WO2020040149A1 - 窒化処理液、窒化処理金属酸化物の製造方法及び窒化処理酸化インジウム膜 - Google Patents
窒化処理液、窒化処理金属酸化物の製造方法及び窒化処理酸化インジウム膜 Download PDFInfo
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- nitriding
- metal oxide
- nitrided
- oxide film
- indium oxide
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- 238000005121 nitriding Methods 0.000 title claims description 93
- 229910044991 metal oxide Inorganic materials 0.000 title claims description 59
- 150000004706 metal oxides Chemical class 0.000 title claims description 59
- 229910003437 indium oxide Inorganic materials 0.000 title claims description 36
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000007788 liquid Substances 0.000 title description 6
- -1 alkali metal amide Chemical class 0.000 claims abstract description 16
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 48
- 239000012298 atmosphere Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 8
- GUVUOGQBMYCBQP-UHFFFAOYSA-N dmpu Chemical compound CN1CCCN(C)C1=O GUVUOGQBMYCBQP-UHFFFAOYSA-N 0.000 claims description 7
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical group [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 53
- 239000010409 thin film Substances 0.000 description 44
- 239000000243 solution Substances 0.000 description 43
- 230000037230 mobility Effects 0.000 description 29
- 229910052757 nitrogen Inorganic materials 0.000 description 29
- 239000010408 film Substances 0.000 description 23
- 239000011521 glass Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- NWAIGJYBQQYSPW-UHFFFAOYSA-N azanylidyneindigane Chemical compound [In]#N NWAIGJYBQQYSPW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/0821—Oxynitrides of metals, boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D229/00—Heterocyclic compounds containing rings of less than five members having two nitrogen atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- 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
Definitions
- the present invention relates to a nitriding solution, a method for producing a nitriding metal oxide using the same, and a nitriding indium oxide film.
- the nitrided metal oxide is a compound containing oxygen and nitrogen, and has the same meaning as a metal oxynitride in a broad sense, and includes a metal oxide containing nitrogen and a nitride containing oxygen.
- Metal oxides have excellent characteristics such as stability, low cost, low toxicity and no corrosiveness, and are widely used as starting samples for nitrogen-doped metal oxides, oxynitrides and nitrides.
- Reduction and nitridation of the metal oxide are required for nitriding the metal oxide. That is, a two-step reaction is required to form a reaction to break the bond with oxygen and a reaction with nitrogen.
- the reductive nitridation uses ammonia gas, nitrogen gas, a mixed gas of nitrogen and hydrogen, carbon reduction, and reaction with lithium nitride, and generally requires high-temperature treatment at 500 to 1700 ° C.
- Non-Patent Document 1 Ca (1-x) La x TaO (2-x) N (1 + x) is obtained by nitriding in an ammonia gas stream at 700 to 1000 ° C. using Ca, La, and Ta oxide as a starting sample. Combined.
- Patent Document 1 (Li, Ga) (O, N) is synthesized by nitriding in an ammonia gas stream at 700 to 1000 ° C. using an oxide sol containing Li and Ga as a starting sample.
- synthesis of nitrides using chlorides, amides and the like described in Patent Document 2 and Non-Patent Documents 2-5 at 500 ° C. or lower has also been reported.
- Patent Document 2 a nitride is synthesized by heating a metal and / or compound containing a Group 13 element and an amide compound at 400 to 500 ° C. in an inert gas.
- Non-Patent Document 2 reports synthesis of indium nitride by heating an indium halide and an amide compound in an organic substance.
- Non-Patent Document 3 reports synthesis of indium nitride by heating gallium chloride and lithium nitride in benzene.
- Non-Patent Document 4 reports the synthesis of nitrides by reacting various metals with sulfur, sodium azide or sodium amide at 500 ° C. or lower.
- Non-Patent Document 5 reports the synthesis of gallium nitride by a mechanochemical reaction of gallium oxide and lithium nitride using a planetary ball mill.
- thermodynamically unstable metal oxynitride is synthesized by using an ammonia gas stream at 700 ° C. or higher, and thus has the following problems. That is, such high-temperature processing requires a large amount of energy. Ammonia gas is a harmful gas and requires careful handling, and must be neutralized or otherwise treated. Further, only a small amount of the ammonia gas stream can be used for the reaction, and the use efficiency is low. In addition, since the decomposition process of ammonia is used, kinetic reaction control is required.
- an object of the present invention is to provide a nitriding solution, a method of manufacturing a nitrided metal oxide, and a nitrided indium oxide film that can relatively easily nitride a metal oxide thin film.
- a first aspect of the present invention that achieves the above object is a nitriding solution characterized in that an alkali metal amide is dissolved in a cyclic alkylene urea represented by the following formula (1).
- R 1 and R 2 each independently represent an alkyl group having 1-3 carbon atoms, and R 3 represents an alkylene group having 1-4 carbon atoms.
- a second aspect of the present invention is the nitriding solution according to the first aspect, wherein the cyclic alkylene urea is dimethylpropylene urea or dimethylethylene urea.
- a third aspect of the present invention provides the nitriding solution according to the first or second aspect, wherein the alkali metal amide is lithium amide, sodium amide, potassium amide, or a mixture thereof. is there.
- a nitriding treatment step in which the nitriding treatment liquid according to any one of the first to third aspects is heated in an inert gas atmosphere while the metal oxide is in contact with the surface.
- a method for producing a nitrided metal oxide comprising:
- a fifth aspect of the present invention is the method according to the fourth aspect, further comprising, after the nitriding step, an annealing step of heating and annealing the treated metal oxide film in a deoxygenated atmosphere.
- the present invention relates to a method for producing a nitrided metal oxide.
- a sixth aspect of the present invention the metal oxide, In 2 O 3, Ga 2 O 3, Al 2 O 3, TiO 2, Fe 2 O 3, MnO 2, WO 3, MoO 3, Li 2 TiO 3, Li 2 ZrO 3, Li 2 MoO 4, Li 2 WO 4, Na 2 selected from MoO 4, LiGaO 2, LiInO 2 , NaGaO 2, FeMoO 4, MnMoO 4, FeWO 4, MnWO 4, LiInO 2, NaInO 2
- a seventh aspect of the present invention is the method for producing a nitrided metal oxide according to any one of the fourth to sixth aspects, wherein the metal oxide is an indium oxide film formed on a substrate. In the way.
- An eighth aspect of the present invention is a nitrided indium oxide film, which is a nitrogen-doped indium oxide film provided on a substrate, wherein the nitrided indium oxide film has a mobility of 6 to 50 cm 2 / Vs.
- the nitrided indium oxide film is characterized in that:
- a ninth aspect of the present invention is the nitrided indium oxide film according to the eighth aspect, wherein the mobility of the nitrided indium oxide film is 30 to 50 cm 2 / Vs.
- the alkali metal amide used for nitriding can be handled as a solution, the nitriding liquid which does not ignite in air can be provided. Further, when the nitriding solution of the present invention is used, a thin film which is weak to alkali such as an indium oxide film can be nitrided, and a nitrided metal oxide having good adhesion to a substrate can be provided. Further, the nitrided indium oxide film produced by using the nitriding solution of the present invention has a mobility as high as 6 to 50 cm 2 / Vs, which is unprecedented, and can be suitably used for applications such as thin film transistors.
- the nitriding solution of the present invention is characterized in that an alkali metal amide is dissolved in a cyclic alkylene urea represented by the following formula (1).
- R 1 and R 2 each independently represent an alkyl group having 1-3 carbon atoms, and R 3 represents an alkylene group having 1-4 carbon atoms.
- cyclic alkylene urea preferably, N, N-dimethylpropyleneamide or N, N-dimethylethyleneamide can be mentioned.
- Alkali metal amides include lithium amide, sodium amide, potassium amide and mixtures thereof.
- the concentration is not particularly limited as long as the alkali metal amide is dissolved in the cyclic alkylene urea, but is preferably about 1 mM to 1000 mM, preferably about 10 mM to 500 mM.
- the nitriding solution of the present invention is to contact the surface of the metal oxide and heat-treat it in an inert gas atmosphere, and it is capable of nitriding the metal oxide. Since it is a solution in which alkali amide is dissolved in a cyclic alkylene urea, it does not ignite in the air and can be used for nitriding metal oxides that are weak to alkali.
- the method for producing a nitriding metal oxide of the present invention includes a nitriding step of heating the nitriding solution of the present invention in an inert gas atmosphere in a state of being in contact with the surface of the metal oxide.
- the metal oxide that can be used here may be a binary oxide or a composite oxide, but specifically, In 2 O 3 , Ga 2 O 3 , Al 2 O 3 , TiO 2 , and Fe 2 O 3, MnO 2, WO 3, MoO 3, Li 2 TiO 3, Li 2 ZrO 3, Li 2 MoO 4, Li 2 WO 4, Na 2 MoO 4, LiGaO 2, LiInO 2, NaGaO 2, FeMoO 4, MnMoO 4 , FeWO 4 , MnWO 4 , LiInO 2 , (In 9 , Sn 1 ) 2 O 3 , NaInO 2 and the like.
- the metal oxide may be granular or a thin film.
- the nitrided metal oxide may be an oxynitride in a broad sense including a state in which the metal oxide is doped with nitrogen, or a oxynitride in a narrow sense in which oxygen and nitrogen are bonded to a metal.
- nitriding solution to attach the nitriding solution to the surface of the metal oxide, specifically, by immersing the metal oxide in the nitriding solution of the present invention.
- the nitriding solution may be brought into contact with the surface of the metal oxide by a method of bringing it into a state, a method of taking out after dipping, or a method of spraying and applying a nitriding solution on the surface of the metal oxide.
- the heat treatment may be performed at 200 ° C. to 400 ° C., preferably 200 ° C. to 300 ° C.
- the heat treatment time may be about 1 to 50 hours, preferably 5 to 30 hours.
- Nitrogen or a rare gas is used as the inert gas for forming the inert gas atmosphere, and nitrogen or argon is preferable.
- the nitriding step by heat treatment may be performed under normal pressure or under pressure.
- the pressure is 20 to 0.1 MPa, more preferably 5 to 0.1 MPa, and more preferably 2 to 0.1 MPa. If the pressure condition is 20 MPa or more, handling is dangerous and manufacturing equipment becomes expensive.
- the method for producing a nitrided metal oxide of the present invention it is preferable to perform an annealing step of heating and annealing the treated metal oxide in a deoxidizing atmosphere after the nitriding step.
- the nitriding process the mobility in the case of mobility 2 ⁇ 4cm 2 / Vs before treatment, a 6 ⁇ 10cm 2 / Vs, and after annealing, a 20 ⁇ 50cm 2 / Vs about .
- the deoxidizing atmosphere refers to a vacuum state in which oxygen does not exist or an inert gas atmosphere.
- the vacuum state is, for example, a vacuum state of 1 Pa or less, preferably 0.1 Pa or less. Nitrogen or a rare gas is used as the inert gas for forming the inert gas atmosphere, but nitrogen is preferable.
- the heating temperature of the annealing treatment is 200 ° C. to 500 ° C., preferably 250 ° C. to 400 ° C., and the treatment time is 30 minutes to 10 hours, preferably 1 hour to 5 hours.
- the present invention be applied to nitriding of a metal oxide film used for a thin film transistor using a metal oxide semiconductor.
- the thickness of the metal oxide thin film is 50 nm to 100 nm.
- the use of the nitriding solution of the present invention enables efficient nitridation of a metal oxide thin film, particularly a metal oxide thin film weak to alkali, and improves the mobility, carrier density, and specific resistance of the thin film. be able to.
- the mobility, carrier density, specific resistance, and the like of the thin film can be further improved.
- a nitrided indium oxide film is a novel one having unprecedented characteristics.
- a nitrided indium oxide film which is provided on a substrate and is characterized by being doped with nitrogen, is a novel one.
- Such a nitrided indium oxide film has a mobility of 6 to 50 cm 2 / Vs, preferably 30 to 50 cm 2 / Vs, and is unprecedented.
- the carrier density is 1 ⁇ 10 16 to 1 ⁇ 10 19 cm ⁇ 3
- the specific resistance is 0.05 to 100 ⁇ cm.
- Such a nitrided indium oxide film can be suitably used for applications such as thin film transistors.
- a precursor thin film was obtained by subjecting this glass substrate to heat treatment at 100 ° C. for 15 minutes, and a uniform thin film made of In 2 O 3 was formed by heat treatment at 500 ° C. for 2 hours. All the glass substrates with an In 2 O 3 thin film in Examples of the present invention were produced by this procedure.
- the scanning electron microscope JEOL JSM-6500F manufactured by JEOL Ltd. was used for measuring the thickness of the In 2 O 3 thin film.
- the film thickness was determined from the fracture surface of the polished film.
- GDOES glow discharge emission spectrometry
- Example 1 nitriding solution A
- nitriding solution A In an Ar atmosphere, 0.03 g of sodium amide was added to 7 ml of N, N'-dimethylpropylene urea, and the mixture was stirred at room temperature for 15 minutes, and then the supernatant was transferred to another container to prepare a treatment liquid A.
- the concentration of sodium amide is about 15 mM.
- Example 2 nitriding solution B
- 0.01 g of sodium amide was added to 7 ml of N, N'-dimethylpropylene urea, and the mixture was stirred for 24 hours while maintaining the solution temperature at 60 ° C. to prepare a treatment solution B.
- the concentration of sodium amide is about 36 mM.
- Example 3 nitriding liquid C
- 0.02 g of sodium amide was added to 7 ml of N, N'-dimethylpropylene urea, and the solution was stirred for 24 hours while maintaining the solution temperature at 100 ° C. to prepare a treatment solution C.
- the concentration of sodium amide is about 73 mM.
- Example 4 nitriding liquid D
- 0.05 g of sodium amide was added to 7 ml of N, N'-dimethylpropylene urea, and the solution was stirred for 24 hours while keeping the solution temperature at 150 ° C. to prepare a treatment solution D.
- the concentration of sodium amide is about 180 mM.
- Example 11 nitriding method A
- a 220-nm-thick glass substrate with an In 2 O 3 thin film and 7.0 g of the nitriding solution A were placed in a pressure decomposition container (manufactured by Yanaco Equipment Development Laboratory, capacity: 70 ml), and the autoclave was sealed.
- the glass substrate with the In 2 O 3 thin film was nitrided by heating the autoclave to 260 ° C. and holding for 18 hours.
- the nitriding substrate was taken out of the autoclave and washed with a mixed solution of water and ethanol.
- the nitriding substrate was annealed at 300 ° C. for 1 hour in a vacuum.
- Example 12 (Production method of nitriding metal oxide thin film)
- Example 12 nitriding method B
- a glass substrate with an In 2 O 3 thin film was nitrided according to the same procedure as in Example 11.
- the nitriding substrate was taken out of the autoclave and washed with a mixed solution of water and ethanol.
- Example 13 nitriding method C
- a nitriding solution C instead of the nitriding solution A used in Example 11
- the glass substrate with the In 2 O 3 thin film was nitrided according to the same procedure as in Example 11.
- the nitriding substrate was taken out of the autoclave and washed with a mixed solution of water and ethanol.
- Example 14 (Production method of nitriding metal oxide thin film) (Example 14: nitriding method D) Using a nitriding solution D in place of the nitriding solution A used in Example 11, a glass substrate with an In 2 O 3 thin film was nitrided according to the same procedure as in Example 11. Next, the nitriding substrate was taken out of the autoclave and washed with a mixed solution of water and ethanol.
- Nitrided indium oxide thin film (Example 21: Nitrided indium oxide thin film A-1)
- a nitriding substrate was manufactured in the same procedure as the nitriding method A of Example 11.
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 3 ⁇ cm, 7 ⁇ 10 16 cm ⁇ 3 , and 40 cm 2 / Vs, respectively.
- Example 22 Nitrided indium oxide thin film A-2
- a nitriding substrate was manufactured using the same procedure as the nitriding method A of Example 11 except that annealing was not performed at 300 ° C. for 1 hour in vacuum.
- the amount of nitrogen in the nitriding substrate was measured by GD-OES.
- the results are shown in FIG. Table 1 shows the N / In ratio of the integrated amounts of the emission intensities of indium and nitrogen during the sputtering time of 4 to 10 (sec).
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 0.1 ⁇ cm, 7 ⁇ 10 18 cm ⁇ 3 , and 9 cm 2 / Vs, respectively.
- Example 23 Nitrided indium oxide thin film B
- a nitriding substrate was manufactured in the same procedure as in the nitriding method B of Example 12.
- the amount of nitrogen in the nitriding substrate was measured by GD-OES.
- Table 1 shows the N / In ratio of the integrated amount of the emission intensities of indium and nitrogen during the sputtering time of 4 to 10 (sec).
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 0.07 ⁇ cm, 6 ⁇ 10 18 cm ⁇ 3 , and 20 cm 2 / Vs, respectively.
- Example 24 Nitrided indium oxide thin film C
- a nitriding substrate was manufactured in the same procedure as the nitriding method C of Example 13.
- the amount of nitrogen in the nitriding substrate was measured by GD-OES.
- Table 1 shows the N / In ratio of the integrated amount of the emission intensities of indium and nitrogen during the sputtering time of 4 to 10 (sec).
- Example 25 Nitrided indium oxide thin film D
- a nitriding substrate was manufactured in the same procedure as in the nitriding method D of Example 14. The amount of nitrogen in the nitriding substrate was measured by GD-OES. Table 1 shows the N / In ratio of the integrated amount of the emission intensities of indium and nitrogen during the sputtering time of 4 to 10 (sec).
- Example 26 Nitrided indium oxide thin film B-2
- a nitriding substrate was manufactured using the same procedure as the nitriding method B of Example 12, and then annealed at 300 ° C. for 1 hour in a vacuum.
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 2 ⁇ cm, 7 ⁇ 10 16 cm ⁇ 3 , and 40 cm 2 / Vs, respectively.
- Comparative Example 3 A processing substrate was manufactured in the same procedure as in Comparative Example 1.
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 0.2 ⁇ cm, 7 ⁇ 10 19 cm ⁇ 3 , and 3 cm 2 / Vs, respectively.
- Comparative Example 4 A processing substrate was produced in the same procedure as in Comparative Example 1 except that annealing was not performed at 300 ° C. for 1 hour in a vacuum.
- the carrier type, specific resistance, carrier density, and mobility of this substrate were measured by the above-described methods.
- the carrier type, specific resistance, carrier density, and mobility were carrier type N, 0.5 ⁇ cm, 4 ⁇ 10 18 cm ⁇ 3 , and 4 cm 2 / Vs, respectively.
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Abstract
Description
金属酸化物の窒化には、金属酸化物の還元及び窒化が必要である。すなわち、酸素との結合を切る反応と窒素との反応を形成する二段階の反応が必要である。
還元窒化には、アンモニアガス、窒素ガス、窒素と水素の混合ガスや炭素還元、窒化リチウムとの反応が用いられ、一般的に500~1700℃の高温処理が必要である。
特許文献1では、LiとGaを含む酸化物ゾルを出発試料として、700~1000℃のアンモニアガス気流中での窒化によって(Li,Ga)(O,N)を合成している。
また、特許文献2、非特許文献2-5の塩化物、アミド等を用いた窒化物の500℃以下での合成も報告されている。
特許文献2では、13族元素を含む金属及び/又は化合物とアミド化合物を不活性ガス中で400~500℃で加熱することによる窒化物の合成を行っている。
非特許文献2では、インジウムハライドとアミド化合物を有機物中で加熱することによる窒化インジウムの合成を報告している。
非特許文献3では、塩化ガリウムと窒化リチウムをベンゼン中で加熱することによる窒化インジウムの合成を報告している。
非特許文献4では、様々な金属と硫黄、アジ化ナトリウムもしくはナトリウムアミドと500℃以下で反応させ、窒化物の合成を報告している。
非特許文献5では、酸化ガリウムと窒化リチウムの遊星ボールミルを用いたメカノケミカル反応によって、窒化ガリウムの合成を報告している。
本発明の窒化処理液は、アルカリ金属アミドを下記式(1)で表される環状アルキレン尿素に溶解させたことを特徴とする。
本発明の窒化処理金属酸化物の製造方法は、本発明の窒化処理液を、金属酸化物の表面に接触させた状態で、不活性ガス雰囲気下で加熱する窒化処理工程を具備する。
例えば、窒化処理工程により、移動度は、処理前の移動度が2~4cm2/Vsの場合、6~10cm2/Vsとなるが、アニール処理後には、20~50cm2/Vs程度となる。
かかる窒化処理酸化インジウム膜は、移動度が、6~50cm2/Vs、好ましくは、30~50cm2/Vsであり、従来にないものである。
また、キャリア密度は、1×1016~1×1019cm-3であり、比抵抗は、0.05~100Ωcmである。
このような窒化処理酸化インジウム膜は、薄膜トランジスタ等の用途に好適に用いることができる。
[測定手順]
(In2O3膜付きガラス基板の作製の手順)
In(NO3)3・3H2O(2.95g)を2-プロパノール(20g)に加え10時間撹拌した後、さらに、酢酸(0.8g)とポリエチレングリコール(0.9g)を加え2時間撹拌し前駆体溶液を調整した。次に、76×26×1.0(mm)の大きさのガラス基板をこの前駆体溶液に浸漬した後、垂直に引き上げる事でガラス基板に前駆体溶液を薄く均一に被覆した。次に、このガラス基板を100℃で15分間の熱処理により、前駆体薄膜を得て、さらに500℃で2時間の熱処理によってIn2O3からなる均一な薄膜を形成した。本発明の実施例におけるIn2O3薄膜付きガラス基板はすべて本手順により作製した。
In2O3薄膜の膜厚の測定には、日本電子株式会社製走査電子顕微鏡JEOL JSM-6500Fを用いた。研磨した膜の破断面から、膜厚を決定した。
窒化処理基板の窒素量の測定には堀場製作所社製JY5000RFを用いた。圧力600Pa、出力35W、デューティサイクル0.1、周波数100Hzの条件にて測定した。
In2O3薄膜及び窒化処理基板のキャリアタイプ、比抵抗、キャリア濃度、移動度の測定は、東陽テクニカ製の比抵抗/ホール係数測定システムResiTest8300を用いた。
(実施例1:窒化処理液A)
Ar雰囲気中において、N,N’-ジメチルプロピレン尿素7ml中にナトリウムアミドを0.03g加え、室温で15分撹拌した後、上澄みを別の容器に移すことで処理液Aを調製した。ナトリウムアミドの濃度は、約15mMである。
Ar雰囲気中において、N,N’-ジメチルプロピレン尿素7ml中にナトリウムアミドを0.01g加え、液温を60℃に保ち24時間撹拌することで処理液Bを調製した。ナトリウムアミドの濃度は、約36mMである。
Ar雰囲気中において、N,N’-ジメチルプロピレン尿素7ml中にナトリウムアミドを0.02g加え、液温を100℃に保ち24時間撹拌することで処理液Cを調整した。ナトリウムアミドの濃度は、約73mMである。
Ar雰囲気中において、N,N’-ジメチルプロピレン尿素7ml中にナトリウムアミドを0.05g加え、液温を150℃に保ち24時間撹拌することで処理液Dを調整した。ナトリウムアミドの濃度は、約180mMである。
(実施例11:窒化処理方法A)
Ar雰囲気中において、加圧分解容器(ヤナコ機器開発研究所製、容量70ml)に膜厚220nmのIn2O3薄膜付きガラス基板と窒化処理液A7.0gを入れオートクレーブを密封した。このオートクレーブを260℃に加熱し18時間保持することで、In2O3薄膜付きガラス基板を窒化処理した。次に、窒化処理基板をオートクレーブから取り出し、水とエタノールの混合溶液を用いて洗浄した。次に、窒化処理基板を真空中で300℃で1時間アニールした。
(実施例12:窒化処理方法B)
実施例11で用いた窒化処理液Aの代わりに窒化処理液Bを用いて、実施例11と同様の手順に従いIn2O3薄膜付きガラス基板を窒化処理した。次に、窒化処理基板をオートクレーブから取り出し、水とエタノールの混合溶液を用いて洗浄した。
(実施例13:窒化処理方法C)
実施例11で用いた窒化処理液Aの代わりに窒化処理液Cを用いて、実施例11と同様の手順に従いIn2O3薄膜付きガラス基板を窒化処理した。次に、窒化処理基板をオートクレーブから取り出し、水とエタノールの混合溶液を用いて洗浄した。
(実施例14:窒化処理方法D)
実施例11で用いた窒化処理液Aの代わりに窒化処理液Dを用いて、実施例11と同様の手順に従いIn2O3薄膜付きガラス基板を窒化処理した。次に、窒化処理基板をオートクレーブから取り出し、水とエタノールの混合溶液を用いて洗浄した。
Ar雰囲気中において、加圧分解容器(ヤナコ機器開発研究所製、容量70ml)に膜厚220nmのIn2O3薄膜付きガラス基板とN,N’-ジメチルプロピレン尿素を入れオートクレーブを密封した。このオートクレーブを260℃に加熱し18時間保持することで、In2O3薄膜付きガラス基板を処理した。次に、処理基板をオートクレーブから取り出し、水とエタノールの混合溶液を用いて洗浄した。次に、処理基板を真空中で300℃で1時間アニールした。
(実施例21:窒化処理酸化インジウム薄膜A-1)
実施例11の窒化処理方法Aと同じ手順で窒化処理基板を作製した。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、3Ωcm、7×1016cm-3、40cm2/Vsであった。
真空中で300℃で1時間のアニールを行わない以外は、実施例11の窒化処理方法Aと同様の手順を用いて窒化処理基板を作製した。GD-OESにより窒化処理基板の窒素量を測定した。結果を図1に示す。また、スパッタリング時間4~10(sec)間のインジウムと窒素の発光強度の積算量のN/In比を表1に示す。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、0.1Ωcm、7×1018cm-3、9cm2/Vsであった。
実施例12の窒化処理方法Bと同じ手順で窒化処理基板を作製した。
GD-OESにより窒化処理基板の窒素量を測定した。スパッタリング時間4~10(sec)間のインジウムと窒素の発光強度の積算量のN/In比を表1に示す。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、0.07Ωcm、6×1018cm-3、20cm2/Vsであった。
実施例13の窒化処理方法Cと同じ手順で窒化処理基板を作製した。
GD-OESにより窒化処理基板の窒素量を測定した。スパッタリング時間4~10(sec)間のインジウムと窒素の発光強度の積算量のN/In比を表1に示す。
実施例14の窒化処理方法Dと同じ手順で窒化処理基板を作製した。
GD-OESにより窒化処理基板の窒素量を測定した。スパッタリング時間4~10(sec)間のインジウムと窒素の発光強度の積算量のN/In比を表1に示す。
実施例12の窒化処理方法Bと同様の手順を用いて窒化処理基板を作製し、次に、真空中で300℃で1時間のアニールを行った。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、2Ωcm、7×1016cm-3、40cm2/Vsであった。
In2O3薄膜付きガラス基板を窒化処理せずに、GD-OESにより窒化処理基板の窒素量を測定した。結果を図1に示す。また、スパッタリング時間4~10(sec)間のインジウムと窒素の発光強度の積算量のN/In比を表1に示す。
この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、6Ωcm、7×1017cm-3、2cm2/Vsであった。
比較例1と同じ手順で処理基板を作製した。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、0.2Ωcm、7×1019cm-3、3cm2/Vsであった。
真空中で300℃で1時間のアニールを行わない以外は、比較例1と同じ手順で処理基板を作製した。この基板のキャリアタイプ、比抵抗、キャリア密度、移動度を前記の方法で測定した。キャリアタイプ、比抵抗、キャリア密度、移動度はそれぞれ、キャリアタイプN、0.5Ωcm、4×1018cm-3、4cm2/Vsであった。
図1に示すように、実施例22の窒化処理酸化インジウム薄膜と、比較例2の窒化処理酸化インジウム薄膜とを比較すると、比較例2の方が窒素の信号強度は弱く、窒化されていないことが確認された。一方、実施例22の窒化処理酸化インジウム薄膜は、比較例2と比較して、インジウムの信号強度が弱く、且つ窒素の信号強度が強いので、窒化されていることが確認された。
また、実施例21、実施例22の移動度を比較例2、3、4と比較すると、実施例11の窒化処理液Aを用いた実施例21、22の移動度が大幅に向上したことが確認された。これはIn2O3薄膜が窒化したことで移動度が向上したものと思われる。
また、実施例21と実施例22を比較すると、アニール処理した実施例21の移動度が大幅に大きく、アニール処理によりさらに移動度が大きく向上することが認められた。
Claims (9)
- 前記環状アルキレン尿素が、ジメチルプロピレン尿素又はジメチルエチレン尿素であることを特徴とする請求項1記載の窒化処理液。
- 前記アルカリ金属アミドが、リチウムアミド、ナトリウムアミド、カリウムアミド又はこれらの混合物であることを特徴とする請求項1又は2記載の窒化処理液。
- 請求項1~3の何れか一項記載の窒化処理液を、金属酸化物を表面に接触させた状態で、不活性ガス雰囲気下で加熱する窒化処理工程を具備することを特徴とする窒化処理金属酸化物の製造方法。
- 前記窒化処理工程の後、処理済の金属酸化膜を脱酸素雰囲気下で加熱してアニールするアニール工程を具備することを特徴とする請求項4記載の窒化処理金属酸化物の製造方法。
- 前記金属酸化物が、In2O3、Ga2O3、Al2O3、TiO2、Fe2O3、MnO2、WO3、MoO3、Li2TiO3、Li2ZrO3、Li2MoO4、Li2WO4、Na2MoO4、LiGaO2、LiInO2、NaGaO2、FeMoO4、MnMoO4、FeWO4、MnWO4、LiInO2、NaInO2から選ばれる1種類、又は複数の混合物であることを特徴とする請求項4又は5記載の窒化処理金属酸化物の製造方法。
- 前記金属酸化物が、基板上に形成された酸化インジウム膜であることを特徴とする請求項4~6の何れか一項記載の窒化処理金属酸化物の製造方法。
- 基板上に設けられ窒素がドープされた酸化インジウム膜である窒化処理酸化インジウム膜であって、前記窒化処理酸化インジウム膜の移動度が、6~50cm2/Vsであることを特徴とする窒化処理酸化インジウム膜。
- 前記窒化処理酸化インジウム膜の移動度が、30~50cm2/Vsであることを特徴とする請求項8記載の窒化処理酸化インジウム膜。
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WO2015136953A1 (ja) * | 2014-03-13 | 2015-09-17 | 国立研究開発法人科学技術振興機構 | ペロブスカイト型金属酸窒化物の製造方法 |
JP6582655B2 (ja) * | 2015-07-14 | 2019-10-02 | 株式会社リコー | 電界効果型トランジスタ、表示素子、画像表示装置、及びシステム |
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2019
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- 2019-08-20 WO PCT/JP2019/032484 patent/WO2020040149A1/ja unknown
- 2019-08-20 US US17/266,188 patent/US20210292168A1/en active Pending
- 2019-08-20 CN CN201980054277.3A patent/CN112585094B/zh active Active
- 2019-08-20 EP EP19853127.9A patent/EP3842388A4/en active Pending
- 2019-08-20 JP JP2020538410A patent/JP7126225B2/ja active Active
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Publication number | Publication date |
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JP7126225B2 (ja) | 2022-08-26 |
EP3842388A4 (en) | 2022-08-17 |
CN112585094A (zh) | 2021-03-30 |
CN112585094B (zh) | 2023-05-02 |
KR20210031960A (ko) | 2021-03-23 |
US20210292168A1 (en) | 2021-09-23 |
JPWO2020040149A1 (ja) | 2021-09-02 |
TW202019884A (zh) | 2020-06-01 |
KR102510135B1 (ko) | 2023-03-14 |
EP3842388A1 (en) | 2021-06-30 |
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