CN112725752A - Magnesium-doped zinc oxide magnetron sputtering target material and preparation method thereof - Google Patents
Magnesium-doped zinc oxide magnetron sputtering target material and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000013077 target material Substances 0.000 title claims abstract description 59
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 41
- 238000001755 magnetron sputter deposition Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 20
- 238000000498 ball milling Methods 0.000 claims abstract description 18
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000000465 moulding Methods 0.000 claims abstract description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000011265 semifinished product Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 9
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910003437 indium oxide Inorganic materials 0.000 claims description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 238000000462 isostatic pressing Methods 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000004544 sputter deposition Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005245 sintering Methods 0.000 description 27
- 239000010408 film Substances 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000007088 Archimedes method Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to the technical field of photoelectric materials, and discloses a magnesium-doped zinc oxide magnetron sputtering target material and a preparation method thereof, wherein the preparation method comprises the following steps: (1) doping magnesium oxide powder and third oxide powder into zinc oxide powder, mixing the mixture with an ethanol solution to form slurry; (2) ball-milling the slurry, drying and sieving to obtain powder for molding; (3) carrying out cold isostatic pressing on the powder to form a blank; (4) slowly heating the blank to 900-1150 ℃, preserving heat for 30-90 min, rapidly heating to 1300-1450 ℃, preserving heat for 120-480 min, and slowly cooling to form a semi-finished product; and cutting and polishing to obtain the magnesium-doped zinc oxide magnetron sputtering target. The target material has high density, relative density more than 95% and low resistivity up to 4X 10‑2The target material resistance is far lower than that of the prior art, the conductive effect is good, and the requirement of medium-frequency rapid sputtering of a coating production line can be met.
Description
Technical Field
The invention relates to the technical field of photoelectric materials, in particular to a magnesium-doped zinc oxide magnetron sputtering target material and a preparation method thereof.
Background
The zinc oxide is used as an environment-friendly multifunctional wide-bandgap oxide photoelectric material with abundant reserves, can be changed into a Transparent Conductive Oxide (TCO) material with higher photoelectric property after degenerate doping of a certain amount of trivalent elements (such as Al, Ga, B and the like), has the advantages of ultraviolet light absorption, visible light transparency, infrared light reflection, adjustable electrical properties and the like, and is increasingly applied to the photoelectric information fields of panel display, thin-film solar cells, Low-E glass for building energy conservation, intelligent glass and the like.
In addition, after the zinc oxide is doped by adopting a wider-bandgap MgO material, the zinc oxide material is endowed with some new characteristics and applications. Due to Mg2+Ionic radius (0.072nm) of (C) and Zn2+Has an ionic radius (0.074nm) close to that of Mg2+Substitution of Zn2+Does not cause large lattice distortion, and further easily forms MgxZn1-xThe related research shows that the Mg isxZn1-xThe band gap and structural characteristics of the O film depend on the Mg content x in the alloy film. The band gap of ZnO is 3.37eV, the band gap of MgO is 7.8eV, theoretically, the Mg prepared is changed along with the content of MgxZn1-xThe forbidden band width of the O film is changed within 3.37-7.8 eV. The MgZnO film with wider forbidden band has important application in high-performance Thin Film Transistor (TFT), ultraviolet detector and Cd-free high-resistance layer of CIGS thin film solar cell with new structure.
At present, MgZnO films are deposited by various techniques, wherein magnetron sputtering film formation is the most mature, and the MgZnO films have the advantages of high film density, good uniformity and repeatability, easy large-area high-speed deposition and the like, and are accepted and widely adopted by the industry. In the magnetron sputtering process, the ceramic target plays a crucial role, and the performance of the ceramic target is closely related to the sputtering stability and the photoelectric characteristic of a final film layer. The basic requirements for high-performance ceramic targets are: high compactness, fine and uniform crystal grains and uniform and consistent components. Recently, based on the new development of the coating industry, higher requirements are provided for the conductivity of the target, and the requirement of intermediate-frequency rapid sputtering in a coating production line can be met only when the resistivity is less than 1000 Ω, so that the production efficiency is further improved, and the cost is reduced.
In order to control the oxygen vacancy content of the zinc oxide target material, the related documents give the following preparation technical means. Gaoqing et al published a Mg component in "preparation and Performance research of MgZnO target" (Shenzhen university Master academic thesis 2015)xZn1-xThe preparation method of the O (x is 0-0.4) target material comprises the steps of grinding commercially available ZnO powder and MgO powder in absolute ethyl alcohol containing polyethylene glycol (PEG) for 36-72 hours, drying, compacting, sintering at 1450 ℃ to achieve density of more than 95%, testing the conductivity of the target material by using a universal meter, wherein when x is 0.12, the resistance of the target material is 1M omega, when x is 0.2, the resistance of the target material is 15M omega, and when x is 0.4, the resistance of the target material is 30M omega.
However, the target material and the preparation method thereof have the following defects: (1) the sintering temperature of the target is high, the requirement of the excessively high sintering temperature on equipment is high, the preparation cost of the target is increased, and in addition, the phenomenon of overburning can also be caused, and the improvement of the density is not facilitated; (2) the resistance of the target is too high, the film can be coated only by adopting a radio frequency magnetron sputtering mode, the cost of a radio frequency power supply is far higher than that of a medium frequency power supply and a direct current power supply, and the deposition rate is lower.
CN 102191466A discloses a preparation method of a gallium oxide doped zinc oxide target, in the method, the obtained target is formed by sintering zinc and gallium oxide powder, wherein the mass content of gallium oxide is 0.5-10%; the purity of the obtained target material is not lower than 99.9%; the relative density of the obtained target material is not less than 95 percent and can reach 99.5 percent at most. CN 108249911a discloses a method for manufacturing a magnesium oxide and zinc oxide target blank, in which a magnesium oxide and zinc oxide mixed powder is put into a mold, and then the magnesium oxide and zinc oxide mixed powder is subjected to a hot-pressing sintering process to form a magnesium oxide and zinc oxide alloy, which is taken out from the mold to obtain the magnesium oxide and zinc oxide target blank.
The target and the preparation method thereof have the following defects: (1) the atmosphere sintering or hot-pressing sintering mode needs a vacuum sintering furnace or a hot-pressing furnace, the threshold degree of the two types of equipment is higher, and the preparation cost of the target material is increased; (2) the conductivity of the target material is taken as one of important performance indexes, and the working power during magnetron coating sputtering is influenced by the conductivity.
Disclosure of Invention
The invention provides the preparation method of the magnesium-doped zinc oxide target material with lower resistance and high sintering density for improving the performances of the target material such as relative density, electric conductivity and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a magnesium-doped zinc oxide magnetron sputtering target material comprises the following steps:
(1) doping magnesium oxide powder and third oxide powder into zinc oxide powder, mixing the mixture with an ethanol solution to form slurry;
(2) ball-milling the slurry, drying and sieving to obtain powder for molding;
(3) carrying out cold isostatic pressing on the powder obtained in the step (2) to form a blank;
(4) slowly heating the blank in an electric furnace to 900-1150 ℃, preserving heat for 30-90 min, rapidly heating to 1300-1450 ℃, preserving heat for 120-480 min, and slowly cooling to form a semi-finished product;
(5) and cutting and polishing the semi-finished product to obtain the magnesium-doped zinc oxide magnetron sputtering target material.
Wherein the slow heating rate is 0.5-10 ℃/min; the temperature rising speed of the rapid temperature rising is 5-50 ℃/min; the cooling speed of the slow cooling is 0.5-10 ℃/min.
The design synthesizes uniformly doped nano powder by screening raw material powder particles, and realizes high-concentration dispersion and close arrangement of high-density single particles by a ball milling process; a cold isostatic pressing process is adopted to obtain a high-density green body; and the normal-pressure low-temperature dense sintering is realized by adopting a two-step sintering process, and the obtained ceramic body has fine grains and high densification.
The key point of the invention is that the uniformly doped nano powder is synthesized, so that the powder has high sintering activity, the sintering temperature is reduced, and the cost and the energy loss are reduced; the second key point is that the ball milling process realizes high-density dispersion, so that high-density single particles are tightly arranged to obtain a high-density green body, the yield of a sintering process can be influenced, and the density of a product is improved; the key point is the sintering process, and the two-step sintering method can realize normal-pressure low-temperature sintering to obtain a product with fine grains and high density, and improve the film coating performance of the product.
Therefore, through the control screening of the granularity and the purity of the raw material powder, the granulation modification of the ball milling process and the doping of a third material phase to form a conductive loop, the sintering can be completed only by a common lifting electric furnace, the requirement on equipment is reduced, and the production cost is low.
The doping mass percentage of the magnesium oxide powder is 5-40%, and the doping mass percentage of the third oxide powder is 1-10%. With varying Mg content, Mg is producedxZn1-xThe forbidden band width of the O film is changed between 3.37 and 7.8 eV. If the doping content of the doped magnesium oxide powder is too low or too high, the Mg prepared cannot be regulated and controlledxZn1-xThe forbidden band width of the O film. The change of the doping amount of the third oxide powder can influence the Mg preparationxZn1-xThe resistivity of the O target material is high or low; if the doping amount is too high, the main phase of the target material is changed.
The third oxide powder comprises any one or more of titanium oxide, aluminum oxide, gallium oxide, indium oxide, cerium oxide, yttrium oxide, tin oxide, tungsten oxide and molybdenum oxide. The doping of the third oxide does not influence the coating function of the target material, and simultaneously, the target material can have electric conductivity, so that the service performance of the target material is improved.
Preferably, the third oxide comprises alumina and/or gallium oxide;
the particle size of the third oxide powder is 100-600 nm, and the purity is not lower than 99.9%. The particle diameter of the doped powder,The purity affects the density and resistivity of the target material, and if the grain size is too small or too large, Mg can be preparedxZn1-xThe O target material cannot be uniformly doped in the granulation link, so that high sintering activity is obtained; a high-density green body cannot be formed in the forming link, and a ceramic body with fine grains and high densification cannot be formed in the sintering link.
The particle size of the zinc oxide powder is 200-500 nm, and the purity is not lower than 99.9%; the particle size of the magnesium oxide powder is 10-200 nm, and the purity is not lower than 99.9%. Similarly, the density and resistivity of the target material can be influenced by the particle size and purity of the zinc oxide and the magnesium oxide, and the particle size of the powder with the overlarge particle size is too large after grinding, so that the formed crystal grains are larger, and the compactness of the sintered blank is reduced.
In the step (1), the mass ratio of the ethanol solution to the powder mixture is 2-5: 1. The water content of the ethanol solution is 2-25 wt%. The mass ratio of the ethanol solution to the powder mixture affects the homogeneity and flowability of the ball-milling slurry. Because the water has polarity, partial water exists in the ethanol solution, the arrangement of particles can be combed, and the high-density single particles are closely arranged, so that a blank with high density and high yield can be obtained. If the water content is too high, the molecular water content in the particles is too high, and the risk of cracking in the sintering link is increased.
In the step (2), the ball milling time is 8-24 h, and the mass ratio of the milling balls to the materials is 4-6: 1; the powder is sieved by a sieve with 60-100 meshes. The ball milling efficiency, and the particle size and particle morphology of the powder obtained after ball milling are affected by the ball milling time and the ball-to-material ratio. The mesh size of the sieved particles can affect the yield and green density of the cold isostatic pressing process.
The ball mill includes a planetary ball mill, a vertical agitator ball mill, a roll mill, or the like.
In the step (3), the pressure of the cold isostatic pressing is 100-200 MPa, and the static pressing time is 10-40 s. The density and yield of the blank body can be influenced by the pressure value of the cold isostatic pressing, the blank body can not be formed when the pressure is too low, and the blank body can be cracked when the pressure is too high; the density of the green body can be influenced by the pressure maintaining time, the density of the green body can be reduced due to the too short pressure maintaining time, the subsequent sintering link is influenced, and the production cost can be increased due to the too long pressure maintaining time.
The invention also provides the magnesium-doped zinc oxide magnetron sputtering target material obtained by the preparation method, and the molecular formula is expressed as follows: xMgO (1-x-y) ZnO yMO, wherein x is 0.05-0.4, y is 0.01-0.1, and n is 1.5-3; MO refers to a third oxide.
The relative density of the magnesium-doped zinc oxide magnetron sputtering target material is more than 95 percent; resistivity of less than 4 x 10-2Ω·cm。
Compared with the prior art, the invention has the following beneficial effects:
(1) the magnesium-doped zinc oxide magnetron sputtering target material prepared by the invention has high density, the relative density is more than 95 percent, and the resistivity is lower and can reach 4 multiplied by 10-2The target material resistance is far lower than that in the prior art, the conductive effect is good, the requirement of intermediate-frequency rapid sputtering of a coating production line can be met, and the production efficiency is further improved and the cost is reduced.
(2) The preparation method of the magnetron sputtering target material only needs to adopt a common lifting electric furnace, has low equipment requirement and low preparation cost, and is more beneficial to industrial production.
Drawings
Fig. 1 shows the optical forbidden band widths of the targets prepared in examples 1 and 3.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
(1) Mixing high-weighing high-purity zinc oxide powder, high-purity magnesium oxide powder and third oxide powder to form an atomic ratio mixture xMgO (1-x-y) ZnO-yMOn, wherein x is 0.1, and y is 0.05; preparing ethanol mixed solution, wherein the content of deionized water is 10 wt%; mixing the powder according to the mass ratio of the mixed solution to the powder of 3:1, and pouring the mixed powder into the mixed solution to form slurry;
(2) and (3) placing the slurry in a planetary ball mill for mixing and ball milling for 15h, wherein the ratio of grinding balls to materials is 5: 1; taking out the slurry subjected to ball milling, drying at 80 ℃, collecting the dried powder, grinding, and sieving with an 80-mesh sieve to obtain powder for molding;
(3) placing the obtained powder in a rubber sleeve mold, and molding in a cold isostatic press under the conditions of 160MPa and 30s of pressure maintaining to form a blank;
(4) and (3) putting the formed blank into a box-type resistance furnace, raising the temperature to 1050 ℃ of the first-step sintering temperature at the heating rate of 5 ℃/min, preserving the heat for 30min, raising the temperature to 1450 ℃ of the second-step sintering temperature at the heating rate of 10 ℃/min, preserving the heat for 180min to obtain an ideal sintered body, and cutting and polishing the obtained sintered body into a specified size to obtain the high-density fine-grain zinc oxide-based magnetron sputtering target material with a certain oxygen loss rate.
The test shows that the target material oxygen loss rate is 5%, the density of the target material in the embodiment 1 is 5.50g/cm by measuring the density by an Archimedes method and calculating the relative density of the target material according to the percentage between the measured density and the theoretical density3And the relative density is 99.10%. The resistivity of the target material was tested using a four-probe station, and the resistivity of the target material prepared in example 1 was 4 × 10-2Omega cm; the relative density and the resistivity of the product prepared by the embodiment can meet the requirement of magnetron coating sputtering, and the preparation method is relatively simple.
Example 2
(1) Mixing high-weighing high-purity zinc oxide powder, high-purity magnesium oxide powder and third oxide powder to form an atomic ratio mixture xMgO (1-x-y) ZnO-yMOn, wherein x is 0.2, and y is 0.01; preparing ethanol mixed solution, wherein the content of deionized water is 20 wt%; mixing the powder according to the mass ratio of the mixed solution to the powder of 3:1, and pouring the mixed powder into the mixed solution to form slurry;
(2) and (3) placing the slurry in a planetary ball mill for mixing and ball milling for 15h, wherein the ratio of grinding balls to materials is 5: 1; taking out the slurry subjected to ball milling, drying at 80 ℃, collecting the dried powder, grinding, and sieving with an 80-mesh sieve to obtain powder for molding;
(3) placing the obtained powder in a rubber sleeve mold, and molding in a cold isostatic press under the conditions of 160MPa and 30s of pressure maintaining to form a blank;
(4) and (3) putting the formed blank into a box-type resistance furnace, increasing the temperature to 950 ℃ of the first-step sintering temperature at the heating rate of 5 ℃/min, preserving the heat for 30min, increasing the temperature to 1400 ℃ of the second-step sintering temperature at the heating rate of 20 ℃/min, preserving the heat for 180min to obtain an ideal sintered body, and cutting and polishing the obtained sintered body into a specified size to obtain the high-density fine-grain zinc oxide-based magnetron sputtering target material with a certain oxygen loss rate.
The density of the target material of this example was measured to be 5.31g/cm by measuring the density using the archimedes method and calculating the relative density of the target material based on the percentage between the measured density and the theoretical density3Relative density 98.52%; the resistivity of the target material was tested using four probe stations, and the resistivity of the target material prepared in this example was 12 × 10-2Omega cm; therefore, the relative density and the resistivity of the prepared product can meet the requirement of magnetron coating sputtering.
Example 3
(1) Mixing high-weighing high-purity zinc oxide powder, high-purity magnesium oxide powder and third oxide powder to form an atomic ratio mixture xMgO (1-x-y) ZnO-yMOn, wherein x is 0.3, and y is 0.05; preparing ethanol mixed solution, wherein the content of deionized water is 10 wt%; mixing the powder according to the mass ratio of the mixed solution to the powder of 3:1, and pouring the mixed powder into the mixed solution to form slurry;
(2) and (3) placing the slurry in a planetary ball mill for mixing and ball milling for 15h, wherein the ratio of grinding balls to materials is 5: 1; taking out the slurry subjected to ball milling, drying at 80 ℃, collecting the dried powder, grinding, and sieving with an 80-mesh sieve to obtain powder for molding;
(3) placing the obtained powder in a rubber sleeve mold, and molding in a cold isostatic press under the conditions of 160MPa and 30s of pressure maintaining to form a blank;
(4) and (3) putting the formed blank into a box-type resistance furnace, raising the temperature to 1050 ℃ of the first-step sintering temperature at the heating rate of 5 ℃/min, preserving the heat for 30min, raising the temperature to 1450 ℃ of the second-step sintering temperature at the heating rate of 30 ℃/min, preserving the heat for 180min to obtain an ideal sintered body, and cutting and polishing the obtained sintered body into a specified size to obtain the high-density fine-grain zinc oxide-based magnetron sputtering target material with a certain oxygen loss rate.
The density of the target material of this example was measured to be 5.31g/cm by measuring the density using the archimedes method and calculating the relative density of the target material based on the percentage between the measured density and the theoretical density3And a relative density of 98.67%. The resistivity of the target material was tested using four probe stations, and the resistivity of the target material prepared in this example was 6 × 10-2Omega cm; therefore, the relative density and the resistivity of the obtained product can meet the requirement of magnetron coating sputtering.
As shown in fig. 1, a magnetron sputtering apparatus is used to perform a film plating test on a target (examples 1 and 3) with Mg content x of 0.1 and 0.3, and an ultraviolet-visible spectrophotometer is used to test the optical forbidden bandwidth of the film, and the forbidden bandwidths of the film are found to be 3.62eV and 4.07eV, respectively, which indicates that the doping of magnesium achieves the purpose of widening the forbidden bandwidth of the film.
Claims (10)
1. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material is characterized by comprising the following steps of:
(1) doping magnesium oxide powder and third oxide powder into zinc oxide powder, mixing the mixture with an ethanol solution to form slurry;
(2) ball-milling the slurry, drying and sieving to obtain powder for molding;
(3) carrying out cold isostatic pressing on the powder obtained in the step (2) to form a blank;
(4) slowly heating the blank in an electric furnace to 900-1150 ℃, preserving heat for 30-90 min, rapidly heating to 1300-1450 ℃, preserving heat for 120-480 min, and slowly cooling to form a semi-finished product; and cutting and polishing to obtain the magnesium-doped zinc oxide magnetron sputtering target.
2. The method for preparing the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1, wherein the doping mass percentage of the magnesium oxide powder is 5-40%, and the doping mass percentage of the third oxide powder is 1-10%.
3. The method for preparing the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1 or 2, wherein the third oxide powder comprises any one or more of titanium oxide, aluminum oxide, gallium oxide, indium oxide, cerium oxide, yttrium oxide, tin oxide, tungsten oxide and molybdenum oxide.
4. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material according to claim 3, wherein the third oxide powder has a particle size of 100-600 nm and a purity of not less than 99.9%.
5. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1, wherein the particle size of the zinc oxide powder is 200-500 nm, and the purity is not lower than 99.9%; the particle size of the magnesium oxide powder is 10-200 nm, and the purity is not lower than 99.9%.
6. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1, wherein in the step (1), the mass ratio of the ethanol solution to the powder mixture is 2-5: 1.
7. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1, wherein in the step (2), the ball milling time is 8-24 h, and the mass ratio of the grinding balls to the materials is 4-6: 1; the powder is sieved by a sieve with 60-100 meshes.
8. The preparation method of the magnesium-doped zinc oxide magnetron sputtering target material according to claim 1, wherein in the step (3), the cold isostatic pressing pressure is 100-200 MPa, and the isostatic pressing time is 10-40 s.
9. The magnesium-doped zinc oxide magnetron sputtering target material obtained by the preparation method according to any one of claims 1 to 8, wherein the molecular formula is expressed as: xMgO (1-x-y) ZnO yMO, wherein x is 0.05-0.4, y is 0.01-0.1, and n is 1.5-3; MO refers to a third oxide.
10. The magnesium-doped zinc oxide magnetron sputtering target according to claim 9, wherein the relative density of the magnesium-doped zinc oxide magnetron sputtering target is greater than 95%; resistivity of less than 4 x 10-2Ω·cm。
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