CN113463053A - Molybdenum-nickel-based multi-component alloy rotary target and preparation method thereof - Google Patents
Molybdenum-nickel-based multi-component alloy rotary target and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a molybdenum-nickel-based multicomponent alloy rotary target material and a preparation method thereof, wherein the atomic composition of the rotary target material is Mo100‑x‑y‑ zNixTiyAlzAnd X, Y, Z represents atomic composition percentage, X is more than or equal to 10 and less than or equal to 40, Y is more than or equal to 1 and less than or equal to 20, and Z is more than or equal to 1 and less than or equal to 18; the preparation method comprises the steps of mixing molybdenum powder, electrolytic nickel powder and titanium-aluminum prealloying powder in proportion, then carrying out deoxidation purification treatment, carrying out ball-milling mixing, powder filling and compaction treatment, cold isostatic pressing, demoulding, vacuum horizontal sintering, rotary forging treatment and annealing treatment to obtain a molybdenum-nickel-titanium-aluminum alloy pipe ingot, and finally carrying out machining slicing to obtain the molybdenum-nickel-titanium-aluminum alloy target. The preparation process of the invention can reduce the introduction of impurity elements, and the produced target material has uniform components, no segregation, fine crystal grains and density reaching over 99 percent of theoretical value, and can completely meet the coating requirements of the prior large-size sputtering target material.
Description
Technical Field
The invention belongs to a magnetron sputtering metal target, and particularly relates to a large-size molybdenum-nickel-titanium-aluminum quaternary alloy tubular sputtering target and a preparation method thereof.
Background
With the upsizing and high precision of flat panel displays, copper has been widely developed as a main wiring thin film material of Thin Film Transistors (TFTs) of FPD driving elements, and copper metallization has been widely developed in the TFT-LCD industry, and in large-area high-frequency driving TFT liquid crystal displays, since copper has low adhesion to a glass substrate, copper needs to be used as an underlayer or overlayer by means of an adhesion metal film layer, such as Mo, Ti, Nb, Ni, Ta, Cr, and the like. When different metals and copper are placed in an etching solution, a typical galvanic reaction occurs, and the copper is weakened after drying or partially smeared on the surface of the metal, resulting in deterioration of the performance and display quality of the thin film transistor. The currently adopted molybdenum titanium or molybdenum titanium nickel alloy film layer has good adhesion to a glass substrate and low contact resistance to silicon and indium tin oxide, but titanium cannot be well dissolved in a solution of phosphoric acid, acetic acid and nitric acid due to titanium-containing elements, so that incomplete etching is caused, residues are left, and the TFT processing quality is seriously influenced. Compared with titanium, aluminum has excellent oxidation resistance and good etching performance in PAN, so that in order to improve the characteristics of the TFT molybdenum alloy film, a certain amount of Al is specially added to form a new alloy film layer (molybdenum nickel titanium aluminum alloy film layer), and the easily-etched characteristic film can be ensured on the premise of good adhesive force, oxidation resistance, heat resistance and low resistivity. The corresponding molybdenum-nickel-titanium-aluminum alloy sputtering target material is relatively few in research at present, and the coating utilization rate of the rotary target is about 75 percent and is far higher than that of a plane target by 30 percent, so that the preparation and development of the molybdenum-nickel-titanium-aluminum alloy rotary target material are very important, and the required target material size is larger and larger.
The melting point of the molybdenum reaches 2620 ℃, and the density of the molybdenum reaches 10.2g/cm3And the melting point of aluminum is 660 ℃ and the density of aluminum is 2.7g/cm3The melting point and the density of the two materials are greatly different, the vacuum melting method is easy to shrink and segregate, the uniformity of the product structure and components cannot be ensured, various brittle phases are generated, the product is easy to crack, and the large-size target material cannot be prepared. If the hot-pressing sintering mode is adopted for preparation, although the method can avoid alloy component segregation to a certain extent, gaseous impurity elements such as oxygen and nitrogen cannot be removed in the hot-pressing process, so that the impurity content and the oxygen content of the product exceed the standard, and arc striking is caused in the sputtering coating process; in addition, it is difficult to prepare targets with lengths exceeding 1.5 m due to the limitation of hot-pressing sintering equipment.
Disclosure of Invention
The purpose of the invention is as follows: the first purpose of the invention is to provide a molybdenum-nickel-titanium-aluminum multi-element alloy rotary sputtering target material with large size, high density, high purity, uniform components and no segregation; the second purpose of the invention is to provide a preparation method of the molybdenum-nickel-titanium-aluminum multi-component alloy rotary sputtering target material.
The technical scheme is as follows: the invention relates to a molybdenum-nickel-based multi-component alloy rotary target material, wherein the atomic composition of the rotary target material is Mo100-x-y-zNixTiyAlzAnd X, Y, Z represents atomic composition percentage, X is more than or equal to 10 and less than or equal to 40, Y is more than or equal to 1 and less than or equal to 20, and Z is more than or equal to 1 and less than or equal to 18.
According to the invention, the rotary target material is prepared by compounding Mo, Ni, Ti and Al, so that the gold coating layer is easy to etch and does not generate residue, has good adhesive force, oxidation resistance, moisture resistance and low resistivity, and completely meets the requirement of a main conductor film layer in a TFT (thin film transistor) manufacturing process. Wherein the addition of Ti and Al can not only remove part of residual oxygen in the alloy powder, but also form a trace amount of Ti with Ni3Al(γ+α)、Ni2TiAl、Ni3Al intermetallic compound, so as to improve the room temperature strength and toughness of the alloy and inhibit the enrichment of Ni. Among the above components, Ni is easier than MoWhen the alloy is thermally diffused into Cu and becomes a Ni-rich alloy, Ni is diffused into Cu of the main wiring film to increase the resistance value, and therefore the amount of Ni added is controlled to 40 at% or less. Ti mainly affects the oxidation resistance and moisture resistance of the whole alloy, and when the addition amount of Ti exceeds 20 at%, the effects of oxidation resistance and moisture resistance are saturated, and the etching property is reduced; secondly, in order to ensure better etching resistance under the premise of better oxidation resistance, the content of the added Al is better not to exceed 18at percent, because the defect of too fast corrosion and lower moisture resistance is caused by too much aluminum content.
Furthermore, the content of impurity elements such as gas in the alloy target material is as low as possible, and is specifically embodied in the selection of raw materials, Mo is provided by molybdenum powder, the granularity of the molybdenum powder is 3-7 mu m, the oxygen content is less than or equal to 1000ppm, and the purity is more than 99.95%; the Ni is provided by electrolytic nickel powder, the granularity of the electrolytic nickel powder is 6-12 mu m, the oxygen content is less than or equal to 2000ppm, and the purity is more than 99.9%; the Ti and the Al are provided by titanium-aluminum prealloying powder, the granularity of the titanium-aluminum prealloying powder is 35-60 mu m, and the oxygen content is less than or equal to 3000 ppm. And other elements such as carbon is less than or equal to 50ppm, potassium is less than or equal to 50ppm and the like, and excessive gas impurity elements can cause arc striking in the sputtering coating process and influence the coating quality.
The invention also provides a preparation method of the molybdenum-nickel-based multi-component alloy rotary target material, which comprises the following steps:
step one, mixing molybdenum powder, electrolytic nickel powder and titanium-aluminum prealloy powder in proportion, then placing the mixture in a vacuum furnace for deoxidation and purification, and then ball-milling and mixing the powder subjected to deoxidation and purification;
filling the ball-milled powder into a tubular mold cavity, compacting the powder by adopting a vibration platform in the whole powder filling process, vacuumizing and sealing after powder filling, then performing cold isostatic pressing, and finally demolding and pressing to obtain an alloy tube blank with the relative density of 68-70%;
thirdly, placing the demolded alloy tube blank in a vacuum sintering furnace for horizontal sintering to obtain an alloy tube blank with the relative density of more than 98%;
fourthly, performing rotary swaging treatment on the sintered alloy pipe blank;
and fifthly, placing the forged tube blank into a vacuum furnace for stress relief annealing treatment to obtain a molybdenum-nickel-titanium-aluminum alloy tube ingot, finally slicing through machining, welding and binding with a copper back plate, cleaning and drying to obtain the molybdenum-nickel-titanium-aluminum alloy target material.
Further, in the second step, the parameters of the horizontal sintering are as follows: the temperature is kept for 2-5 h when the temperature is raised to 950 ℃ at the first stage according to the temperature raising rate of 4-6 ℃/min, the temperature is kept for sintering for 3-7 h when the temperature is raised to 1150-1280 ℃ at the second stage according to the temperature raising rate of 2-4 ℃/min, then the temperature is lowered along with the furnace, and the vacuum degree is not less than 3 x 10 during the sintering process-3pa. When the alloy pipe blank is placed in a horizontal sintering mode, the whole pipe is buried by spherical alumina ceramic particles, and the particle size of the alumina ceramic particles is controlled to be 2-5 mm. The aluminum oxide ceramic particles are adopted to enable the inner hole and the periphery to be well buried, when the tube blank shrinks due to high-temperature sintering, the tube blank is larger in wall thickness and the radial upper end can deform and dent due to self weight, the powder filling mode is adopted to ensure that the tube blank shrinks normally in the sintering process, the phenomenon of elliptical bending caused by overlarge radial deformation is avoided, the alloy tube deforms uniformly after sintering, and the inner hole is free of elliptical dent.
Further, in the third step, the pressure of the cold isostatic pressing is 230-330 MPa, and the pressure maintaining time is 240-500 s; the vibration amplitude of the vibration platform is 3-6 mm when the powder is vibrated, and the exciting force is 110-130 KN. Preferably, during the pressing process, the pressing die structure is as follows: the inner core is a solid steel bar, the surface of the inner core is subjected to high-frequency quenching and polished to Ra0.2, and the inner core has 1-2 mm taper, so that the subsequent demoulding of the blank pipe is facilitated; the outer cover has the cylindrical polyurethane type gum cover of thickness 5~ 15mm, and this gum cover internal diameter bottom is less, the great structure in upper end, and both ends adopt circular plug cooperation sealed. The outer layer of the rubber sleeve is sleeved with a 304 stainless steel drum, the surface of the rubber sleeve is uniformly provided with a plurality of flow guide holes with the aperture of 10-30mm, the rigidity of the rubber sleeve is utilized to fix and control the powder blank not to deform in the charging process, and meanwhile, the flow guide holes can ensure that all points of the powder blank are uniformly stressed in the cold isostatic pressing process.
Further, in the first step, the treatment temperature in the vacuum furnace is 950-1100 ℃, and the time of deoxidation and purification treatment is 2-5 h; the rotating speed of ball milling is 120-210R/M, and the ball milling time under argon protection is 8-12 h. Because the oxygen content of the raw material powder in the market is generally higher, the excessive oxygen content can cause arcing in the sputtering coating process, the coating quality is influenced, out-of-phase impurities such as oxygen, nitrogen, hydrogen, low-melting-point substances and the like of the initial powder can be removed through early-stage vacuum deoxidation treatment, the oxygen content is reduced, the purity of the powder is improved, and the purity of the final target is ensured. In the ball milling process, the ball-material ratio is 3:1, the lining of the ball mill and the grinding balls are made of pure molybdenum materials, so that the introduction of impurity elements can be effectively avoided, the purity of powder is ensured, the mixing is not uniform easily caused by overlarge specific gravity difference between molybdenum powder and aluminum powder, the explosion risk exists in the aluminum powder ball milling process, the extensibility of the aluminum powder ball milling is good, and the powder layering phenomenon is caused by the easy formation of flaky large particles. Because aluminum can be dissolved in alpha-Ti in a large amount, the mechanical ball milling treatment of the titanium-aluminum alloy powder, the molybdenum powder and the nickel powder which are atomized and granulated in advance is adopted, the uneven mixing of the powder can be effectively avoided, meanwhile, partial powder particles of the ball milling powder are extruded into larger flat-long-sheet shapes, partial powder particles are processed, hardened and cold-welded layers and crushed into smaller particles, the particle size distribution of the powder after ball milling is widened, atoms of the powder after ball milling are in a high-energy state, the atom diffusion in the sintering process is accelerated, and the improvement of the sintering density is facilitated.
Further, in the fourth step, the forging force of the rotary swaging treatment is 18-22 MN, the forging temperature is 1030-1100 ℃, and the heat preservation time is 2-4 h. Before the rotary swaging treatment, the method also comprises the step of lining the alloy pipe blank with a TZM steel bar, wherein the TZM steel bar is a molybdenum alloy bar, and the specific process comprises the following steps: and cooling water is introduced into the TZM steel bar, the TZM steel bar and the alloy pipe blank relatively rotate in the reverse direction during rotary swaging, the four mutually perpendicular hammer anvils are oppositely impacted pairwise, and the forging speed is controlled to be 190-250 times/min.
Further, in the fifth step, the annealing temperature is 980-1130 ℃, the heat preservation time is 2-4 hours, and the vacuum degree is not less than 3 x 10-3pa; the length of the molybdenum nickel titanium aluminum alloy target is 1300-3000 mm.
The preparation principle of the invention is as follows: the large-size molybdenum nickel titanium aluminum alloy target material is prepared through the processes of vacuum deoxidation, powder filling and compaction, cold isostatic pressing, horizontal vacuum sintering, rotary swaging, annealing, external processing and binding and welding in sequence. The large-size preparation can be realized through the sequential synergistic effect of the four steps of powder filling compaction, cold isostatic compaction, horizontal vacuum sintering and rotary swaging, and the vibration platform is adopted to greatly vibrate in the powder filling compaction process, so that the larger apparent density is favorably formed, and the molding density and uniformity are improved; the rubber sleeve mould with a specific structure is adopted in the cold isostatic pressing process, so that the phenomena of serious bottom accumulation, overlarge density and thick bottom caused by uneven deformation after pressing due to the dead weight problem of powder during powder loading can be effectively avoided; impurity contents such as gas and the like in powder particles can be removed to the maximum extent in the horizontal vacuum sintering process, the oxygen content is reduced, the high purity of a target product is ensured, the normal shrinkage of a pipe blank in the sintering process can be ensured by using an alumina powder filling mode in the vacuum sintering process, the elliptical bending phenomenon caused by overlarge radial deformation is avoided, and the alloy pipe deforms uniformly after sintering; in the rotary swaging process, the four hammers are utilized to carry out rapid rotary swaging, so that the blank pipe can deform in an approximately closed radial compression cavity, the process has good process plasticity, the defects of air holes and the like can be closed and eliminated, the crystal grains can be fully crushed and refined, and the density of the blank pipe is further improved by over 99.5 percent. The axial component force generated by the hammer anvil inlet angle is beneficial to the axial extension of a workpiece, so that the tube blank is forged and prolonged, the elongation rate is about 5-15%, the straightness of the tube blank can be ensured, the machining allowance can be reduced, the production cost is greatly reduced, and a foundation is laid for finally forming a large size.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: (1) the sputtering coating layer of the alloy target material prepared by the method has good adhesive force, oxidation resistance, moisture resistance, low resistivity and easy etching; the preparation method of the invention can reduce the introduction of impurity elements, the produced tube target has uniform components, no segregation, fine average crystal grains (less than or equal to 50 microns), lower oxygen content, density of more than 99 percent of theoretical value, and completely meets the coating requirements of the prior large-size sputtering target. (2) The horizontal vacuum sintering mode is adopted to prepare target products with larger specifications, the equipment limitation is avoided (for example, the hot pressing or hot isostatic pressing mode is adopted for sintering, the equipment limitation is larger, the length of the finished product is not more than 2 meters), and meanwhile, the sintering cost is also greatly reduced. (3) The tube target produced by the method has the specification of 1300-3000 mm, completely meets the requirements of high-end liquid crystal panel manufacturers, has obvious market competitiveness, and further improves the comprehensive performance of the molybdenum-nickel-base multi-element alloy rotary target.
Drawings
FIG. 1 is a diagram of the phase of the Mo-Ni-Ti-Al multi-alloy rotary target product prepared in example 1;
FIG. 2 is a C-SCAN inspection of a 2.4 m Mo-Ni-Ti-Al multi-element alloy rotary target prepared in example 1;
FIG. 3 is a gold phase diagram of the Mo-Ni-Ti-Al multi-element alloy rotary target product prepared in example 2;
FIG. 4 is a C-SCAN inspection chart of a 3m Mo-Ni-Ti-Al multi-element alloy rotary target prepared in example 2;
FIG. 5 is a schematic structural diagram of a coating layer prepared by bonding and binding the Mo-Ni-Ti-Al alloy target material and the Cu backing plate prepared in example 3.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to examples.
Example 1
Preparation of Mo40Ni30Ti15Al15
S1, Mo is adopted to have particle size of 3-7 um, oxygen content is less than or equal to 1000ppm, and purity is more than 99.95%; the Ni powder is electrolytic nickel powder, the purity is more than 99.9%, the granularity is 6-12 um, and the oxygen content is less than or equal to 2000 ppm; atomized and granulated Ti50Al50The alloy powder has a granularity of 35-60um and an oxygen content of less than or equal to 3000 ppm. Mixing the above materials at the above atomic ratio, placing in a vacuum furnace at 1000 deg.C and vacuum degree of not less than 10-2pa is subjected to vacuum deoxidation purification treatment for 2 h.
And S2, mechanically ball-milling and mixing the powder after vacuum treatment, wherein the ball-material ratio is 3:1, the rotating speed is 170R/M, the ball-milling and mixing are carried out for 12 hours under the protection of argon, and the lining of the ball mill and the grinding balls are made of pure molybdenum materials.
S3, filling the ball-milled powder into a tubular die cavity, continuously compacting the powder by adopting a vibration platform in the whole powder filling process, wherein the vibration amplitude is 3-6 mm, the exciting force is 120KN, vacuumizing (not less than 0.1pa) by using a thin tube after the powder filling process is finished, sealing a rubber plug, then pressing 250MPa by using a cold isostatic press, maintaining the pressure for 300S, finally demolding and pressing into a hollow tube blank with the length of 2500mm, and preparing the alloy tube blank with the relative density of 68%.
S4, placing the long tube blank in a horizontal vacuum sintering furnace, burying the whole tube by spherical alumina ceramic particles (with the particle size of 2-5 mm), enabling the inner hole and the periphery to be buried well, and enabling the sintering vacuum degree to be not lower than 3 x 10-3pa, sintering parameters are: the first section is heated to 930 ℃ for 3h at the heating rate of 3 ℃/min, the second section is heated to 1200 ℃ for heat preservation and sintering for 4h at the heating rate of 2 ℃/min, and then the temperature is reduced along with the furnace, so that the molybdenum-nickel-titanium-aluminum alloy tube with the length of 2350mm and the relative density of more than or equal to 98 percent can be obtained.
S5, adopting an Austrian GFM four-hammer finish forging machine to carry out rotary forging treatment on the sintered tube blank, wherein the forging force is 20MN, the heating forging temperature is 1020 ℃, the temperature is kept for 2h, a TZM steel rod is lined in an inner hole of the hollow tube blank, cooling water is introduced into the steel rod, the inner core steel rod and the hollow tube blank relatively rotate in the opposite direction during rotary forging, four mutually perpendicular hammer anvils are used for carrying out pairwise butt impact, the forging speed is 220 times/min, and finally, the molybdenum-nickel-titanium-aluminum alloy tube with the length of 2510mm is formed through final forging.
S6, putting the forged tube blank into a vacuum furnace for annealing treatment, wherein the annealing temperature is 990 ℃, and the vacuum degree is not less than 3 x 10-3pa, and keeping the temperature for 2 h.
S7, machining the inner circle, the outer circle and the end face through a boring machine to form a molybdenum-nickel-titanium-aluminum alloy tube with the length of 2400mm, binding and welding the molybdenum-nickel-titanium-aluminum alloy tube with a titanium back tube, detecting through C-SCAN, cleaning through ultrasonic waves, and drying to finally prepare the molybdenum-nickel-titanium-aluminum rotary target with the length of 2400 mm.
Referring to fig. 1, in order to obtain a gold phase diagram of the molybdenum-nickel-titanium-aluminum multi-element alloy rotary target finished product, it can be seen that the alloy has uniform crystal grains, close arrangement and fewer hole defects. Through detection, the relative density of the target material prepared by the embodiment is 99.3%, the average grain size is less than or equal to 50um, and the purity of the target material is more than or equal to 99.97%. Referring to fig. 2, the molybdenum-nickel-titanium-aluminum multi-element alloy rotary target has no defects such as air hole cracks and the like, the binding welding rate is more than or equal to 98 percent, and the requirement of high-end sputtering target materials is completely met.
Example 2
Preparation of Mo52Ni25Ti15Al8
S1, Mo is adopted to have particle size of 3-7 um, oxygen content is less than or equal to 1000ppm, and purity is more than 99.95%; ni powder is electrolytic nickel powder with purityMore than 99.9 percent, the granularity of 6-12 um and the oxygen content of less than or equal to 2000 ppm; atomized and granulated Ti70Al30The alloy powder has a granularity of 35-60um and an oxygen content of less than or equal to 3000 ppm. Mixing the above materials at the above atomic ratio, placing in a vacuum furnace at 1030 deg.C with vacuum degree of not less than 10- 2pa is subjected to vacuum deoxidation purification treatment for 5 hours.
And S2, mechanically ball-milling and mixing the powder after vacuum treatment, wherein the ball-material ratio is 3:1, the rotating speed is 180R/M, the ball-milling and mixing are carried out for 10 hours under the protection of argon, and the lining of the ball mill and the grinding balls are made of pure molybdenum materials.
S3, filling the ball-milled powder into a tubular die cavity, continuously compacting the powder by adopting a vibration platform in the whole powder filling process, wherein the vibration amplitude is 3-6 mm, the exciting force is 110KN, vacuumizing (not less than 0.1pa) by using a thin tube after the powder filling process is finished, sealing a rubber plug, pressing by using a cold isostatic press under the pressure of 300MPa for 300S, and finally demoulding and pressing into a hollow tube blank with the length of 3200mm to obtain an alloy tube blank with the relative density of 70%.
S4, placing the long tube blank in a horizontal vacuum sintering furnace, burying the whole tube by spherical alumina ceramic particles (with the particle size of 2-5 mm), enabling the inner hole and the periphery to be buried well, and enabling the sintering vacuum degree to be not lower than 3 x 10-3pa, sintering parameters are: the first section is heated to 950 ℃ for 3h at the heating rate of 4 ℃/min, the second section is heated to 1230 ℃ at the heating rate of 2 ℃/min for 4h through heat preservation and sintering, and then the temperature is reduced along with the furnace, so that the molybdenum-nickel-titanium-aluminum alloy tube with the length of 2920mm and the relative density of more than or equal to 98 percent can be obtained.
S5, adopting an Austrian GFM four-hammer finish forging machine to carry out rotary forging treatment on the sintered tube blank, wherein the forging force is 18MN, the heating forging temperature is 1050 ℃, the temperature is kept for 2h, a TZM steel rod is lined in an inner hole of the hollow tube blank, cooling water is introduced into the steel rod, the inner core steel rod and the hollow tube blank relatively rotate in the opposite direction during rotary forging, four mutually perpendicular hammer anvils are used for carrying out pairwise butt impact, the forging speed is 240 times/min, and finally, the molybdenum-nickel-titanium-aluminum alloy tube with the length of 3130mm is formed through final forging.
S6, putting the forged tube blank into a vacuum furnace for annealing treatment, wherein the annealing temperature is 1020 ℃, and the vacuum degree is not less than 3 x 10-3pa, and keeping the temperature for 3 hours.
S7, machining the inner circle, the outer circle and the end face through a boring machine to obtain a molybdenum-nickel-titanium-aluminum alloy tube with the length of 3000mm, binding and welding the molybdenum-nickel-titanium-aluminum alloy tube with a titanium back tube, detecting through C-SCAN, cleaning through ultrasonic waves, and drying to finally prepare the molybdenum-nickel-titanium-aluminum rotary target with the length of 3000 mm.
As shown in FIG. 3, the phase diagram of the Mo-Ni-Ti-Al multi-element alloy rotary target finished product shows that the alloy has uniform crystal grains, compact arrangement and less hole defects. Through detection, the relative density of the target material prepared by the embodiment is 99.5%, the average grain size is less than or equal to 50um, and the purity of the target material is more than or equal to 99.98%. The diagram 4 is a C-SCAN detection diagram of the prepared 3m molybdenum-nickel-titanium-aluminum multi-element alloy rotary target, no defects such as air hole cracks exist in the interior, the binding welding rate is more than or equal to 98 percent, and the requirement of high-end sputtering target materials is completely met.
Example 3
Preparing a coating sample, wherein the target material is Mo45-Ni30-Ti15-Al10。
S1, Mo is adopted to have particle size of 3-7 um, oxygen content is less than or equal to 1000ppm, and purity is more than 99.95%; the Ni powder is electrolytic nickel powder, the purity is more than 99.9%, the granularity is 6-12 um, and the oxygen content is less than or equal to 2000 ppm; atomized and granulated Ti50AL50 at% alloy powder with the granularity of 35-60um and the oxygen content less than or equal to 3000 ppm. Mo in atomic ratio45-Ni30-Ti15-Al10Mixing at%, placing in a vacuum furnace at 1000 deg.C with vacuum degree of not less than 10-2pa is subjected to vacuum deoxidation purification treatment for 1H.
And S2, mechanically ball-milling and mixing the powder after vacuum treatment, wherein the ball-material ratio is 3:1, the rotating speed is 170R/M, the ball-milling and mixing are carried out for 8 hours under the protection of argon, and the lining of the ball mill and the grinding balls are made of pure molybdenum materials.
S3, filling the ball-milled powder into a tubular die cavity, continuously compacting the powder by adopting a vibration platform in the whole powder filling process, wherein the vibration amplitude is 3-6 mm, the exciting force is 130KN, vacuumizing (not less than 0.1pa) by using a thin tube after the powder filling process is finished, sealing a rubber plug, and pressing into a small round billet with the height of 50mm and the diameter of 180mm by using a cold isostatic press under the pressure of 230MPa and the pressure of 300S.
S4, placing the small billet into a horizontal vacuum sintering furnace, wherein the sintering vacuum degree is not less than 3 x 10-3pa, sintering parameters are: the temperature is increased to 930 ℃ for 2h at the first stage according to the heating rate of 4 ℃/min, and the temperature is increased to 1200 ℃ at the second stage according to the heating rate of 3 ℃/minAnd (3) carrying out warm sintering for 3h, and then cooling along with the furnace to prepare a small molybdenum-nickel-titanium-aluminum alloy ingot with the height of 42mm and the diameter of 165 mm.
S5, performing rotary swaging treatment with forging force of 20MN, heating and forging at 1050 ℃, keeping the temperature for 2h, and then performing annealing treatment with the annealing temperature of 1000 ℃ and the vacuum degree of not less than 3 x 10-3pa, and keeping the temperature for 3 hours.
And S6, machining and slicing to obtain the molybdenum-nickel-titanium-aluminum alloy target material with the outer diameter of 140mm and the thickness of 8 mm.
S7, finally welding and binding with a copper back plate, C-SCAN detecting, ultrasonic cleaning and drying to finally prepare Mo45-Ni30-Ti15-Al10And (4) coating the sample with the alloy target.
Referring to the coating structure of fig. 1, wherein film 1 is substrate glass, film 2 is a bottom alloy coating film, film 3 is a main conductive copper layer, film 4 is a top alloy coating layer, substrate glass area is 100 x 100mm, and coating film thickness is respectively: film 2 is 600A, film 3 is 5000A, and film 4 is 600A.
Comparative example 1
Mo was prepared according to the procedure of example 335-Ni30-Ti15-Al20，Mo75-Ti25And Mo60-Ni20-Ti20The structure of the coating sample target is the same as that of the coating sample target in figure 1.
Then, the film was subjected to measurement and comparison with the film-coated sample of example 3 for oxidation resistance, adhesion, resistivity, high-temperature moisture resistance, corrosion resistance, etc., and the data are shown in tables 1 and 2 below.
TABLE 1
TABLE 2
And (3) detecting the oxidation resistance of the film layer: the change of the reflectivity of the film layer after being heated for 1h at the room temperature, the temperature of 150 ℃, the temperature of 250 ℃ and the temperature of 350 ℃ in the atmosphere is measured by adopting a spectroscopic tester, and the table 1 shows that the reflectivity of the conventional 1# molybdenum-titanium binary alloy film is greatly reduced along with the temperature rise, the fluctuation value is the largest and the oxidation resistance is the worst. After the nickel and the aluminum are added according to a certain proportion, the fluctuation of reflectivity is small, particularly, the oxidation resistance of the film layers 3# and 4# containing the aluminum is better than that of the film layer 2# and the high-temperature oxidation resistance is very stable.
In the high temperature and humidity resistance test, the 4 kinds of films were left to stand in an atmosphere (temperature 85 ℃ C. + humidity 85%) for 100 hours, and after 200 hours, the presence or absence of discoloration on the film surface was visually confirmed. As shown in Table 2, when Al is added to the composition No. 4 at a concentration of 20 at%, the corrosion resistance of the composition is deteriorated due to excessive Al content under high temperature and high humidity conditions, and as time passes, the surface of the composition is deteriorated due to the occurrence of a pinhole defect, and the surface of the film becomes dark due to the deterioration of moisture resistance. The aluminum content of No. 3 is 10at percent, and the film layer does not change color when exposed to a high-temperature and high-humidity environment and has high moisture resistance. Therefore, the amount of aluminum atoms added is preferably less than 18 at%.
The resistivity is measured by a thin film resistance meter, the resistivity is gradually reduced along with the reduction of the contents of molybdenum and titanium and the addition of nickel, and the resistivity of the 3# and 4# film layers is greatly reduced after the aluminum element is added. The adhesion detection adopts a 3M adhesive tape stripping method to evaluate whether a film is remained. No peeling residue exists in 4 film layer materials through testing, and the high adhesion is shown. And (3) detecting the etching performance: the sample was immersed in a Cu etching solution for a certain period of time, and then the substrate was washed with pure water, dried, and observed with an optical microscope for the presence of a metal thin film remaining on the substrate. Because titanium has stronger corrosion resistance, the metal film layer on the substrate is not changed and can not be etched after the 1# titanium-containing film layer is etched. Compared with No. 2 containing 20 at% titanium, although a certain corrosion reaction can occur, a small amount of film residue still remains on the substrate, which indicates that the etching is insufficient. It was found that by reducing the titanium content, no film layer remained on the substrates of sample nos. 3 and 4 after adding a certain amount of corrosion-prone aluminum element, and the etching effect was satisfactory.
In conclusion, the 3# sample Mo45-Ni30-Ti15-Al10The comprehensive performance is optimal. The preferred titanium content is due to the fact that titanium is present in excess and remains after etching<20 at%. Aluminum elementHas good oxidation resistance and etching performance, the defects of too fast corrosion and low high-temperature moisture resistance caused by too much aluminum content, and the preferred aluminum content is controlled within 18at percent. Therefore, the more preferable alloy film layer material is provided: mo100-x-y-zNixTiyAlz(X is more than or equal to 10 and less than or equal to 40, Y is more than or equal to 1 and less than or equal to 20, and Z is more than or equal to 1 and less than or equal to 18), and the sputter coating layer of the alloy target material has good adhesive force, oxidation resistance, moisture resistance, low resistivity and easy etching property.
Claims (10)
1. The molybdenum-nickel-based multi-component alloy rotary target material is characterized in that the atomic composition of the rotary target material is Mo100-x-y- zNixTiyAlzAnd X, Y, Z represents atomic composition percentage, X is more than or equal to 10 and less than or equal to 40, Y is more than or equal to 1 and less than or equal to 20, and Z is more than or equal to 1 and less than or equal to 18.
2. The molybdenum-nickel based multi-component alloy rotary target of claim 1, wherein: mo is provided by molybdenum powder, the granularity of the molybdenum powder is 3-7 mu m, the oxygen content is less than or equal to 1000ppm, and the purity is more than 99.95%; the Ni is provided by electrolytic nickel powder, the granularity of the electrolytic nickel powder is 6-12 mu m, the oxygen content is less than or equal to 2000ppm, and the purity is more than 99.9%; the Ti and the Al are provided by titanium-aluminum prealloying powder, the granularity of the titanium-aluminum prealloying powder is 35-60 mu m, and the oxygen content is less than or equal to 3000 ppm.
3. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material of any one of claims 1 to 2, which is characterized by comprising the following steps:
step one, mixing molybdenum powder, electrolytic nickel powder and titanium-aluminum prealloy powder in proportion, then placing the mixture in a vacuum furnace for deoxidation and purification, and then ball-milling and mixing the powder subjected to deoxidation and purification;
filling the ball-milled powder into a tubular mold cavity, compacting the powder by adopting a vibration platform in the whole powder filling process, vacuumizing and sealing after powder filling, then performing cold isostatic pressing, and finally demolding and pressing to obtain an alloy tube blank with the relative density of 68-70%;
thirdly, placing the demolded alloy tube blank in a vacuum sintering furnace for horizontal sintering to obtain an alloy tube blank with the relative density of more than 98%;
fourthly, performing rotary swaging treatment on the sintered alloy pipe blank;
and fifthly, putting the forged tube blank into a vacuum furnace for stress relief annealing treatment to obtain a molybdenum-nickel-titanium-aluminum alloy tube ingot, and finally, slicing through machining to prepare the molybdenum-nickel-titanium-aluminum alloy target.
4. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 3, wherein the method comprises the following steps: in the second step, the parameters of the horizontal sintering are as follows: and (3) carrying out heat preservation for 2-5 h at 930-950 ℃ at the first section according to the heating rate of 4-6 ℃/min, carrying out heat preservation sintering for 3-7 h at 1150-1280 ℃ at the second section according to the heating rate of 2-4 ℃/min, and then cooling along with the furnace.
5. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 4, wherein the method comprises the following steps: when the alloy pipe blank is placed in a horizontal sintering mode, the whole pipe is buried by spherical alumina ceramic particles, and the particle size of the alumina ceramic particles is controlled to be 2-5 mm.
6. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 3, wherein the method comprises the following steps: in the third step, the pressure of the cold isostatic pressing is 230-330 MPa, and the pressure maintaining time is 240-500 s; the vibration amplitude of the vibration platform is 3-6 mm when the powder is vibrated, and the exciting force is 110-130 KN.
7. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 3, wherein the method comprises the following steps: in the first step, the treatment temperature in a vacuum furnace is 950-1100 ℃, and the time of deoxidation and purification treatment is 2-5 h; the rotation speed of ball milling is 120-210R/M, and the ball milling time is 8-12 h.
8. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 3, wherein the method comprises the following steps: in the fourth step, the forging force of the rotary forging treatment is 18-22 MN, the forging temperature is 1030-1100 ℃, and the heat preservation time is 2-4 h.
9. The method for preparing the nickel-based multi-component alloy rotary target material according to claim 8, wherein the method comprises the following steps: before the rotary swaging treatment, the method also comprises the step of lining the TZM steel bar in the alloy pipe blank, and specifically comprises the following steps: and (3) introducing cooling water into the TZM steel bar, and controlling the forging speed to be 190-250 times/min when the TZM steel bar and the alloy pipe blank rotate oppositely during rotary swaging.
10. The method for preparing the molybdenum-nickel-based multi-component alloy rotary target material according to claim 3, wherein the method comprises the following steps: in the fifth step, the annealing temperature is 980-1130 ℃, and the heat preservation time is 2-4 h; the length of the molybdenum nickel titanium aluminum alloy target is 1300-3000 mm.
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