CN113402261B - IZO target precursor and preparation method and application thereof - Google Patents
IZO target precursor and preparation method and application thereof Download PDFInfo
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- CN113402261B CN113402261B CN202110625158.8A CN202110625158A CN113402261B CN 113402261 B CN113402261 B CN 113402261B CN 202110625158 A CN202110625158 A CN 202110625158A CN 113402261 B CN113402261 B CN 113402261B
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- 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
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- 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
Abstract
The invention discloses an IZO target precursor, a preparation method and application thereof, wherein the precursor comprises the following components: indium oxide and zinc oxide; the mass ratio of the indium oxide to the zinc oxide is 1: 0.05-0.2; the specific surface area of the IZO target precursor is 5m2G to 20m2Between/g. The invention solves the problem of uniformity of the IZO target material by controlling the preparation method of the precursor; the preparation method of the invention reduces the mechanical mixing and crushing procedures of IZO powder and reduces the introduction of impurities in the mixing and crushing process; meanwhile, the production cost is effectively reduced. The IZO target material prepared by the invention has good uniformity, does not form nodules in the use process, does not generate point discharge, and improves the uniformity of a film layer.
Description
Technical Field
The invention relates to the technical field of photoelectric functional materials, in particular to an IZO target precursor and a preparation method and application thereof.
Background
Transparent Conductive Oxide (TCO) is an important photoelectronic functional material, and has high transmittance for visible light, high reflectance for infrared light, and excellent conductivity. Therefore, the TCO is widely used in the fields of solar cells, flat panel and liquid crystal displays, light emitting diodes, and heat radiation reflectors. Tin-doped indium Oxide (Indi μm Tin Oxide, ITO for short) is the most widely used transparent conductive film at present, and the mass content of indium Oxide in the film reaches 90%. As is well known, the content of metal indium in the earth crust is rare, and the metal indium is a rare resource and is expensive; and ITO is unstable in hydrogen plasma. Therefore, it is necessary to develop a novel transparent conductive film with a low indium content instead of ITO. The zinc oxide has rich raw material sources, low price, no toxicity and good stability in hydrogen plasma; the conductive film is a wide-bandgap semiconductor, has high transmittance to visible light, is easy to realize n-type doping, and the conductivity of the n-type doped transparent conductive film is close to that of ITO. Therefore, a transparent conductive film doped with zinc oxide as a matrix has become a focus of current research, and ITO is gradually replaced in many fields.
Therefore, development of an IZO target precursor is required, and the IZO target prepared by using the IZO target precursor has high uniformity.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the IZO target precursor, and the IZO target prepared by using the IZO target precursor has high uniformity.
The invention also provides a preparation method of the IZO target precursor.
The invention also provides application of the IZO target precursor.
The invention also provides an IZO target which has high uniformity.
The invention also provides a preparation method of the IZO target material.
The invention also provides the application of the IZO target.
The first aspect of the present invention provides an IZO target precursor, which includes the following components: indium oxide and zinc oxide;
the mass ratio of the indium oxide to the zinc oxide is 1: 0.05-0.2;
the specific surface area of the IZO target precursor is 5m2G to 20m2Between/g.
The higher the specific surface area of the precursor, the higher the sintering activity and the easier the sintering, but the finer the powder, the too large the elastic after-effect of the press forming, the easy delamination or cracking of the target material, the lower the specific surface area, the higher the sintering temperature needed and the more difficult the sintering.
According to some embodiments of the invention, the IZO target precursor has a specific surface area of 8m2G to 12m2Between/g.
The second aspect of the present invention provides a method for preparing an IZO target precursor, comprising the following steps:
mixing indium raw material liquid and zinc raw material liquid, adding a pH regulator, regulating the pH to 7.7-8.6, reacting, performing solid-liquid separation after the reaction is finished, collecting a solid phase, drying and calcining the solid phase to obtain an IZO precursor;
the reaction requires ball milling or emulsification.
ITO powder is easy to be subjected to coprecipitation to obtain uniform powder, but IZO (indium zinc oxide) is easy to agglomerate, and conventional coprecipitation can cause zinc hydroxide precipitate to be coated with a large amount of anions, so that large agglomerates are formed in the final powder calcination process, and sintering of a target material is not facilitated.
The pH value in the reaction process is regulated, so that the agglomeration degree of zinc hydroxide precipitate is reduced, and the coating of anions is reduced, so that the powder still keeps very good activity after being calcined, and the sintering is facilitated.
Meanwhile, in the reaction process, the liquid is strongly emulsified, so that large-range area agglomeration is not generated in the reaction process.
According to some embodiments of the invention, the indium raw material liquid includes at least one of indium sulfate, indium nitrate, and indium chloride.
According to some embodiments of the invention, the indium raw material liquid is indium chloride.
According to some embodiments of the invention, the zinc feed solution comprises at least one of zinc sulfate, zinc nitrate, and zinc chloride.
According to some embodiments of the invention, the zinc feedstock solution is zinc chloride.
According to some embodiments of the invention, the molar concentration of indium in the indium raw material liquid is 0.05mol/L to 0.3 mol/L.
According to some embodiments of the invention, the molar concentration of zinc in the zinc feed solution is between 0.05mol/L and 0.3 mol/L.
Too high a salt concentration can result in too high a local concentration and can therefore exacerbate agglomeration. If the salt concentration is too low, the reaction speed is slower, and the specific surface area value of the precursor generated by the reaction is higher, which is not beneficial to subsequent production.
According to some embodiments of the invention, the pH adjusting agent is an inorganic base or a carbonate.
According to some embodiments of the invention, the inorganic base is at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide and ammonia monohydrate.
According to some embodiments of the invention, the carbonate salt is at least one of sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate and cesium bicarbonate.
The reaction speed of different alkalis is different, and the stronger the alkalinity, the faster the reaction speed, the more difficult it is to control the reaction degree. Control of the pH is critical, but is dependent on the base added.
Generally, the reaction speed of high-concentration strong base is faster, agglomeration is aggravated, and target sintering is not facilitated. Therefore, low concentrations of strong or weak bases are usually chosen to achieve a slow adjustment of the pH.
An excessive amount of the precipitant causes the pH of the system to become high. Thereby causing poor dispersibility of the reacted precursor.
According to some embodiments of the invention, the temperature of the reaction is between 20 ℃ and 45 ℃.
According to some embodiments of the invention, the temperature of the calcination is from 600 ℃ to 1500 ℃.
According to some embodiments of the invention, the temperature of the calcination is from 1100 ℃ to 1450 ℃.
The third aspect of the invention provides an application of the IZO target precursor in preparing the IZO target.
The fourth aspect of the invention provides an IZO target prepared from the IZO target precursor.
The fifth aspect of the present invention provides a method for preparing an IZO target, comprising the following steps:
and S1, performing spray granulation on the IZO precursor to obtain the IZO powder.
S2, carrying out compression molding on the IZO powder, and carrying out cold isostatic pressing to obtain a blank target material;
and S3, degreasing the blank target material and sintering to obtain the IZO target material.
According to some embodiments of the present invention, the IZO powder has D50 of 5 to 15 μm.
According to some embodiments of the present invention, the step S2 is compression molded at a pressure of 0.1MPa to 0.8 MPa.
According to some embodiments of the invention, the cold isostatic pressing in step S2 is performed at a pressure of 200MPa to 400 MPa.
According to some embodiments of the invention, the temperature of the degreasing in the step S3 is 400 ℃ to 700 ℃.
According to some embodiments of the invention, the temperature increase rate of the degreasing in the step S3 is 0.5 ℃/min to 2 ℃/min.
According to some embodiments of the invention, the temperature increase rate of the degreasing in the step S3 is 0.5 ℃/min to 1 ℃/min.
According to some embodiments of the invention, the sintering temperature in step S3 is 1000 ℃ to 1500 ℃.
According to some embodiments of the invention, the temperature increase rate of the sintering in the step S3 is 0.5 ℃/min to 5 ℃/min.
According to some embodiments of the invention, the temperature increase rate of the sintering in the step S3 is 2 ℃/min to 3 ℃/min.
According to some embodiments of the present invention, the cooling rate of the sintering in the step S3 is 5 ℃/min to 10 ℃/min.
According to some embodiments of the present invention, the cooling rate of the sintering in the step S3 is 6 ℃/min to 7 ℃/min.
The sixth aspect of the invention provides the application of the IZO target material in the preparation of OLED displays.
The invention has at least the following beneficial effects: the invention solves the problem of uniformity of the IZO target material by controlling the preparation method of the precursor; the preparation method of the invention reduces the mechanical mixing and crushing process of IZO powder and reduces the introduction of impurities in the mixing and crushing process; meanwhile, the production cost is effectively reduced. The IZO target material prepared by the invention has good uniformity, does not generate nodulation and point discharge in the use process, and improves the uniformity of a film layer.
Drawings
Fig. 1 shows the overall film coating condition of the IZO target in embodiment 1 of the present invention;
fig. 2 shows a partial film-coating condition (left side) of the IZO target in embodiment 1 of the present invention;
fig. 3 shows a partial coating condition (middle region) of the IZO target in embodiment 1 of the present invention;
fig. 4 shows a partial coating of an IZO target according to embodiment 1 of the present invention (right side);
fig. 5 shows the overall film coating condition of the IZO target in embodiment 8 of the present invention;
fig. 6 shows a partial plating of an IZO target according to embodiment 8 of the present invention (right side).
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 8.4 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, spraying and granulating the IZO precursor to obtain the IZO powder, wherein D50 is 10 mu m.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 650 ℃, and sintering at 1200 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 500 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at a speed of 6 ℃/min after sintering.
Installing the IZO target material into a direct current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the film coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the power of the film coating is 1.5W/cm2The outlet temperature of the cooling water is 15 ℃.
Example 2
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.3mol/L and a zinc chloride solution with the concentration of 0.3mol/L, adjusting the pH value to 8.4 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, carrying out spray granulation on the IZO precursor to obtain the IZO powder, wherein D50 is 10 microns.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 600 ℃, and sintering at 1300 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 0.5 ℃/min, and the degreasing temperature is kept for 5 hours after being heated to 500 ℃; the temperature rise speed of sintering is 3 ℃/min; heating to 1500 ℃, and keeping for 6 hours, wherein the cooling speed after sintering is 7 ℃/min.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The temperature of the cooling water is 15 ℃.
Example 3
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 8.6 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, spraying and granulating the IZO precursor to obtain the IZO powder, wherein D50 is 10 mu m.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 400 ℃, and sintering at 1000 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 0.5 ℃/min, and the degreasing temperature is kept for 5 hours after being heated to 500 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at a speed of 6 ℃/min after sintering.
Installing the IZO target material into a direct current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The outlet temperature of the cooling water is 15 ℃.
Example 4
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 9 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, spraying and granulating the IZO precursor to obtain the IZO powder, wherein D50 is 10 mu m.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 500 ℃, and sintering at 1500 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 500 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at a speed of 6 ℃/min after sintering.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The outlet water temperature of the cooling water is15℃。
Example 5
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 7.7 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 50 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, spraying and granulating the IZO precursor to obtain the IZO powder, wherein D50 is 10 mu m.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 600 ℃, and sintering at 1300 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 0.5 ℃/min, and the degreasing temperature is kept for 5 hours after being heated to 500 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at 6 ℃/min after sintering.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The outlet temperature of the cooling water is 15 ℃.
Example 6
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 7 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 50 ℃, circulating a reaction liquid through ball milling in the reaction process, and performing solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, carrying out spray granulation on the IZO precursor to obtain the IZO powder, wherein D50 is 10 microns.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 700 ℃, and sintering at 1200 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 500 ℃; the temperature rise speed of sintering is 3 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at 6 ℃/min after sintering.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, then Ar gas (purity 99.99%) and O are introduced2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The outlet temperature of the cooling water is 15 ℃.
Example 7
The present embodiment is a method for preparing an IZO target, including the following steps:
s1, mixing an indium chloride solution with the concentration of 0.2mol/L and a zinc chloride solution with the concentration of 0.2mol/L, adjusting the pH value to 8.4 by dropwise adding a sodium hydroxide solution for reaction, controlling the reaction temperature to be about 30 ℃, and carrying out solid-liquid separation after the reaction is finished; collecting solid phase, washing and freeze-drying; calcining at 900 deg.C for 1h to obtain IZO precursor.
S2, spraying and granulating the IZO precursor to obtain the IZO powder, wherein D50 is 10 mu m.
And S3, carrying out compression molding on the IZO powder under the pressure of 0.4MPa, and carrying out cold isostatic pressing after compression molding, wherein the pressure is 350MPa, so as to obtain the blank target material.
S4, degreasing the blank target material at 650 ℃, and sintering at 1200 ℃ after degreasing to obtain an IZO target material (the mass ratio of indium oxide to zinc oxide in the target material is 9: 1); wherein the heating rate of the degreasing temperature is 1 ℃/min, and the degreasing temperature is kept for 5h after being heated to 500 ℃; the temperature rise speed of sintering is 2 ℃/min; heating to 1500 ℃, keeping for 6 hours, and cooling at a speed of 6 ℃/min after sintering.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, then Ar gas (purity 99.99%) and O are introduced2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the film coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the power of the film coating is 1.5W/cm2The outlet temperature of the cooling water is 15 ℃.
Example 8
In this embodiment, a japanese JX target (japanese yen) is selected as the IZO target.
Installing the IZO target into a direct-current magnetron sputtering device, and sputtering and coating on the alkali-free glass at room temperature, wherein the initial pressure of a vacuum chamber is 8 x 10-4Pa, introducing Ar gas (purity 99.99%) and O2The gas (purity is 99.99 percent), the volume ratio of the gas is 98/2, the coating is carried out after the pressure of the vacuum chamber is adjusted to be 0.2Pa, and the coating power is 1.5W/cm2The temperature of the cooling water is 15 ℃.
The results of the performance tests in inventive examples 1-8 are shown in Table 1.
TABLE 1 Performance test results in inventive examples 1 to 8
Example 2 when the concentrations of zinc salt and indium salt were higher, the reaction became slightly more vigorous, the precipitates agglomerated slightly, and the target density was lower in the same coating process).
From a comparison of examples 3 and 4 with example 1, it is apparent that: after the pH value is higher, the powder is easy to agglomerate, the sintering density is lower, and the target material is slightly uneven.
From a comparison of example 6 with example 1, it is apparent that: the lack of ball milling during the reaction process can lead to poor uniformity of the finally prepared target material, thereby causing the target material to be intensively poisoned during the film plating process.
The coating conditions of the target material prepared in the embodiment 1 of the invention are shown in fig. 1-4, and it can be seen from fig. 1-4 that the target material prepared in the embodiment 1 of the invention has uniform film formation and no poisoning.
The coating conditions of the target material of embodiment 8 of the invention are shown in fig. 5 to 6, and it can be seen from fig. 1 to 4 that the target material prepared in embodiment 1 of the invention has poor film-forming uniformity and is poisoned intensively.
In conclusion, the uniformity problem of the IZO target material is solved by controlling the preparation method of the precursor; the preparation method of the invention reduces the mechanical mixing and crushing process of IZO powder and also reduces the introduction of impurities in the mixing and crushing process; meanwhile, the production cost is effectively reduced. The IZO target material prepared by the invention has good uniformity, does not generate nodulation and point discharge in the use process, and improves the uniformity of a film layer.
While the embodiments of the present invention have been described in detail with reference to the description and the drawings, the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the spirit of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (16)
1. A preparation method of an IZO target precursor is characterized by comprising the following steps: the method comprises the following steps: mixing indium raw material liquid and zinc raw material liquid, adding a pH regulator, regulating the pH to 7.7-8.4, reacting, performing solid-liquid separation after the reaction is finished, collecting a solid phase, drying and calcining the solid phase to obtain an IZO target precursor;
the reaction needs ball milling or emulsification;
the indium raw material solution is at least one selected from an indium sulfate solution, an indium nitrate solution and an indium chloride solution;
the zinc raw material solution is at least one selected from a zinc sulfate solution, a zinc nitrate solution and a zinc chloride solution;
the molar concentration of indium in the indium raw material liquid is 0.05-0.3 mol/L;
the molar concentration of zinc in the zinc raw material liquid is 0.05-0.3 mol/L;
the reaction temperature is 20-45 ℃;
the pH regulator is at least one of sodium hydroxide, potassium hydroxide, cesium hydroxide, ammonia monohydrate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate and cesium bicarbonate;
the IZO target precursor comprises the following components: indium oxide and zinc oxide;
the mass ratio of the indium oxide to the zinc oxide is 1: 0.05-0.2;
the specific surface area of the IZO target precursor is 10m2G to 20m2Between/g.
2. The method of claim 1, wherein: the indium raw material liquid is indium chloride.
3. The method of claim 1, wherein: the zinc raw material liquid is zinc chloride.
4. The method of claim 1, wherein: the calcining temperature is 600-1500 ℃.
5. The method of claim 4, wherein: the calcining temperature is 1100-1450 ℃.
6. Use of the IZO target precursor according to any one of claims 1 to 5 in the preparation of IZO targets.
7. An IZO target, characterized in that: the raw material for preparing the IZO target is the precursor of the IZO target prepared by the preparation method in any one of claims 1 to 5.
8. A method for producing the IZO target material according to claim 7, wherein: the method comprises the following steps:
s1, carrying out spray granulation on the IZO precursor to obtain IZO powder;
s2, carrying out compression molding on the IZO powder, and carrying out cold isostatic pressing to obtain a blank target material;
and S3, degreasing the blank target material and sintering to obtain the IZO target material.
9. The method of claim 8, wherein the IZO target is prepared by: and S2, performing compression molding under the pressure of 0.1-0.8 MPa.
10. The method of claim 8, wherein the IZO target is prepared by: and cold isostatic pressing in the step S2, wherein the pressure is 200 MPa-400 MPa.
11. The method of claim 8, wherein the IZO target is prepared by: the degreasing temperature in the step S3 is 400-700 ℃; the heating speed of degreasing in the step S3 is 0.5-2 ℃/min.
12. The method of claim 11, wherein the manufacturing method comprises: the temperature rise speed of degreasing in the step S3 is 0.5-1 ℃/min.
13. The method of claim 8, wherein the IZO target is prepared by: the sintering temperature in the step S3 is 1000-1500 ℃; the temperature rise speed of the sintering in the step S3 is 0.5-5 ℃/min; and the temperature reduction speed of the sintering in the step S3 is 5-10 ℃/min.
14. The method of claim 13, wherein the IZO target is prepared by: the temperature rise speed of the sintering in the step S3 is 2-3 ℃/min.
15. The method of claim 13, wherein the IZO target is prepared by: and the temperature reduction speed of the sintering in the step S3 is 6-7 ℃/min.
16. Use of the IZO target material according to claim 7 in the manufacture of an OLED display device.
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| CN113831120A (en) * | 2021-10-12 | 2021-12-24 | 长沙壹纳光电材料有限公司 | ATO target precursor, preparation method and application thereof |
| CN116288181A (en) * | 2022-09-09 | 2023-06-23 | 长沙壹纳光电材料有限公司 | Lanthanide metal doped IZO target material and preparation method and application thereof |
| CN115418618A (en) * | 2022-09-09 | 2022-12-02 | 长沙壹纳光电材料有限公司 | Indium tin zinc oxide target material, oxide film and preparation method thereof |
| CN115572167A (en) * | 2022-10-18 | 2023-01-06 | 长沙壹纳光电材料有限公司 | IWZO target material and preparation method and application thereof |
| CN115849896B (en) * | 2022-11-30 | 2024-02-23 | 长沙壹纳光电材料有限公司 | Zinc oxide target material and preparation method and application thereof |
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| CN116041047A (en) * | 2022-12-15 | 2023-05-02 | 先导薄膜材料（广东）有限公司 | IZO doped target material for sputtering and preparation method thereof |
| CN116216770A (en) * | 2022-12-15 | 2023-06-06 | 先导薄膜材料（广东）有限公司 | Blue IZO powder and preparation method thereof |
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