CN114702304B - Indium-tungsten oxide target material and preparation method thereof - Google Patents

Indium-tungsten oxide target material and preparation method thereof Download PDF

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CN114702304B
CN114702304B CN202210511038.XA CN202210511038A CN114702304B CN 114702304 B CN114702304 B CN 114702304B CN 202210511038 A CN202210511038 A CN 202210511038A CN 114702304 B CN114702304 B CN 114702304B
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iwo
indium
target material
powder
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CN114702304A (en
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刘洋
左仲恒
孙本双
曾学云
王之君
刘苗
陈杰
舒永春
何季麟
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Zhengzhou University
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Abstract

The invention provides an indium-tungsten oxide target material and a preparation method thereof, belonging to the technical field of photoelectric materials. The method comprises the steps of mixing indium oxide and tungsten oxide In a stoichiometric ratio, calcining the mixture to ensure that the indium oxide and the tungsten oxide can be completely subjected to solid-phase reaction to obtain In 6 WO 12 (ii) a The generation of oxygen vacancies can be inhibited by calcining in the oxygen atmosphere, so that the density of the product is improved; in is mixed with 6 WO 12 Mixing with indium oxide, water, dispersant and binder, pressure grouting to increase In 6 WO 12 The degree of dispersion of the phase in the target material further improves the density of the target material; the dispersing agent and the binder are removed through degreasing treatment, and the obtained target material is uniform in tissue refinement and high in density by combining step variable-temperature sintering. The experimental result of the embodiment shows that the relative density of the indium-tungsten oxide target material prepared by the preparation method provided by the invention is 98.1-99.6%.

Description

Indium-tungsten oxide target material and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an indium-tungsten oxide target material and a preparation method thereof.
Background
Transparent conductive oxide films (TCO) are materials with special functions, have good optical performance and electrical conductivity, and are widely applied to the fields of electronic screens, touch screen panels, light Emitting Diodes (LEDs), solar cells and the like. The material is easy to produce and can be prepared by using the techniques of chemical vapor deposition, magnetron sputtering, spray pyrolysis and the like. The most commonly used TCO at present is tin-doped indium oxide (indium tin oxide or ITO).
In contrast to tin-doped indium oxide (ITO) and aluminum-doped zinc oxide (AZO) material systems, WO 3 Doping with In 2 O 3 The IWO film prepared by the material system has higher carrier mobility, high light transmittance in visible light and near infrared bands and better high temperature and physical and chemical stability. IWO possesses higher electron mobility, and therefore, its excellent photoelectric properties can be further improved without increasing the carrier concentration (maintaining high light transmittance).
Meanwhile, the IWO film can also be used as a channel layer material in a TFT device, and compared with an IGZO film, the IWO film has stronger acid-base-resistant etching performance because of WO x Except hydrofluoric acid, ga and Zn atoms in the IGZO material are not dissolved in any acid solution easily, so that the etching rate is not easy to control, the etching process needs to be stabilized by increasing the thickness (100 nm) of the deposited IGZO film, the IWO film with strong acid-base etching resistance can reduce the use thickness (10 nm), the cost is reduced, and the key is to avoid the formation of a large number of crystal boundaries, so that the electron mobility is improved.
At present, the IWO film is mainly prepared by a magnetron sputtering method, and a sputtering target material is an important factor influencing the sputtering stability and the film property. In the prior art, the IWO target is generally prepared by mixing indium oxide and tungsten oxide powder and then sintering at normal pressure. However, the IWO target prepared by the method has low density, belongs to a non-compact body, easily generates protrusions in the using process, has the problem of powder falling, and causes great hidden troubles for continuous production.
Therefore, how to improve the compactness of the IWO target becomes a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide an indium-tungsten oxide target material and a preparation method thereof. The indium-tungsten oxide target material prepared by the preparation method provided by the invention has higher relative density.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an indium-tungsten oxide target material, which comprises the following steps:
(1) Mixing indium oxide and tungsten oxide according to stoichiometric ratio, and calcining In oxygen atmosphere to obtain In 6 WO 12 ；
(2) In obtained In the step (1) 6 WO 12 Mixing with indium oxide, water, a dispersing agent and a binder to obtain IWO slurry;
(3) Performing pressure grouting on the IWO slurry obtained in the step (2) to obtain an IWO biscuit;
(4) And (4) sequentially carrying out degreasing treatment and step variable-temperature sintering on the IWO biscuit obtained in the step (3) to obtain the indium-tungsten oxide target material.
Preferably, the calcining temperature in the step (1) is 700-1000 ℃, and the calcining time is 2-20 h.
Preferably, in said step (2) 6 WO 12 The amount of (B) is 1 to 6% by mass of the indium oxide.
Preferably, the mass of the dispersing agent In the step (2) is In 6 WO 12 And 1.2 to 1.8 percent of the total mass of the indium oxide.
Preferably, the mass of the binder In the step (2) is In 6 WO 12 And 0.3 to 1.0% by mass of indium oxide.
Preferably, the solid content of the IWO slurry in the step (2) is more than 80%, and the viscosity of the IWO slurry is less than 100 mPas.
Preferably, the temperature of the degreasing treatment in the step (4) is 500-800 ℃, and the heat preservation time of the degreasing treatment is 5-24 h.
Preferably, the step temperature-changing sintering in the step (4) comprises:
and (3) performing first temperature rise on the product obtained by degreasing treatment to the first step temperature for first heat preservation, then performing second temperature rise to the second step temperature, then immediately performing first temperature reduction to the third step temperature for second heat preservation, and then performing second temperature reduction to 600 ℃.
Preferably, the temperature of the first step is 900-1100 ℃, the temperature of the second step is 1400-1500 ℃, and the temperature of the third step is 1000-1300 ℃.
The invention provides the indium-tungsten oxide target material prepared by the preparation method in the technical scheme.
The invention provides a preparation method of an indium-tungsten oxide target material, which comprises the following steps: mixing indium oxide and tungsten oxide according to stoichiometric ratio, and calcining In oxygen atmosphere to obtain In 6 WO 12 (ii) a Putting the In 6 WO 12 Mixing with indium oxide, water, a dispersing agent and a binder to obtain IWO slurry; performing pressure grouting on the IWO slurry to obtain an IWO biscuit; and sequentially carrying out degreasing treatment and step variable-temperature sintering on the IWO biscuit to obtain the indium-tungsten oxide target material. The method comprises the steps of mixing indium oxide and tungsten oxide In a stoichiometric ratio, calcining the mixture to ensure that the indium oxide and the tungsten oxide can be completely subjected to solid-phase reaction to obtain In 6 WO 12 (ii) a The generation of oxygen vacancies can be inhibited by calcining in the oxygen atmosphere, so that the density of the product is improved; in is mixed with 6 WO 12 Mixing with indium oxide, water, dispersant and binder, pressure grouting to increase In 6 WO 12 The degree of dispersion of the phase in the target material further improves the density of the target material; the dispersing agent and the binder are removed through degreasing treatment, and the obtained target material is uniform in tissue refinement and high in density by combining step variable-temperature sintering. The experimental result of the embodiment shows that the relative density of the indium-tungsten oxide target material prepared by the preparation method provided by the invention is 98.1-99.6% (the theoretical density is 7.18 g/cm) 3 Meter).
Detailed Description
The invention provides a preparation method of an indium-tungsten oxide target material, which comprises the following steps:
(1) Mixing indium oxide and tungsten oxide according to stoichiometric ratio, and calcining In oxygen atmosphere to obtain In 6 WO 12 ；
(2) In obtained In the step (1) 6 WO 12 Mixing with indium oxide, water, a dispersing agent and a binder to obtain IWO slurry;
(3) Performing pressure grouting on the IWO slurry obtained in the step (2) to obtain an IWO biscuit;
(4) And (4) sequentially carrying out degreasing treatment and step variable-temperature sintering on the IWO biscuit obtained in the step (3) to obtain the indium-tungsten oxide target.
In the present invention, the sources of the components are not particularly limited, unless otherwise specified, and commercially available products known to those skilled in the art may be used.
The invention mixes indium oxide and tungsten oxide according to stoichiometric ratio and then calcines the mixture In oxygen atmosphere to obtain In 6 WO 12 。
In the present invention, the stoichiometric ratio of indium oxide to tungsten oxide is 3:1. The invention ensures the proportion of indium and tungsten In the second phase by controlling the molar ratio of indium oxide to tungsten oxide, so that the second phase In the target material is In 6 WO 12 。
In the invention, the indium oxide and the tungsten oxide are preferably nano powder; the particle size of the indium oxide and the tungsten oxide is preferably 100 to 300nm, and more preferably 150 to 250nm. In the present invention, the particle diameters of the indium oxide and the tungsten oxide are In the above ranges, which is advantageous for the solid-phase reaction of the indium oxide and the tungsten oxide to be more sufficient and for In to be completely generated 6 WO 12 The phases are beneficial to the uniform distribution of the whole composition of the target material phases.
The operation of mixing the indium oxide and the tungsten oxide is not particularly limited, and the indium oxide and the tungsten oxide can be uniformly mixed by adopting a powder mixing technical scheme known to those skilled in the art. In the present invention, the mixing of the indium oxide and the tungsten oxide is preferably performed in a high-efficiency mixer, a jet mill, or a ball mill.
In the present invention, the calcination is performed in an oxygen atmosphere, preferably a high purity oxygen atmosphere.
In the present invention, the temperature of the calcination is preferably 700 to 1000 ℃, more preferably 750 to 950 ℃, and most preferably 800 to 900 ℃; the calcination time is preferably 2 to 20 hours, more preferably 5 to 18 hours, and most preferably 10 to 15 hours. In the present invention, the heating rate for raising the temperature to the calcination temperature is preferably 10 to 20 ℃/min, more preferably 15 ℃/min.
Passing limit of the inventionThe calcination temperature and time are determined, so that the tungsten oxide and the indium oxide powder can be ensured to be completely reacted In a solid phase manner to generate In 6 WO 12 The secondary phase can inhibit the generation of oxygen vacancies by calcining in an oxygen atmosphere, and the purity of the secondary phase and the compactness of the product are improved.
After calcination is completed, the present invention preferably crushes the calcined product to obtain In 6 WO 12 . In the present invention, the In 6 WO 12 The particle diameter of (A) is preferably 500 to 800nm. The present invention is not particularly limited to the above-mentioned crushing operation, and In can be used 6 WO 12 The particle size of the particles meets the requirement. In the present invention, the means for crushing is preferably a jet mill.
To obtain In 6 WO 12 Then, the invention converts the In 6 WO 12 Mixing with indium oxide, water, a dispersant and a binder to obtain IWO slurry.
In the present invention, the indium oxide is preferably used for preparing In 6 WO 12 The indium oxide used is the same and will not be described further herein. In the present invention, the In 6 WO 12 The mass of (b) is preferably 1 to 6%, more preferably 2 to 5%, most preferably 3 to 4% of the mass of indium oxide. In the invention 6 WO 12 The mass ratio of indium oxide to indium oxide is controlled within the above range to avoid In 6 WO 12 Too high mass ratio and too high doping concentration of (A) lead to the reduction of the electrical properties of the target material, and In is avoided 6 WO 12 Too low a mass fraction of (a) results in incomplete densification of the target.
In the present invention, the dispersant is preferably ammonium polyacrylate or a polycarboxylic acid-based dispersant. In the present invention, the mass of the dispersant is preferably In 6 WO 12 And indium oxide 1.2 to 1.8%, more preferably 1.4 to 1.6%, most preferably 1.5% by mass. The invention controls the quality of the dispersant in the above range, can ensure that the oxide powder is fully and uniformly dispersed in the slurry, and is beneficial to obtaining the target material with fine tissue and uniform second phase distribution.
In the present invention, the binder is preferably polyvinyl alcohol or gum arabic. In the present inventionIn the invention, the mass of the binder is preferably In 6 WO 12 And indium oxide, 0.3 to 1.0% by mass, more preferably 0.4 to 0.9% by mass, most preferably 0.5 to 0.8% by mass. According to the invention, the quality of the binder is controlled within the range, so that the slurry can have proper viscosity, and the obtained biscuit has proper density, thereby improving the density of the target.
In the present invention, the water is preferably deionized water. In the present invention, the mass of the water is preferably In 6 WO 12 And indium oxide 16 to 20%, more preferably 17 to 19%, most preferably 18% by mass. The invention controls the water consumption in the range, can ensure that the slurry has proper solid content, promotes oxide powder to be fully and uniformly dispersed in the slurry, and is favorable for obtaining the target material with fine tissue and uniform second phase distribution.
In the present invention, the solid content of the IWO slurry is preferably greater than 80%, more preferably 85% or less. In the present invention, the viscosity of the IWO slurry is preferably less than 100 mPas, more preferably more than 50 mPas. The invention controls the viscosity and solid content of IWO slurry in the range, is beneficial to fully and uniformly dispersing oxide powder in the slurry, simultaneously enables the slurry to have proper viscosity, and is beneficial to obtaining the target material with fine tissue, uniform second phase distribution and high density.
In the present invention, the In 6 WO 12 The mixing with indium oxide, water, dispersant and binder is preferably: in is mixed with 6 WO 12 Mixing with indium oxide to obtain mixed powder; and then mixing the mixed powder with indium oxide, water, a dispersing agent and a binder.
In the present invention, the In 6 WO 12 Mixing with indium oxide is preferably ball milling. The invention can mix In by ball milling 6 WO 12 The mixture is uniformly mixed with indium oxide, which is beneficial to obtaining the target material with uniform second phase distribution and fine tissue.
In the present invention, the mixing of the mixed powder with indium oxide, water, a dispersant and a binder is preferably high energy sanding. In the present invention, the rotation speed of the sand mill during the high-energy sanding is preferably 1000 to 2400rpm, more preferably 1200 to 2000rpm, and most preferably 1600 to 1800rpm. In the present invention, the time for the high-energy sanding is preferably 30 to 120min, more preferably 50 to 100min, and most preferably 60 to 80min. In the invention, the high-energy sand mill is beneficial to dispersing oxide powder in the slurry into single particles in a nanometer mode, and the sintering activity of the powder is increased.
In the present invention, the pH of the slurry changes with the addition of the dispersant. The Zeta potential value of the slurry along with the change of the pH is preferably detected by a nano-particle size potentiometer, so that the slurry is ensured to be in an optimal dispersion state.
After IWO slurry is obtained, the invention carries out pressure grouting on the IWO slurry to obtain IWO biscuit.
In the present invention, the pressure of the pressure grouting is preferably 0.1 to 0.6MPa, and more preferably 0.2 to 0.4MPa. In the present invention, the mold used for the pressure grouting is preferably made of a polymer material. The invention can prepare the target biscuit with larger size by adopting a pressure slip casting method, has simple and convenient operation and saves the cost.
According to the invention, the IWO slurry is subjected to vacuum defoaming treatment before pressure grouting; the vacuum pressure of the vacuum debubbling treatment is preferably less than 0.1Pa. In the invention, the vacuum defoaming treatment can remove gas in the slurry, and is favorable for obtaining the biscuit with high density.
After the pressure grouting is finished, the invention preferably dries the product obtained by the pressure grouting to obtain the IWO biscuit. The present invention can remove residual moisture by drying.
In the present invention, the drying preferably includes low-temperature drying and medium-temperature drying which are sequentially performed. In the present invention, the temperature of the low-temperature drying is preferably 25 to 35 ℃, and more preferably 30 ℃; the ambient humidity of the low-temperature drying is preferably 70 to 80% rh, more preferably 75% rh; the time for low-temperature drying is preferably 24 to 36 hours, and more preferably 30 hours. In the invention, the temperature of the medium-temperature drying is preferably 35-45 ℃, and more preferably 40 ℃; the ambient humidity of the low-temperature drying is preferably 50 to 60% rh, more preferably 55% rh; the time for low-temperature drying is preferably 36 to 48 hours, and more preferably 40 hours.
In the present invention, the drying is preferably performed in a constant temperature and humidity chamber.
In the present invention, the IWO biscuit preferably has a relative density of 60% or more (in terms of theoretical density, 7.18 g/cm) 3 Meter).
After IWO biscuit, the invention carries out degreasing treatment and step variable-temperature sintering on the IWO biscuit in sequence to obtain the indium-tungsten oxide target.
In the present invention, the temperature of the degreasing treatment is preferably 500 to 800 ℃, more preferably 600 to 700 ℃, and most preferably 650 ℃; the heat preservation time for the degreasing treatment is preferably 5 to 24 hours, more preferably 10 to 20 hours, and most preferably 14 to 18 hours. In the present invention, the rate of raising the temperature to the degreasing treatment temperature is preferably 0.5 to 1.5 ℃/min, more preferably 1 ℃/min. The invention can remove the binder and the dispersant in the IWO biscuit by degreasing treatment.
In the invention, after the degreasing treatment is finished, the step temperature-changing sintering is directly carried out without cooling. According to the invention, the sintering activity of the surface of the powder is improved through step variable-temperature sintering, so that the density of the target material is improved, and the resistivity is reduced.
In the present invention, the step varying temperature sintering preferably includes:
and (3) performing first temperature rise on the product obtained by degreasing treatment to the first step temperature for first heat preservation, then performing second temperature rise to the second step temperature, then immediately performing first temperature reduction to the third step temperature for second heat preservation, and then performing second temperature reduction to 600 ℃.
In the present invention, the rate of the first temperature rise is preferably 2 to 4 ℃/min, more preferably 3 ℃/min; the first step temperature is preferably 900-1100 ℃, more preferably 950-1050 ℃, and most preferably 1000 ℃; the time of the first heat preservation is preferably 10 to 20 hours, more preferably 12 to 18 hours, and most preferably 14 to 16 hours. In the invention, the organic additive is mainly removed in the first heat preservation stage when the first temperature is raised to the first step temperature, and the nano particles are basically solidified.
In the present invention, the rate of the second temperature rise is preferably 5 to 10 ℃/min, more preferably 6 to 8 ℃/min; the second step temperature is preferably 1400 to 1500 ℃, more preferably 1420 to 1480 ℃, and most preferably 1440 to 1460 ℃. In the invention, in the second stage of heating to the second step temperature, the size of the target crystal grains is basically determined, and the phase structure is formed.
In the invention, the first cooling rate is preferably 10-20 ℃/min, more preferably 12-18 ℃/min; the temperature of the third step is preferably 1000-1300 ℃, more preferably 1050-1250 ℃, and most preferably 1100-1200 ℃; the time of the third heat preservation is preferably 10 to 30 hours, more preferably 15 to 25 hours, and most preferably 20 hours. In the invention, the target material is completely densified in the heat preservation process from the first temperature reduction to the third step temperature.
In the present invention, the rate of the second temperature reduction is preferably 1 to 2 ℃/min.
After the step variable-temperature sintering is finished, the invention preferably cools the product of the step variable-temperature sintering to room temperature along with the furnace to obtain the indium-tungsten oxide target material.
The preparation method provided by the invention can control the indium-tungsten atomic ratio In the secondary phase by regulating and controlling the mass ratio of tungsten oxide to indium oxide to obtain In 6 WO 12 Thereby being beneficial to obtaining the IWO target material with uniform and refined tissue and high density; the target biscuit with larger size can be prepared by adopting a pressure slip casting method, the operation is simple and convenient, and the cost is saved.
The invention provides the indium-tungsten oxide target material prepared by the preparation method in the technical scheme. The indium-tungsten oxide target material provided by the invention has the advantages of uniform and refined structure and high density.
In the invention, the microstructure of the indium-tungsten oxide target material comprises In 2 O 3 A matrix and In uniformly distributed In 2 O 3 Secondary phase In on the substrate 6 WO 12 。
In the invention, the relative density of the indium-tungsten oxide target material is 98.1-99.6% (the theoretical density is 7.18 g/cm) 3 Meter), the volume resistivity is 0.6-3 m omega cm.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing nanoscale (20-200 nm) indium oxide powder and tungsten oxide powder according to a molar ratio of 3:1, wherein the total mass of the powder is 500g, uniformly mixing the powder by using a high-efficiency mixer, calcining the mixture at 800 ℃ In the atmosphere of high-purity oxygen for 10 hours to obtain secondary-phase In 6 WO 12 ；
Then In is obtained by crushing and grading treatment through a jet mill 6 WO 12 Powder of and nano-scale In 2 O 3 In mass ratio of powder 6 WO 12 /In 2 O 3 Weighing In a weight ratio of =1wt%, weighing 1000g In 2 O 3 990g of powder, in 6 WO 12 10g of powder, 200g of deionized water accounting for 20 percent of the total mass of the powder and 1.2 percent of ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder are added into the mixed powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 90mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 1800rpm, the time is 50min, vacuumizing and defoaming the IWO slurry after sanding, avoiding large air bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the dwell time is 5h, taking out the target biscuit and putting the target biscuit into a constant-temperature constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and the drying time is 36h; then, the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, and the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
degreasing the IWO biscuit, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1450 ℃ at 8 ℃/min, and keeping the temperature; and rapidly cooling to the third step sintering temperature T3=1200 ℃ at the speed of 18 ℃/min, preserving the heat for 20h at the temperature, cooling to 600 ℃ at the speed of 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished to obtain the IWO target.
The IWO target material prepared in the present example was subjected to density and resistivity tests according to Archimedes' principle and a four-probe apparatus to obtain a relative density of 98.1% (in terms of theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 3m Ω · cm.
Example 2
Weighing nano-scale (20-200 nm) tungsten oxide powder and indium oxide powder according to a molar ratio of 3:1, wherein the total mass of the powder is 500g, uniformly mixing the powder by using a high-efficiency mixer, calcining the mixture for 10 hours at a calcining temperature of 800 ℃ In a high-purity oxygen atmosphere to obtain secondary-phase In 6 WO 12 ；
Pulverizing with jet mill and grading to obtain In 6 WO 12 Powder of and nano-scale In 2 O 3 Powder In mass ratio 6 WO 12 /In 2 O 3 Weighing 1000g of the mixture with the weight ratio of 3wt%, wherein In 2 O 3 970g of powder and in 6 WO 12 30g of powder, 200g of deionized water accounting for 20 percent of the total mass of the powder and 1.2 percent of ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder are added into the mixed powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 90mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 1800rpm, the time is 50min, vacuumizing and defoaming the IWO slurry after sanding, avoiding large air bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the dwell time is 5h, taking out the target biscuit and putting the target biscuit into a constant-temperature constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and the drying time is 36h; then the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
carrying out degreasing sintering treatment, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1450 ℃ at 8 ℃/min, and keeping the temperature; and (3) rapidly cooling to the third step sintering temperature T3=1300 ℃ at 18 ℃/min, preserving the temperature for 20h, cooling to 600 ℃ at 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished.
The IWO target material prepared in the present example was subjected to density and resistivity tests according to Archimedes' principle and a four-probe apparatus to obtain a relative density of 98.5% (in terms of theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 2.8 m.OMEGA.cm.
Example 3
Weighing nanometer tungsten oxide powder (80-200 nm) and indium oxide powder according to the molar ratio of 3:1, wherein the total mass of the powder is 500g, uniformly mixing the powder by using a high-efficiency mixer, calcining the mixture at 800 ℃ In the atmosphere of high-purity oxygen for 10 hours to obtain secondary-phase In 6 WO 12 ；
Pulverizing with jet mill and grading to obtain In 6 WO 12 Powder of and nano-scale In 2 O 3 Powder In mass ratio 6 WO 12 /In 2 O 3 Weighing 1000g of the mixture with the weight ratio of 3wt%, wherein In 2 O 3 970g of powder and in 6 WO 12 30g of powder, 200g of deionized water accounting for 20 percent of the total mass of the powder and 1.2 percent of ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder are added into the mixed powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 100mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 2000rpm, the time is 50min, performing vacuum-pumping bubble-removing treatment on the IWO slurry after sanding to avoid the generation of large bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the pressure maintaining time is 5h, taking out the target biscuit, putting the target biscuit into a constant-temperature and constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and drying for 36h; then, the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, and the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
carrying out degreasing sintering treatment, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1450 ℃ at 8 ℃/min, and keeping the temperature; and (3) rapidly cooling to the third step sintering temperature T3=1200 ℃ at 18 ℃/min, preserving the temperature for 20h, cooling to 600 ℃ at 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished.
The IWO target material prepared in the present example was subjected to density and resistivity tests according to Archimedes' principle and a four-probe apparatus to obtain a relative density of 99.5% (in terms of theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 1m Ω · cm.
Example 4
Weighing nanometer tungsten oxide powder (80-200 nm) and indium oxide powder according to the molar ratio of 3:1, wherein the total mass of the powder is 500g, uniformly mixing the powder by using a high-efficiency mixer, calcining the mixture at 800 ℃ In the atmosphere of high-purity oxygen for 10 hours to obtain secondary-phase In 6 WO 12 ；
Pulverizing with jet mill and grading to obtain In 6 WO 12 Powder of and nano-scale In 2 O 3 Powder In mass ratio 6 WO 12 /In 2 O 3 Weighing 1000g at ratio of =5wt%, wherein In 2 O 3 Powder 952g, in 6 WO 12 48g of powder, adding into the mixed powder200g of deionized water accounting for 20 percent of the total mass of the powder, and ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 100mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 2000rpm, the time is 50min, performing vacuum-pumping bubble-removing treatment on the IWO slurry after sanding to avoid the generation of large bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the pressure maintaining time is 5h, taking out the target biscuit, putting the target biscuit into a constant-temperature and constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and drying for 36h; then, the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, and the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
carrying out degreasing sintering treatment, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1400 ℃ at the speed of 8 ℃/min, and keeping the temperature; and rapidly cooling to the third step sintering temperature T3=1200 ℃ at the speed of 18 ℃/min, preserving the heat for 20h at the temperature, cooling to 600 ℃ at the speed of 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished.
The IWO target material prepared in the embodiment was subjected to density and resistivity tests according to Archimedes principle and a four-probe apparatus to obtain a relative density of 99.1% (in terms of theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 1.3 m.OMEGA.cm.
Example 5
Weighing nanometer tungsten oxide powder (80-200 nm) and indium oxide powder according to the molar ratio of 3:1, wherein the total mass of the powder is 500g, uniformly mixing the powder by using a high-efficiency mixer, calcining the mixture at the calcining temperature of 900 ℃ In the atmosphere of high-purity oxygen for 10 hours to obtain secondary phase In 6 WO 12 ；
Pulverizing with jet mill and grading to obtain In 6 WO 12 Powder of and nano-scale In 2 O 3 Powder In mass ratio 6 WO 12 /In 2 O 3 Weighing 1000g at ratio of =2wt%, wherein In 2 O 3 980g of powder, in 6 WO 12 20g of powder, 200g of deionized water accounting for 20 percent of the total mass of the powder and 1.2 percent of ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder are added into the mixed powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 100mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 2000rpm, the time is 50min, performing vacuum-pumping bubble-removing treatment on the IWO slurry after sanding to avoid the generation of large bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the pressure maintaining time is 5h, taking out the target biscuit, putting the target biscuit into a constant-temperature and constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and drying for 36h; then the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
carrying out degreasing sintering treatment, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1450 ℃ at 8 ℃/min, and keeping the temperature; and (3) rapidly cooling to the third step sintering temperature T3=1200 ℃ at 18 ℃/min, preserving the temperature for 20h, cooling to 600 ℃ at 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished.
The IWO target material prepared in the embodiment was subjected to density and resistivity tests according to Archimedes principle and a four-probe apparatus to obtain a relative density of 99.3% (in terms of theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 0.8 m.OMEGA.cm.
Example 6
Weighing nano-scale (80-200 nm) oxygen according to the molar ratio of 3:1Tungsten powder and indium oxide powder, the total mass of the powder is 500g, then the tungsten powder and the indium oxide powder are uniformly mixed by a high-efficiency mixer, the mixture is calcined for 10 hours at the calcining temperature of 900 ℃ under the atmosphere of high-purity oxygen to obtain secondary phase In 6 WO 12 ；
Pulverizing with jet mill and grading to obtain In 6 WO 12 Powder of and nano-scale In 2 O 3 Powder In mass ratio 6 WO 12 /In 2 O 3 Weighing 1000g at ratio of =6wt%, wherein In 2 O 3 980g of powder, in 6 WO 12 20g of powder, 200g of deionized water accounting for 20 percent of the total mass of the powder and 1.2 percent of ammonium polyacrylate (NH) accounting for 1.2 percent of the total mass of the powder are added into the mixed powder 4 PAA) 12g and polyvinyl alcohol (PVA) 5g accounting for 0.5 percent of the total mass of the powder to prepare IWO slurry with the solid content of 82.17 percent and the viscosity of 100mPa & s;
performing high-energy sanding dispersion on the prepared slurry, wherein the rotating speed of a sand mill is 2000rpm, the time is 50min, performing vacuum-pumping bubble-removing treatment on the IWO slurry after sanding to avoid the generation of large bubbles in the slurry, then preparing an IWO biscuit by adopting a pressure grouting forming process, wherein the grouting pressure is 0.3MPa, the pressure maintaining time is 5h, taking out the target biscuit, putting the target biscuit into a constant-temperature and constant-humidity box for drying treatment, the temperature in an oven is 28 ℃, the humidity is 75% RH, and drying for 36h; then, the temperature of the oven is adjusted to 45 ℃, the humidity is 50%, and the drying is carried out for 36 hours until the quality of the target biscuit is kept constant, and finally the IWO biscuit with the relative density of 60% is obtained;
carrying out degreasing sintering treatment, wherein the heating rate is 1 ℃/min, the degreasing temperature is 600 ℃, the heat preservation time is 18h, the degreased IWO target biscuit directly enters a sintering process, a step temperature-changing sintering process is adopted, the temperature is firstly increased to the first step sintering temperature T1=1000 ℃ at 3 ℃/min, and the heat preservation time is 15h; then rapidly heating to the highest step temperature T2=1450 ℃ at 8 ℃/min, and keeping the temperature; and (3) rapidly cooling to the third step sintering temperature T3=1200 ℃ at 18 ℃/min, preserving the temperature for 20h, cooling to 600 ℃ at 2 ℃/min, and cooling the target sintered body along with the furnace after the furnace heating is finished.
According to Archimedes principle and four-probe instrument respectivelyThe IWO target material prepared in this example was subjected to density and resistivity tests to obtain a relative density of 99.6% (based on the theoretical density of 7.18 g/cm) 3 Meter), the volume resistivity was 0.6 m.OMEGA.cm.
From the above embodiments, it can be seen that the preparation method provided by the invention can control the atomic ratio of indium to tungsten in the secondary phase by regulating the mass ratio of tungsten oxide to indium oxide, is simple and convenient to operate, and the prepared IWO target tissue with reduced cost is uniform and refined, high in density and low in resistivity.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. A preparation method of an indium-tungsten oxide target material comprises the following steps:
(1) Mixing indium oxide and tungsten oxide according to stoichiometric ratio, and calcining In oxygen atmosphere to obtain In 6 WO 12 ；
(2) In obtained In the step (1) 6 WO 12 Mixing with indium oxide, water, a dispersing agent and a binder to obtain IWO slurry;
(3) Performing pressure grouting on the IWO slurry obtained in the step (2) to obtain an IWO biscuit;
(4) Sequentially carrying out degreasing treatment and step variable-temperature sintering on the IWO biscuit obtained in the step (3) to obtain an indium-tungsten oxide target material;
the step variable-temperature sintering in the step (4) comprises the following steps of:
performing first temperature rise on a product obtained by degreasing treatment to a first step temperature for first heat preservation, then performing second temperature rise to a second step temperature, then immediately performing first temperature reduction to a third step temperature for second heat preservation, and then performing second temperature reduction to 600 ℃; the temperature of the first step is 900-1100 ℃, the temperature of the second step is 1400-1500 ℃, and the temperature of the third step is 1000-1300 ℃.
2. The preparation method according to claim 1, wherein the calcination temperature in the step (1) is 700 to 1000 ℃ and the calcination time is 2 to 20 hours.
3. The method according to claim 1, wherein In the step (2) 6 WO 12 The amount of (B) is 1 to 6% by mass of the indium oxide.
4. The production method according to claim 1, wherein the dispersant In the step (2) is In by mass 6 WO 12 And 1.2 to 1.8 percent of the total mass of the indium oxide.
5. The production method according to claim 1, wherein the mass of the binder In the step (2) is In 6 WO 12 And 0.3 to 1.0% by mass of indium oxide.
6. The method according to claim 1, wherein the IWO slurry in the step (2) has a solid content of more than 80% and a viscosity of less than 100 mPa-s.
7. The method according to claim 1, wherein the temperature of the degreasing treatment in the step (4) is 500 to 800 ℃, and the holding time of the degreasing treatment is 5 to 24 hours.
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