CN114230332A - AZO target and preparation method thereof - Google Patents
AZO target and preparation method thereof Download PDFInfo
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- CN114230332A CN114230332A CN202210045461.5A CN202210045461A CN114230332A CN 114230332 A CN114230332 A CN 114230332A CN 202210045461 A CN202210045461 A CN 202210045461A CN 114230332 A CN114230332 A CN 114230332A
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Abstract
The invention provides a preparation method of an AZO target material, belonging to the technical field of photoelectric materials, and the preparation method comprises the steps of sequentially mixing and granulating nano zinc oxide, nano aluminum oxide and a binder to obtain a granular material; 3D printing and forming the granular material to obtain an AZO biscuit; and sintering the AZO biscuit to obtain the AZO target. According to the invention, through 3D printing forming and sintering control procedures, the AZO target material provided by the invention has the advantages of uniform structure, high relative density and simple preparation method.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to an AZO target material and a preparation method thereof.
Background
With the rapid development of the fields of liquid crystal displays, touch panels, solar cells and the like, Transparent Conductive Oxide (TCO) films are widely applied as transparent conductive electrodes in the fields of photoelectricity and related fields. At present, the most widely used transparent conductive oxide film in industry is an ITO thin film, but because of the disadvantages of relatively high cost, unstable supply, high processing temperature, low toxicity and chemical compatibility, etc., the development of ITO substitutes has been paid much attention. ZnO has a wider forbidden band width (3.37 eV) and higher atomic bonding energy (60meV), is a unique semiconductor material, can improve the photoelectric property of ZnO due to the addition of Al, has rich reserves of Zn and Al elements, low cost, simple processing, no toxicity and good thermal stability, and in recent years, AZO further becomes a research hotspot in transparent conductive oxide films.
In the preparation of the transparent conductive oxide film, the performance of the target material required by magnetron sputtering has great influence on the performance of the prepared film. In the preparation process of the target material, forming and sintering are two important technological processes, and the performance of the prepared target material is determined. At present, the forming process of the AZO target mainly comprises three types of gel forming, slip casting and cold isostatic pressing, wherein the density of the compression molding is not uniform due to non-uniform pressure, the upper density and the lower density of the slip casting are not uniform due to the gravity action, and the preparation of a mold required by the cold isostatic pressing is difficult.
Disclosure of Invention
In view of this, the present invention aims to provide an AZO target and a preparation method thereof, and the AZO target provided by the present invention has the advantages of uniform structure, high relative density and simple preparation method.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a preparation method of an AZO target, which comprises the following steps:
mixing and granulating the nano zinc oxide, the nano aluminum oxide and the binder in sequence to obtain a granular material;
3D printing and forming are carried out on the granular material to obtain an AZO biscuit;
and sintering the AZO biscuit to obtain the AZO target.
Preferably, the binder is at least two of paraffin wax, stearic acid, polyethylene, polypropylene, and polyvinyl alcohol cellulose-based binder.
Preferably, the mass ratio of the nano zinc oxide to the nano aluminum oxide to the binder is 98: 2: (5-10).
Preferably, the particle size of the particle material is 0.3-5 mm.
Preferably, the diameter of a nozzle of a 3D printer used for 3D printing is 0.3-0.8 mm, the temperature of the nozzle is 150-170 ℃, and the temperature of a substrate is 50-60 ℃; the thickness of the 3D printing layer is 0.05-0.3 mm, and the printing speed is 20-60 mm/s.
Preferably, the relative density of the AZO biscuit is more than or equal to 60 percent.
Preferably, the sintering method comprises the following steps:
carrying out first temperature rise on the AZO biscuit in an air atmosphere to a first temperature, and carrying out first heat preservation to obtain a degreased biscuit;
secondly heating the degreased biscuit to a second temperature in an oxygen atmosphere for second heat preservation to obtain a second heat-preserved biscuit;
carrying out third heat preservation on the biscuit subjected to the second heat preservation in an oxygen atmosphere after the first temperature reduction to a third temperature to obtain a third heat-preserved biscuit;
sequentially carrying out second cooling, third cooling and fourth cooling on the biscuit subjected to the third heat preservation in an oxygen atmosphere to obtain an AZO target;
the first temperature rise rate is 1-3 ℃/min, the first temperature is 500-800 ℃, and the first heat preservation time is 36-48 h;
the second heating rate is 1 ℃/min, the second temperature is 1400-1500 ℃, and the second heat preservation time is 0.5-1 h;
the first cooling rate is 1 ℃/min, the third temperature is 1300-1400 ℃, and the third heat preservation time is 8-12 h;
the second cooling rate is 1 ℃/min, and the temperature after the second cooling is 1000 ℃;
the rate of the third cooling is 2 ℃/min, and the temperature after the third cooling is 500 ℃.
The invention also provides the AZO target prepared by the preparation method, and the relative density of the AZO target is more than or equal to 98%.
The beneficial technical effects are as follows: the invention provides a preparation method of an AZO target material, which comprises the steps of sequentially mixing and granulating nano zinc oxide, nano aluminum oxide and a binder to obtain a granular material; 3D printing and forming the granular material to obtain an AZO biscuit; and sintering the AZO biscuit to obtain the AZO target. The AZO target material provided by the invention has the advantages of uniform structure, high relative density and simple preparation method.
Detailed Description
The invention provides a preparation method of an AZO target, which comprises the following steps:
mixing and granulating the nano zinc oxide, the nano aluminum oxide and the binder in sequence to obtain a granular material;
3D printing and forming are carried out on the granular material to obtain an AZO biscuit;
and sintering the AZO biscuit to obtain the AZO target.
According to the invention, nano zinc oxide, nano aluminum oxide and a binder are sequentially mixed and granulated to obtain the granular material.
In the present invention, at least two of the paraffin wax, stearic acid, polyethylene, polypropylene, and polyvinyl alcohol cellulose-based binder; the mass ratio of the nano zinc oxide to the nano aluminum oxide to the binder is preferably 98: 2: (5-10); more preferably 8%. The particle size of the particle material is preferably 0.3-5 mm, and more preferably 1-3 mm. The nano zinc oxide, the nano aluminum oxide and the binder are preferably mixed by an internal mixer and then extruded and granulated by a screw granulator. According to the invention, the biscuit obtained by controlling the dosage of the binder has higher light degree and lower porosity, and the compactness of the biscuit is enhanced.
After the granular material is obtained, the granular material is subjected to 3D printing forming to obtain an AZO biscuit.
In the invention, the diameter of a nozzle of the 3D printer for 3D printing is preferably 0.3-0.8 mm, and more preferably 0.5 mm; the temperature of the 3D printer nozzle is preferably 150-170 ℃, and more preferably 155-165 ℃; the temperature of the 3D printer substrate is preferably 50-60 ℃, and more preferably 55 ℃; the thickness of the 3D printing layer is preferably 0.05-0.3 mm, more preferably 0.1-0.2 mm, and the printing speed of the 3D printing layer is preferably 20-60 mm/s, more preferably 30-50 mm/s, and most preferably 40-45 mm/s. The invention optimizes the nozzle diameter, the nozzle temperature, the substrate temperature of the 3D printer, the layer thickness and the printing speed of the 3D printing, so that the 3D printing is carried out at the manuscript delivery speed and the printing precision is ensured.
In the invention, the relative density of the AZO biscuit is more than or equal to 60 percent, and more preferably 62 to 65 percent.
And sintering the AZO biscuit to obtain the AZO target.
Specifically, the AZO biscuit is subjected to first temperature rise to a first temperature in an air atmosphere for first heat preservation to obtain a degreased biscuit;
in the invention, the first heating rate is preferably 1-3 ℃/min; preferably, multiple sections of heat preservation are set in the first temperature rise process, and the time for each section of heat preservation is preferably 20-40 min; the first temperature is preferably 500-800 ℃, more preferably 600-700 ℃, and most preferably 650-675 ℃; the first heat preservation time is preferably 36-48 h, and more preferably 40-44 h. The degreasing is carried out through first heating and first heat preservation.
After the first heat preservation, the degreased biscuit is heated to a second temperature in an oxygen atmosphere for second heat preservation to obtain a second heat preserved biscuit.
In the present invention, the second temperature rise rate is preferably 1 ℃/min; the second temperature is preferably 1400-1500 ℃, and more preferably 1450-1475 ℃; the second heat preservation time is preferably 0.5-1 h, and more preferably 0.5-0.75 h. The invention achieves a primary densification through the second temperature rise and heat preservation, and prepares for the second section of sintering.
After the second heat preservation, the biscuit after the second heat preservation is subjected to the first temperature reduction to a third temperature for carrying out third heat preservation, and a biscuit after the third heat preservation is obtained.
In the present invention, the first cooling rate is preferably 1 ℃/min; the third temperature is preferably 1300-1400 ℃, and more preferably 1350-1375 ℃; the third heat preservation time is preferably 8-12 hours, and more preferably 10 hours. The invention achieves the purpose of inhibiting the growth of crystal grains through the first temperature reduction and the third temperature preservation.
After the third heat preservation, sequentially carrying out second cooling, third cooling and fourth cooling on the biscuit subjected to the third heat preservation in an oxygen atmosphere to obtain an AZO target;
in the invention, the second cooling rate is 1 ℃/min; the temperature after the second temperature reduction is preferably 700-1000 ℃, and more preferably 800-900 ℃; the third cooling rate is preferably 2 ℃/min, and the temperature after the third cooling is preferably 500-600 ℃, and more preferably 500-550 ℃; the fourth cool down is preferably furnace cooled. In the present invention, it is preferable that the third temperature reduction is performed without performing heat preservation after the second temperature reduction. According to the invention, the target material is prevented from cracking due to too high temperature reduction rate through the second temperature reduction and the third temperature reduction.
The invention also provides the AZO target prepared by the preparation method, and the relative density of the AZO target is preferably more than or equal to 98%.
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
Example 1
1) Uniformly mixing nano zinc oxide, nano aluminum oxide powder and a binder by a mixer, wherein the mass ratio of the nano zinc oxide to the nano aluminum oxide to the binder is 98: 2: 10. the adhesive is a paraffin-based multi-component adhesive composed of paraffin, stearic acid and polyethylene, and the mass ratio of the paraffin, the stearic acid and the polyethylene is 2: 1: 5;
2) granulating the mixed powder through a screw granulator to obtain granules with the particle size of 1-3 mm;
3) melting the granular material by using a 3D printer, extruding the granular material through a nozzle, and preparing an AZO cylindrical biscuit with a required size on a printing platform, wherein the diameter of the biscuit is 20mm, and the height of the biscuit is 5 mm; the printing parameters of the 3D printer are that the diameter of a printer nozzle is 0.3mm, the thickness of a printing layer is 0.1mm, the temperature of the nozzle is 160 ℃, the printing speed is 40mm/s, the temperature of a substrate is 50 ℃, and the relative density of the prepared biscuit is 60%;
4) and (3) sintering the AZO biscuit obtained in the step (3) in a sintering furnace, wherein the required sintering conditions are as follows: heating to 300 ℃ at a speed of 3 ℃/min in the air atmosphere, preserving heat for 30min, heating to 600 ℃ at a speed of 3 ℃/min, and preserving heat for 48 h; then switching to an oxygen atmosphere, heating to 1400 ℃ at the speed of 2 ℃/min, preserving heat for 30min, cooling to 1250 ℃ at the speed of 1 ℃/min, and preserving heat for 10 h; and then cooling to 1000 ℃ at a speed of 1 ℃/min, then cooling to 500 ℃ at a speed of 2 ℃/min, and then cooling to room temperature along with the furnace to obtain the AZO target.
Through an Archimedes density test, the prepared AZO target has the relative density of 98.2 percent, uniform microstructure and no cracking condition.
Example 2
1) Uniformly mixing the nano zinc oxide powder, the nano aluminum oxide powder and the binder through a mixer to obtain mixed powder, wherein the mass ratio of the addition amount of the nano zinc oxide to the addition amount of the nano aluminum oxide to the addition amount of the binder is 98: 2: 10, the binder is paraffin-based multi-component binder consisting of paraffin, stearic acid and polypropylene, and the mass ratio of the paraffin, the stearic acid and the polypropylene is 2: 1: 5.
2) granulating the mixed powder obtained in the step 1) through a screw granulator to obtain granules with the particle size of 1-3 mm;
3) melting the granules by using a 3D printer, extruding the granules through a nozzle, and preparing an AZO cylindrical biscuit with a required size on a printing platform, wherein the diameter of the biscuit is 20mm, the height of the biscuit is 5mm, the 3D printing parameters are that the diameter of the printer nozzle is 0.3mm, the thickness of a printing layer is 0.1mm, the temperature of the nozzle is 170 ℃, the printing speed is 50mm/s, the temperature of a substrate is 60 ℃, and the relative density of the prepared biscuit is 62%;
4) and (4) sintering the AZO biscuit obtained in the step (3) in a sintering furnace, wherein the required sintering conditions are as follows: heating to 300 ℃ at a speed of 4 ℃/min in the air atmosphere, preserving heat for 30min, heating to 600 ℃ at a speed of 3 ℃/min, and preserving heat for 48 h; then switching to an oxygen atmosphere, heating to 1450 ℃ at the speed of 2 ℃/min, preserving heat for 30min, cooling to 1300 ℃ at the speed of 1 ℃/min, and preserving heat for 10 h; then cooling to 1000 ℃ at a speed of 1 ℃/min, then cooling to 500 ℃ at a speed of 2 ℃/min, and then cooling to room temperature along with the furnace to obtain the AZO target.
Through an Archimedes density test, the prepared AZO target has the relative density of 98.6 percent, uniform microstructure and no cracking condition.
Comparative example 1
1) Uniformly mixing nano zinc oxide, nano alumina powder and a binder by a mixer, wherein the mass ratio of the addition amounts of the nano zinc oxide, the nano alumina and the binder is 89: 1: 10, the binder is paraffin-based multi-component binder consisting of paraffin, stearic acid and polypropylene; the mass ratio of the paraffin, the stearic acid and the polypropylene is 2: 1: 5;
2) granulating the mixed powder obtained in the step 1) through a screw granulator to obtain granules with the particle size of 1-3 mm;
3) melting the granular material obtained in the step 2) by using a 3D printer, extruding the granular material through a nozzle, and preparing an AZO cylindrical biscuit with a required size on a printing platform, wherein the diameter is 20mm, the height is 5mm, the 3D printing parameters are that the diameter of the printer nozzle is 0.4mm, the thickness of a printing layer is 0.15mm, the temperature of the nozzle is 150 ℃, the printing speed is 60mm/s, the temperature of a substrate is 60 ℃, and the relative density of the prepared biscuit is 58%;
4) putting the biscuit obtained in the step 3) into a sintering furnace for degreasing and sintering, wherein the required sintering conditions are as follows: heating to 300 ℃ at a speed of 4 ℃/min under the air atmosphere, preserving heat for 30min, heating to 500 ℃ at a speed of 3 ℃/min, and preserving heat for 12 h; then, the temperature is raised to 1400 ℃ at the speed of 2 ℃/min under the oxygen atmosphere, the temperature is kept for 10h, and then the temperature is lowered to the room temperature at the speed of 3 ℃/min. Obtaining the AZO target material.
Through an Archimedes density test, the relative density of the target prepared from the prepared AZO target is 89%, black spots and macrocracks exist on the surface, and the interlayer bonding strength is low. Due to insufficient degreasing time, part of the binder is not removed completely inside the sample, so that the binder volatilizes during sintering, resulting in black spots and cracks on the surface of the sample.
Comparative example 2
1) Uniformly mixing nano zinc oxide, nano aluminum oxide powder and a binder through a mixer to obtain mixed powder; wherein the mass ratio of the addition amounts of the nano zinc oxide, the nano aluminum oxide and the binder is 89: 1: 10, wherein the binder is paraffin-based multi-component binder consisting of paraffin, stearic acid and polypropylene, and the mass ratio of the paraffin, the stearic acid and the polypropylene is 2: 1: 5;
2) granulating the mixed powder obtained in the step 1) through a screw granulator to obtain granules with the particle size of 1-3 mm;
3) melting the granular material obtained in the step 2) by using a 3D printer, extruding the granular material through a nozzle, and preparing an AZO cylindrical biscuit with a required size on a printing platform, wherein the diameter of the biscuit is 20mm, the height of the biscuit is 5mm, the 3D printing parameters are that the diameter of the printer nozzle is 0.3mm, the thickness of a printing layer is 0.1mm, the temperature of the nozzle is 150 ℃, the printing speed is 50mm/s, the temperature of a substrate is 60 ℃, and the relative density of the prepared biscuit is 60%;
4) and (3) pressing the printed biscuit in a cold isostatic press at the pressing pressure of 250MPa for 30min, and then taking out the biscuit.
5) Putting the biscuit subjected to isostatic pressing into a sintering furnace for degreasing sintering, wherein the required sintering conditions are as follows: heating to 300 ℃ at a speed of 4 ℃/min in the air atmosphere, preserving heat for 30min, heating to 600 ℃ at a speed of 3 ℃/min, and preserving heat for 24 h; then, the temperature is raised to 1400 ℃ at the speed of 2 ℃/min under the oxygen atmosphere, the temperature is kept for 10h, and then the temperature is lowered to the room temperature at the speed of 3 ℃/min. Obtaining the AZO target material.
Through an Archimedes density test, the relative density of the prepared target material is 91%, and the sample has bulges and macrocracks. After the sample is subjected to cold isostatic pressing, the density of the biscuit is further improved, the binder in the biscuit is more difficult to remove, and the binder on the surface layer is removed. Therefore, during the sintering process, a shrinkage non-uniformity phenomenon occurs, resulting in a swelling phenomenon.
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 (8)
1. The preparation method of the AZO target is characterized by comprising the following steps:
mixing and granulating the nano zinc oxide, the nano aluminum oxide and the binder in sequence to obtain a granular material;
3D printing and forming are carried out on the granular material to obtain an AZO biscuit;
and sintering the AZO biscuit to obtain the AZO target.
2. The method of claim 1, wherein the binder is at least two of paraffin wax, stearic acid, polyethylene, polypropylene, and polyvinyl alcohol cellulose-based binder.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of the nano zinc oxide to the nano aluminum oxide is 98: 2: (5-10).
4. The preparation method according to claim 1, wherein the particle size of the granules is 0.3 to 5 mm.
5. The preparation method according to claim 1, wherein the 3D printer used for 3D printing has a nozzle diameter of 0.3-0.8 mm, a nozzle temperature of 150-170 ℃, and a substrate temperature of 50-60 ℃; the thickness of the 3D printing layer is 0.05-0.3 mm, and the printing speed is 20-60 mm/s.
6. The method according to claim 1, wherein the AZO biscuit has a relative density of 60% or more.
7. The method of claim 1, wherein the sintering is performed by:
carrying out first temperature rise on the AZO biscuit in an air atmosphere to a first temperature, and carrying out first heat preservation to obtain a degreased biscuit;
secondly heating the degreased biscuit to a second temperature in an oxygen atmosphere for second heat preservation to obtain a second heat-preserved biscuit;
carrying out first cooling on the biscuit subjected to the second heat preservation to a third temperature in an oxygen atmosphere to carry out third heat preservation to obtain a third heat-preserved biscuit;
sequentially carrying out second cooling, third cooling and fourth cooling on the biscuit subjected to the third heat preservation in an oxygen atmosphere to obtain an AZO target;
the first temperature rise rate is 1-3 ℃/min, the first temperature is 500-800 ℃, and the first heat preservation time is 36-48 h;
the second heating rate is 1 ℃/min, the second temperature is 1400-1500 ℃, and the second heat preservation time is 0.5-1 h;
the first cooling rate is 1 ℃/min, the third temperature is 1300-1400 ℃, and the third heat preservation time is 8-12 h;
the second cooling rate is 1 ℃/min, and the temperature after the second cooling is 1000 ℃;
the rate of the third cooling is 2 ℃/min, and the temperature after the third cooling is 500 ℃.
8. The AZO target prepared by the preparation method of any one of claims 1 to 7, wherein the relative density of the AZO target is not less than 98%.
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