Preparation method of SAZO alloy rotating target material
During the preparation process of SAZO alloy target, multiple component detection and vacuum hot press sintering were performed, and combined with plasma spraying technology, the problems of cracking and low density during the target preparation process were solved, achieving more uniform density control and high-quality target preparation.
Patent Information
- Application Number
- CN202510349061.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-24
- Publication Date
- 2025-05-23
AI Technical Summary
During the preparation of SAZO alloy targets, cracking and low density problems are prone to occur, and the shrinkage of high-hardness and high resistance targets is difficult to control evenly during the sintering process.
After mixing zinc oxide powder, tin oxide powder and alumina powder, and mixing uniformly in a vacuum rolling mixer, multiple tests were performed to ensure that the average content error of each component was less than 0.03%. Then, vacuum hot press sintering technology is used to perform sintering under a hydrogen atmosphere, followed by demolding and annealing. At the same time, the surface of the target material is supplemented by plasma spraying technology to ensure surface flatness.
Through this method, the uniformity and density of the SAZO alloy target can be significantly improved, cracking and low density problems can be reduced, and the shrinkage of the target can be controlled more evenly during the sintering process, and the quality and performance of the product can be improved.
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Figure CN120025163A_ABST
Abstract
Description
Technical Field
[0001] The present application belongs to the technical field of alloy targets, and in particular, relates to a method for preparing a SAZO alloy rotating target. Background Art
[0002] Doping Al and Sn in the ZnO system to obtain ZnO: AlSn transparent conductive film is referred to as SAZO, that is, SAZO thin film metal target. After doping, the conductivity of the film is greatly improved, and the stability of the transparent conductive film SAZO film in hydrogen plasma is better than ITO. At the same time, it has photoelectric properties comparable to ITO. In addition, SAZO film is easy to prepare, and its element resources are richer than In elements, and it is non-toxic. It has gradually become the best substitute for ITO film. SAZO film has been partially used in flat panel displays and thin-film solar cells. There are many methods for preparing SAZO films, mainly magnetron sputtering, metal organic chemical vapor deposition, pulsed laser deposition, spray thermal decomposition, molecular beam epitaxy and sol-gel method. Among them, magnetron sputtering SAZO film has the advantages of high deposition rate, low substrate temperature and good substrate adhesion and is widely used.
[0003] Among the preparation methods of magnetron sputtering SAZO film, the most widely studied and applied is magnetron sputtering technology. Magnetron sputtering technology has been applied in practice since the 1970s. The principle of preparing thin films is: while the vacuum chamber is filled with an inert gas (Ar) with a pressure of 0.1-10 Pa, a 100-1600 Gauss strong magnet is placed under the cathode target. Under the action of high voltage, electrons are accelerated to fly to the substrate under the action of the electric field and collide with argon atoms, ionizing a large number of argon ions and electrons, and the electrons fly to the substrate. Argon ions are accelerated to bombard the target under the action of the electric field, sputtering a large number of target atoms, and neutral target atoms (or molecules) are deposited on the substrate to form a film. In the process of accelerating to the substrate, the secondary electrons are affected by the Lorentz magnetic force of the magnetic field and are bound in the plasma area close to the target surface. The plasma density in this area is very high. Under the action of the magnetic field, the secondary electrons move in a circle around the target surface. The movement path of the electrons is very long. During the movement, they constantly collide with argon atoms to ionize a large number of argon ions to bombard the target material. After multiple collisions, the energy of the electrons gradually decreases, and they get rid of the constraints of the magnetic lines of force, move away from the target material, and finally deposit on the substrate. It has the advantages of high deposition rate, low substrate deposition temperature, good film adhesion, easy control, low cost, and can achieve large-area film formation. The high-hardness and high-resistance SAZO film has the advantages of anti-static, anti-radiation, anti-magnetic interference, high brightness, and high contrast, but the target material is prone to cracking and low density problems during the control molding process, and the shrinkage of the high-hardness and high-resistance target material during the sintering process is difficult to control uniformly. The most difficult aspects of quality control in existing melting and casting technology are mainly the following: first, quantitative control of gas, trace impurities and inclusions in the melt; second, control of shrinkage, cracks and uneven structure in large-sized ingots; third, surface pores, inclusions and chemical waste are also difficult to control. Summary of the invention
[0004] The present application provides a method for preparing a SAZO alloy rotating target material, which aims to solve, to a certain extent, the problems of cracking and low density that are prone to occur during the controlled molding process of the target material, and the problem that the shrinkage of the high-hardness and high-resistance target material is difficult to uniformly control during the sintering process.
[0005] In a first aspect, the present application provides a method for preparing a SAZO alloy target, comprising the following steps:
[0006] S1, mixing zinc oxide powder, tin oxide powder and aluminum oxide powder to obtain a mixed material;
[0007] S2. arbitrarily select several points in the mixed material to detect the aluminum oxide content, tin oxide content and zinc oxide content, until the average error of the zinc oxide content, tin oxide content and aluminum oxide content at each detection point is lower than the error setting value, thereby obtaining a SAZO target powder;
[0008] S3, filling the mixed material tested in S2 into a mold for pre-pressing to obtain a rough blank, and then performing secondary pressing on the rough blank, solidifying and static pressing to obtain a SAZO alloy target green blank;
[0009] S4, plane target material preparation: vacuum hot pressing the SAZO alloy target material green body, demolding, cooling to obtain a SAZO alloy target material crude product; machining the SAZO alloy target material crude product to a desired size, annealing, cleaning to obtain a SAZO alloy plane target material;
[0010] S5. Preparation of rotating target: ball-mill and sieve the mixed material tested in S2 to obtain AZO spray powder; take the SAZO alloy target green cylinder obtained in step S3, cold spray it onto the cylindrical target, and the spraying thickness is 0.1 mm each time. Plasma spray SAZO powder multiple times to obtain an excellent rotating target; after processing, a SAZO alloy rotating target is obtained.
[0011] In some embodiments, the addition amount of the zinc oxide powder, tin oxide powder, and aluminum oxide powder in S1 is any one of 5:4:1, 5:3:2, 7:2:2, and 8:1:1; and the mixing is carried out in a vacuum rolling mixer at a rotation speed of 50 to 80 r / min.
[0012] In some embodiments, the zinc oxide powder in S1 has a theoretical density of more than 98% and a Fisher average particle size of 1 to 7 μm, the tin oxide powder has a theoretical density of more than 98% and a Fisher average particle size of 1 to 7 μm, and the aluminum oxide powder has a theoretical density of more than 98% and a Fisher average particle size of 1 to 7 μm.
[0013] In some embodiments, the error setting value in S2 is less than 0.03%. When the content exceeds 0.03%, it will affect the film resistance and transmittance index after coating.
[0014] In some embodiments, the pre-pressing pressure in S3 is 10-60 MPa, the secondary pressing in S3 is 50-200 MPa, and the green density of the SAZO alloy target material reaches 60-62% of the theoretical density, and the theoretical density is ≥99.5%.
[0015] In some embodiments, the vacuum hot pressing conditions in S4 are: hot pressing and sintering under a hydrogen protective atmosphere, a pressure of 20-30 MPa, a temperature of 1800-1980°C, and keeping the temperature and pressure for 3-4 hours; the demolding is performed at 500-600°C.
[0016] In some embodiments, the annealing conditions in S4 are: heating to 1800-1980° C. in a vacuum annealing furnace and annealing for 3-4 hours.
[0017] In some embodiments, the ball milling in S5 is performed for 3-5 hours, and the powder is sieved through a 1000 mesh sieve to obtain AZO spray powder.
[0018] Compared with the prior art, the beneficial effects of this application are:
[0019] 1. In the present application, the zinc oxide content and the aluminum oxide content are detected at several points of the mixed material at random until the errors of the aluminum oxide content, the tin oxide content and the zinc oxide content at each detection point are less than 0.03%. The mixing is completed to ensure the uniformity of the alloy target material, which is conducive to obtaining an alloy target material with uniform structure and fine grains.
[0020] 2. This solution carries out plasma spraying after mechanical processing to spray and supplement the defective surface so that the surface meets the flatness requirements and reduces the dimensional loss caused by the mechanical processing process. BRIEF DESCRIPTION OF THE DRAWINGS
[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0022] Figure 1 This is a schematic diagram of the application of rotating targets and planar targets in this scheme. DETAILED DESCRIPTION
[0023] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.
[0024] In this application, the term "and / or" describes the association relationship of associated objects, indicating that there may be three relationships. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the associated objects are in an "or" relationship.
[0025] In the present application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, a~b (i.e. a and b), a~c, b~c, or a~b~c, where a, b, c can be single or multiple, respectively.
[0026] The terms "first" and "second" are used only for descriptive purposes to distinguish objects such as substances from each other, and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. For example, without departing from the scope of the implementation regulations of this application, the first XX may also be referred to as the second XX, and similarly, the second XX may also be referred to as the first XX. Therefore, the features defined as "first" and "second" may explicitly or implicitly include one or more of the features.
[0027] The terms used in the embodiments of the present application are only for the purpose of describing specific implementation rules, and are not intended to limit the present application. The singular forms "a", "said" and "the" used in the implementation rules of the present application and the appended claims are also intended to include plural forms, unless the context clearly indicates other meanings.
[0028] It should be understood that in the various embodiments of the present application, the size of the serial number of each process does not mean the order of execution, some or all of the steps can be executed in parallel or sequentially, and the execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the implementation regulations of this application.
[0029] The weight of the relevant components mentioned in the embodiment description of the present application can not only refer to the specific content of each component, but also represent the proportional relationship between the weights of the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the embodiment description of the present application, it is within the scope disclosed in the embodiment description of the present application. Specifically, the mass described in the embodiment description of the present application can be a mass unit known in the chemical industry such as μg, mg, g, kg, etc.
[0030] Unless otherwise defined, all professional terms used below have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.
[0031] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.
[0032] The technical solution of the present application is illustrated below through specific embodiments and comparative examples.
[0033] In order to enable the above implementation details and operations of the present application to be clearly understood by those skilled in the art, and to significantly demonstrate the improved performance of the embodiments of the present application, the above technical solutions are illustrated by means of multiple embodiments below.
[0034] Example 1
[0035] A method for preparing a SAZO alloy rotating target:
[0036] S1, the vacuum rolling mixer has a furnace capacity of 10.0kg, weighs 5.00kg of zinc oxide, 3.00kg of tin oxide, and 2.00kg of aluminum oxide, mixes them, and puts them into the vacuum rolling mixer to obtain a mixture; the speed of the vacuum rolling mixer is 75r / min, and rolling is performed to remove moisture and impurity residual gas;
[0037] S2. arbitrarily select several points in the mixed material to detect the aluminum oxide content, tin oxide content and zinc oxide content, until the average error of the aluminum oxide content, tin oxide content and zinc oxide content at each detection point is lower than the error set value, thereby obtaining a SAZO target powder;
[0038] S3, the mixed raw materials are filled into a mold for pre-pressing to obtain a rough blank; the rough blank is placed in a vacuum hot pressing furnace under a hydrogen atmosphere, the pressure is 23MPa, the temperature is 1850°C, and after vacuum hot pressing sintering, it is demolded at 500°C, cooled to room temperature, and annealed at a temperature of 1850-1980°C to obtain a rough SAZO alloy target;
[0039] S4, heating the obtained SAZO alloy target crude product to 200°C on a copper heating plate, and pressing for 2 minutes using a 10,000-ton press, with the pressure maintained at 180 MPa;
[0040] The hot pressed slab is processed by a milling machine. A carbide milling cutter is used to mill the slab to a suitable length, width and thickness. The surface is plasma sprayed onto the surface of the annealed SAZO alloy target rough product to obtain a (5:3:2) SAZO alloy target.
[0041] S5. Production of rotating target: cold spray the target material SAZO spray powder prepared by mixing in proportion onto the cylinder of the target material, with a spray thickness of 0.1 mm each time. Repeated spraying produces a high-quality rotating target material, which is processed to obtain a high-quality rotating target product. Since the rotating target material can rotate 360° during the coating process, the cylindrical rotating target is evenly etched 360°, and the target material utilization rate can reach 90% at one time. The zinc oxide aluminum alloy target material prepared as above is used as the rotating target material, the Ar flow rate in the coating chamber is 200-550sccm, the oxygen flow rate is 0.5-3.0sccm, and the vacuum degree in the coating chamber is 3.0×10 -1 Pa-5.0×10 -1 Pa, the total gas pressure is 0.30-0.5Pa, the coating temperature is 200℃-550℃, the thickness of the film obtained after coating is 1.5nm, and the resistance of the coated product is 4×10 7 Europe, transmittance>96%.
[0042] Figure 1 This is a schematic diagram of the application of rotating targets and planar targets in this scheme.
[0043] Example 2
[0044] A method for preparing a SAZO alloy rotating target:
[0045] S1, the vacuum rolling mixer has a furnace capacity of 10.0 kg, weighs 5.00 kg of zinc oxide, 4.00 kg of tin oxide, and 1.00 kg of aluminum oxide, mixes them, and puts them into the vacuum rolling mixer to obtain a mixture; the speed of the vacuum rolling mixer is 60 r / min, and rolling is performed to remove moisture and impurity residual gas;
[0046] S2. arbitrarily select several points in the mixed material to detect the aluminum oxide content, tin oxide content and zinc oxide content, until the average error of the aluminum oxide content, tin oxide content and zinc oxide content at each detection point is lower than the error set value, thereby obtaining a SAZO target powder;
[0047] S3, the mixed raw materials are placed in a vacuum hot pressing furnace and sintered under a hydrogen atmosphere. The vacuum sintering pressure is 24MPa and the temperature is 1858°C. After vacuum hot pressing sintering, the raw materials are demoulded at 500°C, cooled to room temperature, and annealed at a temperature of 1890°C to obtain a crude SAZO alloy target.
[0048] S4. Heat the obtained SAZO alloy target crude product to 200°C on a copper heating plate, and press it for 2 minutes using a 10,000-ton press, with the pressure maintained at 180 MPa.
[0049] The hot pressed slab is processed by a milling machine. A carbide milling cutter is used to mill the slab to a suitable length, width and thickness. The surface is plasma sprayed onto the surface of the annealed SAZO alloy target rough product to obtain a (5:4:1) SAZO alloy target.
[0050] S5. Rotary target preparation: cold spray the target material SAZO spray powder prepared in proportion onto the target cylinder, with a spray thickness of 0.1 mm each time. Repeated spraying to obtain a high-quality rotary target material, and after processing, a high-quality rotary target product is obtained. The zinc oxide aluminum alloy target prepared above is used as the rotary target material, the Ar flow rate in the coating chamber is 260 sccm, the oxygen flow rate is 0.5-3.0 sccm, and the vacuum degree in the coating chamber is 3.0×10 -1 Pa-5.0×10 -1 Pa, the total gas pressure is 0.30-0.5Pa, the coating temperature is 200℃-550℃, the thickness of the film obtained after coating is 1.0-1.5nm, and the resistance of the obtained coated product is 4.1×10 6 Europe, transmittance>94.6%.
[0051] Example 3
[0052] A method for preparing a SAZO alloy rotating target:
[0053] S1. The furnace capacity of the vacuum rolling mixer is 10.0 kg. 8.00 kg of zinc oxide, 1.00 kg of tin oxide and 1.00 kg of aluminum oxide are weighed, mixed and put into the vacuum rolling mixer to obtain a mixture; the vacuum rolling mixer rotates at a speed of 70 r / min to remove moisture and impurity residual gas.
[0054] S2. arbitrarily select several points in the mixed material to detect the aluminum oxide content, tin oxide content and zinc oxide content, until the average error of the aluminum oxide content, tin oxide content and zinc oxide content at each detection point is lower than the error set value, thereby obtaining a SAZO target powder;
[0055] S3, the mixed raw materials are placed in a vacuum hot pressing sintering furnace, and the vacuum sintering is carried out under a hydrogen atmosphere. The pressure of the vacuum sintering is 27MPa and the temperature is 1900°C. After the vacuum hot pressing sintering, the raw materials are demolded at 600°C, cooled to room temperature, and annealed at a temperature of 1920°C to obtain a crude SAZO alloy target;
[0056] S4. The crude SAZO alloy target material is heated to 200°C on a copper heating plate and pressed for 2 minutes using a 10,000-ton press, with the pressure maintained at 180 MPa.
[0057] The hot pressed slab was processed by a milling machine. A carbide milling cutter was used to mill the slab to a suitable length, width and thickness. The surface was plasma sprayed onto the surface of the annealed SAZO alloy target rough product to obtain a (8:1:1) SAZO alloy target.
[0058] S5. Rotary target material preparation: cold spray the target material SAZO spray powder prepared in the mixed proportion onto the target cylinder, with a spray thickness of 0.1 mm each time, and spray repeatedly to obtain a high-quality rotary target material. After processing, a high-quality rotary target product is obtained. The zinc oxide aluminum alloy target material prepared above is used as the rotary target material. The Ar flow rate in the coating chamber is 220 sccm, the oxygen flow rate is 0.7 sccm, and the vacuum degree in the coating chamber is 3.0×10 -1 Pa-5.0×10 -1 Pa, the total gas pressure is 0.45Pa, the coating temperature is 400℃, the thickness of the film obtained after coating is 1.0-1.5nm, and the resistance of the coated product is 8×10 6 Europe, transmittance>94.3%.
[0059] In the above embodiments, the description of each embodiment has its own emphasis. For parts that are not described or recorded in detail in a certain embodiment, reference can be made to the relevant descriptions of other embodiments.
[0060] The embodiments described above are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the embodiments of the present application, and should all be included in the protection scope of the present application.
Claims
1. A method for preparing a SAZO alloy target, characterized in that: The following steps are involved: S1, mixing zinc oxide powder, tin oxide powder and aluminum oxide powder to obtain a mixed material; S2. arbitrarily select several points in the mixed material to detect the aluminum oxide content, tin oxide content and zinc oxide content, until the average error of the zinc oxide content, tin oxide content and aluminum oxide content at each detection point is lower than the error setting value, thereby obtaining a SAZO target powder; S3, filling the mixed material tested in S2 into a mold for pre-pressing to obtain a rough blank, and then performing secondary pressing on the rough blank, solidifying and static pressing to obtain a SAZO alloy target green blank; S4, plane target material preparation: vacuum hot pressing the SAZO alloy target material green body, demolding, cooling to obtain a SAZO alloy target material crude product; machining the SAZO alloy target material crude product to a desired size, annealing, cleaning to obtain a SAZO alloy plane target material; S5. Preparation of rotating target: ball-mill and sieve the mixed material tested in S2 to obtain AZO spray powder; take the SAZO alloy target green cylinder obtained in step S3, cold spray it onto the cylindrical target, and the spraying thickness is 0.1 mm each time. Plasma spray SAZO powder multiple times to obtain an excellent rotating target; after processing, a SAZO alloy rotating target is obtained.
2. The preparation method according to claim 1, characterized in that: The addition amount of the zinc oxide powder, tin oxide powder and aluminum oxide powder in S1 is any one of 5:4:1, 5:3:2, 7:2:2 and 8:1:1; the mixing is carried out in a vacuum rolling mixer at a rotation speed of 50 to 80 r / min.
3. The preparation method according to claim 1, characterized in that: The theoretical density of the zinc oxide powder in S1 is above 98%, and the Fisher average particle size is 1 to 7 μm. The theoretical density of the tin oxide powder is above 98%, and the Fisher average particle size is 1 to 7 μm. The theoretical density of the aluminum oxide powder is above 98%, and the Fisher average particle size is 1 to 7 μm.
4. The preparation method according to claim 1, characterized in that: The error setting value in S2 is less than 0.03%.
5. The preparation method according to claim 1, characterized in that: The pre-pressing pressure in S3 is 10-60 MPa, the secondary pressing in S3 is 50-200 MPa, and the green density of the SAZO alloy target material reaches 60-62% of the theoretical density, and the theoretical density is ≥99.5%.
6. The preparation method according to claim 1, characterized in that: The vacuum hot pressing conditions in S4 are: hot pressing and sintering under a hydrogen protective atmosphere, a pressure of 20-30 MPa, a temperature of 1800-1980°C, and heat preservation and pressure maintenance for 3-4 hours; the demolding is carried out at a temperature of 500-600°C.
7. The preparation method according to claim 1, characterized in that: The annealing conditions in S4 are: heating to 1800-1980° C. in a vacuum annealing furnace and annealing for 3-4 hours.
8. The preparation method according to claim 1, characterized in that: The ball milling step in S5 was performed for 3-5 hours, and the powder was passed through a 1000 mesh sieve to obtain AZO spray powder.