CN112479683A - Preparation method of doped IGZO material - Google Patents

Preparation method of doped IGZO material Download PDF

Info

Publication number
CN112479683A
CN112479683A CN202011494732.2A CN202011494732A CN112479683A CN 112479683 A CN112479683 A CN 112479683A CN 202011494732 A CN202011494732 A CN 202011494732A CN 112479683 A CN112479683 A CN 112479683A
Authority
CN
China
Prior art keywords
powder
igzo
preparation
zno
doped
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011494732.2A
Other languages
Chinese (zh)
Inventor
王晨
丁金铎
葛春桥
柳春锡
金志洸
崔恒
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhongshan Zhilong New Material Technology Co Ltd
Original Assignee
Zhongshan Zhilong New Material Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhongshan Zhilong New Material Technology Co Ltd filed Critical Zhongshan Zhilong New Material Technology Co Ltd
Priority to CN202011494732.2A priority Critical patent/CN112479683A/en
Publication of CN112479683A publication Critical patent/CN112479683A/en
Pending legal-status Critical Current

Links

Images

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
    • 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
    • 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
    • C04B35/64—Burning or sintering processes
    • 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
    • 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
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • 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
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6583—Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density

Abstract

The invention belongs to the technical field of target material manufacturing, and discloses a preparation method of a doped IGZO material. The preparation method comprises the following steps: (1) to ZnO and In2O3、Ga2O3Adding ammonium molybdate solution into the powder, mixing, drying, sieving and heating to obtain IGZO powder; (2) adding a forming agent into the IGZO powder prepared in the step (1), mixing, drying, sieving, forming, removing the forming agent, and sintering to obtain the IGZO material; ZnO and In2O3、Ga2O3The particle size of the powder is 300-800 nm. The IGZO material prepared by the preparation method has the relative density of more than 99.6 percent and the resistivity of less than 9.5 multiplied by 10‑4Omega cm; the IGZO thin film material prepared from the IGZO material has strong stability and high quality. The preparation method is simple and easy to operate.

Description

Preparation method of doped IGZO material
Technical Field
The invention belongs to the technical field of target material manufacturing, and particularly relates to a preparation method of a doped IGZO material.
Background
The Indium Gallium Zinc Oxide (IGZO) film as a novel semiconductor material has the advantages of high carrier mobility, strong chemical stability, simple preparation process and the like. Therefore, the IGZO thin film is applied to a channel layer material in a new generation Thin Film Transistor (TFT) technology, and the prepared TFT has the characteristics of high-speed driving performance, high resolution, large size, low power consumption and the like.
At present, the IGZO film is mainly prepared by adopting a mode of magnetron sputtering an IGZO ceramic target material. IGZO ceramic powder is volatile at high temperature, densification and sintering are difficult, and increasing the sintering aid is easy to reduce the service performance of IGZO materials. Therefore, while ensuring the excellent photoelectric properties of the IGZO material, the sintering activity of the material is improved by doping, and the reduction of the sintering temperature is an important research direction of the IGZO material. The molybdenum trioxide has a lower melting point, and the doped molybdenum oxide can reduce the densification temperature of the IGZO ceramic, inhibit the growth of grains and facilitate the preparation of fine-grain IGZO targets. By doping a small amount of molybdenum oxide, the light transmittance of the IGZO film is not reduced, the resistivity of the IGZO film is improved, and the stability of the IGZO film material is improved.
At present, the doped IGZO target material is prepared by adding trace element oxide powder into IGZO powder and mixing the powder by adopting a ball milling method. In order to achieve a good mixing effect, long-time ball milling and multiple times of pre-dispersion are needed, and the time for preparing the powder is greatly prolonged. And the micro solid powder is difficult to homogenize by adopting a mechanical ball milling method, and powder is easy to gather at one position, so that the doping elements are not uniform, and the quality of the target material is influenced. More importantly, the ball milling is easy to cause the abrasion of the ball milling medium, new impurities are introduced, and the target material is polluted.
Therefore, it is desirable to provide a method for preparing a micro-doped IGZO material, which can prepare an IGZO material with uniform doping and low resistivity.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a preparation method of the doped IGZO material, which can be used for preparing the IGZO material with uniform doping and low resistivity.
The conception of the invention is as follows: uniformly mixing raw material powder of an IGZO material and an ammonium molybdate aqueous solution by utilizing the characteristic that ammonium molybdate is dissolved in water, forming an ammonium molybdate coating layer which is uniformly dispersed on the surface of the raw material powder after drying, and then pyrolyzing the ammonium molybdate into MoO by heating3Realization of micro MoO3While ammonium molybdate is pyrolyzed to generate NH thermally dissociated3Can be fully escaped along with heating, and can not introduce new impurities into the raw material powder. In order to prepare an IGZO material having uniform doping and low resistivity, it is also important to control the particle size of the raw material powder.
IGZO is composed of ZnO and In2O3、Ga2O3Three oxides, different from the materials consisting of other ternary or binary oxides, Ga2O3Melting point of (2) and ZnO, In2O3The difference in melting point of (b) is large, and the crystal structure is easily transformed at high temperature, so that the doping is more difficult.
A method of preparing a doped IGZO material, comprising the steps of:
(1) to ZnO and In2O3、Ga2O3Adding ammonium molybdate solution into the powder, mixing, drying, sieving and heating to obtain IGZO powder;
(2) adding a forming agent into the IGZO powder prepared in the step (1), mixing, drying, sieving, forming, removing the forming agent, and sintering to obtain the IGZO material; the ZnO and In2O3、Ga2O3The particle size of the powder is 300-800 nm.
Preferably, the particle size of the IGZO powder is 300-800 nm.
Preferably, In the step (1), the ZnO and In are2O3And Ga2O3The mol ratio of the powder is (1-2): (1-2): (1-8); more preferably, In the step (1), the ZnO or In is2O3And Ga2O3The molar ratio of the powder is 1: 1: (1-8).
Preferably, the IGZO material is doped with molybdenum, and the doping amount of the molybdenum is 0.01-0.2 wt%; further preferably, the doping amount of the molybdenum in the IGZO material is 0.02-0.2 wt%.
Preferably, the concentration of ammonium molybdate in the ammonium molybdate solution in the step (1) is 0.01 to 0.3 wt%; further preferably, the concentration of ammonium molybdate in the ammonium molybdate solution in step (1) is 0.05 to 0.3 wt%.
Preferably, in the step (1), the mixing process is mixing by means of wet milling, and the time of the wet milling is 24-48 h.
Preferably, in the step (1), the heating temperature is 280-380 ℃; further preferably, the temperature of the heating in the step (1) is 300-350 ℃. At which temperature the ammonium molybdate pyrolyzes more fully.
Preferably, in the step (2), the forming agent is polyethylene glycol or polyvinyl alcohol; further preferably, in the step (2), the forming agent is polyethylene glycol.
Preferably, in the step (2), the amount of the forming agent is 0.5 to 5 wt%.
Preferably, in the step (2), the molding process comprises molding and static pressure, the pressure of the molding is 20-40MPa, and the pressure of the static pressure is 200-400 MPa; further preferably, the pressure of the molding is 20-30MPa, and the pressure of the static pressure is 200-300 MPa.
Preferably, in the step (2), the sintering process is sintering at 1300-1500 ℃ and under the oxygen atmosphere at normal pressure for 5-12 h; further preferably, in the step (2), the sintering process is sintering at 1300-1450 ℃ under oxygen atmosphere at normal pressure for 6-10 h.
Specifically, the preparation method of the doped IGZO material comprises the following steps:
(1) according to the molar ratio (1-2): (1-2): (1-8) weighing ZnO and In2O3、Ga2O3Adding the powder into 0.01-0.3 wt% ammonium molybdate solution, wet-grinding for 24-48h, mixing uniformly, drying, sieving with 5000-8000 mesh sieve, heating to 280-380 deg.C to pyrolyze ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding a forming agent polyethylene glycol into the powder prepared in the step (1), wet-grinding, mixing, drying, sieving, then carrying out die pressing under the pressure of 20-40MPa, preparing a green compact under the pressure static pressure of 200-400MPa, removing the forming agent, and sintering at 1300-1500 ℃ and under the oxygen atmosphere for 5-12h at normal pressure to obtain the IGZO material.
The doped IGZO material is prepared by the preparation method, the relative density of the IGZO material is more than 99.6%, and the resistivity of the IGZO material is less than 9.5 multiplied by 10-4Ω·cm。
The doped IGZO material is applied to the field of semiconductors. The target material is mainly used as a target material for sputtering coating, comprises a plane target and a rotating target and is used as an active layer material of a thin film transistor.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, by utilizing the characteristic that ammonium molybdate is dissolved in water, the ammonium molybdate and IGZO powder are mixed, dried and pyrolyzed to obtain MoO3The coated IGZO powder greatly improves the trace MoO3The degree of homogeneity of the powder mixing under doping. And a trace of MoO3The solid solution is dissolved in zinc oxide crystal lattices, and the conductivity and the relative density of the IGZO material can be greatly improved under the condition of not influencing a target material phase. The IGZO material has a relative density of more than 99.6% and a resistivity of less than 9.5 × 10-4Omega cm. The IGZO thin film material prepared from the IGZO material has strong stability and high quality.
(2) The preparation method is simple and easy to operate, and can economically and efficiently prepare the IGZO materials with various complex shapes.
Drawings
FIG. 1 is a flow chart of a process for preparing IGZO powder in an IGZO material according to example 1;
FIG. 2 is a flow chart of the sintering process for preparing IGZO powder in IGZO material in example 1.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples are given for illustration. It should be noted that the following examples are not intended to limit the scope of the claimed invention.
The starting materials, reagents or apparatuses used in the following examples are conventionally commercially available or can be obtained by conventionally known methods, unless otherwise specified.
Example 1
A preparation method of a doped IGZO material refers to a preparation process flow chart of IGZO powder in figure 1 and a sintering process flow chart of IGZO powder in figure 2, and comprises the following steps:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 30MPa, a green body is prepared under the pressure of 350MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (the forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.90% and a resistivity of less than 2 × 10-4Ω·cm。
Example 2
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 2: 8 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.01 wt% ammonium molybdate aqueous solution, wet-grinding for 24h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; heating to 320 ℃ to pyrolyze ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 1 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 20MPa, a green body is prepared under the pressure of 400MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.85% and a resistivity of less than 3.5 × 10-4Ω·cm。
Example 3
A method of preparing a doped IGZO material, comprising the steps of:
(1) and (2) according to molar ratio: 1: 5 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 5 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then carrying out die pressing under the pressure of 40MPa, preparing a green body under the pressure of 200MPa, heating to 750 ℃, keeping the temperature for 4h, carrying out furnace cooling (removing the forming agent), and then sintering at 1420 ℃ under the atmospheric pressure in an oxygen atmosphere for 10h to obtain the IGZO material. The IGZO material has a relative density of 99.82% and a resistivity of less than 3.2 × 10-4Ω·cm。
Example 4
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 2: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 48h, uniformly mixing, then drying by hot air, and fully grinding until the powder is completely groundPassing through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then carrying out die pressing under the pressure of 35MPa, preparing a green body under the pressure of 350MPa, heating to 750 ℃, keeping the temperature for 4h, carrying out furnace cooling (removing the forming agent), and then sintering at 1500 ℃ under the oxygen atmosphere for 8h at normal pressure to obtain the IGZO material. The IGZO material has a relative density of 99.80% and a resistivity of less than 4.2 × 10-4Ω·cm。
Example 5
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; then heated to 280 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 30MPa, a green body is prepared under the pressure of 350MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (the forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.78% and a resistivity of less than 5.6 × 10-4Ω·cm。
Example 6
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The powder has a particle size of 300-800nm), adding the mixture into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the mixture passes through a 200-mesh sieve; then heated to 350 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 30MPa, a green body is prepared under the pressure of 350MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (the forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.76% and a resistivity of less than 7.2 × 10-4Ω·cm。
Example 7
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 45MPa, a green body is prepared under the pressure of 450MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.62% and a resistivity of less than 9.4 × 10-4Ω·cm。
Example 8
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), adding the powder into 0.1 wt% ammonium molybdate aqueous solution, wet-grinding for 36h, uniformly mixing, then drying by hot air, and fully grinding until all the powder passes through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 30MPa, a green body is prepared under the pressure of 350MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (the forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 99.75% and a resistivity of less than 6.8 × 10-4Ω·cm。
Comparative example 1
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 2-4 mu m), adding the powder into 0.1 wt% ammonium molybdate solution, wet-grinding for 36h, uniformly mixing, drying by hot air, and fully grinding until the powder passes through a 200-mesh sieve; then heated to 320 ℃ to pyrolyze the ammonium molybdate into MoO3To prepare IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until all the powder passes through a 200-mesh sieve; and then mould pressing is carried out under the pressure of 30MPa, a green body is prepared under the pressure of 350MPa, the temperature is increased to 750 ℃, furnace cooling is carried out for 4h (the forming agent is removed), and then sintering is carried out for 10h under the atmospheric pressure in the oxygen atmosphere at 1380 ℃, thus obtaining the IGZO material. The IGZO material has a relative density of 98.5% and a resistivity of less than 7.5 × 10-3Ω·cm。
Comparative example 2
A method of preparing a doped IGZO material, comprising the steps of:
(1) according to the mol ratio of 1: 1: 1 weighing ZnO and In2O3、Ga2O3Powder (ZnO, In)2O3、Ga2O3The particle size of the powder is 300-800nm), wet grinding is carried out for 36h, the mixture is uniformly mixed, and then the mixture is dried by hot air and fully ground until the mixture completely passes through a 200-mesh sieve, so as to prepare the IGZO powder;
(2) adding 3 wt% of polyethylene glycol into the powder prepared in the step (1), wet-grinding for 24h, uniformly mixing, fully drying, crushing, fully grinding until the powder completely passes through a 200-mesh sieve, then carrying out die pressing under the pressure of 30MPa to prepare a green body under the pressure of 350MPa, heating to 750 ℃, keeping the temperature for 4h, carrying out furnace cooling (removing a forming agent), and then carrying out normal pressure sintering at 1380 ℃ in an oxygen atmosphere for 10h to prepare the IGZO material. The IGZO material has a relative density of 98.1% and a resistivity of less than 9 × 10-2Ω·cm。

Claims (10)

1. A preparation method of a doped IGZO material is characterized by comprising the following steps:
(1) to ZnO and In2O3、Ga2O3Adding ammonium molybdate solution into the powder, mixing, drying, sieving and heating to obtain IGZO powder;
(2) adding a forming agent into the IGZO powder prepared in the step (1), mixing, drying, sieving, forming, removing the forming agent, and sintering to obtain the IGZO material; the ZnO and In2O3、Ga2O3The particle size of the powder is 300-800 nm.
2. The preparation method according to claim 1, wherein in step (1), the particle size of the IGZO powder is preferably 300-800 nm.
3. The production method according to claim 2, wherein In the step (1), the ZnO or In is2O3And Ga2O3The mol ratio of the powder is (1-2): (1-2): (1-8).
4. The preparation method according to claim 1, wherein in the step (1), the IGZO material is doped with molybdenum, and the doping amount of the molybdenum is 0.01-0.2 wt%.
5. The method as claimed in claim 1, wherein the heating temperature in step (1) is 280-380 ℃.
6. The method according to claim 1, wherein in the step (2), the forming agent is polyethylene glycol or polyvinyl alcohol.
7. The preparation method according to claim 1, wherein in the step (2), the molding process comprises molding and static pressure, the pressure of the molding is 20-40MPa, and the pressure of the static pressure is 200-400 MPa.
8. The method according to claim 1, wherein in the step (2), the sintering process is: sintering at 1300-1500 ℃ and oxygen atmosphere for 5-12 h.
9. A doped IGZO material produced by the production method according to any one of claims 1 to 8, wherein the IGZO material has a relative density of more than 99.6% and a resistivity of less than 9.5 x 10-4Ω·cm。
10. Use of the doped IGZO material according to claim 9 in the semiconductor field.
CN202011494732.2A 2020-12-17 2020-12-17 Preparation method of doped IGZO material Pending CN112479683A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011494732.2A CN112479683A (en) 2020-12-17 2020-12-17 Preparation method of doped IGZO material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011494732.2A CN112479683A (en) 2020-12-17 2020-12-17 Preparation method of doped IGZO material

Publications (1)

Publication Number Publication Date
CN112479683A true CN112479683A (en) 2021-03-12

Family

ID=74917447

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011494732.2A Pending CN112479683A (en) 2020-12-17 2020-12-17 Preparation method of doped IGZO material

Country Status (1)

Country Link
CN (1) CN112479683A (en)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102959122A (en) * 2010-08-05 2013-03-06 三菱综合材料株式会社 Method for producing sputtering target, and sputtering target
CN103130493A (en) * 2011-11-23 2013-06-05 财团法人工业技术研究院 Indium Gallium Zinc Oxide (IGZO) nano powder and preparation method and application thereof
CN103193262A (en) * 2013-04-09 2013-07-10 桂林电子科技大学 Indium-gallium-zinc oxide powder and preparation method of ceramic target thereof
CN103819178A (en) * 2013-12-11 2014-05-28 广西晶联光电材料有限责任公司 Preparation method of IGZO (Indium Gallium Zinc Oxide) target
CN103890986A (en) * 2011-10-19 2014-06-25 富士胶片株式会社 Thermoelectric conversion element and process for producing same
CN106435490A (en) * 2015-08-06 2017-02-22 清华大学 Sputtering target, oxide semiconductor film, preparing method of sputtering target and preparing method of oxide semiconductor film
CN107176840A (en) * 2016-03-11 2017-09-19 深圳大学 A kind of MoO3Coat preparation and its sintering method of AZO powders
US20170316847A1 (en) * 2014-11-07 2017-11-02 Plansee Se Metal oxide thin film, method for depositing metal oxide thin film and device comprising metal oxide thin film
US20180065893A1 (en) * 2015-03-23 2018-03-08 Jx Nippon Mining & Metals Corporation Oxide sintered compact and sputtering target formed from said oxide sintered compact
CN107793145A (en) * 2016-09-07 2018-03-13 深圳大学 A kind of MoO3Coat preparation and its sintering method of TZO powders

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102959122A (en) * 2010-08-05 2013-03-06 三菱综合材料株式会社 Method for producing sputtering target, and sputtering target
CN103890986A (en) * 2011-10-19 2014-06-25 富士胶片株式会社 Thermoelectric conversion element and process for producing same
CN103130493A (en) * 2011-11-23 2013-06-05 财团法人工业技术研究院 Indium Gallium Zinc Oxide (IGZO) nano powder and preparation method and application thereof
CN103193262A (en) * 2013-04-09 2013-07-10 桂林电子科技大学 Indium-gallium-zinc oxide powder and preparation method of ceramic target thereof
CN103819178A (en) * 2013-12-11 2014-05-28 广西晶联光电材料有限责任公司 Preparation method of IGZO (Indium Gallium Zinc Oxide) target
US20170316847A1 (en) * 2014-11-07 2017-11-02 Plansee Se Metal oxide thin film, method for depositing metal oxide thin film and device comprising metal oxide thin film
US20180065893A1 (en) * 2015-03-23 2018-03-08 Jx Nippon Mining & Metals Corporation Oxide sintered compact and sputtering target formed from said oxide sintered compact
CN106435490A (en) * 2015-08-06 2017-02-22 清华大学 Sputtering target, oxide semiconductor film, preparing method of sputtering target and preparing method of oxide semiconductor film
CN107176840A (en) * 2016-03-11 2017-09-19 深圳大学 A kind of MoO3Coat preparation and its sintering method of AZO powders
CN107793145A (en) * 2016-09-07 2018-03-13 深圳大学 A kind of MoO3Coat preparation and its sintering method of TZO powders

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
俞志明: "《中国化工商品大全 第二卷（1995年版）》", 31 January 1996, 中国物资出版社 *
岳兰等: "非晶氧化物半导体薄膜晶体管沟道层的研究进展", 《SEMICONDUCTOR TECHNOLOGY》 *
徐克玷: "《钼的材料科学与工程》", 31 July 2014, 冶金工业出版社 *
李光等: "非晶铟镓锌氧化物薄膜的制备及其在薄膜晶体管中的应用", 《硅酸盐通报》 *
葛春桥等: "掺杂透明导电半导体薄膜的光电性能研究", 《应用光学》 *
赵光明: "《功能材料 第七届中国功能材料及其应用学术会议论文集 6》", 31 October 2010 *

Similar Documents

Publication Publication Date Title
CN101931009B (en) Thin film transistor and method of producing thin film transistor
JP5096250B2 (en) Oxide sintered body manufacturing method, oxide sintered body, sputtering target, oxide thin film, thin film transistor manufacturing method, and semiconductor device
CN106129259A (en) A kind of perovskite solaode with black phosphorus and Graphene as hole transmission layer and preparation method
CN112341159A (en) Preparation method of indium gallium zinc oxide target material
CN102664151B (en) High-temperature annealing method for manufacturing silicon carbide device
CN106206684B (en) Oxide semiconductor film and method for producing same
CN101325227A (en) Method for preparing ZnO/nanometer diamond coplane grid ultraviolet light detector
CN113981370A (en) Deep ultraviolet transparent high-conductivity Si-doped Ga2O3Film and preparation method thereof
CN112299823A (en) Oxide target material and preparation method thereof
CN114736013A (en) Zinc-magnesium oxide target material and preparation method thereof
CN106435490A (en) Sputtering target, oxide semiconductor film, preparing method of sputtering target and preparing method of oxide semiconductor film
Li et al. Enhanced electrical properties of ZnO transparent conducting films prepared by electron beam annealing
CN100565716C (en) Transparent conductive film and preparation method thereof
CN112479683A (en) Preparation method of doped IGZO material
CN115925410B (en) Praseodymium-doped indium zinc oxide sputtering target material and preparation method thereof
CN109354497B (en) Ho-doped transparent scandium oxide ceramic and preparation method thereof
CN104078513A (en) Amorphous oxide semiconductor film and preparation method and application thereof
Zhang et al. The high quantum efficiency of exponential-doping AlGaAs/GaAs photocathodes grown by metalorganic chemical vapor deposition
CN113754436B (en) Preparation method of nanocrystalline laser-grade sesquioxide transparent ceramic
US20130334688A1 (en) Multi-elements-doped zinc oxide film, manufacturing method and application thereof
CN109305811A (en) A kind of microwave-assisted zinc oxide ceramics sintering method
CN115536368A (en) NiO with controllable oxygen content x Target material preparation method
CN106435491A (en) Sputtering target, oxide semiconductor film, preparing method of sputtering target and preparing method of oxide semiconductor film
CN112537954B (en) Preparation method of IGZO target material
CN110867383B (en) Method for preparing copper zinc tin sulfide film absorption layer by three-step vulcanization process

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210312