slow, which causes inconveniences such as adversely affecting productivity.
- the film is formed with a sputtering power of about 200 to 1200 W. If the sputtering power is too low, the film forming speed is low and the productivity is poor. Conversely, if the sputtering power is too high, problems such as cracking of the target occur. 200 ⁇ 1200 W when converted to a sputtering power density is 1.1W / cm 2 ⁇ 6.6W / cm 2, it is desirable that the 3.2 ⁇ 4.5W / cm 2.
- the sputtering power density is a value obtained by dividing the sputtering power by the area of the sputtering target, and even with the same sputtering power, the power actually received by the sputtering target varies depending on the sputtering target size, and the film formation speed differs. It is an index for uniformly expressing the power applied to the sputtering target.
- a vacuum deposition method As a method for obtaining a film from an oxide sintered body, a vacuum deposition method, an ion plating method, a PLD (pulse laser deposition) method, or the like can be used.
- This is a DC magnetron sputtering method that satisfies requirements such as film formation and discharge stability.
- the substrate there is no need to heat the substrate during sputter deposition. This is because a relatively high mobility can be obtained without heating the substrate, and it is not necessary to spend time and energy for raising the temperature.
- the resulting film becomes amorphous.
- the film since the same effect as annealing after film formation at room temperature can be expected by heating the substrate, the film may be formed by heating the substrate.
- carrier concentration of oxide film correlates with various characteristics of the transistor when the film is used for the channel layer of the transistor. If the carrier concentration is too high, a minute leakage current is generated even when the transistor is turned off, and the on / off ratio is lowered. On the other hand, if the carrier concentration is too low, the current flowing through the transistor becomes small.
- the carrier concentration of the oxide film can be set to 10 16 to 10 18 cm ⁇ 3 depending on an appropriate range of the composition and the like, and a transistor with favorable characteristics can be manufactured within this range.
- the mobility is one of the most important characteristics of the transistor, and the oxide semiconductor has a mobility of 1 cm 2 / Vs or more which is the mobility of amorphous silicon which is a competitive material used as a channel layer of the transistor. Is desirable. Basically, the higher the mobility, the better.
- the oxide film according to the present invention can have a mobility of 1 cm 2 / Vs or more, preferably a mobility of 3 cm 2 / Vs or more, more preferably 5 cm 2 depending on an appropriate range of the composition. It can have a mobility of / Vs or higher. Thereby, it becomes a characteristic superior to amorphous silicon, and industrial applicability is further increased.
- the oxide semiconductor thin film according to the present invention can be used, for example, as an active layer of a thin film transistor.
- the thin film transistor obtained by using the above manufacturing method can be used as an active element and used for an active matrix drive display panel.
- the physical properties of the sintered bodies and films were measured by the following methods.
- A Relative density of sintered body It was determined from the measurement results of weight and outer dimensions and the theoretical density from the constituent elements.
- B Bulk resistance of sintered body The bulk resistance was determined by a four probe method (JIS K7194) using a model ⁇ -5 + apparatus manufactured by NPS.
- C Composition of sintered body and film It was determined by an ICP (high frequency inductively coupled plasma) analysis method using a model SPS3000 manufactured by SII Nanotechnology.
- D Film thickness It was determined using a step meter (Veeco, Model Dektak8 STYLUS PROFILER).
- Example 1 Indium oxide (In 2 O 3 ) powder (average particle size 1.0 ⁇ m), iron oxide (Fe 2 O 3 ) powder (average particle size 1.0 ⁇ m), and zinc oxide (ZnO) powder (average particle size 1.0 ⁇ m) ) was weighed so that the atomic ratio of metal elements (In: Fe: Zn) was 0.4: 0.3: 0.3, and wet mixed and pulverized. The average particle size of the mixed powder after pulverization was 0.8 ⁇ m. After this mixed powder was granulated with a spray dryer, the mixed powder was filled in a mold, subjected to pressure molding, and then sintered in an air atmosphere at a high temperature of 1450 ° C. for 10 hours.
- the obtained sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm, and was subjected to surface grinding to obtain a sputtering target.
- the relative density was calculated from the measurement results of the weight and the external dimensions, and the theoretical density, which was 99.6%.
- the bulk resistance of the sintered body measured by the four probe method was 2.0 m ⁇ cm.
- ICP high frequency inductively coupled plasma
- the sputtering target prepared above was attached to a copper backing plate using indium as a brazing material, and was installed in a DC magnetron sputtering apparatus (APLVA SPL-500 sputtering apparatus).
- the glass substrate uses Corning 1737, and the sputtering conditions are as follows: substrate temperature: 25 ° C., ultimate pressure: 1.2 ⁇ 10 ⁇ 4 Pa, atmospheric gas: Ar 99%, oxygen 1%, sputtering pressure (total pressure): 0.
- a thin film having a thickness of about 100 nm was prepared at 5 Pa and input power of 500 W. No abnormal discharge was observed during the formation of the oxide semiconductor thin film.
- Example 2 to Example 12 An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
- the indium oxide as a supply source of In 3+ (In 2 O 3) powder (average particle size 1.0 .mu.m), iron oxide as a source of Fe 3+ (Fe 2 O 3) powder (average particle size 1.0 .mu.m ), Zinc 2+ (ZnO) powder (average particle size: 1.0 ⁇ m) as a source of Zn 2+ , (CuO) powder (average particle size: 1.0 ⁇ m) as a source of Cu 2+, and a source of Fe 2+ As an iron oxide (FeO) powder (average particle size 1.0 ⁇ m) was used.
- the oxide sintered bodies according to the examples of the present invention have a high relative density and a low bulk resistance.
- an oxide semiconductor thin film having an appropriate carrier concentration and high mobility can be obtained.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thin Film Transistor (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physical Deposition Of Substances That Are Components Of Semiconductor Devices (AREA)
Abstract
The present invention addresses the problem of providing a sintered oxide for use in producing an oxide semiconductor thin film which is free from expensive gallium (Ga) and the problem of providing an oxide semiconductor thin film having the same composition as that of the sintered oxide. A sintered oxide which consists of trivalent indium ions (In3+), trivalent iron ions (Fe3+), divalent X ions (X2+) [wherein X is at least one element selected from among Cu, Zn and Fe], and oxide ions (O2-), wherein the atomic ratios of trivalent indium ions (In3+), trivalent iron ions (Fe3+) and divalent X ions (X2+) satisfy 0.2 ≤ (In3+)/{(In3+)+(Fe3+)+(X2+)} ≤ 0.8, 0.1 ≤ (Fe3+)/{(In3+)+(Fe3+) +(X2+)} ≤ 0.5, and 0.1 ≤ (X2+)/{(In3+)+(Fe3+)+(X2+)} ≤ 0.5 respectively; and an oxide semiconductor thin film which has the same composition as that of the sintered oxide.
Description
本発明は表示装置中の薄膜トランジスタの作製に有用な酸化物焼結体及び酸化物半導体薄膜に関する。
The present invention relates to an oxide sintered body and an oxide semiconductor thin film useful for manufacturing a thin film transistor in a display device.
酸化物半導体は液晶表示装置、プラズマ表示装置及び有機EL表示装置などの表示装置中の薄膜トランジスタの活性層のほか、太陽電池及びタッチパネル等の電極として利用されている。従来、酸化物半導体としては透明なIn-Ga-Zn-O系(以降、「IGZO系」と記載)が知られており(非特許文献1参照)、更に、特性改善を意図して錫(Sn)を添加した系についての報告もある(特許文献1及び2参照)。しかし、これらの系の必須構成要素であるガリウム(Ga)は希少元素であり、価格も高い等の理由から、産業上、大量に使用するには大きな制約があった。
Oxide semiconductors are used as active layers of thin film transistors in display devices such as liquid crystal display devices, plasma display devices, and organic EL display devices, as well as electrodes for solar cells and touch panels. Conventionally, a transparent In—Ga—Zn—O-based (hereinafter referred to as “IGZO-based”) is known as an oxide semiconductor (see Non-Patent Document 1). There is also a report on a system to which Sn) is added (see Patent Documents 1 and 2). However, gallium (Ga), which is an essential component of these systems, is a rare element and has a large limitation in terms of industrial use because of its high price.
Gaを使用しない透明酸化物半導体としては、In-Zn-O系(特許文献3参照)、In-Zn-Sn-O系(特許文献4参照)、及びZn-Sn-O系(特許文献5参照)の報告がある。
As a transparent oxide semiconductor not using Ga, an In—Zn—O system (see Patent Document 3), an In—Zn—Sn—O system (see Patent Document 4), and a Zn—Sn—O system (Patent Document 5). Report).
上記特許文献3~5に記載のIGZO系代替候補材料は、IGZO系が透明半導体であることから、酸化物として透明な元素の材料系にのみ、絞られてきたのが実情である。しかしながら、IGZO系は、トランジスタのチャネル層として使用され、必ずしも透明性が必要とされていない場合が殆どである。従って、透明ではないが、トランジスタのチャネル層として使用可能な材料系については、これまでIGZO代替材料として検討がなされてこなかった。
The IGZO-based alternative candidate materials described in Patent Documents 3 to 5 above have been limited to only the material system of elements that are transparent as oxides because the IGZO-based material is a transparent semiconductor. However, the IGZO system is used as a channel layer of a transistor, and in most cases, transparency is not necessarily required. Therefore, a material system that is not transparent but can be used as a channel layer of a transistor has not been studied as an alternative material for IGZO.
そこで、本発明は、希少資源であり、高価なガリウム(Ga)を含有しない酸化物半導体膜製造用の酸化物焼結体を提供することを課題とする。また、本発明は当該酸化物焼結体と同一組成をもつ酸化物半導体薄膜を提供することを別の課題とする。
Therefore, an object of the present invention is to provide an oxide sintered body for manufacturing an oxide semiconductor film which is a scarce resource and does not contain expensive gallium (Ga). Another object of the present invention is to provide an oxide semiconductor thin film having the same composition as the oxide sintered body.
本発明は一側面において、3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とからなる酸化物焼結体であって、3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、2価のXイオン(X2+)の原子数比が、0.2≦(In3+)/{(In3+)+(Fe3+)+(X2+)}≦0.8、0.1≦(Fe3+)/{(In3+)+(Fe3+)+(X2+)}≦0.5、0.1≦(X2+)/{(In3+)+(Fe3+)+(X2+)}≦0.5を満たす酸化物焼結体である。
In one aspect of the present invention, trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and divalent X ions (X 2+ ) (where X is Cu, Zn, And an oxide sintered body composed of oxygen ions (O 2− ) and trivalent indium ions (In 3+ ), The atomic ratio of iron ions (Fe 3+ ) and divalent X ions (X 2+ ) is 0.2 ≦ (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2 + )} ≦ 0.8, 0.1 ≦ (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5, 0.1 ≦ (X 2+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5.
本発明に係る酸化物焼結体は一実施形態において、相対密度が98%以上である。
In one embodiment, the oxide sintered body according to the present invention has a relative density of 98% or more.
本発明に係る酸化物焼結体は別の一実施形態において、バルク抵抗が3mΩ以下である。
In another embodiment, the oxide sintered body according to the present invention has a bulk resistance of 3 mΩ or less.
本発明は別の一側面において、3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とからなる酸化物半導体薄膜であって、3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、及び2価のXイオン(X2+)の原子数比がそれぞれ、0.2≦(In3+)/{(In3+)+(Fe3+)+(X2+)}≦0.8、0.1≦(Fe3+)/{(In3+)+(Fe3+)+(X2+)}≦0.5、及び0.1≦(X2+)/{(In3+)+(Fe3+)+(X2+)}≦0.5を満たす酸化物半導体薄膜である。
In another aspect of the present invention, a trivalent indium ion (In 3+ ), a trivalent iron ion (Fe 3+ ), and a divalent X ion (X 2+ ) (where X is Cu, An oxide semiconductor thin film composed of oxygen ions (O 2− ) and trivalent indium ions (In 3+ ), trivalent. The atomic ratio of iron ions (Fe 3+ ) and divalent X ions (X 2+ ) is 0.2 ≦ (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.8, 0.1 ≦ (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5, and 0.1 ≦ The oxide semiconductor thin film satisfies (X 2+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5.
本発明に係る酸化物半導体薄膜は一実施形態において、非晶質である。
In one embodiment, the oxide semiconductor thin film according to the present invention is amorphous.
本発明に係る酸化物半導体薄膜は別の一実施形態において、キャリア濃度が1016~1018cm-3である。
In another embodiment, the oxide semiconductor thin film according to the present invention has a carrier concentration of 10 16 to 10 18 cm −3 .
本発明に係る酸化物半導体薄膜は更に別の一実施形態において、移動度が1cm2/Vs以上である。
In still another embodiment, the oxide semiconductor thin film according to the present invention has a mobility of 1 cm 2 / Vs or more.
本発明は更に別の一側面において、上記酸化物半導体薄膜を活性層として備えた薄膜トランジスタである。
In still another aspect, the present invention is a thin film transistor including the oxide semiconductor thin film as an active layer.
本発明は更に別の一側面において、上記薄膜トランジスタを備えたアクティブマトリックス駆動表示パネルである。
In still another aspect, the present invention is an active matrix drive display panel including the thin film transistor.
本発明によればガリウム(Ga)を含有しない酸化物半導体膜製造用の酸化物焼結体を提供することができる。本酸化物焼結体はスパッタリングターゲットとして有用である。本ターゲットを用いてスパッタ成膜することにより、酸化物半導体膜を作製することができる。
According to the present invention, an oxide sintered body for producing an oxide semiconductor film that does not contain gallium (Ga) can be provided. This oxide sintered body is useful as a sputtering target. An oxide semiconductor film can be formed by sputtering using this target.
(酸化物焼結体の組成)
本発明に係る酸化物焼結体は、3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とから構成される。但し、通常入手可能な原料の精製工程上、不可避的に含まれてくる元素や、酸化物焼結体製造プロセス上不可避的に混入する不純物元素を、不可避的に含まれる濃度程度、例えば各元素10ppm程度まで含むものは本発明に係る焼結体に包含される。 (Composition of oxide sinter)
The oxide sintered body according to the present invention includes a trivalent indium ion (In 3+ ), a trivalent iron ion (Fe 3+ ), and a divalent X ion (X 2+ ) (where X is It represents one or more elements selected from Cu, Zn, and Fe.) And oxygen ions (O 2− ). However, elements that are inevitably included in the purification process of raw materials that are usually available, and impurity elements that are inevitably mixed in the oxide sintered body manufacturing process, are inevitably contained at a concentration, for example, each element. What contains about 10 ppm is included in the sintered compact which concerns on this invention.
本発明に係る酸化物焼結体は、3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とから構成される。但し、通常入手可能な原料の精製工程上、不可避的に含まれてくる元素や、酸化物焼結体製造プロセス上不可避的に混入する不純物元素を、不可避的に含まれる濃度程度、例えば各元素10ppm程度まで含むものは本発明に係る焼結体に包含される。 (Composition of oxide sinter)
The oxide sintered body according to the present invention includes a trivalent indium ion (In 3+ ), a trivalent iron ion (Fe 3+ ), and a divalent X ion (X 2+ ) (where X is It represents one or more elements selected from Cu, Zn, and Fe.) And oxygen ions (O 2− ). However, elements that are inevitably included in the purification process of raw materials that are usually available, and impurity elements that are inevitably mixed in the oxide sintered body manufacturing process, are inevitably contained at a concentration, for example, each element. What contains about 10 ppm is included in the sintered compact which concerns on this invention.
3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、及び2価のXイオン(X2+)の合計原子数に対する3価のインジウムイオン(In3+)の原子数の比(In3+)/{(In3+)+(Fe3+)+(X2+)}は0.2~0.8であることが望ましい。(In3+)/{(In3+)+(Fe3+)+(X2+)}が0.2未満であると、膜のキャリア濃度が小さくなりすぎてしまい、ターゲット作製時の相対密度が小さくなり、バルク抵抗が高くなって、スパッタ時の異常放電が発生し易くなってしまう。逆に、(In3+)/{(In3+)+(Fe3+)+(X2+)}が0.8を超えると、その組成のターゲットをスパッタして得られる膜のキャリア濃度が高くなりすぎてしまい、トランジスタのチャネル層としてはオンオフ比が小さくなってしまう。(In3+)/{(In3+)+(Fe3+)+(X2+)}は、より望ましくは0.25~0.6の範囲であり、更に望ましくは0.3~0.5の範囲である。
Atoms of trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and trivalent indium ions (In 3+ ) with respect to the total number of atoms of divalent X ions (X 2+ ) The number ratio (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is preferably 0.2 to 0.8. If (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is less than 0.2, the carrier concentration of the film becomes too small, and the relative value during target fabrication Density decreases, bulk resistance increases, and abnormal discharge during sputtering is likely to occur. Conversely, when (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} exceeds 0.8, the carrier concentration of the film obtained by sputtering the target having that composition Becomes too high, and the on / off ratio of the channel layer of the transistor becomes small. (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is more preferably in the range of 0.25 to 0.6, more preferably 0.3 to 0. .5 range.
3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、及び2価のXイオン(X2+)の合計原子数に対する3価の鉄イオン(Fe3+)の原子数の比(Fe3+)/{(In3+)+(Fe3+)+(X2+)}は0.1~0.5であることが望ましい(Fe3+)/{(In3+)+(Fe3+)+(X2+)}が0.1未満であると、その組成のターゲットをスパッタして得られる膜のキャリア濃度が高くなりすぎてしまい、トランジスタのチャネル層としてはオンオフ比が小さくなってしまう。逆に、(Fe3+)/{(In3+)+(Fe3+)+(X2+)}が0.5を超えると、膜のキャリア濃度が小さくなりすぎてしまい、ターゲット作製時の相対密度が小さくなり、バルク抵抗が高くなって、スパッタ時の異常放電が発生し易くなってしまう。(Fe3+)/{(In3+)+(Fe3+)+(X2+)}は、より望ましくは0.15~0.4の範囲であり、更に望ましくは0.2~0.35の範囲である。
Atoms of trivalent iron ions (Fe 3+ ) relative to the total number of trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and divalent X ions (X 2+ ) The ratio of numbers (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is preferably 0.1 to 0.5 (Fe 3+ ) / {(In 3 + ) + (Fe 3+ ) + (X 2+ )} is less than 0.1, the carrier concentration of the film obtained by sputtering the target having that composition becomes too high, and the channel layer of the transistor As a result, the on / off ratio becomes small. Conversely, if (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} exceeds 0.5, the carrier concentration of the film becomes too small, and the target is produced. The relative density of the metal becomes small, the bulk resistance becomes high, and abnormal discharge during sputtering is likely to occur. (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is more preferably in the range of 0.15 to 0.4, and more preferably 0.2 to 0. .35 range.
3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、及び2価のXイオン(X2+)の合計原子数に対する金属元素Xの合計の原子数の比(X2+)/{(In3+)+(Fe3+)+(X2+)}は0.1~0.5であることが望ましい。(X2+)/{(In3+)+(Fe3+)+(X2+)}が0.1未満であると、膜のキャリア濃度が大きくなりすぎてしまう。逆に、(X2+)/{(In3+)+(Fe3+)+(X2+)}が0.5を超えると、膜のキャリア濃度が小さくなりすぎてしまい、ターゲット作製時の相対密度が小さくなってしまう。(X2+)/{(In3+)+(Fe3+)+(X2+)}は、より望ましくは0.15~0.4の範囲であり、更に望ましくは0.2~0.35の範囲である。
Ratio of total number of atoms of metal element X to total number of trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), and divalent X ions (X 2+ ) (X 2 + ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is preferably 0.1 to 0.5. If (X 2+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is less than 0.1, the carrier concentration of the film becomes too large. On the other hand, if (X 2+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} exceeds 0.5, the carrier concentration of the film becomes too small and the target is produced. The relative density of becomes small. (X 2+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} is more preferably in the range of 0.15 to 0.4, more preferably 0.2 to 0. .35 range.
2価のXイオンとして鉄イオン(Fe2+)を選択した場合、金属イオンの種類としては、インジウムと鉄のみとなる。しかしながら、鉄イオンについては、2価及び3価の種類があり、酸化物焼結体中に存在することになる。鉄は遷移金属であり、複数の価数を取ることができ、ある化合物中にも価数の異なる鉄イオンが存在することがある。本発明の好ましい実施形態では、予め、鉄イオンの価数を制御して化合物を形成する。このことによって、所望の特性をより容易に得ることができるのである。
When iron ions (Fe 2+ ) are selected as the divalent X ions, the only types of metal ions are indium and iron. However, there are divalent and trivalent types of iron ions, which are present in the oxide sintered body. Iron is a transition metal and can take a plurality of valences, and iron ions having different valences may exist in a certain compound. In a preferred embodiment of the present invention, the compound is formed in advance by controlling the valence of iron ions. Thus, desired characteristics can be obtained more easily.
(酸化物焼結体の相対密度)
酸化物焼結体の相対密度は、スパッタ時の表面のジュール発生と相関があり、酸化物焼結体が低密度であると、その酸化物焼結体をターゲットに加工してスパッタ成膜する際に、スパッタの成膜の経過に従って、表面にインジウムの低級酸化物である、突起状のノジュールと呼ばれる高抵抗部分が発生してきて、その後のスパッタ時に異常放電の起点となり易い。本発明では、組成の適正範囲の適正化によって酸化物焼結体の相対密度を98%以上とすることができ、この程度の高密度であれば、スパッタ時のノジュールによる悪影響は殆どない。相対密度は好ましくは99%以上であり、より好ましくは99.5%以上である。
なお、酸化物焼結体の相対密度は、酸化物焼結体を所定の形状に加工した後の重量と外形寸法より算出した密度を、その酸化物焼結体の理論密度で除することで求めることができる。 (Relative density of sintered oxide)
The relative density of the oxide sintered body correlates with the generation of joules on the surface during sputtering. If the oxide sintered body has a low density, the oxide sintered body is processed into a target to form a sputter film. At the same time, a high-resistance portion called a protruding nodule, which is a lower oxide of indium, is generated on the surface as the film formation of the sputtering is performed, and it tends to be a starting point of abnormal discharge during the subsequent sputtering. In the present invention, the relative density of the oxide sintered body can be set to 98% or more by optimizing the appropriate range of the composition, and if this density is high, there is almost no adverse effect due to nodules during sputtering. The relative density is preferably 99% or more, more preferably 99.5% or more.
The relative density of the oxide sintered body is obtained by dividing the density calculated from the weight and outer dimensions after processing the oxide sintered body into a predetermined shape by the theoretical density of the oxide sintered body. Can be sought.
酸化物焼結体の相対密度は、スパッタ時の表面のジュール発生と相関があり、酸化物焼結体が低密度であると、その酸化物焼結体をターゲットに加工してスパッタ成膜する際に、スパッタの成膜の経過に従って、表面にインジウムの低級酸化物である、突起状のノジュールと呼ばれる高抵抗部分が発生してきて、その後のスパッタ時に異常放電の起点となり易い。本発明では、組成の適正範囲の適正化によって酸化物焼結体の相対密度を98%以上とすることができ、この程度の高密度であれば、スパッタ時のノジュールによる悪影響は殆どない。相対密度は好ましくは99%以上であり、より好ましくは99.5%以上である。
なお、酸化物焼結体の相対密度は、酸化物焼結体を所定の形状に加工した後の重量と外形寸法より算出した密度を、その酸化物焼結体の理論密度で除することで求めることができる。 (Relative density of sintered oxide)
The relative density of the oxide sintered body correlates with the generation of joules on the surface during sputtering. If the oxide sintered body has a low density, the oxide sintered body is processed into a target to form a sputter film. At the same time, a high-resistance portion called a protruding nodule, which is a lower oxide of indium, is generated on the surface as the film formation of the sputtering is performed, and it tends to be a starting point of abnormal discharge during the subsequent sputtering. In the present invention, the relative density of the oxide sintered body can be set to 98% or more by optimizing the appropriate range of the composition, and if this density is high, there is almost no adverse effect due to nodules during sputtering. The relative density is preferably 99% or more, more preferably 99.5% or more.
The relative density of the oxide sintered body is obtained by dividing the density calculated from the weight and outer dimensions after processing the oxide sintered body into a predetermined shape by the theoretical density of the oxide sintered body. Can be sought.
(酸化物焼結体のバルク抵抗)
酸化物焼結体のバルク抵抗は、スパッタ時の異常放電の発生のし易さと相関があり、バルク抵抗が高いとスパッタ時に異常放電が発生し易い。本発明では、組成の適正範囲や製造条件の適正化によってバルク抵抗を3mΩcm以下とすることができ、この程度の低バルク抵抗であれば、スパッタ時の異常放電発生への悪影響は殆どない。バルク抵抗は好ましくは2.7mΩcm以下であり、より好ましくは2.5mΩcm以下である。
なお、バルク抵抗は四探針法により抵抗率計を使用して測定することができる。 (Bulk resistance of sintered oxide)
The bulk resistance of the oxide sintered body has a correlation with the ease of occurrence of abnormal discharge during sputtering, and when the bulk resistance is high, abnormal discharge is likely to occur during sputtering. In the present invention, the bulk resistance can be reduced to 3 mΩcm or less by optimizing the appropriate range of the composition and the manufacturing conditions. With such a low bulk resistance, there is almost no adverse effect on the occurrence of abnormal discharge during sputtering. The bulk resistance is preferably 2.7 mΩcm or less, more preferably 2.5 mΩcm or less.
Bulk resistance can be measured using a resistivity meter by the four-probe method.
酸化物焼結体のバルク抵抗は、スパッタ時の異常放電の発生のし易さと相関があり、バルク抵抗が高いとスパッタ時に異常放電が発生し易い。本発明では、組成の適正範囲や製造条件の適正化によってバルク抵抗を3mΩcm以下とすることができ、この程度の低バルク抵抗であれば、スパッタ時の異常放電発生への悪影響は殆どない。バルク抵抗は好ましくは2.7mΩcm以下であり、より好ましくは2.5mΩcm以下である。
なお、バルク抵抗は四探針法により抵抗率計を使用して測定することができる。 (Bulk resistance of sintered oxide)
The bulk resistance of the oxide sintered body has a correlation with the ease of occurrence of abnormal discharge during sputtering, and when the bulk resistance is high, abnormal discharge is likely to occur during sputtering. In the present invention, the bulk resistance can be reduced to 3 mΩcm or less by optimizing the appropriate range of the composition and the manufacturing conditions. With such a low bulk resistance, there is almost no adverse effect on the occurrence of abnormal discharge during sputtering. The bulk resistance is preferably 2.7 mΩcm or less, more preferably 2.5 mΩcm or less.
Bulk resistance can be measured using a resistivity meter by the four-probe method.
(酸化物焼結体の製造方法)
本発明に係る各種組成の酸化物焼結体は、例えば、原料である酸化インジウム(In2O3)、酸化鉄(3価鉄の供給源としてFe2O3、2価鉄の供給源としてFeO)、酸化亜鉛(ZnO)、酸化銅(CuO)等の各原料粉体の配合比や原料粉体の粒径、粉砕時間、焼結温度、焼結時間、焼結雰囲気ガス種類等の条件を調整することにより得ることができる。 (Oxide sintered body manufacturing method)
The oxide sintered body having various compositions according to the present invention includes, for example, raw materials such as indium oxide (In 2 O 3 ), iron oxide (Fe 2 O 3 as a supply source of trivalent iron, and a supply source of divalent iron. Conditions such as mixing ratio of raw material powders such as FeO), zinc oxide (ZnO), copper oxide (CuO), particle size of raw material powder, pulverization time, sintering temperature, sintering time, kind of sintering atmosphere gas, etc. Can be obtained by adjusting.
本発明に係る各種組成の酸化物焼結体は、例えば、原料である酸化インジウム(In2O3)、酸化鉄(3価鉄の供給源としてFe2O3、2価鉄の供給源としてFeO)、酸化亜鉛(ZnO)、酸化銅(CuO)等の各原料粉体の配合比や原料粉体の粒径、粉砕時間、焼結温度、焼結時間、焼結雰囲気ガス種類等の条件を調整することにより得ることができる。 (Oxide sintered body manufacturing method)
The oxide sintered body having various compositions according to the present invention includes, for example, raw materials such as indium oxide (In 2 O 3 ), iron oxide (Fe 2 O 3 as a supply source of trivalent iron, and a supply source of divalent iron. Conditions such as mixing ratio of raw material powders such as FeO), zinc oxide (ZnO), copper oxide (CuO), particle size of raw material powder, pulverization time, sintering temperature, sintering time, kind of sintering atmosphere gas, etc. Can be obtained by adjusting.
原料粉は平均粒径1~2μmであることが望ましい。平均粒径が2μmを超えると、焼結体の密度が向上し難くなるため、その原料粉単独又は混合粉として湿式微粉砕等を行って、平均粒径を約1μm程度に小さくすると良い。湿式混合粉砕前に焼結性の向上を目的として、仮焼することも有効である。一方、1μm未満の原料は入手し難く、また、あまり小さいと粒子間の凝集が起き易くなって扱い難くなるので、焼結前の混合粉の平均粒径は1~2μmが好ましい。ここで、原料粉の平均粒径はレーザ回折式粒度分布測定装置によって測定した体積分布におけるメディアン径を指す。なお、本発明の均等と解釈できる範囲で、所定の原料粉の外に焼結体特性に悪影響を及ぼさず、焼結性を向上させる等の効果を有する他の成分を添加しても良い。粉砕後の原料混合粉をスプレードライヤー等で造粒して流動性や成形性を高めた後に成型するのが好ましい。成型は通常の加圧成形や冷間静水圧加圧等の方法を採用することができる。
The raw material powder preferably has an average particle size of 1 to 2 μm. When the average particle diameter exceeds 2 μm, the density of the sintered body is difficult to improve. Therefore, wet pulverization or the like is performed as the raw material powder alone or as a mixed powder, and the average particle diameter is preferably reduced to about 1 μm. For the purpose of improving the sinterability before wet mixing and pulverization, it is also effective to perform calcination. On the other hand, raw materials having a particle size of less than 1 μm are difficult to obtain, and if the particle size is too small, agglomeration between particles tends to occur and handling becomes difficult. Here, the average particle diameter of the raw material powder refers to the median diameter in the volume distribution measured by a laser diffraction particle size distribution measuring apparatus. In addition, within the range which can be interpreted as equivalent to this invention, you may add the other component which has the effect of improving a sinterability etc. without having a bad influence on a sintered compact characteristic besides a predetermined raw material powder | flour. It is preferable to mold the pulverized raw material mixed powder after granulating it with a spray dryer or the like to improve fluidity and moldability. For molding, a method such as normal pressure molding or cold isostatic pressing can be employed.
その後、成形物を焼結して焼結体を得る。焼結は、1400~1600℃で2~20時間焼結することが好ましい。これにより、相対密度を98%以上とすることができる。焼結温度が1400℃未満では、密度が向上し難く、逆に、焼結温度が1600℃を超えると、構成成分元素の揮発等により、焼結体の組成が変化したり、揮発による空隙発生による密度低下の原因となったりする。焼結時の雰囲気ガスには、大気を用いることができ、焼結体への酸素欠損量を増加させて、バルク抵抗を小さくすることができる。但し、焼結体の組成によっては、雰囲気ガスを酸素としても充分高密度の焼結体を得ることもできる。
Thereafter, the molded product is sintered to obtain a sintered body. The sintering is preferably performed at 1400 to 1600 ° C. for 2 to 20 hours. Thereby, a relative density can be 98% or more. If the sintering temperature is less than 1400 ° C., the density is difficult to improve. Conversely, if the sintering temperature exceeds 1600 ° C., the composition of the sintered body changes due to volatilization of the constituent elements, and voids are generated due to volatilization. May cause a decrease in density. Air can be used as the atmosphere gas during sintering, and the amount of oxygen vacancies in the sintered body can be increased to reduce the bulk resistance. However, depending on the composition of the sintered body, a sufficiently high density sintered body can be obtained even if the atmospheric gas is oxygen.
(スパッタ成膜)
上記の様にして得られた酸化物焼結体は、研削や研磨等の加工を施すことによりスパッタリング用ターゲットとすることができ、これを使用して成膜することにより、当該ターゲットと同一組成をもつ酸化物膜を形成することができる。加工の際は、平面研削等の方法で表面を研削することによって、表面粗さ(Ra)を5μm以下とすることが望ましい。表面粗さを小さくすることによって、異常放電の原因となるノジュール発生の起点を減少させることができる。 (Sputter deposition)
The oxide sintered body obtained as described above can be used as a sputtering target by performing processing such as grinding and polishing, and by using this film, the same composition as that of the target can be obtained. It is possible to form an oxide film having At the time of processing, it is desirable that the surface roughness (Ra) be 5 μm or less by grinding the surface by a method such as surface grinding. By reducing the surface roughness, the starting point of nodule generation that causes abnormal discharge can be reduced.
上記の様にして得られた酸化物焼結体は、研削や研磨等の加工を施すことによりスパッタリング用ターゲットとすることができ、これを使用して成膜することにより、当該ターゲットと同一組成をもつ酸化物膜を形成することができる。加工の際は、平面研削等の方法で表面を研削することによって、表面粗さ(Ra)を5μm以下とすることが望ましい。表面粗さを小さくすることによって、異常放電の原因となるノジュール発生の起点を減少させることができる。 (Sputter deposition)
The oxide sintered body obtained as described above can be used as a sputtering target by performing processing such as grinding and polishing, and by using this film, the same composition as that of the target can be obtained. It is possible to form an oxide film having At the time of processing, it is desirable that the surface roughness (Ra) be 5 μm or less by grinding the surface by a method such as surface grinding. By reducing the surface roughness, the starting point of nodule generation that causes abnormal discharge can be reduced.
スパッタリング用ターゲットは、銅製等のバッキングプレートに貼り付けて、スパッタ装置内に設置して、適切な真空度、雰囲気ガス、スパッタパワー等の適切条件でスパッタすることで、ターゲットとほぼ同組成の膜を得ることができる。
The sputtering target is affixed to a backing plate made of copper or the like, placed in a sputtering apparatus, and sputtered under appropriate conditions such as an appropriate degree of vacuum, atmospheric gas, and sputtering power, so that the film has almost the same composition as the target. Can be obtained.
スパッタ法の場合、成膜前のチャンバー内到達真空度を、2×10-4Pa以下とするのが望ましい。圧力が高すぎると、残留雰囲気ガス中の不純物の影響によって、得られた膜の移動度が低下する可能性がある。
In the case of sputtering, it is desirable that the degree of vacuum reached in the chamber before film formation is 2 × 10 −4 Pa or less. If the pressure is too high, the mobility of the obtained film may decrease due to the influence of impurities in the residual atmospheric gas.
スパッタガスとして、アルゴン及び酸素の混合ガスを使用することができる。混合ガス中の酸素濃度を調整する方法としては、例えば、アルゴン100%のガスボンベと、アルゴン中の酸素が2%のガスボンベを用いて、それぞれのガスボンベからチャンバーへの供給流量をマスフローで適宜設定することで行うことができる。ここで、混合ガス中の酸素濃度とは、酸素分圧/(酸素分圧+アルゴン分圧)を意味するものであり、酸素の流量を酸素とアルゴンの流量の合計で除したものとも等しい。酸素濃度は所望のキャリア濃度に応じて適宜変更すればよいが、典型的には1~3%とすることができ、より典型的には1~2%とすることができる。
A mixed gas of argon and oxygen can be used as the sputtering gas. As a method for adjusting the oxygen concentration in the mixed gas, for example, a gas cylinder with 100% argon and a gas cylinder with 2% oxygen in argon are used, and the supply flow rate from each gas cylinder to the chamber is appropriately set by mass flow. Can be done. Here, the oxygen concentration in the mixed gas means oxygen partial pressure / (oxygen partial pressure + argon partial pressure), and is equal to the oxygen flow rate divided by the sum of oxygen and argon flow rates. The oxygen concentration may be appropriately changed according to the desired carrier concentration, but it can typically be 1 to 3%, more typically 1 to 2%.
スパッタガスの全圧は0.3~0.8Pa程度とする。全圧がこれより低いと、プラズマ放電が立ち難くなり、立ったとしてもプラズマが不安定となってしまう。また、全圧がこれより高いと、成膜速度が遅くなり、生産性に悪影響を及ぼす等の不都合が生じる。
The total pressure of the sputtering gas is about 0.3 to 0.8 Pa. If the total pressure is lower than this, the plasma discharge is difficult to stand up, and even if it stands, the plasma becomes unstable. On the other hand, if the total pressure is higher than this, the film formation rate becomes slow, which causes inconveniences such as adversely affecting productivity.
スパッタパワーは、ターゲットサイズが6インチの場合、200~1200W程度で成膜する。スパッタパワーが小さすぎると、成膜速度が小さく、生産性に劣るし、逆に、大き過ぎると、ターゲットの割れ等の問題が生ずる。200~1200Wは、スパッタパワー密度に換算すると、1.1W/cm2~6.6W/cm2であり、3.2~4.5W/cm2とすることが望ましい。ここで、スパッタパワー密度とは、スパッタパワーをスパッタリングターゲットの面積で除したものであり、同じスパッタパワーでもスパッタリングターゲットサイズによって、スパッタリングターゲットが実際に受けるパワーが異なり、成膜速度が異なることから、スパッタリングターゲットに印加するパワーを統一的に表現するための指標である。
When the target size is 6 inches, the film is formed with a sputtering power of about 200 to 1200 W. If the sputtering power is too low, the film forming speed is low and the productivity is poor. Conversely, if the sputtering power is too high, problems such as cracking of the target occur. 200 ~ 1200 W when converted to a sputtering power density is 1.1W / cm 2 ~ 6.6W / cm 2, it is desirable that the 3.2 ~ 4.5W / cm 2. Here, the sputtering power density is a value obtained by dividing the sputtering power by the area of the sputtering target, and even with the same sputtering power, the power actually received by the sputtering target varies depending on the sputtering target size, and the film formation speed differs. It is an index for uniformly expressing the power applied to the sputtering target.
酸化物焼結体から膜を得る方法としては、真空蒸着法、イオンプレーティング法、PLD(パルスレーザーディポジション)法等も用いることもできるが、産業上利用し易いのは、大面積、高速成膜、放電安定性等の要件を満たすDCマグネトロンスパッタ法である。
As a method for obtaining a film from an oxide sintered body, a vacuum deposition method, an ion plating method, a PLD (pulse laser deposition) method, or the like can be used. This is a DC magnetron sputtering method that satisfies requirements such as film formation and discharge stability.
スパッタ成膜時には、基板を加熱する必要がない。基板を加熱せずとも、比較的高移動度を得ることができるためであり、また、昇温のための時間やエネルギーを掛ける必要がない。基板を加熱することなくスパッタ成膜すると、得られる膜は非晶質となる。但し、基板を加熱することで、室温成膜後のアニールと同様の効果を得ることも期待できるので、基板加熱で成膜しても良い。
There is no need to heat the substrate during sputter deposition. This is because a relatively high mobility can be obtained without heating the substrate, and it is not necessary to spend time and energy for raising the temperature. When sputter deposition is performed without heating the substrate, the resulting film becomes amorphous. However, since the same effect as annealing after film formation at room temperature can be expected by heating the substrate, the film may be formed by heating the substrate.
(酸化物膜のキャリア濃度)
酸化物膜のキャリア濃度は、その膜をトランジスタのチャネル層に使用した際に、トランジスタの各種特性と相関がある。キャリア濃度が高すぎると、トランジスタのオフ時にも、微少漏れ電流が発生してしまい、オンオフ比が低下してしまう。一方、キャリア濃度が低すぎると、トランジスタを流れる電流が小さくなってしまう。本発明では、組成の適正範囲等によって、酸化物膜のキャリア濃度を1016~1018cm-3とすることができ、この範囲であれば、特性が良好なトランジスタを作製することができる。 (Carrier concentration of oxide film)
The carrier concentration of the oxide film correlates with various characteristics of the transistor when the film is used for the channel layer of the transistor. If the carrier concentration is too high, a minute leakage current is generated even when the transistor is turned off, and the on / off ratio is lowered. On the other hand, if the carrier concentration is too low, the current flowing through the transistor becomes small. In the present invention, the carrier concentration of the oxide film can be set to 10 16 to 10 18 cm −3 depending on an appropriate range of the composition and the like, and a transistor with favorable characteristics can be manufactured within this range.
酸化物膜のキャリア濃度は、その膜をトランジスタのチャネル層に使用した際に、トランジスタの各種特性と相関がある。キャリア濃度が高すぎると、トランジスタのオフ時にも、微少漏れ電流が発生してしまい、オンオフ比が低下してしまう。一方、キャリア濃度が低すぎると、トランジスタを流れる電流が小さくなってしまう。本発明では、組成の適正範囲等によって、酸化物膜のキャリア濃度を1016~1018cm-3とすることができ、この範囲であれば、特性が良好なトランジスタを作製することができる。 (Carrier concentration of oxide film)
The carrier concentration of the oxide film correlates with various characteristics of the transistor when the film is used for the channel layer of the transistor. If the carrier concentration is too high, a minute leakage current is generated even when the transistor is turned off, and the on / off ratio is lowered. On the other hand, if the carrier concentration is too low, the current flowing through the transistor becomes small. In the present invention, the carrier concentration of the oxide film can be set to 10 16 to 10 18 cm −3 depending on an appropriate range of the composition and the like, and a transistor with favorable characteristics can be manufactured within this range.
(酸化物膜の移動度)
移動度はトランジスタの特性の中でも、最も重要な特性の一つであり、酸化物半導体がトランジスタのチャネル層として使用される競合材料であるアモルファスシリコンの移動度である1cm2/Vs以上であることが望ましい。移動度は基本的には、高ければ高いほど良い。本発明に係る酸化物膜は組成の適正範囲等によって、1cm2/Vs以上の移動度を有することができ、好ましくは3cm2/Vs以上の移動度を有することができ、より好ましくは5cm2/Vs以上の移動度を有することができる。これによって、アモルファスシリコンより優れた特性となって、産業上の応用可能性がより高まる。 (Mobility of oxide film)
The mobility is one of the most important characteristics of the transistor, and the oxide semiconductor has a mobility of 1 cm 2 / Vs or more which is the mobility of amorphous silicon which is a competitive material used as a channel layer of the transistor. Is desirable. Basically, the higher the mobility, the better. The oxide film according to the present invention can have a mobility of 1 cm 2 / Vs or more, preferably a mobility of 3 cm 2 / Vs or more, more preferably 5 cm 2 depending on an appropriate range of the composition. It can have a mobility of / Vs or higher. Thereby, it becomes a characteristic superior to amorphous silicon, and industrial applicability is further increased.
移動度はトランジスタの特性の中でも、最も重要な特性の一つであり、酸化物半導体がトランジスタのチャネル層として使用される競合材料であるアモルファスシリコンの移動度である1cm2/Vs以上であることが望ましい。移動度は基本的には、高ければ高いほど良い。本発明に係る酸化物膜は組成の適正範囲等によって、1cm2/Vs以上の移動度を有することができ、好ましくは3cm2/Vs以上の移動度を有することができ、より好ましくは5cm2/Vs以上の移動度を有することができる。これによって、アモルファスシリコンより優れた特性となって、産業上の応用可能性がより高まる。 (Mobility of oxide film)
The mobility is one of the most important characteristics of the transistor, and the oxide semiconductor has a mobility of 1 cm 2 / Vs or more which is the mobility of amorphous silicon which is a competitive material used as a channel layer of the transistor. Is desirable. Basically, the higher the mobility, the better. The oxide film according to the present invention can have a mobility of 1 cm 2 / Vs or more, preferably a mobility of 3 cm 2 / Vs or more, more preferably 5 cm 2 depending on an appropriate range of the composition. It can have a mobility of / Vs or higher. Thereby, it becomes a characteristic superior to amorphous silicon, and industrial applicability is further increased.
本発明に係る酸化物半導体薄膜は例えば薄膜トランジスタの活性層として使用することができる。また、上記製造方法を使用して得られた薄膜トランジスタをアクティブ素子として使用し、アクティブマトリックス駆動表示パネルに利用することができる。
The oxide semiconductor thin film according to the present invention can be used, for example, as an active layer of a thin film transistor. In addition, the thin film transistor obtained by using the above manufacturing method can be used as an active element and used for an active matrix drive display panel.
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。従って、本発明は、本発明の技術思想の範囲内で、実施例以外の態様あるいは変形を全て包含するものである。
EXAMPLES Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention. Accordingly, the present invention encompasses all aspects or modifications other than the examples within the scope of the technical idea of the present invention.
下記の実施例及び比較例において、焼結体及び膜の物性は以下の方法によって測定した。
(ア)焼結体の相対密度
重量及び外形寸法の測定結果と、構成元素からの理論密度とにより求めた。
(イ)焼結体のバルク抵抗
四探針法(JIS K7194)により、NPS(エヌピイエス)社製型式Σ-5+装置を用いて求めた。
(ウ)焼結体及び膜の組成
SIIナノテクノロジー社製型式SPS3000を用いてICP(高周波誘導結合プラズマ)分析法によって求めた。
(エ)膜厚
段差計(Veeco社製、型式Dektak8 STYLUS PROFILER)を用いて求めた。
(オ)膜のキャリア濃度及び移動度
成膜したガラス基板を約10mm角に切り出し、四隅にインジウム電極をつけて、ホール測定装置(東陽テクニカ社製、型式Resitest8200)にセットして測定した。
(カ)膜の結晶又は非晶質構造
リガク社製RINT-1100X線回折装置を用いて結晶性を判定した。バックグランドレベル以上の有意なピークが認められない場合、非晶質と判断した。
(キ)粉体の平均粒径
島津製作所製SALD-3100で平均粒径を測定した。 In the following Examples and Comparative Examples, the physical properties of the sintered bodies and films were measured by the following methods.
(A) Relative density of sintered body It was determined from the measurement results of weight and outer dimensions and the theoretical density from the constituent elements.
(B) Bulk resistance of sintered body The bulk resistance was determined by a four probe method (JIS K7194) using a model Σ-5 + apparatus manufactured by NPS.
(C) Composition of sintered body and film It was determined by an ICP (high frequency inductively coupled plasma) analysis method using a model SPS3000 manufactured by SII Nanotechnology.
(D) Film thickness It was determined using a step meter (Veeco, Model Dektak8 STYLUS PROFILER).
(E) Carrier concentration and mobility of film The formed glass substrate was cut into about 10 mm square, indium electrodes were attached to the four corners, and the measurement was carried out by setting in a Hall measuring device (manufactured by Toyo Technica, Model Reset 8200).
(F) Crystal or amorphous structure of film Crystallinity was determined using a RINT-1100 X-ray diffractometer manufactured by Rigaku Corporation. When no significant peak above the background level was observed, it was judged as amorphous.
(G) Average particle diameter of powder The average particle diameter was measured with SALD-3100 manufactured by Shimadzu Corporation.
(ア)焼結体の相対密度
重量及び外形寸法の測定結果と、構成元素からの理論密度とにより求めた。
(イ)焼結体のバルク抵抗
四探針法(JIS K7194)により、NPS(エヌピイエス)社製型式Σ-5+装置を用いて求めた。
(ウ)焼結体及び膜の組成
SIIナノテクノロジー社製型式SPS3000を用いてICP(高周波誘導結合プラズマ)分析法によって求めた。
(エ)膜厚
段差計(Veeco社製、型式Dektak8 STYLUS PROFILER)を用いて求めた。
(オ)膜のキャリア濃度及び移動度
成膜したガラス基板を約10mm角に切り出し、四隅にインジウム電極をつけて、ホール測定装置(東陽テクニカ社製、型式Resitest8200)にセットして測定した。
(カ)膜の結晶又は非晶質構造
リガク社製RINT-1100X線回折装置を用いて結晶性を判定した。バックグランドレベル以上の有意なピークが認められない場合、非晶質と判断した。
(キ)粉体の平均粒径
島津製作所製SALD-3100で平均粒径を測定した。 In the following Examples and Comparative Examples, the physical properties of the sintered bodies and films were measured by the following methods.
(A) Relative density of sintered body It was determined from the measurement results of weight and outer dimensions and the theoretical density from the constituent elements.
(B) Bulk resistance of sintered body The bulk resistance was determined by a four probe method (JIS K7194) using a model Σ-5 + apparatus manufactured by NPS.
(C) Composition of sintered body and film It was determined by an ICP (high frequency inductively coupled plasma) analysis method using a model SPS3000 manufactured by SII Nanotechnology.
(D) Film thickness It was determined using a step meter (Veeco, Model Dektak8 STYLUS PROFILER).
(E) Carrier concentration and mobility of film The formed glass substrate was cut into about 10 mm square, indium electrodes were attached to the four corners, and the measurement was carried out by setting in a Hall measuring device (manufactured by Toyo Technica, Model Reset 8200).
(F) Crystal or amorphous structure of film Crystallinity was determined using a RINT-1100 X-ray diffractometer manufactured by Rigaku Corporation. When no significant peak above the background level was observed, it was judged as amorphous.
(G) Average particle diameter of powder The average particle diameter was measured with SALD-3100 manufactured by Shimadzu Corporation.
<実施例1>
酸化インジウム(In2O3)粉(平均粒径1.0μm)、酸化鉄(Fe2O3)粉(平均粒径1.0μm)、及び酸化亜鉛(ZnO)粉(平均粒径1.0μm)、を金属元素の原子数比(In:Fe:Zn)が0.4:0.3:0.3となる様に秤量し、湿式混合粉砕した。粉砕後の混合粉の平均粒径0.8μmであった。この混合粉を、スプレードライヤーで造粒後、この混合粉を金型に充填し、加圧成形した後、大気雰囲気中1450℃の高温で10時間焼結した。得られた焼結体を直径6インチ、厚さ6mmの円盤状に加工し、平面研削してスパッタリングターゲットとした。当該ターゲットについて、重量と外形寸法との測定結果と理論密度から相対密度を算出したところ99.6%であった。また、四探針法により測定した焼結体のバルク抵抗は2.0mΩcmだった。ICP(高周波誘導結合プラズマ)分析法による焼結体組成分析の結果、In3+:Fe3+:Zn2+=0.4:0.3:0.3(原子比)であった。 <Example 1>
Indium oxide (In 2 O 3 ) powder (average particle size 1.0 μm), iron oxide (Fe 2 O 3 ) powder (average particle size 1.0 μm), and zinc oxide (ZnO) powder (average particle size 1.0 μm) ) Was weighed so that the atomic ratio of metal elements (In: Fe: Zn) was 0.4: 0.3: 0.3, and wet mixed and pulverized. The average particle size of the mixed powder after pulverization was 0.8 μm. After this mixed powder was granulated with a spray dryer, the mixed powder was filled in a mold, subjected to pressure molding, and then sintered in an air atmosphere at a high temperature of 1450 ° C. for 10 hours. The obtained sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm, and was subjected to surface grinding to obtain a sputtering target. With respect to the target, the relative density was calculated from the measurement results of the weight and the external dimensions, and the theoretical density, which was 99.6%. Further, the bulk resistance of the sintered body measured by the four probe method was 2.0 mΩcm. As a result of analyzing the composition of the sintered body by ICP (high frequency inductively coupled plasma) analysis, it was In 3+ : Fe 3+ : Zn 2+ = 0.4: 0.3: 0.3 (atomic ratio).
酸化インジウム(In2O3)粉(平均粒径1.0μm)、酸化鉄(Fe2O3)粉(平均粒径1.0μm)、及び酸化亜鉛(ZnO)粉(平均粒径1.0μm)、を金属元素の原子数比(In:Fe:Zn)が0.4:0.3:0.3となる様に秤量し、湿式混合粉砕した。粉砕後の混合粉の平均粒径0.8μmであった。この混合粉を、スプレードライヤーで造粒後、この混合粉を金型に充填し、加圧成形した後、大気雰囲気中1450℃の高温で10時間焼結した。得られた焼結体を直径6インチ、厚さ6mmの円盤状に加工し、平面研削してスパッタリングターゲットとした。当該ターゲットについて、重量と外形寸法との測定結果と理論密度から相対密度を算出したところ99.6%であった。また、四探針法により測定した焼結体のバルク抵抗は2.0mΩcmだった。ICP(高周波誘導結合プラズマ)分析法による焼結体組成分析の結果、In3+:Fe3+:Zn2+=0.4:0.3:0.3(原子比)であった。 <Example 1>
Indium oxide (In 2 O 3 ) powder (average particle size 1.0 μm), iron oxide (Fe 2 O 3 ) powder (average particle size 1.0 μm), and zinc oxide (ZnO) powder (average particle size 1.0 μm) ) Was weighed so that the atomic ratio of metal elements (In: Fe: Zn) was 0.4: 0.3: 0.3, and wet mixed and pulverized. The average particle size of the mixed powder after pulverization was 0.8 μm. After this mixed powder was granulated with a spray dryer, the mixed powder was filled in a mold, subjected to pressure molding, and then sintered in an air atmosphere at a high temperature of 1450 ° C. for 10 hours. The obtained sintered body was processed into a disk shape having a diameter of 6 inches and a thickness of 6 mm, and was subjected to surface grinding to obtain a sputtering target. With respect to the target, the relative density was calculated from the measurement results of the weight and the external dimensions, and the theoretical density, which was 99.6%. Further, the bulk resistance of the sintered body measured by the four probe method was 2.0 mΩcm. As a result of analyzing the composition of the sintered body by ICP (high frequency inductively coupled plasma) analysis, it was In 3+ : Fe 3+ : Zn 2+ = 0.4: 0.3: 0.3 (atomic ratio).
上記で作製したスパッタリングターゲットを銅製のバッキングプレートにインジウムをロウ材として使用して貼り付けて、DCマグネトロンスパッタ装置(ANELVA製SPL-500スパッタ装置)に設置した。ガラス基板はコーニング1737を用いて、スパッタ条件を、基板温度:25℃、到達圧力:1.2×10-4Pa、雰囲気ガス:Ar99%、酸素1%、スパッタ圧力(全圧):0.5Pa、投入電力500Wとして、膜厚が約100nmの薄膜を作製した。酸化物半導体薄膜の成膜時には、異常放電は認められなかった。
The sputtering target prepared above was attached to a copper backing plate using indium as a brazing material, and was installed in a DC magnetron sputtering apparatus (APLVA SPL-500 sputtering apparatus). The glass substrate uses Corning 1737, and the sputtering conditions are as follows: substrate temperature: 25 ° C., ultimate pressure: 1.2 × 10 −4 Pa, atmospheric gas: Ar 99%, oxygen 1%, sputtering pressure (total pressure): 0. A thin film having a thickness of about 100 nm was prepared at 5 Pa and input power of 500 W. No abnormal discharge was observed during the formation of the oxide semiconductor thin film.
得られた膜のホール測定を行ったところ、キャリア濃度5.2×1017cm-3、移動度5.0cm2/Vsを得た。ICP(高周波誘導結合プラズマ)分析法による膜組成分析の結果、In3+:Fe3+:Zn2+=0.4:0.3:0.3(原子比)であった。X線回折による測定の結果、当該膜は非晶質であった。
When hole measurement was performed on the obtained film, a carrier concentration of 5.2 × 10 17 cm −3 and a mobility of 5.0 cm 2 / Vs were obtained. As a result of film composition analysis by ICP (high frequency inductively coupled plasma) analysis, it was In 3+ : Fe 3+ : Zn 2+ = 0.4: 0.3: 0.3 (atomic ratio). As a result of measurement by X-ray diffraction, the film was amorphous.
<実施例2~実施例12>
原料粉の組成比を表1に記載のそれぞれの値となる様にした以外は、実施例1と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表1に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。
なお、In3+の供給原として酸化インジウム(In2O3)粉(平均粒径1.0μm)、Fe3+の供給源として酸化鉄(Fe2O3)粉(平均粒径1.0μm)、Zn2+の供給源として酸化亜鉛(ZnO)粉(平均粒径1.0μm)、Cu2+の供給源として(CuO)粉(平均粒径1.0μm)、Fe2+の供給源として酸化鉄(FeO)粉(平均粒径1.0μm)を使用した。 <Example 2 to Example 12>
An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
Incidentally, the indium oxide as a supply source of In 3+ (In 2 O 3) powder (average particle size 1.0 .mu.m), iron oxide as a source of Fe 3+ (Fe 2 O 3) powder (average particle size 1.0 .mu.m ), Zinc 2+ (ZnO) powder (average particle size: 1.0 μm) as a source of Zn 2+ , (CuO) powder (average particle size: 1.0 μm) as a source of Cu 2+, and a source of Fe 2+ As an iron oxide (FeO) powder (average particle size 1.0 μm) was used.
原料粉の組成比を表1に記載のそれぞれの値となる様にした以外は、実施例1と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表1に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。
なお、In3+の供給原として酸化インジウム(In2O3)粉(平均粒径1.0μm)、Fe3+の供給源として酸化鉄(Fe2O3)粉(平均粒径1.0μm)、Zn2+の供給源として酸化亜鉛(ZnO)粉(平均粒径1.0μm)、Cu2+の供給源として(CuO)粉(平均粒径1.0μm)、Fe2+の供給源として酸化鉄(FeO)粉(平均粒径1.0μm)を使用した。 <Example 2 to Example 12>
An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
Incidentally, the indium oxide as a supply source of In 3+ (In 2 O 3) powder (average particle size 1.0 .mu.m), iron oxide as a source of Fe 3+ (Fe 2 O 3) powder (average particle size 1.0 .mu.m ), Zinc 2+ (ZnO) powder (average particle size: 1.0 μm) as a source of Zn 2+ , (CuO) powder (average particle size: 1.0 μm) as a source of Cu 2+, and a source of Fe 2+ As an iron oxide (FeO) powder (average particle size 1.0 μm) was used.
<比較例1~比較例10>
原料粉の組成比を表1に記載のそれぞれの値となる様にした以外は、実施例1と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表1に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。 <Comparative Examples 1 to 10>
An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
原料粉の組成比を表1に記載のそれぞれの値となる様にした以外は、実施例1と同様にして、酸化物焼結体及び酸化物半導体薄膜を得た。それぞれの相対密度、バルク抵抗、キャリア濃度、移動度は、表1に記載の通りであった。また、焼結体及び膜の組成はそれぞれ原料粉の組成比と同一であった。 <Comparative Examples 1 to 10>
An oxide sintered body and an oxide semiconductor thin film were obtained in the same manner as in Example 1 except that the composition ratio of the raw material powder was set to the respective values shown in Table 1. The relative density, bulk resistance, carrier concentration, and mobility of each were as shown in Table 1. The composition of the sintered body and the film was the same as the composition ratio of the raw material powder.
表1に記載の結果から分かるように、本発明の実施例に係る酸化物焼結体は相対密度が高く、バルク抵抗が小さい。また、本発明に係る酸化物焼結体をスパッタリングターゲットとして成膜した場合、適切なキャリア濃度及び高い移動度をもつ酸化物半導体薄膜が得られる。
As can be seen from the results shown in Table 1, the oxide sintered bodies according to the examples of the present invention have a high relative density and a low bulk resistance. In addition, when the oxide sintered body according to the present invention is formed as a sputtering target, an oxide semiconductor thin film having an appropriate carrier concentration and high mobility can be obtained.
Claims (9)
- 3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とからなる酸化物焼結体であって、3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、及び2価のXイオン(X2+)の原子数比がそれぞれ、0.2≦(In3+)/{(In3+)+(Fe3+)+(X2+)}≦0.8、0.1≦(Fe3+)/{(In3+)+(Fe3+)+(X2+)}≦0.5、及び0.1≦(X2+)/{(In3+)+(Fe3+)+(X2+)}≦0.5を満たす酸化物焼結体。 Trivalent indium ion (In 3+ ), trivalent iron ion (Fe 3+ ), and divalent X ion (X 2+ ) (where X is selected from Cu, Zn and Fe) An oxide sintered body composed of oxygen ions (O 2− ) and trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ). , And the divalent X ion (X 2+ ) atomic ratio is 0.2 ≦ (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0 .8, 0.1 ≦ (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5, and 0.1 ≦ (X 2+ ) / {( In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5.
- 相対密度が98%以上である請求項1に記載の酸化物焼結体。 The oxide sintered body according to claim 1, wherein the relative density is 98% or more.
- バルク抵抗が3mΩ以下である請求項1又は2に記載の酸化物焼結体。 The oxide sintered body according to claim 1 or 2, wherein the bulk resistance is 3 mΩ or less.
- 3価のインジウムイオン(In3+)と、3価の鉄イオン(Fe3+)と、2価のXイオン(X2+)(但し、XはCu、Zn、及びFeから選択される1種以上の元素を表す。)と、酸素イオン(O2-)とからなる酸化物半導体薄膜であって、3価のインジウムイオン(In3+)、3価の鉄イオン(Fe3+)、2価のXイオン(X2+)の原子数比が、0.2≦(In3+)/{(In3+)+(Fe3+)+(X2+)}≦0.8、0.1≦(Fe3+)/{(In3+)+(Fe3+)+(X2+)}≦0.5、0.1≦(X2+)/{(In3+)+(Fe3+)+(X2+)}≦0.5を満たす酸化物半導体薄膜。 Trivalent indium ion (In 3+ ), trivalent iron ion (Fe 3+ ), and divalent X ion (X 2+ ) (where X is selected from Cu, Zn and Fe) An oxide semiconductor thin film composed of oxygen ions (O 2− ), trivalent indium ions (In 3+ ), trivalent iron ions (Fe 3+ ), The atomic ratio of divalent X ions (X 2+ ) is 0.2 ≦ (In 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.8, 0.1 ≦ (Fe 3+ ) / {(In 3+ ) + (Fe 3+ ) + (X 2+ )} ≦ 0.5, 0.1 ≦ (X 2+ ) / {(In 3+ ) An oxide semiconductor thin film satisfying + (Fe 3+ ) + (X 2+ )} ≦ 0.5.
- 非晶質である請求項4に記載の酸化物半導体薄膜。 The oxide semiconductor thin film according to claim 4, which is amorphous.
- キャリア濃度が1016~1018cm-3である請求項4又は5に記載の酸化物半導体薄膜。 6. The oxide semiconductor thin film according to claim 4, wherein the carrier concentration is 10 16 to 10 18 cm −3 .
- 移動度が1cm2/Vs以上である請求項4~6の何れか一項に記載の酸化物半導体薄膜。 The oxide semiconductor thin film according to any one of claims 4 to 6, which has a mobility of 1 cm 2 / Vs or more.
- 請求項4~7の何れか一項に記載の酸化物半導体薄膜を活性層として備えた薄膜トランジスタ。 A thin film transistor comprising the oxide semiconductor thin film according to any one of claims 4 to 7 as an active layer.
- 請求項8記載の薄膜トランジスタを備えたアクティブマトリックス駆動表示パネル。 An active matrix drive display panel comprising the thin film transistor according to claim 8.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137008042A KR101303987B1 (en) | 2010-08-31 | 2011-07-27 | Sintered oxide and oxide semiconductor thin film |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010194469A JP5081960B2 (en) | 2010-08-31 | 2010-08-31 | Oxide sintered body and oxide semiconductor thin film |
JP2010-194469 | 2010-08-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012029454A1 true WO2012029454A1 (en) | 2012-03-08 |
Family
ID=45772563
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2011/067131 WO2012029454A1 (en) | 2010-08-31 | 2011-07-27 | Sintered oxide and oxide semiconductor thin film |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP5081960B2 (en) |
KR (1) | KR101303987B1 (en) |
TW (1) | TWI410393B (en) |
WO (1) | WO2012029454A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140363719A1 (en) * | 2013-06-10 | 2014-12-11 | Hyundai Motor Company | Apparatus for indirectly cooling and heating battery module of vehicle |
JP2016027195A (en) * | 2014-06-27 | 2016-02-18 | 三菱マテリアル株式会社 | Sputtering target, optical function film, and multilayer wiring film |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6078288B2 (en) * | 2012-06-13 | 2017-02-08 | 出光興産株式会社 | Sputtering target, semiconductor thin film, and thin film transistor using the same |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004079038A1 (en) * | 2003-03-04 | 2004-09-16 | Nikko Materials Co., Ltd. | Sputtering target, thin film for optical information recording medium and process for producing the same |
JP2009231613A (en) * | 2008-03-24 | 2009-10-08 | Fujifilm Corp | Thin film field effect transistor and display unit |
JP2009253204A (en) * | 2008-04-10 | 2009-10-29 | Idemitsu Kosan Co Ltd | Field-effect transistor using oxide semiconductor, and its manufacturing method |
JP2010150093A (en) * | 2008-12-25 | 2010-07-08 | Tosoh Corp | Method for producing sintered compact for transparent electroconductive film |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100778429B1 (en) * | 2004-07-09 | 2007-11-21 | 미쓰이 긴조꾸 고교 가부시키가이샤 | Sputtering target material |
TWI487118B (en) * | 2007-03-23 | 2015-06-01 | Idemitsu Kosan Co | Semiconductor device |
TWI387497B (en) * | 2009-01-22 | 2013-03-01 | China Steel Corp | Manufacturing method of nickel alloy target |
-
2010
- 2010-08-31 JP JP2010194469A patent/JP5081960B2/en active Active
-
2011
- 2011-07-27 KR KR1020137008042A patent/KR101303987B1/en active IP Right Grant
- 2011-07-27 WO PCT/JP2011/067131 patent/WO2012029454A1/en active Application Filing
- 2011-08-11 TW TW100128648A patent/TWI410393B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004079038A1 (en) * | 2003-03-04 | 2004-09-16 | Nikko Materials Co., Ltd. | Sputtering target, thin film for optical information recording medium and process for producing the same |
JP2009231613A (en) * | 2008-03-24 | 2009-10-08 | Fujifilm Corp | Thin film field effect transistor and display unit |
JP2009253204A (en) * | 2008-04-10 | 2009-10-29 | Idemitsu Kosan Co Ltd | Field-effect transistor using oxide semiconductor, and its manufacturing method |
JP2010150093A (en) * | 2008-12-25 | 2010-07-08 | Tosoh Corp | Method for producing sintered compact for transparent electroconductive film |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20140363719A1 (en) * | 2013-06-10 | 2014-12-11 | Hyundai Motor Company | Apparatus for indirectly cooling and heating battery module of vehicle |
JP2016027195A (en) * | 2014-06-27 | 2016-02-18 | 三菱マテリアル株式会社 | Sputtering target, optical function film, and multilayer wiring film |
Also Published As
Publication number | Publication date |
---|---|
JP5081960B2 (en) | 2012-11-28 |
JP2012054336A (en) | 2012-03-15 |
TW201209007A (en) | 2012-03-01 |
KR20130046449A (en) | 2013-05-07 |
TWI410393B (en) | 2013-10-01 |
KR101303987B1 (en) | 2013-09-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR101228160B1 (en) | Process for producing thin film of a-igzo oxide | |
JP5081959B2 (en) | Oxide sintered body and oxide semiconductor thin film | |
WO2014042138A1 (en) | Oxide sintered body and sputtering target, and method for producing same | |
WO2015122417A1 (en) | Sintered oxide and sputtering target | |
JP2019038735A (en) | Oxide sintered compact, method for producing oxide sintered compact, target for sputtering, and amorphous oxide semiconductor thin film | |
KR101644767B1 (en) | Sintered oxide body and sputtering target comprising said sintered oxide body | |
JP5081960B2 (en) | Oxide sintered body and oxide semiconductor thin film | |
JP5367660B2 (en) | Oxide sintered body and oxide semiconductor thin film | |
JP5367659B2 (en) | Oxide sintered body and oxide semiconductor thin film | |
JP6722736B2 (en) | Sintered body and sputtering target | |
JP6233233B2 (en) | Sputtering target and manufacturing method thereof | |
WO2013065785A1 (en) | Oxide sintered body, sputtering target, and method for producing same | |
TW201522689A (en) | Sputtering target and method for producing same | |
JP2013193945A (en) | SINTERED BODY OF In-Ga-Zn-O-BASED OXIDE, METHOD FOR PRODUCING THE SAME, SPUTTERING TARGET AND OXIDE SEMICONDUCTOR FILM | |
WO2013042747A1 (en) | Oxide sintered body, method for producing same, and oxide transparent conductive film | |
JP2020164957A (en) | Sputtering target and manufacturing method of sputtering target | |
JP2017179595A (en) | Sputtering target material, and its production method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11821472 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137008042 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 11821472 Country of ref document: EP Kind code of ref document: A1 |