Method for preparing multi-element-doped interdependent zinc oxide whisker-based high-conductivity and high-density sputtering target material and product thereof

Abstract

A method for preparing a multi-element-doped interdependent zinc oxide whisker-based high-conductivity and high-density sputtering target material and a product thereof, relating to the technical field of photoelectric materials. The method for preparing a multi-element-doped interdependent zinc oxide whisker-based high-conductivity and high-density sputtering target material comprises the following steps: preparing a doped interdependent zinc oxide whisker powder; adding a wetting agent and a dispersing agent to the doped zinc oxide whisker powder, and carrying out ball milling to obtain a primary milled slurry; then carrying out sand milling on the primary milled slurry to obtain a secondary milled slurry; drying the secondary milled slurry, and then granulating the secondary milled slurry to obtain granules; adding a forming agent to the granules for compression molding to obtain a green body; and degumming the green body, and then carrying out sintering in stages to obtain a sputtering target material. The obtained sputtering target material has both a high conductivity and a high density, and compared with a conventional sputtering target material, has greatly improved electrical performance.

Description

Preparation method of multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target and its product Technical Field

[0001] The present application relates to the technical field of optoelectronic materials, and in particular to a method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target and its product. Background Art

[0002] Magnetron sputtering is a new type of physical vapor coating method. It uses an electron gun system to emit and focus electrons onto the material being coated. The sputtered atoms follow the principle of momentum conversion and fly away from the material with high kinetic energy to the substrate, where they are deposited into a film. The material being coated is called a sputtering target. Sputtering targets are primarily used in the electronics and information industries, such as integrated circuits, information storage, liquid crystal displays, laser memory, and electronic control devices. They are also used in glass coating, wear-resistant materials, high-temperature corrosion resistance, and high-end decorative products. Zinc oxide is inexpensive, abundant, and stable in hydrogen ion atmospheres. It can be made into excellent semiconductor and piezoelectric films, and can also be made into excellent transparent conductive films through doping. The quality of the doped zinc oxide target directly determines the quality of the film.

[0003] Currently, the main methods for preparing doped zinc oxide targets involve mixing zinc salts with salts of the doping element and sintering them at high temperatures, or dissolving the zinc salts and the salts of the doping element, then co-precipitating them and sintering them. However, these methods struggle to achieve a complete symbiosis of the doping element and zinc, resulting in high resistivity and potential improvements in both conductivity and relative density.

[0004] Summary of the Invention

[0005] The main purpose of this application is to provide a preparation method of a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target and its product, aiming to solve the technical problems of low conductivity and relative density of existing sputtering targets.

[0006] To achieve the above objectives, the present application proposes a method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target, comprising the following steps:

[0007] preparing doped symbiotic zinc oxide whisker powder;

[0008] adding a wetting agent and a dispersant to the doped zinc oxide whisker powder, and performing ball milling to obtain a grinding slurry;

[0009] Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry;

[0010] After drying the second-stage grinding slurry, granulation is performed to obtain granules;

[0011] Adding a forming agent to the pellets and performing compression molding to obtain a green compact;

[0012] The green compact is debonded and then sintered in stages to obtain a sputtering target.

[0013] Optionally, the step of preparing the doped symbiotic zinc oxide whisker powder comprises:

[0014] Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles;

[0015] filtering again to remove the gel and obtain zinc particles attached with doping element oxides;

[0016] The zinc particles with the doping element oxide attached thereto are dried at 75° C.-85° C. for 30 min-180 min, then placed in a box-type resistance furnace, heated to 500° C.-1200° C., reacted for 10 min-25 min, cooled to room temperature, and then ground to obtain doped symbiotic zinc oxide whisker powder.

[0017] Optionally, the doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, barium, lanthanum, , cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

[0018] Optionally, the step of adding a wetting agent and a dispersant to the doped zinc oxide whisker powder and performing ball milling to obtain a grinding slurry comprises:

[0019] adding a wetting agent and a dispersant to the doped zinc oxide whisker powder to obtain a mixed powder;

[0020] A mechanical ball milling method is adopted, and alumina grinding balls are selected. The mixed powder, the alumina grinding balls and water are ball milled for 25h-35h in a mass ratio of (1-2): (2-3): (2-3) to obtain a grinding slurry.

[0021] Optionally, the wetting agent includes triethanolamine and tromethamine, and the dispersant includes tetramethylammonium hydroxide siliconate, sodium hydroxycitrate and polycarboxylate.

[0022] Optionally, the step of drying the second-stage grinding slurry and then granulating to obtain granules comprises:

[0023] The second-stage grinding slurry is dried at 80° C.-90° C. for 40 h-50 h, passed through a 200-300 mesh sieve, and then subjected to rolling granulation for 15 min-30 min to obtain granules.

[0024] Optionally, the step of adding a molding agent to the granules and performing compression molding to obtain a green body comprises:

[0025] A dry pressing method is adopted, wherein a forming agent is added to the granules and bidirectional pressing is performed under a pressure of 3MPa-5MPa, and the pressure holding time is 2min-4min to obtain a green body;

[0026] Wherein, the molding agent is polyvinyl alcohol modified by carboxymethyl cellulose.

[0027] Optionally, the step of degumming the green body comprises:

[0028] The green body is heated to 350-400° C. at a rate of 2-3° C. / min and kept at this temperature for 1-2 hours, and then heated to 500-600° C. at a rate of 5-7° C. / min and kept at this temperature for 2-3 hours.

[0029] Optionally, the step of performing segmented sintering to obtain a sputtering target comprises:

[0030] The debonded green body is heated to 700-800°C at a rate of 8-12°C / min and kept at this temperature for 1-2 hours for low temperature sintering.

[0031] The green body after low-temperature sintering is then heated to 1100-1300°C at a rate of 15-25°C / min and kept at this temperature for 1-2 hours for high-temperature sintering, and then cooled in a spark plasma sintering furnace to obtain a sputtering target.

[0032] The present application also proposes a sputtering target product, which is obtained by adopting the above-mentioned preparation method of the multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target.

[0033] The present application uses element-doped symbiotic zinc oxide whisker powder as a raw material to prepare a sputtering target. Compared with undoped zinc oxide whiskers, the doped symbiotic zinc oxide whisker powder has a lower resistivity, so that the prepared sputtering target has a lower resistivity, thereby improving the electrical properties of the sputtering target. Then, a wetting agent and a dispersant are added and the doped zinc oxide whisker powder is ball-milled and sand-milled in sequence. On the one hand, the doped zinc oxide whisker powder can be refined by friction, and on the other hand, the doped zinc oxide whisker powder can be prevented from agglomerating, which makes it difficult to break during the molding process, which is not conducive to the sintering process, thereby affecting the sputtering target. The relative density of the material can be improved by ball milling to eliminate the soft agglomerates in the doped zinc oxide whisker powder and reduce the hard agglomerates. The hard agglomerates can be further removed by sand milling. A forming agent is then added to the granules to improve the fluidity of the granules, which is beneficial to the pressing and molding of the green body. The green body is then degummed to remove the forming agent, dispersant and other organic solvents to improve the relative density of the sputtering target. Finally, the green body is sintered by segmented sintering, which is beneficial for the doped symbiotic zinc oxide whiskers to enter the middle or even late sintering stage from the early sintering stage, and promotes the uniformity of the sintering of the doped symbiotic zinc oxide whisker powder, thereby further improving the relative density of the sputtering target. Thus, a sputtering target with both high conductivity and high density can be obtained through the preparation method of the present application. After testing, the resistivity of the sputtering target is 10 -5 Ω·cm-10 -6 Ω·cm, the relative density is 95%-99%, and its electrical performance is greatly improved compared with conventional sputtering targets. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the structures shown in these drawings without paying any creative work.

[0035] FIG1 is a scanning electron microscope image of the four-needle zinc oxide whisker described in Example 1 of the present application;

[0036] FIG2 is an XRD diffraction pattern of the four-needle zinc oxide whiskers described in Example 1 of the present application;

[0037] FIG3 is a schematic diagram of the sputtering target described in Example 1 of the present application.

[0038] The realization of the objectives, functional features and advantages of this application will be further explained in conjunction with embodiments and with reference to the accompanying drawings. DETAILED DESCRIPTION

[0039] The following will be combined with the drawings in the embodiments of this application to clearly and completely describe the technical solutions in the embodiments of this application. Obviously, the embodiments described are only part of the embodiments of this application, not all of the embodiments. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0040] In order to solve the technical problems existing in the prior art, the embodiments of the present application provide a method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target, comprising the following steps:

[0041] preparing doped symbiotic zinc oxide whisker powder;

[0042] adding a wetting agent and a dispersant to the doped zinc oxide whisker powder, and performing ball milling to obtain a grinding slurry;

[0043] Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry;

[0044] After drying the second-stage grinding slurry, granulation is performed to obtain granules;

[0045] Adding a forming agent to the pellets and performing compression molding to obtain a green compact;

[0046] The green compact is debonded and then sintered in stages to obtain a sputtering target.

[0047] The present application uses element-doped symbiotic zinc oxide whisker powder as a raw material to prepare a sputtering target. Compared with undoped zinc oxide whiskers, the doped symbiotic zinc oxide whisker powder has a lower resistivity, so that the prepared sputtering target has a lower resistivity, thereby improving the electrical properties of the sputtering target. Then, a wetting agent and a dispersant are added and the doped zinc oxide whisker powder is ball-milled and sand-milled in sequence. On the one hand, the doped zinc oxide whisker powder can be refined by friction, and on the other hand, the doped zinc oxide whisker powder can be prevented from agglomerating, which makes it difficult to break during the molding process, which is not conducive to the sintering process, thereby affecting the sputtering target. The relative density of the material can be improved by ball milling to eliminate the soft agglomerates in the doped zinc oxide whisker powder and reduce the hard agglomerates. The hard agglomerates can be further removed by sand milling. A forming agent is then added to the granules to improve the fluidity of the granules, which is beneficial to the pressing and molding of the green body. The green body is then degummed to remove organic solvents such as the forming agent and dispersant to improve the relative density of the sputtering target. Finally, the green body is sintered by staged sintering, which is beneficial for the doped symbiotic zinc oxide whiskers to enter the middle or even late sintering stage from the early sintering stage, thereby promoting the uniformity of the sintering of the doped symbiotic zinc oxide whisker powder, thereby further improving the relative density of the sputtering target. Thus, a sputtering target having both high electrical conductivity and high density can be obtained through the preparation method of the present application, and its electrical performance is greatly improved compared to conventional sputtering targets.

[0048] As an embodiment of the present application, the step of preparing the doped symbiotic zinc oxide whisker powder includes:

[0049] Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles;

[0050] filtering again to remove the gel and obtain zinc particles attached with doping element oxides;

[0051] The zinc particles with the doping element oxide attached thereto are dried at 75° C.-85° C. for 30 min-180 min, then placed in a box-type resistance furnace, heated to 500° C.-1200° C., reacted for 10 min-25 min, cooled to room temperature, and then ground to obtain doped symbiotic zinc oxide whisker powder.

[0052] The present invention forms a gel by polyethylene glycol, allowing the oxide of the doping element to adhere to the zinc particles through the gel. After filtering and removing the gel, zinc particles with the oxide of the doping element attached are obtained. Then, by heating, the zinc element and the doping element are combined to form four-needle zinc oxide whiskers. The four-needle zinc oxide whiskers are in a single crystal state with a micron structure. Microscopically, they are three-dimensional four-needle structures. The whiskers have a core, and four needle-like crystals extend radially from the core. Each needle-like body is a single crystal microfiber. The overall shape is four-needle, which can be used as an ideal material for making transparent conductive targets and field emission cathodes. The process is simple, the production cost is low, and it is easy to implement. It does not need to use the formed four-needle zinc oxide as the intrinsic material to complete the doping. The complete symbiotic doping of the doping element and zinc is achieved. The doping element can be selected according to the performance requirements to form a four-needle zinc oxide whisker semiconductor material with excellent photoelectric properties.

[0053] As an embodiment of the present invention, the doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, Iodine, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

[0054] In this embodiment, according to the performance requirements of the four-needle zinc oxide whiskers, the doping elements can be beryllium (Be), boron (B), carbon (C), silicon (Si), phosphorus (P), sulfur (S), calcium (Ca), magnesium (Mg), scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), gallium (Ga), germanium (Ge), arsenic (As), selenium (Se), bromine (Br), strontium (Br), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), indium (In), tin (Sn), antimony (Sb), tellurium (Te), iodine (I), barium (Ba), lanthanum (La), cerium ( Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), thallium (Tl), lead (Pb), bismuth (Bi), polonium (Po), astatine (At), francium (Fr), radium (Ra), actinium (Ac), thorium (Th), protactinium (Pa), uranium (U), neptunium (Np), plutonium (Pu), americium (Am), curium (Cm), berkelium (Bk), californium (Cf), einsteinium (Es), fermium (Fm), mendelevium (Md), nobelium (No), lawrencium (Lr), ruthenium (Rf), (Db), (Sg), (Bh), (Hs), (Mt), (Ds), (Rg), cobalt (Cn), niobium (Nh), ferrum (Fl), magnesium (Mc), leucium (Lv), and One or more of the above compounds (Ts) are selected to dope zinc oxide. The doping elements enter the four-needle lattice structure as doping ions to replace Zn. The doping elements and zinc co-generate four needles without changing the crystal structure of the four needles. The doping process is a symbiotic doping of the doping elements and zinc, thereby effectively improving the performance of the four-needle zinc oxide whiskers as semiconductor nanodevices.

[0055] As an embodiment of the present application, the step of adding a wetting agent and a dispersant to the doped zinc oxide whisker powder and performing ball milling to obtain a grinding slurry includes:

[0056] adding a wetting agent and a dispersant to the doped zinc oxide whisker powder to obtain a mixed powder;

[0057] A mechanical ball milling method is adopted, and alumina grinding balls are selected. The mixed powder, the alumina grinding balls and water are ball milled for 25h-35h in a mass ratio of (1-2): (2-3): (2-3) to obtain a grinding slurry.

[0058] Specifically, the density of the alumina grinding balls used in this application is 3.9 g / cm 3 Through ball milling, the gravity of the mixed powder and the friction generated by the rotation of the alumina grinding balls can be used to impact, collide, shear, etc. on the mixed powder, thereby achieving further refinement of the mixed powder. In addition, since the van der Waals force and electrostatic force between the mixed powders can easily cause soft agglomeration, the mutual diffusion between the particles can easily form hard agglomerates with higher strength. Soft agglomeration and hard agglomeration will have a greater impact on the sintering performance, and thus affect the electrical properties of the sputtering target. Therefore, ball milling can eliminate soft agglomeration and reduce hard agglomeration.

[0059] As an embodiment of the present application, the wetting agent includes triethanolamine and tromethamine, and the dispersant includes tetramethylammonium hydroxide siliconate, sodium hydroxycitrate and polycarboxylate.

[0060] Specifically, triethanolamine and tromethamine both contain hydroxyl groups and amino groups in their molecular structures, which can form an adsorption hydration layer on the surface of the doped zinc oxide whisker powder particles. At the same time, triethanolamine and tromethamine can further form a "hydrogen bond"-like effect together, thereby further enhancing the wetting effect on the doped zinc oxide whisker powder. The dispersant uses tetramethylammonium hydroxide silicon alkoxide, sodium hydroxycitrate and polycarboxylate. Tetramethylammonium hydroxide silicon alkoxide is a silicon-containing polymer, which has a certain wetting effect on the doped zinc oxide whisker powder and can enhance the dispersion of the doped zinc oxide whisker powder. Sodium hydroxycitrate has both hydroxyl groups and citrate ions. The hydroxyl groups can enhance the hydration effect on the doped zinc oxide whisker powder particles. At the same time, the citrate ions can improve the stability of the dispersion system through an electrostatic stabilization mechanism. The polycarboxylate, as a polymer dispersant, has a long carbon chain, a large number of active adsorption points and side chains that can play a spatial repulsive role, which can play a spatial stabilizing role in the dispersion system, so that the dispersant has a better dispersion effect.

[0061] As an embodiment of the present application, the step of drying the second-stage grinding slurry and then granulating to obtain granules includes:

[0062] The second-stage grinding slurry is dried at 80° C.-90° C. for 40 h-50 h, passed through a 200-300 mesh sieve, and then subjected to rolling granulation for 15 min-30 min to obtain granules.

[0063] Specifically, drying, screening and granulating the second-stage grinding slurry can increase the fluidity of the doped zinc oxide whisker powder, making it easier for the doped zinc oxide whisker powder to evenly fill the grinding tool during the subsequent pressing process, thereby increasing the molding density of the green body and facilitating subsequent sintering.

[0064] As an embodiment of the present application, the step of adding a forming agent to the granules and performing compression molding to obtain a green body includes:

[0065] A dry pressing method is adopted, wherein a forming agent is added to the granules and bidirectional pressing is performed under a pressure of 3MPa-5MPa, and the pressure holding time is 2min-4min to obtain a green body;

[0066] Wherein, the molding agent is polyvinyl alcohol modified by carboxymethyl cellulose.

[0067] To facilitate compression molding, this application incorporates a molding agent and employs bidirectional pressure. Carboxymethyl cellulose-modified polyvinyl alcohol exhibits superior dispersion properties, improving the fluidity of the doped zinc oxide whisker powder. However, the pressure and dwell time significantly influence green body properties. Both excessively low and high pressures fail to achieve ideal green bodies. Short dwell times hinder pressure transmission to the desired depth, while long dwell times lead to excessive compression depth. Therefore, the preferred pressure for this application is 4 MPa and a dwell time of 3 minutes.

[0068] As an embodiment of the present application, the step of degumming the green body includes:

[0069] The green body is heated to 350-400° C. at a rate of 2-3° C. / min and kept at this temperature for 1-2 hours, and then heated to 500-600° C. at a rate of 5-7° C. / min and kept at this temperature for 2-3 hours.

[0070] This application adopts a thermal degumming method to degumming the green body. In order to prevent the evaporation of a large amount of organic solvents such as the forming agent and dispersant when the heating speed is too fast, causing a large amount of gas accumulation inside the green body, causing cracks to form in the green body, and affecting the strength of the sputtering target, this application adopts a slow heating method, and when the temperature is raised to 350℃-400℃, it is kept warm for 1h-2h. When the quality change of the green body is stable, it is continued to be heated to 500℃-600℃. At this time, the quality change of the green body slows down, thereby completing the degumming.

[0071] As an embodiment of the present application, the step of performing segmented sintering to obtain a sputtering target includes:

[0072] The debonded green body is heated to 700-800°C at a rate of 8-12°C / min and kept at this temperature for 1-2 hours for low temperature sintering.

[0073] The green body after low-temperature sintering is then heated to 1100-1300°C at a rate of 15-25°C / min and kept at this temperature for 1-2 hours for high-temperature sintering, and then cooled in a spark plasma sintering furnace to obtain a sputtering target.

[0074] Specifically, the segmented sintering includes low-temperature sintering and high-temperature sintering. During low-temperature sintering, the doped symbiotic zinc oxide whiskers begin to react violently. Preferably, the heating rate is 10°C / min, the temperature is raised to 750°C, and the temperature is kept for 1.5 hours before high-temperature sintering. Since zinc oxide will volatilize in large quantities at 1350°C, the present application determines that the temperature of high-temperature sintering is preferably 1200°C. First, low-temperature sintering and then high-temperature sintering are beneficial for the doped symbiotic zinc oxide whiskers to enter the middle or even late sintering stage from the early sintering stage, thereby promoting the uniformity of the sintering of the doped symbiotic zinc oxide whisker powder, thereby further improving the relative density of the sputtering target.

[0075] The embodiments of the present application also provide a sputtering target product obtained by the above-mentioned method for preparing the multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target.

[0076] The above technical solutions of the present application are described in detail below with reference to specific embodiments.

[0077] Example 1

[0078] A method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target comprises the following steps:

[0079] Stirring and dissolving polyethylene glycol in water to form a gel, then placing zinc particles in the gel, and simultaneously adding aluminum oxide and gallium oxide so that the aluminum oxide and gallium oxide adhere to the zinc particles;

[0080] Filtering again to remove the gel, obtaining zinc particles attached with aluminum oxide and gallium oxide, wherein the molar ratio of Zn, Al, and Ga is 98.5:0.5:1;

[0081] The zinc particles with aluminum oxide and gallium oxide attached thereto were dried at 80° C. for 100 minutes, then placed in a box-type resistance furnace, heated to 800° C., reacted for 18 minutes, cooled to room temperature, and then ground to obtain aluminum- and gallium-doped intergrown zinc oxide whisker powder, a scanning electron microscope image of which at 10 μm is shown in FIG1 ;

[0082] A wetting agent and a dispersant are added to aluminum and gallium doped intergrown zinc oxide whisker powder to obtain a mixed powder, wherein the wetting agent is triethanolamine and tromethamine, and the dispersant is tetramethylammonium hydroxide siliconate, sodium hydroxycitrate and polycarboxylate;

[0083] A mechanical ball milling method was used, using alumina grinding balls, and the mixed powder was ball milled with alumina grinding balls and water at a mass ratio of 1:2:2 for 30 hours to obtain a grinding slurry;

[0084] Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry;

[0085] The second-stage grinding slurry was dried at 85° C. for 45 h, passed through a 250-mesh sieve, and then subjected to rolling granulation for 25 min to obtain pellets;

[0086] A dry pressing method is adopted, wherein polyvinyl alcohol modified with carboxymethyl cellulose is added to the pellets and bidirectionally pressed under a pressure of 4 MPa for 3 minutes to obtain a green body;

[0087] The green body was heated to 370°C at a rate of 2.5°C / min and kept at that temperature for 1.5 hours, then heated to 550°C at a rate of 6°C / min and kept at that temperature for 2.5 hours, and then the debonded green body was heated to 750°C at a rate of 10°C / min and kept at that temperature for 1.5 hours for low temperature sintering;

[0088] The green body after low-temperature sintering was then heated to 1200°C at a rate of 20°C / min and kept at that temperature for 1.5 hours for high-temperature sintering. It was then cooled in a spark plasma sintering furnace to obtain a sputtering target, as shown in FIG3 .

[0089] The aluminum and gallium doped symbiotic zinc oxide whisker powder prepared in the present application was subjected to X-ray diffraction, and the results are shown in Figure 2. In the figure, (100), (002), (101), (102), (110), (103), (200), (112), and (201) are all diffraction peaks of different crystal planes of zinc oxide. The positions and relative intensities of the diffraction peaks are basically consistent with the diffraction data of JCPDS card NO.36-1451, which is a wurtzite structure and no second phase is found. If there is single Al or Ga, different diffraction peaks will be shown, indicating that a complete symbiotic doping of Al, Ga and Zn is formed during the doping process. Al and Ga enter the lattice structure of the four-needle as doping ions to replace Zn. After the four-needle is co-generated, the crystal structure of the four-needle is not changed. Among them, the (002) crystal plane diffraction peak position (34.450°) has no deviation compared with the standard peak position (34.450°). It can be seen that the prepared symbiotic doped four-needle zinc oxide whiskers are preferentially oriented lead-zinc mineral ZnO structures with C-axis preferential orientation.

[0090] Example 2

[0091] A method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target comprises the following steps:

[0092] Stir and dissolve polyethylene glycol in water to form a gel, then place zinc particles in the gel and add magnesium oxide to adhere to the zinc particles;

[0093] Filtering again to remove the gel, obtaining zinc particles attached with magnesium oxide, wherein the molar ratio of Zn to Mg is 97.5:2.5;

[0094] The zinc particles with magnesium oxide attached thereto are dried at 75° C. for 180 minutes, then placed in a box-type resistance furnace, heated to 500° C., reacted for 25 minutes, cooled to room temperature, and then ground to obtain magnesium-doped intergrown zinc oxide whisker powder;

[0095] A wetting agent and a dispersant are added to magnesium-doped intergrown zinc oxide whisker powder to obtain a mixed powder, wherein the wetting agent is triethanolamine and tromethamine, and the dispersant is tetramethylammonium hydroxide siliconate, sodium hydroxycitrate and polycarboxylate;

[0096] The mixed powder was milled with alumina grinding balls and water at a mass ratio of 1:2:2 for 25 h to obtain a grinding slurry.

[0097] Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry;

[0098] The second-stage grinding slurry was dried at 80° C. for 50 h, passed through a 200-mesh sieve, and then subjected to rolling granulation for 15 min to obtain pellets;

[0099] A dry pressing method is adopted, wherein polyvinyl alcohol modified with carboxymethyl cellulose is added to the pellets and bidirectionally pressed under a pressure of 3 MPa for 4 minutes to obtain a green body;

[0100] The green body was heated to 350°C at a rate of 2°C / min and kept at that temperature for 2 hours, then heated to 500°C at a rate of 5°C / min and kept at that temperature for 2 hours, and then the debonded green body was heated to 700°C at a rate of 8°C / min and kept at that temperature for 1 hour for low temperature sintering;

[0101] The green body after low-temperature sintering was then heated to 1100°C at a rate of 15°C / min and kept at that temperature for 1 hour for high-temperature sintering, and then cooled in a spark plasma sintering furnace to obtain a sputtering target.

[0102] Example 3

[0103] A method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target comprises the following steps:

[0104] Stirring and dissolving polyethylene glycol in water to form a gel, then placing zinc particles in the gel, and simultaneously adding indium oxide and tin oxide to adhere the indium oxide and tin oxide to the zinc particles;

[0105] Filtering again to remove the gel, obtaining zinc particles attached with indium oxide and tin oxide, wherein the molar ratio of Zn, In, and Sn is 98:1:1;

[0106] The zinc particles with indium oxide and tin oxide attached thereto are dried at 85° C. for 30 minutes, then placed in a box-type resistance furnace, heated to 1200° C., reacted for 10 minutes, cooled to room temperature, and then ground to obtain indium and tin doped symbiotic zinc oxide whisker powder;

[0107] A wetting agent and a dispersant are added to indium and tin doped intergrowth zinc oxide whisker powder to obtain a mixed powder, wherein the wetting agent is triethanolamine and tromethamine, and the dispersant is tetramethylammonium hydroxide siliconate, sodium hydroxycitrate and polycarboxylate;

[0108] The mixed powder was milled with alumina grinding balls and water at a mass ratio of 2:3:3 for 35 h to obtain a grinding slurry.

[0109] Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry;

[0110] The second-stage grinding slurry was dried at 90° C. for 40 h, passed through a 300-mesh sieve, and then subjected to rolling granulation for 30 min to obtain granules;

[0111] A dry pressing method is adopted, wherein polyvinyl alcohol modified with carboxymethyl cellulose is added to the pellets and bidirectionally pressed under a pressure of 5 MPa for a holding time of 2 minutes to obtain a green body;

[0112] The green body was heated to 400°C at a rate of 3°C / min and kept at that temperature for 2 hours, then heated to 600°C at a rate of 7°C / min and kept at that temperature for 3 hours, and then the debonded green body was heated to 800°C at a rate of 12°C / min and kept at that temperature for 2 hours for low temperature sintering;

[0113] The green body after low-temperature sintering is then heated to 1300°C at a rate of 25°C / min and kept at this temperature for 2 hours for high-temperature sintering, and then cooled in a spark plasma sintering furnace to obtain a sputtering target.

[0114] Experimental example

[0115] The performance of the sputtering target prepared in the examples of the present application was tested, and the results are shown in Table 1 below.

[0116] Table 1

[0117] As can be seen from Table 1, the resistivity of the sputtering target obtained by the preparation method of the present application is 10 -5 Ω·cm-10 -6 Ω·cm, and the relative density is 95%-99%. Compared with conventional sputtering targets, it has lower resistivity and higher relative density, and its electrical performance is greatly improved.

[0118] The above are merely optional embodiments of the present application and do not limit the patent scope of the present application. All equivalent structural transformations made using the contents of the present application specification and drawings under the inventive concept of the present application, or direct / indirect application in other related technical fields are included in the patent protection scope of the present application.

Claims

1. A method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target, characterized in that: The following steps are involved: preparing doped symbiotic zinc oxide whisker powder; adding a wetting agent and a dispersant to the doped zinc oxide whisker powder, and performing ball milling to obtain a grinding slurry; Then, the first-stage grinding slurry is sand-milled to obtain the second-stage grinding slurry; After drying the second-stage grinding slurry, granulation is performed to obtain granules; Adding a forming agent to the pellets and performing compression molding to obtain a green compact; The green compact is debonded and then sintered in sections to obtain a sputtering target.

2. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of preparing the doped symbiotic zinc oxide whisker powder comprises: Stirring and dissolving polyethylene glycol in water to form a gel, placing zinc particles in the gel, and simultaneously adding an oxide of a doping element so that the oxide of the doping element adheres to the zinc particles; filtering again to remove the gel and obtain zinc particles attached with doping element oxides; The zinc particles with the doping element oxide attached thereto are dried at 75° C.-85° C. for 30 min-180 min, then placed in a box-type resistance furnace, heated to 500° C.-1200° C., reacted for 10 min-25 min, cooled to room temperature, and then ground to obtain doped symbiotic zinc oxide whisker powder.

3. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 2, characterized in that: The doping elements include beryllium, boron, carbon, silicon, phosphorus, sulfur, calcium, magnesium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, arsenic, selenium, bromine, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, antimony, tellurium, iodine, barium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, Rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, astatine, francium, radium, actinium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, ruthenium, Copper, niobium, feldspar, molybdenum, lead, and At least one of .

4. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of adding a wetting agent and a dispersant to the doped zinc oxide whisker powder and performing ball milling to obtain a grinding slurry comprises: adding a wetting agent and a dispersant to the doped zinc oxide whisker powder to obtain a mixed powder; A mechanical ball milling method is adopted, and alumina grinding balls are selected to ball mill the mixed powder, the alumina grinding balls and water in a mass ratio of (1-2): (2-3): (2-3) for 25h-35h to obtain a grinding slurry.

5. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1 or 4, characterized in that: The wetting agent includes triethanolamine and tromethamine, and the dispersant includes tetramethylammonium silicon hydroxide, sodium hydroxycitrate and polycarboxylate.

6. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of drying the second-stage grinding slurry and then granulating the granules to obtain granules comprises: The second-stage grinding slurry is dried at 80° C.-90° C. for 40 h-50 h, passed through a 200-300 mesh sieve, and then subjected to rolling granulation for 15 min-30 min to obtain granules.

7. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of adding a forming agent to the granules and performing compression molding to obtain a green body comprises: A dry pressing method is adopted, wherein a forming agent is added to the granules and bidirectional pressing is performed under a pressure of 3MPa-5MPa, and the pressure holding time is 2min-4min to obtain a green body; Wherein, the molding agent is polyvinyl alcohol modified by carboxymethyl cellulose.

8. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of degumming the green compact comprises: The green body is heated to 350-400° C. at a rate of 2-3° C. / min and kept at this temperature for 1-2 hours, and then heated to 500-600° C. at a rate of 5-7° C. / min and kept at this temperature for 2-3 hours.

9. The method for preparing a multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target according to claim 1, characterized in that: The step of performing segmented sintering to obtain a sputtering target comprises: The debonded green body is heated to 700-800°C at a rate of 8-12°C / min and kept at this temperature for 1-2 hours for low temperature sintering. The green body after low-temperature sintering is then heated to 1100-1300°C at a rate of 15-25°C / min and kept at this temperature for 1-2 hours for high-temperature sintering, and then cooled in a spark plasma sintering furnace to obtain a sputtering target.

10. Sputtering target product, characterized in that: The target is obtained by the preparation method of the multi-element doped symbiotic zinc oxide whisker high-conductivity and high-density sputtering target as described in any one of claims 1 to 9.

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