US20200308671A1 - Alloy powder and method for preparing the same - Google Patents
Alloy powder and method for preparing the same Download PDFInfo
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- US20200308671A1 US20200308671A1 US16/085,827 US201716085827A US2020308671A1 US 20200308671 A1 US20200308671 A1 US 20200308671A1 US 201716085827 A US201716085827 A US 201716085827A US 2020308671 A1 US2020308671 A1 US 2020308671A1
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- alloy powder
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- 239000000843 powder Substances 0.000 title claims abstract description 111
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 92
- 239000000956 alloy Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 50
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 238000002844 melting Methods 0.000 claims abstract description 30
- 230000008018 melting Effects 0.000 claims abstract description 30
- 229910000807 Ga alloy Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 229910052733 gallium Inorganic materials 0.000 claims description 34
- 239000007789 gas Substances 0.000 claims description 33
- 239000002245 particle Substances 0.000 claims description 20
- 239000011261 inert gas Substances 0.000 claims description 18
- 238000000889 atomisation Methods 0.000 claims description 15
- 229910052738 indium Inorganic materials 0.000 claims description 11
- 238000009689 gas atomisation Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000007873 sieving Methods 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 230000006698 induction Effects 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 9
- KTSFMFGEAAANTF-UHFFFAOYSA-N [Cu].[Se].[Se].[In] Chemical compound [Cu].[Se].[Se].[In] KTSFMFGEAAANTF-UHFFFAOYSA-N 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000010409 thin film Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001338 liquidmetal Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910000905 alloy phase Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000007751 thermal spraying Methods 0.000 description 2
- 230000006399 behavior Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
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- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/04—Making non-ferrous alloys by 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
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- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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Definitions
- the present application relates to, but not limited to, the field of solar application materials, and particularly to, but not limited to, an alloy powder and a method for preparing the same.
- Copper Indium Gallium Selenide (CIGS) alloy used in CIGS thin-film solar cells, is a chalcopyrite structured compound semiconductor composed of four elements Cu, In, Ga, Se.
- CIGS thin-film solar cells Currently, maximizing conversion efficiency of CIGS thin-film solar cells is 22.3%.
- the CIGS thin-film solar cell is especially attractive for the third generation solar cell investigation and application because of its advantages, such as high conversion efficiency, high power generation performance under weak sunlight, high annual generation capacity and wide applicability for its flexible encapsulation.
- CIGS thin-film solar cells have a multilayer film structure, including a metal gate electrode, an anti-reflection film, a window layer (ZnO), a transition layer (CdS), a light absorption layer (CIGS), a metal back electrode (Mo), a glass substrate and so on.
- the light absorption layer CIGS is most important, and is generally deposited by method of magnetron sputtering using Cu—In—Ga based target materials.
- Cu—In—Ga alloy has an extensively wide solid-liquid coexisting temperature zone of about 160-500° C.
- the alloy will be completely melted above 500° C. and solidified below 160° C. Therefore, significant volume shrinkage usually occurs with the conversion from liquid to solid, which consequently for example causes that Cu—In—Ga alloy target produced by traditional melting and casting method has low density with the generation of considerable shrinkage porosities and cavities, and also has an uneven distribution of the main compositions. Otherwise, the above-mentioned problem may be solved, if Cu—In—Ga alloy powder is prepared and then formed into the target by powder metallurgy method or thermal spray deposition method.
- the powder alloy phase is mainly composed of Cu-Ga intermetallic compound and In-based alloy phase. Because of the much lower melting point of In, there exists liquid phases in the alloy powder produced by traditional gas atomization method, which tends to cause severe aggregation and cohesion of the particulates during the cooling process or at the room temperature. Consequently, the surfaces of particulates are attached by a plurality of small satellite particles. As a result, the prepared alloy powder has a quite low yield and poor flowability, so that it may not satisfy the requirements of the process and may not be formed into a target with high performance. Moreover, during the following deposition process, the prepared powder may not be fed fluently, that often make the powder feeding system of a thermal spraying device obstructed.
- the inventors of the present invention provide a method of preparing an alloy powder with low aggregation and high flowability.
- the quite lower aggregation and much higher flowability of the alloy powder prepared by the method result in an increase of the yield rate, and are very useful to the following production of the target.
- the present invention provides an alloy powder, selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga, and having an oxygen concentration below 5000 ppm.
- the alloy powder may have an oxygen concentration in a range from 100 ppm to 3000 ppm.
- the alloy powder may have a particle size in a range from 10 ⁇ m to 50 ⁇ m or from 30 ⁇ m to 100 ⁇ m.
- Cu/(In+Ga) is 0.5 to 1.1
- In/(In+Ga) is 0.2 to 0.9
- Ga/(In+Ga) is 0.1 to 0.8
- In/(In+Ga)+Ga/(In+Ga) is 1, in which Cu may be partially or totally substituted by Ag or Au, and In may be partially or totally substituted by Sn.
- the present invention also provides a method of preparing said alloy powder, comprising the steps of:
- the alloy powder is selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga.
- the method according to the present invention is not limited to prepare the alloy powders exemplified above, and also may be used to prepare other alloy powders.
- the descriptions, along with the examples of alloy powders, are made only by way of example and are not intended to limit the scope of this invention in any manner.
- said alloy powder may be Cu—In—Ga alloy powder, in which, based on the atomic ratio, Cu/(In+Ga) may be 0.5 to 1.1, In/(In+Ga) may be 0.2 to 0.9, Ga/(In+Ga) may be 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) may be 1.
- Cu may be partially or totally substituted by Ag or Au, and In may be partially or totally substituted by Sn.
- the metal elements may be melted under vacuum atmosphere below 1000 Pa, to produce the alloy solution.
- the metal elements may be melted under vacuum atmosphere in a range from 50 Pa to 500 Pa, to produce the alloy solution.
- the metal elements may be melted at temperature not lower than 650° C.
- the metal elements may be melted at temperature in a range from 750° C. to 1050° C.
- the metal elements may be melted for a period not shorter than 30 min.
- the present invention also provides a method of preparing Cu—In—Ga alloy powder, comprising the steps of:
- the weight of In may be 30% to 70%, the weight of Ga may be 5% to 35%, the weight of Cu may be the balance.
- each of the components In, Cu and Ga may have a purity not lower than 99.99%.
- the metal elements may be melted in the reactor under vacuum atmosphere in a range from 50 Pa to 500 Pa.
- the metal elements may be melted at temperature in a range from 750° C. to 1050° C.
- the metal elements may be melted for a period not shorter than 30 min.
- the high-pressure inert gas may be N 2 or Ar gas, with the pressure of 0.5 MPa to 5 MPa and the flow rate of 50 m 3 /h to 500 m 3 /h.
- the inert gas may have the pressure of 1 MPa to 3 MPa and the flow rate of 100 m 3 /h to 400 m 3 /h.
- the oxygen-containing gas may be O 2 gas, compressed air or a combination of O 2 gas and compressed air.
- both high-pressure inert gas and O 2 gas may be fed into the atomization device at the same time, and the flow rate of O 2 gas may be 10 ml/min to 2000 ml/min, optionally, 50 ml/min to 1000 ml/min.
- both high-pressure inert gas and compressed air may be fed into the atomization device at the same time, and the flow rate of compressed air may be 0.05 L/min to 20 L/min, in which the pressure of compressed air will not affect the characteristics of the prepared alloy powder, so it is not desired to limit it.
- both high-pressure inert gas and oxygen-containing gas may be each independently fed into the atomization device at the same time through different pipelines, or alternatively, may be mixed from different pipelines and then fed into the atomization device together.
- the method may be implemented in a gas atomization powder preparing apparatus, and the reactor may be a vacuum induction melting furnace of the apparatus, in which the pressure difference between the melting chamber and the atomizing chamber of the apparatus may be 500 Pa to 0.05 MPa.
- the pressure difference between the melting chamber and the atomizing chamber of the apparatus may be 1000 Pa to 10000 Pa.
- the alloy solution may be delivered into the atomization device though a conducting pipe with the diameter of 0.5 mm to 2 mm.
- the high-pressure inert gas and the oxygen-containing gas delivered may be sprayed via a high-pressure gas spray disc of the atomization device.
- the method may further comprise the steps of collecting and sieving the prepared alloy powder.
- the step of sieving may be achieved by use of an ultrasonic auxiliary vibration sieve.
- the prepared alloy powder may have a particle size of 10 ⁇ m to 50 ⁇ m or 30 ⁇ m to 100 ⁇ m.
- the prepared alloy powder may have an oxygen concentration lower than 5000 ppm.
- the prepared alloy powder may have an oxygen concentration in a range from 100 ppm to 3000 ppm.
- the present invention provides an alloy powder prepared by the method as described above.
- the alloy powder has a particle size in a range from 10 ⁇ m to 50 ⁇ m or 30 ⁇ m to 100 ⁇ m, and has an oxygen concentration lower than 5000 ppm.
- the prepared alloy powder has an oxygen concentration in a range from 100 ppm to 3000 ppm.
- the performance of the film deposited on the target may be affected by the oxygen concentration in the target, and specifically, the performance may be worse with increasing of the oxygen concentration. Therefore, it is desired to decrease the oxygen concentration in the target.
- feeding a controlled oxygen-containing gas during the gas atomization preparing process of an alloy powder may induce the generation of the satellite particles, increase the characteristics and the yield rate of the alloy powder, and may make the oxygen concentration in the target controlled to a desired range as well.
- the inventors of the present invention estimate that, the alloy powder is subjected to a surface modification by the controlled oxygen-containing gas, and subsequently a much thinner oxide layer is formed on the surface of the powder and makes the powder passivated, which accordingly decreases the generation of the satellite particles and prevents the occurrence of cohesion during storage and transport of the powder.
- the generation of the satellite particles and the occurrence of cohesion in the process of atomizing are significantly decreased, so that the yield rate and the flowability of the powder are increased accordingly.
- the prepared alloy powder is subsequently formed into the target (for example, Cu—In—Ga target), the processing behaviors of the target may be considerably improved, and the problems of the delivery of the alloy powder arising during the thermal spraying deposition may be solved as well.
- FIG. 1 is a process flow chart for the method of preparing the Cu—In—Ga alloy powder according to Examples of the present invention.
- FIGS. 2 a , 2 b respectively show the morphology of the Cu—In—Ga alloy powder prepared by traditional gas atomization method and prepared according to Example 1 of the present invention.
- the method of preparing the Cu—In—Ga alloy powder according to the Examples below comprises the steps of:
- the gas atomization powder preparing apparatus includes a main part, in which a vacuum chamber and an atomizing chamber are disposed in sequence from top to bottom, and connected to each other via an intermediate package with liquid metal pipelines.
- the vacuum chamber has a melting device and a heating device disposed therein, and the heating device heats the melting device.
- the melting device has an outlet connected to the top of the atomizing chamber via a conducting pipe.
- the atomizing chamber has a gas nozzle connected to a high-pressure inert gas pipeline, and the gas nozzle ejects out high-pressure inert gas toward outlet of the conducting pipe.
- the atomizing chamber has an oxygen-containing gas pipeline and a spraying device connected with each other. The oxygen-containing gas pipeline delivers the oxygen-containing gas into the atomizing chamber though the spraying device.
- the components described above are disposed into a crucible of the melting chamber. Subsequently, the power is turned on, and the melting chamber is vacuumized to a pressure of 200 Pa. The components are melted by heating at 900° C. for 60 min to obtain an uniform alloy solution with electromagnetic stirring of an induction coil. Then, the vacuum pump is turned off. N 2 gas is fed into the melting chamber and the atomizing chamber, to make the pressure of the atomizing chamber to be atmospheric pressure and 2000 Pa lower than that of the melting chamber.
- the alloy solution Immediately after the alloy solution exits from the end of the conducting pipe, it is atomized into small drops under the impact of the high-pressure flow. The small drops are forced to be cooled quickly under the driving of the atomizing flow, to obtain the alloy powder. The whole atomization process is accomplished for about 1 hour.
- the alloy powder prepared in the gas atomization preparing apparatus is collected and then sieved by an ultrasonic auxiliary vibration sieve to obtain the Cu—In—Ga alloy powder with the particle size of 30 ⁇ m to 100 ⁇ m, which is desired to form the Cu—In—Ga target.
- the yield rate of the Cu—In—Ga alloy powder is not lower than 98%, and the yield rate of the powder with the particle size of 30 ⁇ m to 100 ⁇ m is 44%.
- the prepared powder shows a good flowability of 14 s/50g tested by Hall flow meter, so that no obvious aggregation and cohesion among the particulates of the powder exist.
- the oxygen concentration of the powder is 300 ppm.
- Example 2 (2) conducting the steps of melting and atomizing in the gas atomization powder preparing apparatus as described in Example 1 to prepare the alloy powder.
- the components described above are disposed into the crucible of the melting chamber. Subsequently, the power is turned on, and the melting chamber is vacuumized to the pressure of 500 Pa. The components are melted by heating at 1000° C. for 40 min to obtain an uniform alloy solution with electromagnetic stirring of an induction coil.
- the alloy powder prepared in the gas atomization preparing apparatus is collected and then sieved by an ultrasonic auxiliary vibration sieve to obtain the Cu—In—Ga alloy powder with the particle size of 30 ⁇ m to 100 ⁇ m, which is desired to form the Cu—In—Ga target.
- the yield rate of the Cu—In—Ga alloy powder is not lower than 98%, and the yield rate of the powder with the particle size of 30 ⁇ m to 100 ⁇ m is 45%.
- the prepared powder shows a flowability of 18 s/50g tested by Hall flow meter, so that no obvious aggregation and cohesion among the particulates of the powder exist.
- the oxygen concentration of the powder is 420 ppm.
- Example Example Example 3 4 5 6 7 melting temperature, °C. 900 950 1050 750 800 flow rate of N 2 gas, m 3 /h 200 180 300 350 150 pressure of N 2 gas, MPa 3 3.5 1 2 2 flow rate of compressed 16 0.1 5 5 2 air, L/min diameter of liquid metal 2 0.5 1.5 1 2 conducting pipe, mm yield rate of the powder 44 33 40 37 42 with a particle size of 30 to 100 ⁇ m, % flowability of the powder, 25 19 16 14 13 s/50 g oxygen concentration of 1480 120 380 280 230 the powder, ppm
- Comparative Example 1 is similar as Example 1, except that no compressed air is fed during the atomizing process.
- the yield rate of the Cu—In—Ga alloy powder is 98%, and the yield rate of the powder with the particle size of 30 ⁇ m to 100 ⁇ m is 20%.
- the prepared powder shows a poor flowability of 30 s/50g tested by Hall flow meter, resulting in the occurrence of aggregation and cohesion among the particulates of the powder and the generation of considerable satellite particles.
- the Cu—In—Ga alloy powder prepared in Comparative example 1 had a large number of small satellite particles attached to the surfaces of the particulates, and there also existed cohesion among the particulates. While, the Cu—In—Ga alloy powder prepared in Example 1 had the spherical particulates with smooth surfaces and quite few small satellite particles attached thereon.
- the Cu—In—Ga alloy powder prepared according to Examples 1 to 7 was formed into the Cu—In—Ga targets, with the thickness of 7 mm, the relative density of 95%, the purity higher than 99.99% and the oxygen concentration not higher than 3000 ppm.
- the formed targets When used as the sputtering targets in the production of Cu—In—Ga-Se thin film solar cells, the formed targets had a stable plasma arcing and no irregular discharge, satisfying the desired characteristic requirements.
- embodiments of the present invention include any possible combination of some or all of the various embodiments described herein, as well as within the scope of the present invention as defined by the claims. All patents, patent applications and other cited articles mentioned anywhere in the present invention or in any cited patent, cited patent application, or other cited articles are hereby incorporated by reference in their entirety.
- the yield and the qualification of the alloy powder may be improved, and the prepared alloy powder has the advantages of less surface satellite particles, less occurrence of cohesion, and better flowability.
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Abstract
Provided is a method of preparing an alloy powder, comprising the steps of: melting the metal elements to produce the alloy solution; atomizing the alloy solution into small drops under oxygen-containing atmosphere; forcing the small drops to be quickly cooled under the driving of the atomizing flow to obtain the alloy powder; wherein, when the method is used to prepare Cu—In—Ga alloy powder, Cu/(In+Ga) is 0.5 to 1.1, In/(In+Ga) is 0.2 to 0.9, Ga/(In+Ga) is 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) is 1. Also provided is an alloy powder and a method of preparing Cu—In—Ga alloy powder.
Description
- The present application relates to, but not limited to, the field of solar application materials, and particularly to, but not limited to, an alloy powder and a method for preparing the same.
- Copper Indium Gallium Selenide (CIGS) alloy, used in CIGS thin-film solar cells, is a chalcopyrite structured compound semiconductor composed of four elements Cu, In, Ga, Se. Currently, maximizing conversion efficiency of CIGS thin-film solar cells is 22.3%. The CIGS thin-film solar cell is especially attractive for the third generation solar cell investigation and application because of its advantages, such as high conversion efficiency, high power generation performance under weak sunlight, high annual generation capacity and wide applicability for its flexible encapsulation.
- CIGS thin-film solar cells have a multilayer film structure, including a metal gate electrode, an anti-reflection film, a window layer (ZnO), a transition layer (CdS), a light absorption layer (CIGS), a metal back electrode (Mo), a glass substrate and so on. Among these layers, the light absorption layer CIGS is most important, and is generally deposited by method of magnetron sputtering using Cu—In—Ga based target materials.
- Hereinafter, it's a brief summary of the objects of the invention which will be described in the detailed description. Although, it is not intended to limit the scope of the claims.
- The inventors of the present invention discovered that Cu—In—Ga alloy has an extensively wide solid-liquid coexisting temperature zone of about 160-500° C. The alloy will be completely melted above 500° C. and solidified below 160° C. Therefore, significant volume shrinkage usually occurs with the conversion from liquid to solid, which consequently for example causes that Cu—In—Ga alloy target produced by traditional melting and casting method has low density with the generation of considerable shrinkage porosities and cavities, and also has an uneven distribution of the main compositions. Otherwise, the above-mentioned problem may be solved, if Cu—In—Ga alloy powder is prepared and then formed into the target by powder metallurgy method or thermal spray deposition method. However, since the melting points of metal elements (In 156.6° C., Ga 29.8° C., Cu 1083° C.) are considerably different, the powder alloy phase is mainly composed of Cu-Ga intermetallic compound and In-based alloy phase. Because of the much lower melting point of In, there exists liquid phases in the alloy powder produced by traditional gas atomization method, which tends to cause severe aggregation and cohesion of the particulates during the cooling process or at the room temperature. Consequently, the surfaces of particulates are attached by a plurality of small satellite particles. As a result, the prepared alloy powder has a quite low yield and poor flowability, so that it may not satisfy the requirements of the process and may not be formed into a target with high performance. Moreover, during the following deposition process, the prepared powder may not be fed fluently, that often make the powder feeding system of a thermal spraying device obstructed.
- Similarly, when preparing other alloy powders with extensively wide solid-liquid coexisting temperature zone and even comprising a metal component with much low melting point, the problems described above will also be caused accordingly.
- Based on the deep analysis to the above-mention problems, the inventors of the present invention provide a method of preparing an alloy powder with low aggregation and high flowability. The quite lower aggregation and much higher flowability of the alloy powder prepared by the method result in an increase of the yield rate, and are very useful to the following production of the target.
- Specifically, the present invention provides an alloy powder, selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga, and having an oxygen concentration below 5000 ppm.
- According to some embodiments, the alloy powder may have an oxygen concentration in a range from 100 ppm to 3000 ppm.
- According to some embodiments, the alloy powder may have a particle size in a range from 10 μm to 50 μm or from 30 μm to 100 μm.
- According to some embodiments, based on the atomic ratio, in the Cu—In—Ga alloy powder, Cu/(In+Ga) is 0.5 to 1.1, In/(In+Ga) is 0.2 to 0.9, Ga/(In+Ga) is 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) is 1, in which Cu may be partially or totally substituted by Ag or Au, and In may be partially or totally substituted by Sn.
- Further, the present invention also provides a method of preparing said alloy powder, comprising the steps of:
- Melting metal elements for preparing the alloy powder to produce an alloy solution;
- atomizing the alloy solution into small drops in an oxygen-containing atmosphere;
- Under the driving of atomizing flow, forcing the small drops to be quickly cooled to obtain the alloy powder.
- According to some embodiments, the alloy powder is selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga.
- It should be understood that, the method according to the present invention is not limited to prepare the alloy powders exemplified above, and also may be used to prepare other alloy powders. The descriptions, along with the examples of alloy powders, are made only by way of example and are not intended to limit the scope of this invention in any manner. When the melting points of alloy components are distributed in a large temperature range, as described above, resulting in the cohesion among particulates and/or the attachment of satellite particles on the surfaces in the alloy powder if prepared by traditional method, it is especially adapted to use the method according to the present invention.
- According to some embodiments, said alloy powder may be Cu—In—Ga alloy powder, in which, based on the atomic ratio, Cu/(In+Ga) may be 0.5 to 1.1, In/(In+Ga) may be 0.2 to 0.9, Ga/(In+Ga) may be 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) may be 1.
- Optionally, in said Cu—In—Ga alloy powder, Cu may be partially or totally substituted by Ag or Au, and In may be partially or totally substituted by Sn.
- According to some embodiments, the metal elements may be melted under vacuum atmosphere below 1000 Pa, to produce the alloy solution.
- Optionally, the metal elements may be melted under vacuum atmosphere in a range from 50 Pa to 500 Pa, to produce the alloy solution.
- According to some embodiments, the metal elements may be melted at temperature not lower than 650° C.
- Optionally, the metal elements may be melted at temperature in a range from 750° C. to 1050° C.
- According to some embodiments, the metal elements may be melted for a period not shorter than 30 min.
- Further, the present invention also provides a method of preparing Cu—In—Ga alloy powder, comprising the steps of:
- Disposing metal elements of In, Cu and Ga into a reactor;
- Making the reactor in vacuum state, and then sealing and heating the reactor, to produce an alloy solution by melting said metal elements;
- Delivering the alloy solution into atomizing center of an atomization device, meanwhile feeding a flow of high-pressure inert gas and oxygen-containing gas, to make the alloy solution atomized into small drops under the impact of the high-pressure flow;
- Under the driving of atomizing flow, forcing the small drops to be quickly cooled, to obtain the alloy powder.
- According to some embodiments, based on that the total weight of the metal elements is 100%, the weight of In may be 30% to 70%, the weight of Ga may be 5% to 35%, the weight of Cu may be the balance.
- According to some embodiments, each of the components In, Cu and Ga may have a purity not lower than 99.99%.
- According to some embodiments, the metal elements may be melted in the reactor under vacuum atmosphere in a range from 50 Pa to 500 Pa.
- According to some embodiments, the metal elements may be melted at temperature in a range from 750° C. to 1050° C.
- According to some embodiments, the metal elements may be melted for a period not shorter than 30 min.
- According to some embodiments, the high-pressure inert gas may be N2 or Ar gas, with the pressure of 0.5 MPa to 5 MPa and the flow rate of 50 m3/h to 500 m3/h.
- Optionally, the inert gas may have the pressure of 1 MPa to 3 MPa and the flow rate of 100 m3/h to 400 m3/h.
- According to some embodiments, the oxygen-containing gas may be O2 gas, compressed air or a combination of O2 gas and compressed air.
- According to some embodiments, both high-pressure inert gas and O2 gas may be fed into the atomization device at the same time, and the flow rate of O2 gas may be 10 ml/min to 2000 ml/min, optionally, 50 ml/min to 1000 ml/min.
- According to some embodiments, both high-pressure inert gas and compressed air may be fed into the atomization device at the same time, and the flow rate of compressed air may be 0.05 L/min to 20 L/min, in which the pressure of compressed air will not affect the characteristics of the prepared alloy powder, so it is not desired to limit it.
- According to some embodiments, both high-pressure inert gas and oxygen-containing gas may be each independently fed into the atomization device at the same time through different pipelines, or alternatively, may be mixed from different pipelines and then fed into the atomization device together.
- According to some embodiments, the method may be implemented in a gas atomization powder preparing apparatus, and the reactor may be a vacuum induction melting furnace of the apparatus, in which the pressure difference between the melting chamber and the atomizing chamber of the apparatus may be 500 Pa to 0.05 MPa.
- Optionally, the pressure difference between the melting chamber and the atomizing chamber of the apparatus may be 1000 Pa to 10000 Pa.
- According to some embodiments, the alloy solution may be delivered into the atomization device though a conducting pipe with the diameter of 0.5 mm to 2 mm.
- According to some embodiments, the high-pressure inert gas and the oxygen-containing gas delivered may be sprayed via a high-pressure gas spray disc of the atomization device.
- According to some embodiments, the method may further comprise the steps of collecting and sieving the prepared alloy powder.
- Optionally, the step of sieving may be achieved by use of an ultrasonic auxiliary vibration sieve.
- Optionally, after the step of sieving, the prepared alloy powder may have a particle size of 10 μm to 50 μm or 30 μm to 100 μm.
- According to some embodiments, the prepared alloy powder may have an oxygen concentration lower than 5000 ppm.
- Optionally, the prepared alloy powder may have an oxygen concentration in a range from 100 ppm to 3000 ppm.
- Further, the present invention provides an alloy powder prepared by the method as described above. The alloy powder has a particle size in a range from 10 μm to 50 μm or 30 μm to 100 μm, and has an oxygen concentration lower than 5000 ppm.
- According to some embodiments, the prepared alloy powder has an oxygen concentration in a range from 100 ppm to 3000 ppm.
- Generally, the performance of the film deposited on the target may be affected by the oxygen concentration in the target, and specifically, the performance may be worse with increasing of the oxygen concentration. Therefore, it is desired to decrease the oxygen concentration in the target. However, the inventors of the present invention discovered that, feeding a controlled oxygen-containing gas during the gas atomization preparing process of an alloy powder may induce the generation of the satellite particles, increase the characteristics and the yield rate of the alloy powder, and may make the oxygen concentration in the target controlled to a desired range as well. Although, it is not expected to be limited to the theory, the inventors of the present invention estimate that, the alloy powder is subjected to a surface modification by the controlled oxygen-containing gas, and subsequently a much thinner oxide layer is formed on the surface of the powder and makes the powder passivated, which accordingly decreases the generation of the satellite particles and prevents the occurrence of cohesion during storage and transport of the powder. By use of the method of preparing an alloy powder according to the present invention, the generation of the satellite particles and the occurrence of cohesion in the process of atomizing are significantly decreased, so that the yield rate and the flowability of the powder are increased accordingly. When the prepared alloy powder is subsequently formed into the target (for example, Cu—In—Ga target), the processing behaviors of the target may be considerably improved, and the problems of the delivery of the alloy powder arising during the thermal spraying deposition may be solved as well.
- Other features and advantages will be explained in the following description, and will become more obvious partially from the description or be understood by realizing the present invention. The objects and other advantages of the present invention may be achieved via the structure particularly indicated in the specification, the claims and the drawings.
- A further understanding of the invention may be achieved in conjunction with the accompanying drawings, which constitute a part of the specification and interpret the invention together with the examples, but may not be regarded as a limitation to the invention by any way.
-
FIG. 1 is a process flow chart for the method of preparing the Cu—In—Ga alloy powder according to Examples of the present invention. -
FIGS. 2a, 2b respectively show the morphology of the Cu—In—Ga alloy powder prepared by traditional gas atomization method and prepared according to Example 1 of the present invention. - To make the objects, the technical solutions and the advantages of the invention understood more clearly, the present invention will be described in more detail with reference to the drawings. It is noted that, the Examples and the features referred in the Examples may be arbitrarily combined with each other.
- The parameters measured in the Examples below are determined by conventional methods in the art, except otherwise indicated.
- As shown in
FIG. 1 , the method of preparing the Cu—In—Ga alloy powder according to the Examples below comprises the steps of: - Weighing the components of In, Cu and Ga in proportion;
- Disposing the weighed components into a reactor, making the reactor in vacuum state, and then sealing and heating the reactor;
- Melting the components, to produce the alloy solution;
- Atomizing the alloy solution into small drops under the oxygen-containing atmosphere, and forcing the small drops to be quickly cooled, to obtain the alloy powder;
- Collecting the alloy powder;
- Sieving the alloy powder by use of an ultrasonic auxiliary vibration sieve.
- (1) weighing 50 kg In, 35 kg Cu and 15 kg Ga (purity 99.9999%, commercially available products) respectively, i.e. based on the atomic ratio, Cu/(In+Ga) is 0.86, In/(In+Ga) is 0.67, Ga/(In+Ga) is 0.33;
- (2) conducting the steps of melting and atomizing in a gas atomization powder preparing apparatus to prepare the alloy powder.
- The gas atomization powder preparing apparatus includes a main part, in which a vacuum chamber and an atomizing chamber are disposed in sequence from top to bottom, and connected to each other via an intermediate package with liquid metal pipelines. The vacuum chamber has a melting device and a heating device disposed therein, and the heating device heats the melting device. The melting device has an outlet connected to the top of the atomizing chamber via a conducting pipe. The atomizing chamber has a gas nozzle connected to a high-pressure inert gas pipeline, and the gas nozzle ejects out high-pressure inert gas toward outlet of the conducting pipe. The atomizing chamber has an oxygen-containing gas pipeline and a spraying device connected with each other. The oxygen-containing gas pipeline delivers the oxygen-containing gas into the atomizing chamber though the spraying device.
- The components described above are disposed into a crucible of the melting chamber. Subsequently, the power is turned on, and the melting chamber is vacuumized to a pressure of 200 Pa. The components are melted by heating at 900° C. for 60 min to obtain an uniform alloy solution with electromagnetic stirring of an induction coil. Then, the vacuum pump is turned off. N2 gas is fed into the melting chamber and the atomizing chamber, to make the pressure of the atomizing chamber to be atmospheric pressure and 2000 Pa lower than that of the melting chamber.
- (3) The melted alloy solution is poured slowly and evenly into the intermediate package, and then, under the gravity and the pressure difference (9000 Pa) between the vacuum melting chamber and the atomizing chamber, flows toward the atomizing chamber via the liquid metal conducting pipe with the diameter of 2 mm. Meanwhile, N2 gas, with the pressure of 3 MPa and the flow rate of 200 m3/h, is fed into the atomizing chamber through the high-pressure inert gas pipeline as an atomizing medium, and at the same time, clean compressed air, with the pressure of 0.8 MPa and the flow rate of 3 L/min, is fed into the atomizing chamber through the oxygen-containing gas pipeline. Immediately after the alloy solution exits from the end of the conducting pipe, it is atomized into small drops under the impact of the high-pressure flow. The small drops are forced to be cooled quickly under the driving of the atomizing flow, to obtain the alloy powder. The whole atomization process is accomplished for about 1 hour.
- (4) The alloy powder prepared in the gas atomization preparing apparatus is collected and then sieved by an ultrasonic auxiliary vibration sieve to obtain the Cu—In—Ga alloy powder with the particle size of 30 μm to 100 μm, which is desired to form the Cu—In—Ga target.
- The yield rate of the Cu—In—Ga alloy powder is not lower than 98%, and the yield rate of the powder with the particle size of 30 μm to 100 μm is 44%. The prepared powder shows a good flowability of 14 s/50g tested by Hall flow meter, so that no obvious aggregation and cohesion among the particulates of the powder exist. The oxygen concentration of the powder is 300 ppm.
- (1) weighing 35 kg In, 40 kg Cu and 25 kg Ga (purity 99.999%, commercially available products) respectively, i.e. based on the atomic ratio, Cu/(In+Ga) is 0.95, In/(In+Ga) is 0.46, Ga/(In+Ga) is 0.54;
- (2) conducting the steps of melting and atomizing in the gas atomization powder preparing apparatus as described in Example 1 to prepare the alloy powder. The components described above are disposed into the crucible of the melting chamber. Subsequently, the power is turned on, and the melting chamber is vacuumized to the pressure of 500 Pa. The components are melted by heating at 1000° C. for 40 min to obtain an uniform alloy solution with electromagnetic stirring of an induction coil.
- (3) The melted alloy solution is poured slowly and evenly into the intermediate package, and then, under the gravity and the pressure difference (20000 Pa) between the vacuum melting chamber and the atomizing chamber, flows toward the atomizing chamber via the liquid metal conducting pipe with the diameter of 1.5 mm. Meanwhile, N2 gas, with the pressure of 2 MPa and the flow rate of 120 m3/h, is fed into the atomizing chamber through the high-pressure inert gas pipeline as an atomizing medium, and at the same time, O2 gas, with the pressure of 0.8 MPa and the flow rate of 500 ml/min, is fed into the atomizing chamber through the oxygen-containing gas pipeline. Immediately after the alloy solution exits from the end of the conducting pipe, it is atomized into small drops under the impact of the high-pressure flow. The small drops are forced to be cooled quickly under the driving of the atomizing flow, to obtain the alloy powder.
- (4) The alloy powder prepared in the gas atomization preparing apparatus is collected and then sieved by an ultrasonic auxiliary vibration sieve to obtain the Cu—In—Ga alloy powder with the particle size of 30 μm to 100 μm, which is desired to form the Cu—In—Ga target.
- The yield rate of the Cu—In—Ga alloy powder is not lower than 98%, and the yield rate of the powder with the particle size of 30 μm to 100 μm is 45%. The prepared powder shows a flowability of 18 s/50g tested by Hall flow meter, so that no obvious aggregation and cohesion among the particulates of the powder exist. The oxygen concentration of the powder is 420 ppm.
- Parts of the process parameters of Examples 3 to 7 are shown in Table 1, and other steps and process parameters are similar as Example 1.
-
TABLE 1 Example Example Example Example Example 3 4 5 6 7 melting temperature, °C. 900 950 1050 750 800 flow rate of N2 gas, m3/ h 200 180 300 350 150 pressure of N2 gas, MPa 3 3.5 1 2 2 flow rate of compressed 16 0.1 5 5 2 air, L/min diameter of liquid metal 2 0.5 1.5 1 2 conducting pipe, mm yield rate of the powder 44 33 40 37 42 with a particle size of 30 to 100 μm, % flowability of the powder, 25 19 16 14 13 s/50 g oxygen concentration of 1480 120 380 280 230 the powder, ppm - Comparative Example 1 is similar as Example 1, except that no compressed air is fed during the atomizing process.
- The yield rate of the Cu—In—Ga alloy powder is 98%, and the yield rate of the powder with the particle size of 30 μm to 100 μm is 20%. The prepared powder shows a poor flowability of 30 s/50g tested by Hall flow meter, resulting in the occurrence of aggregation and cohesion among the particulates of the powder and the generation of considerable satellite particles.
- Characteristic Tests
- 1. The Cu—In—Ga alloy powder prepared respectively according to Example 1 and Comparative Example 1 were observed under the scanning electron microscope. The results were shown in
FIG. 2 . - It may be noted that, the Cu—In—Ga alloy powder prepared in Comparative example 1 had a large number of small satellite particles attached to the surfaces of the particulates, and there also existed cohesion among the particulates. While, the Cu—In—Ga alloy powder prepared in Example 1 had the spherical particulates with smooth surfaces and quite few small satellite particles attached thereon.
- 2. By conventional plasma spraying method in the art, the Cu—In—Ga alloy powder prepared according to Examples 1 to 7 was formed into the Cu—In—Ga targets, with the thickness of 7 mm, the relative density of 95%, the purity higher than 99.99% and the oxygen concentration not higher than 3000 ppm. When used as the sputtering targets in the production of Cu—In—Ga-Se thin film solar cells, the formed targets had a stable plasma arcing and no irregular discharge, satisfying the desired characteristic requirements.
- The present disclosure is an illustration of the principle of the embodiments according to the present invention, but not intended to do any formal or substantial limitation to the present invention, or limit the present invention to specific embodiments. For those skilled in the art, it is obvious that the elements, methods and systems of the technical solutions in the embodiments of the present invention may be changed, altered, modified and evolved, without departing from the principle, spirit and scope as defined in the claims of the embodiments and technical solutions of the present invention as described above. These changed, altered, modified and evolved embodiments are all included in the equivalent embodiments of the present invention, and these equivalent embodiments are all included in the scope of the present invention defined by the claims. Although embodiments of the present invention may be embodied in many different forms, some embodiments of the present invention are described in detail herein. Furthermore, embodiments of the present invention include any possible combination of some or all of the various embodiments described herein, as well as within the scope of the present invention as defined by the claims. All patents, patent applications and other cited articles mentioned anywhere in the present invention or in any cited patent, cited patent application, or other cited articles are hereby incorporated by reference in their entirety.
- The above disclosure is intended to be illustrative and not exhaustive. For those skilled in the art, this specification will suggest many changes and alternatives. All these alternatives and variations are intended to be included within the scope of the claims, where the term “comprising” means “including, but not limited to”.
- The description of alternative embodiments of the present application is concluded herein. Those skilled in the art will recognize other equivalent variations of the embodiments described herein, which equivalents are also included by the claims attached hereto.
- Using the method of preparing the alloy powder provided by the present invention, the yield and the qualification of the alloy powder may be improved, and the prepared alloy powder has the advantages of less surface satellite particles, less occurrence of cohesion, and better flowability.
Claims (18)
1. An alloy powder, selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga alloy powders, with oxidized particulate surfaces and an oxygen concentration lower than 5000 ppm.
2. The alloy powder according to claim 1 , wherein the alloy powder has an oxygen concentration in a range from 100 ppm to 3000 ppm.
3. The alloy powder according to claim 1 , wherein the alloy powder has a particle size in a range from 10 μm to 50 μm or 30 μm to 100 μm.
4. A method of preparing an alloy powder, comprising the steps of:
melting metal elements for preparing the alloy powder to produce an alloy solution;
atomizing the alloy solution into small drops under oxygen-containing atmosphere;
under the driving of atomizing flow, forcing the small drops to be quickly cooled, to obtain the alloy powder.
5. The method according to claim 4 , wherein the alloy powder is selected from any one of Cu—In—Ga, Ag—In—Ga, Au—In—Ga, Cu—Sn—Ga, Ag—Sn—Ga, Au—Sn—Ga, Cu—Ag—In—Ga and Cu—Au—In—Ga, and based on the atomic ratio, Cu/(In+Ga) is 0.5 to 1.1, In/(In+Ga) is 0.2 to 0.9, Ga/(In+Ga) is 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) is 1, Cu may be partially or totally substituted by Ag or Au, and In may be partially or totally substituted by Sn.
6. The method according to claim 4 , wherein the metal elements are melted under vacuum atmosphere below 1000 Pa, optionally, in a range from 50 Pa to 500 Pa, to produce the alloy solution.
7. The method according to claim 4 , wherein the metal elements are melted at temperature not lower than 650° C., optionally in a range from 750° C. to 1050° C., and for a period not shorter than 30 min.
8. A method of preparing Cu—In—Ga alloy powder, comprising the steps of:
disposing metal elements of Cu, In and Ga into a reactor;
making the reactor in vacuum state, and then sealing and heating the reactor, to produce an alloy solution by melting the metal elements;
delivering the alloy solution into atomizing center of an atomization device, meanwhile, feeding a flow of high-pressure inert gas and oxygen-containing gas, to make the alloy solution atomized into small drops under the impact of the high-pressure inert gas;
under the driving of atomizing flow, forcing the small drops to be quickly cooled, to obtain the alloy powder.
9. The method according to claim 8 , wherein, based on that the total weight of the metal elements is 100%, the weight of In is 30% to 70%, the weight of Ga is 5% to 35%, and the weight of Cu is the balance, and each of the components In, Cu and Ga has a purity not lower than 99.99% and is melted in the reactor under vacuum atmosphere in a range from 50 Pa to 500 Pa at a temperature in a range from 750° C. to 1050° C. for a period not shorter than 30 min.
10. The method according to claim 8 , wherein the high-pressure inert gas is N2 or Ar gas with the pressure of 0.5 MPa to 5 MPa and the flow rate of 50 m3/h to 500 m3/h, and optionally, with the pressure of 1 MPa to 3 MPa and the flow rate of 100 m3/h to 400 m3/h.
11. The method according to claim 8 , wherein the oxygen-containing gas is O2, compressed air or a combination of O2 and compressed air, and optionally, both high-pressure inert gas and O2 gas are fed into the atomization device at the same time with the flow rate of O2 gas in a range from 10 ml/min to 2000 ml/min, further optionally, 50 ml/min to 1000 ml/min, or both high-pressure inert gas and compressed air are fed into the atomization device at the same time with the flow rate of compressed air in a range from 0.05 L/min to 20 L/min.
12. The method according to claim 8 , wherein both high-pressure inert gas and oxygen-containing gas are each independently fed into the atomization device at the same time through different pipelines, or mixed from different pipelines and then fed into the atomization device together.
13. The method according to claim 8 , wherein the method is implemented in a gas atomization powder preparing apparatus, the reactor is a vacuum induction melting furnace of the apparatus, and the pressure difference between the melting chamber and the atomizing chamber of the apparatus is 500 Pa to 0.05 MPa, optionally, 1000 Pa to 10000 Pa, and the alloy solution is delivered into the atomization device though a conducting pipe with the diameter of 0.5 mm to 2 mm, and the high-pressure inert gas and the oxygen-containing gas delivered are sprayed via a high-pressure gas spray disc of the atomization device of the apparatus.
14. The method according to claim 8 , wherein the method further comprise the steps of collecting and sieving the prepared alloy powder, optionally, by use of an ultrasonic auxiliary vibration sieve, and optionally, after the step of sieving, the prepared alloy powder has a particle size of 10 μm to 50 μm or 30 μm to 100 μm.
15. The method according to claim 8 , wherein the prepared alloy powder has an oxygen concentration lower than 5000 ppm, optionally, in a range from 100 ppm to 3000 ppm.
16-18. (canceled)
19. The alloy powder according to claim 1 , wherein, based on the atomic ratio, Cu/(In+Ga) is 0.5 to 1.1, In/(In+Ga) is 0.2 to 0.9, Ga/(In+Ga) is 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) is 1, and Cu may be partially or totally substituted by Ag or Au, In may be partially or totally substituted by Sn.
20. The alloy powder according to claim 2 , wherein, based on the atomic ratio, Cu/(In+Ga) is 0.5 to 1.1, In/(In+Ga) is 0.2 to 0.9, Ga/(In+Ga) is 0.1 to 0.8, In/(In+Ga)+Ga/(In+Ga) is 1, and Cu may be partially or totally substituted by Ag or Au, In may be partially or totally substituted by Sn.
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CN201710661557.3A CN107626929B (en) | 2017-08-04 | 2017-08-04 | Method for preparing alloy powder |
PCT/CN2017/120072 WO2019024420A1 (en) | 2017-08-04 | 2017-12-29 | Alloy powder and preparation method therefor |
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US20190217393A1 (en) | 2018-01-12 | 2019-07-18 | Hammond Group, Inc. | Methods for processing metal-containing materials |
CN110605399A (en) * | 2018-06-15 | 2019-12-24 | 米亚索乐装备集成(福建)有限公司 | Preparation method of copper-indium-gallium alloy powder |
CN111378839A (en) * | 2018-12-28 | 2020-07-07 | 汉能新材料科技有限公司 | Method for preparing alloy powder by using copper indium gallium selenide-containing waste |
US20210178468A1 (en) * | 2019-09-27 | 2021-06-17 | Ap&C Advanced Powders & Coatings Inc. | Aluminum Based Metal Powders and Methods of Their Production |
CN111531172B (en) * | 2020-05-29 | 2021-12-31 | 同济大学 | 3D printing process method of high-strength aluminum-silicon alloy |
CN112517917B (en) * | 2020-11-25 | 2023-04-18 | 河南东微电子材料有限公司 | Preparation method of CrTiLa alloy powder for chromium-titanium target material |
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JP2004162109A (en) * | 2002-11-12 | 2004-06-10 | Nikko Materials Co Ltd | Sputtering target and powder for producing the same |
CN101362206B (en) * | 2008-10-09 | 2011-03-23 | 陈新国 | Preparation method of continuous high quality soldering powder |
JP5883022B2 (en) * | 2010-11-30 | 2016-03-09 | ダウ グローバル テクノロジーズ エルエルシー | Repair of alloy sputter targets containing copper and indium. |
CN102248171A (en) * | 2011-07-12 | 2011-11-23 | 中南大学 | Gas atomization method for preparing oxygen supersaturated iron-based alloy powder |
CN102689015B (en) * | 2012-06-21 | 2014-03-26 | 北京有色金属研究总院 | Metal powder preparation device and method therefor |
CN202684094U (en) * | 2012-06-21 | 2013-01-23 | 北京有色金属研究总院 | Device for preparing metal powder |
CN103600084A (en) * | 2013-09-12 | 2014-02-26 | 苏州米莫金属科技有限公司 | Powder metallurgy high-pressure water atomization pulverizing device |
JP6412401B2 (en) * | 2014-10-23 | 2018-10-24 | Dowaエレクトロニクス株式会社 | Metal powder and method for producing the same |
CN104325147B (en) * | 2014-11-25 | 2019-07-19 | 北京康普锡威科技有限公司 | A kind of in-situ passivation method of atomized producing ball-shaped brazing powder |
TWI551704B (en) * | 2015-05-21 | 2016-10-01 | China Steel Corp | Copper gallium alloy composite sodium element target manufacturing method |
CN106378460B (en) * | 2016-09-22 | 2018-05-11 | 成都优材科技有限公司 | Prepare the plasma atomization method and equipment of spherical pure titanium or titanium alloy powder |
CN107377983A (en) * | 2017-08-04 | 2017-11-24 | 米亚索乐装备集成(福建)有限公司 | A kind of atomising device for preparing alloyed metal powder |
CN107557737B (en) * | 2017-08-04 | 2019-12-20 | 领凡新能源科技(北京)有限公司 | Method for preparing tubular target material |
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BR112018014868A2 (en) | 2020-02-11 |
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CN107626929A (en) | 2018-01-26 |
KR20190088002A (en) | 2019-07-25 |
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