CN114318255B - High-density NiV alloy sputtering target material prepared by easily-oxidized metal coating protection and preparation method thereof - Google Patents
High-density NiV alloy sputtering target material prepared by easily-oxidized metal coating protection and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-density NiV alloy sputtering target material prepared by easy-oxidation metal coating protection and a preparation method thereof, wherein the base material of the sputtering target material consists of Ni and V metals with the purity of more than or equal to 99.99 wt%, wherein V: 5-8 wt%, Ni: 92-95 wt%; the surface of the base material is provided with an easily oxidized metal protective coating, and the thickness of the coating is less than or equal to 5 mu m; the density of the sputtering target material is more than or equal to 99.5 percent, no macroscopic defect exists on the surface, the oxygen content is less than 30ppm, the grain size of the target material is uniform, and the average grain size is 10-30 mu m; the removing depth of the surface layer of the sputtering target material after machining treatment is less than or equal to 0.5 mm. The preparation method is realized by the processes of base material ingot casting and cleaning treatment, base material film coating, blank rolling, recrystallization treatment and machining treatment. Based on the principle of oxygen control and preferential protection, the oxygen content of the substrate is reduced, the surface of the substrate is sputtered with an easily-oxidized metal protective coating preferentially, the 'entrainment' brittle oxide is inhibited, the high-quality material rate of the target is improved, the surface layer removal depth is reduced, the waste of the target is reduced, and the cost is saved.
Description
Technical Field
The invention belongs to the technical field of sputtering target materials, and particularly relates to a high-density nickel-vanadium alloy sputtering target material capable of effectively improving the performance of the sputtering target material used as a semiconductor integrated circuit and a preparation method thereof.
Background
With the rapid development of semiconductor integrated circuits, the application of obtaining corresponding films by taking sputtering targets as source materials and adopting a magnetron sputtering technology is becoming more and more extensive; nonferrous metals and their alloy targets are increasingly in demand as important materials for supporting semiconductor processes. Pure gold is generally used as a surface conductive layer in the integrated circuit manufacturing, but the gold and a silicon wafer are easy to generate a brittle AuSi compound, so that the gold and silicon interface is poor in combination. Therefore, researchers have proposed that a pure nickel bonding layer is added between gold and a silicon wafer, but diffusion is also formed between a nickel layer and a gold layer, and a barrier layer is further added between the gold layer and the nickel layer to block diffusion between a gold conductive layer and the nickel bonding layer. Vanadium is an ideal material for the barrier layer due to its high melting point and ability to withstand large current densities. Research finds that the nickel-vanadium alloy target has the following advantages: firstly, the sputtering of a nickel layer (bonding layer) and a vanadium layer (barrier layer) can be completed at one time, and the coating process is effectively simplified; secondly, compared with a nickel target with stronger magnetism, the nickel-vanadium alloy has no magnetism, and is beneficial to improving the magnetron sputtering coating efficiency. Therefore, the nickel-vanadium target material is widely applied. However, the defects also exist, which are mainly reflected in that in the hot forging, hot rolling and heat treatment processes in the prior art, because vanadium is easily oxidized and forms a large amount of brittle oxides, the brittle oxides are peeled off to form surface holes and other defects in subsequent turning/milling processing, and the surface oxides can be removed only by processing to a certain depth, so that the problems of high production cost, low yield and the like are caused. Therefore, the problems that the target material is easy to generate brittle oxides due to vanadium oxidation in the preparation process of the nickel-vanadium alloy target material, the density is low, the target material components are not uniform, and the sputtering quality is influenced are urgent and needed in the industry. The problem is solved, the yield and the utilization rate of the nickel-vanadium sputtering target material are improved, the waste of the target material is reduced, the quality of an integrated circuit is improved, the significance is high, and the application prospect is wide.
Disclosure of Invention
The invention aims to provide a high-density NiV alloy sputtering target material prepared by the protection of an easily oxidized metal coating; a further aim is to provide a preparation method aiming at the high-density NiV alloy sputtering target material.
The first purpose of the invention is realized by that the high-density NiV alloy sputtering target material prepared by the protection of the easily oxidized metal coating is characterized in that the base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5-8 wt%, Ni: 92-95 wt% of oxygen scavenger, and 0.01-0.08% of total weight ratio; the surface of the base material is provided with an easily oxidized metal protective coating, and the thickness of the coating is less than or equal to 5 mu m; the density of the sputtering target material is more than or equal to 99.5 percent, and no visible defect exists; the purity is more than or equal to 99.99 wt%, the oxygen content is less than 30ppm, the grain size of the target material is uniform, and the average grain size is 10-30 mu m; the removing depth of the surface layer of the sputtering target material after machining treatment is less than or equal to 0.5 mm.
The further purpose of the invention is realized by that the preparation method of the high-density NiV alloy sputtering target material is realized by the processes of base material ingot casting and cleaning treatment, base material film coating, blank rolling, recrystallization treatment and machining treatment, and the specific process steps are as follows:
(1) casting ingots on a base material and cleaning: using Ni and V with the purity of more than or equal to 99.99 wt% as raw materials, and mixing the raw materials according to the ratio of V: 5-8 wt%, Ni: proportioning 92-95 wt%, putting the mixture into a medium-frequency vacuum induction melting furnace, adding an oxygen scavenger according to the weight ratio of 0.01-0.08% after the raw materials are completely melted, continuously keeping the molten state for 3-10 min, erecting a funnel on a casting mold, pouring an alloy melt into the mold, taking out after the cast ingot is completely cooled, and carrying out ultrasonic cleaning and drying by adopting absolute ethyl alcohol to obtain the cast ingot;
(2) coating a film on a substrate: placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, taking easily-oxidizable metal particles as an evaporation material to carry out evaporation coating, controlling the evaporation coating current to be 50-200A and the evaporation coating time to be 5-15 min, and obtaining an easily-oxidizable metal protection coating substrate blank with the required film thickness;
(3) blank rolling: firstly, carrying out hot rolling and longitudinal rolling on a coated substrate at the temperature of 1100-1300 ℃, wherein the deformation of single-pass rolling is 12-30%, the reheating is carried out between passes, the heating time is 5-10 min, and the total rolling deformation is 60%; after cooling the blank, performing cold rolling and transverse rolling, wherein the single-pass rolling deformation is 3-6%, and the total rolling deformation is 30%;
(4) and (3) recrystallization treatment: carrying out recrystallization treatment on the rolled substrate blank at the temperature of 300-600 ℃, wherein the recrystallization time is 1-3 h, taking out and air-cooling to obtain a finished coated substrate;
(5) and (3) machining treatment: and turning or milling the finished product substrate to obtain the high-density NiV alloy sputtering target material.
The invention is based on the principle of oxygen control and preferential protection, namely, oxygen content control and easy-oxidation film isolation protection. Firstly adopting Mg in the smelting process 2 Ni、MgNi 2 、NiTi 2 、NiTi、Ni 3 Ti、NiAl 3 、Ni 2 Al、NiAl、Ni 5 Al 3 、Ni 3 Al is an oxygen scavenger and effectively captures oxygen in the smelting process to form light MgO and TiO 2 And Al 2 O 3 Oxide particles float on the surface of the molten metal liquid, and are filtered by using a funnel in the subsequent casting process, so that the oxygen content in the cast ingot is effectively reduced, and MgO and TiO are also effectively prevented 2 And Al 2 O 3 Pollution caused by oxide particles; then sputtering a layer of compact protective coating of easily oxidized metal (nickel, aluminum and titanium) on the surface of the base material to form nickelThe vanadium substrate is protected, so that the oxidation of the nickel-vanadium alloy is effectively prevented, the vanadium which is very easy to oxidize is prevented from forming oxides, the 'entrainment' brittle oxides in the process are inhibited, the initiation and expansion of surface defects are greatly reduced, the density of the target material is improved, and the high-quality material rate of the target material is greatly improved. The method reduces the removal depth of the target material plate blank in the machining process, overcomes the defects that the target material in the prior art generates too much brittle oxide due to vanadium oxidation, the brittle oxide is peeled off to form surface holes and the like in subsequent turning/milling processing, and the surface oxide can be removed only by machining to a certain depth, so that the production cost is high, the yield is low and the like, improves the yield of the target material, reduces the waste of the target material, saves the cost, effectively shortens the machining time, and improves the economic benefit.
The specific implementation mode is as follows:
the present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way, and any variations or modifications of the technical idea of the present invention are within the scope of the present invention.
The high-density NiV alloy sputtering target material prepared by the protection of the easily oxidized metal coating film comprises the following raw materials of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5-8 wt%, Ni: 92-95 wt% of oxygen scavenger with the total weight ratio of 0.01-0.08%; the surface of the base material is provided with an easily oxidized metal protective coating, and the thickness of the coating is less than or equal to 5 mu m; the density of the sputtering target material is more than or equal to 99.5%, no macroscopic defect exists, the oxygen content is less than 30ppm, the grain size of the target material is uniform, and the average grain size is 10-30 mu m; the removing depth of the surface layer of the sputtering target material after machining treatment is less than or equal to 0.5 mm.
The base material of the target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 6.5-7.5 wt%, Ni: 92.5-93.5 wt%; and an oxygen scavenger with the total weight ratio of 0.03-0.06 percent is added.
The deoxidant is Mg 2 Ni、MgNi 2 、NiTi 2 、NiTi、Ni 3 Ti、NiAl 3 、Ni 2 Al、NiAl、Ni 5 Al 3 、Ni 3 Al or a mixture of two or more thereof.
The surface of the base material is provided with an easily oxidized metal protective coating which is formed by sputtering Ni, Al or Ti with the purity of more than or equal to 99.99 wt%,
the preparation method of the high-density NiV alloy sputtering target material is realized by the processes of base material ingot casting and cleaning treatment, base material film coating, blank material rolling, recrystallization treatment and machining treatment, and is characterized by comprising the following specific process steps:
(1) casting ingots on a base material and cleaning: using Ni and V with the purity of more than or equal to 99.99 wt% as raw materials, and mixing the raw materials according to the ratio of V: 5-8 wt%, Ni: proportioning 92-95 wt%, putting the mixture into a medium-frequency vacuum induction melting furnace, adding an oxygen scavenger according to the weight ratio of 0.01-0.08% after the raw materials are completely melted, continuously keeping the molten state for 3-10 min, erecting a funnel on a casting mold, pouring an alloy melt into the mold, taking out after the cast ingot is completely cooled, and carrying out ultrasonic cleaning and drying by adopting absolute ethyl alcohol to obtain the cast ingot;
(2) coating a film on a substrate: placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, taking easily-oxidizable metal particles as an evaporation material to carry out evaporation coating, controlling the evaporation coating current to be 50-200A and the evaporation coating time to be 5-15 min, and obtaining an easily-oxidizable metal protection coating substrate blank with the required film thickness;
(3) blank rolling: firstly, carrying out hot rolling and longitudinal rolling on a coated substrate at the temperature of 1100-1300 ℃, wherein the deformation of single-pass rolling is 12-30%, the reheating is carried out between passes, the heating time is 5-10 min, and the total rolling deformation is 60%; after cooling the blank, performing cold rolling and transverse rolling, wherein the single-pass rolling deformation is 3-6%, and the total rolling deformation is 30%;
(4) and (3) recrystallization treatment: carrying out recrystallization treatment on the rolled substrate blank at the temperature of 300-600 ℃, wherein the recrystallization time is 1-3 h, taking out and air-cooling to obtain a finished coated substrate;
(5) and (3) machining treatment: and turning or milling the finished product substrate to obtain the high-density NiV alloy sputtering target material.
The oxygen scavenger in the step (1) is Mg 2 Ni、MgNi 2 、NiTi 2 、NiTi、Ni 3 Ti、NiAl 3 、Ni 2 Al、NiAl、Ni 5 Al 3 、Ni 3 Al or a mixture of two or more thereof.
The oxidizable metal in the step (1) is one or more of Ni, Al or Ti with the purity of more than or equal to 99.99 wt%.
And (3) the deformation of single-pass rolling of the hot rolling in the longitudinal rolling in the step (3) is 15-25%, and the time for reheating in a furnace is 6-8 min between passes.
And (3) the deformation of the single-pass rolling of the transverse rolling of the cold rolling in the step (3) is 4-5%.
And (4) carrying out recrystallization treatment on the substrate blank at the temperature of 400-500 ℃, wherein the recrystallization time is 1.5-2.5 h, taking out and air-cooling to obtain the finished coated substrate.
Example 1
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5 wt%, Ni: 95 wt% of oxygen scavenger Mg with the additional total weight ratio of 0.01% 2 And (3) Ni. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding a deoxidant Mg according to the weight ratio of 0.01 percent after the raw materials are completely melted 2 Continuously maintaining the molten state of Ni for 3min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out after the ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol, drying, and determining the oxygen content of the ingot to be 22 ppm; placing the base material ingot into a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, performing evaporation coating by taking the easily oxidized Ni metal particles as an evaporation material, wherein the coating current is 50A, and the evaporation coating time is controlled to be 5min to obtain an easily oxidized metal protection coating substrate blank with the thickness of 0.5 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1100 ℃, wherein the deformation of single-pass rolling is 12%, the reheating is carried out between passes, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 3%, and the total rolling deformation is 30%; the rolled base material blank is rejoined at the temperature of 300 DEG CCarrying out crystal treatment, wherein the recrystallization time is 3 hours, taking out and air-cooling to obtain a finished product of a coated substrate; turning or milling the substrate to remove 0.5mm of surface layer, and the density is 8.67g/cm 3 99.5 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 25ppm, the grain size of the target material is uniform, and the average grain size of the target material is 10.2 mu m.
Example 2
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 7 wt%, Ni: 93 wt% and 0.03 wt% of oxygen scavenger Mg 2 Ni and 0.03% of Ni 2 And Al. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding Mg according to the weight ratio of 0.03 percent after the raw materials are completely melted 2 Ni and 00.03 wt% Ni 2 Continuously keeping the Al in a molten state for 8min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out after the ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol, drying, and determining the oxygen content of the ingot to be 15 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, performing evaporation coating by taking the easily oxidized Ni metal particles as an evaporation material, controlling the evaporation coating current to be 150A and the evaporation coating time to be 8min, and obtaining an easily oxidized metal protection coating substrate blank with the film thickness of 3.5 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1200 ℃, wherein the deformation of single-pass rolling is 20%, the reheating is carried out between passes, the heating time is 7min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 6%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 500 ℃, wherein the recrystallization time is 1.5h, taking out and air-cooling to obtain a finished coated substrate; turning or milling the substrate to remove 0.35mm of surface layer, with density of 8.60g/cm 3 99.6 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 18ppm, the grain size of the target material is uniform, and the average grain size of the target material is 25.8 mu m.
Example 3
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 8 wt%, Ni: 92 wt% and 0.08% oxygen scavenger in total weight ratio. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding Ni according to the weight ratio of 0.04 percent after the raw materials are completely melted 3 Ti and Ni in an amount of 0.04 wt% 5 Al 3 After continuously keeping the molten state for 10min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out the alloy melt after the ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol and drying, and determining that the oxygen content of the ingot is 8 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, carrying out evaporation coating by taking the easily oxidized Ni metal particles as an evaporation material, wherein the coating current is 200A, and the evaporation coating time is controlled to be 10min to obtain an easily oxidized metal protection coating substrate blank with the thickness of 5 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at 1300 ℃, wherein the deformation of single-pass rolling is 30%, the remelting heating is carried out between passes, the heating time is 5min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, wherein the single-pass rolling deformation is 6%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 600 ℃, taking out the substrate blank and air-cooling the substrate blank to obtain a finished coated substrate; turning or milling the substrate to remove 0.15mm of surface layer, and the density is 8.55g/cm 3 99.5 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 12ppm, the grain size of the target material is uniform, and the average grain size of the high-density NiV alloy sputtering target material is 27.3 mu m.
Example 4
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 6 wt%, Ni: 94 wt% of oxygen scavenger Mg with the additional total weight ratio of 0.04% 2 Ni、MgNi 2 . Proportioning Ni and V metals, putting the mixture into a medium-frequency vacuum induction smelting furnace, and adding 0.03 wt% of deoxidant Mg into the furnace after the raw materials are completely melted 2 Ni and 0.01% MgNi 2 Continue to maintainAfter the alloy is molten for 8min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out the alloy melt after the ingot is completely cooled, carrying out ultrasonic cleaning and drying by adopting absolute ethyl alcohol, and determining that the oxygen content of the ingot is 18 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, carrying out evaporation coating by taking easily-oxidized Ti metal particles as an evaporation material, controlling the evaporation coating current to be 100A and the evaporation coating time to be 6min, and obtaining an easily-oxidized metal protection coating substrate blank with the thickness of 2 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1150 ℃, wherein the deformation of single-pass rolling is 15%, the reheating is carried out between passes, the heating time is 6min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 5%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 400 ℃, wherein the recrystallization time is 2.5h, taking out and air-cooling to obtain a finished coated substrate; the surface layer with the thickness of 0.4mm is removed by turning or milling the base material, and the density is 8.63g/cm 3 99.6 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 21ppm, the grain size of the target material is uniform, and the average grain size of the target material is 15.3 mu m.
Example 5
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 6.5 wt%, Ni: 93.5 wt% and oxygen scavenger MgNi of which the total weight ratio is 0.08% additionally 2 、Ni 3 Ti、NiAl 3 And NiAl. Proportioning Ni and V metals, putting the mixture into a medium-frequency vacuum induction smelting furnace, and adding MgNi according to 0.01 wt% after the raw materials are completely melted 2 0.02% by weight of Ni 3 Ti, 0.03% by weight of NiAl 3 0.02% by weight of NiAl ， Continuously maintaining the molten state for 8min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out after the ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol, drying, and determining the oxygen content of the ingot to be 12 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, in order toCarrying out evaporation coating by taking the Al oxide metal particles as an evaporation material, controlling the evaporation coating current to be 80A and the evaporation coating time to be 7min, and obtaining an easily oxidized metal protection coating substrate blank with the thickness of 4 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at 1300 ℃, wherein the deformation of single-pass rolling is 15%, the remelting heating is carried out between passes, the heating time is 6min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 5%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 600 ℃, wherein the recrystallization time is 3h, taking out and air-cooling to obtain a finished coated substrate; turning or milling the substrate to remove 0.25mm of surface layer, and the density is 8.62g/cm 3 99.7 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 15ppm, the grain size of the target material is uniform, and the average grain size of the target material is 29.5 mu m.
Example 6
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5.5 wt%, Ni: 94.5 wt% of oxygen scavenger Ni, and 0.04% of the total weight of the oxygen scavenger 3 Ti + NiAl. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding a deoxidant Ni according to the weight ratio of 0.02 percent after the raw materials are completely melted 3 Continuously keeping the Ti and 0.02 percent NiAl in a molten state for 4min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out the alloy melt after the ingot is completely cooled, ultrasonically cleaning and drying the alloy melt by adopting absolute ethyl alcohol, and measuring the oxygen content of the ingot to be 13 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, carrying out evaporation coating by taking easily-oxidized Ti metal particles as an evaporation material, wherein the coating current is 50A, and the evaporation coating time is controlled to be 4.5min to obtain an easily-oxidized metal protection coating substrate blank with the film thickness of 0.35 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1200 ℃, wherein the deformation of single-pass rolling is 15%, the reheating is carried out between passes, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the deformation of single-pass rolling is 5 percent, and the total rolling is carried outThe deformation amount is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 300 ℃, wherein the recrystallization time is 2.5h, taking out and air-cooling to obtain a finished coated substrate; turning or milling the substrate to remove 0.37mm of surface layer, and the density is 8.65g/cm 3 99.6 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 17ppm, the grain size of the target material is uniform, and the average grain size of the target material is 28.3 mu m.
Example 7
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 6 wt%, Ni: 94 wt% of oxygen scavenger NiAl + NiTi, and 0.06% of external total weight ratio 2 . Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding a deoxidant NiAl and 0.025 percent NiTi according to the weight ratio of 0.035 percent after the raw materials are completely melted 2 After continuously keeping the molten state for 3.5min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out after the ingot is completely cooled, carrying out ultrasonic cleaning and drying by adopting absolute ethyl alcohol, and determining that the oxygen content of the ingot is 17 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, carrying out evaporation coating by taking easily-oxidized Al metal particles as an evaporation material, controlling the evaporation coating current to be 50A and the evaporation coating time to be 5min, and obtaining an easily-oxidized metal protection coating substrate blank with the film thickness of 1.25 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1200 ℃, wherein the deformation of single-pass rolling is 20%, the reheating is carried out between passes, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 5%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 300 ℃, wherein the recrystallization time is 2h, taking out and air-cooling to obtain a finished coated substrate; turning or milling the substrate to remove 0.34mm of surface layer, and the density is 8.64g/cm 3 99.7 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 24ppm, the grain size of the target material is uniform, and the average grain size of the target material is 23.5 mu m.
Example 8
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 7 wt%, Ni: 93 wt% and oxygen scavenger Ni with the additional total weight ratio of 0.08% 5 Al 3 . Proportioning Ni and V metals, putting the mixture into a medium-frequency vacuum induction smelting furnace, and adding deoxidant Ni according to the weight ratio of 0.08 percent after the raw materials are completely melted 5 Al 3 After continuously keeping the molten state for 4min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out the alloy melt after the ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol and drying, and determining the oxygen content of the ingot to be 10 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, carrying out evaporation coating by taking the easily oxidized Ni metal particles as an evaporation material, controlling the evaporation coating current to be 50A and the evaporation coating time to be 8min, and obtaining an easily oxidized metal protection coating substrate blank with the thickness of 0.85 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1200 ℃, wherein the deformation of single-pass rolling is 20%, the reheating is carried out between passes, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 6%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled substrate blank at the temperature of 300 ℃, wherein the recrystallization time is 2.5h, taking out and air-cooling to obtain a finished coated substrate; turning or milling the substrate to remove 0.30mm of surface layer, and the density is 8.68g/cm 3 99.7 percent of theoretical density is achieved, no macroscopic defect exists, the oxygen content is 13ppm, the grain size of the target material is uniform, and the average grain size of the target material is 18.0 mu m.
Comparative example 1
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5.5 wt%, Ni: 94.5 wt%. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, continuously keeping the molten state for 3min after the raw materials are completely molten, pouring the alloy melt into a mold, taking out after the cast ingot is completely cooled, performing ultrasonic cleaning by adopting absolute ethyl alcohol and drying, and determining the oxygen content of the cast ingot to be 215 ppm; carrying out hot rolling and longitudinal rolling on the cast ingot at the temperature of 1100 ℃, wherein the deformation of single-pass rolling is 12%, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 3%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled blank at the temperature of 300 ℃, taking out the blank and air-cooling the blank to obtain a plate blank, wherein the recrystallization time is 3 h; when the surface of the plate blank is turned or milled to remove 0.5mm, the surface still has holes visible to naked eyes, the oxygen content is 950ppm, and the surface layer with the thickness of 2.5mm is removed to realize that the surface has no visible defects to naked eyes, the oxygen content is 650pm, and the average grain size is 46.5 mu m.
Comparative example 2
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5 wt%, Ni: 95 wt% of oxygen scavenger Mg with the additional total weight ratio of 0.01% 2 And (3) Ni. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, and adding a deoxidant Mg according to the weight ratio of 0.01 percent after the raw materials are completely melted 2 Continuously keeping the Ni in a molten state for 3min, erecting a funnel on a casting mold, pouring the alloy melt into the mold, taking out the alloy melt after the ingot is completely cooled, performing ultrasonic cleaning by using absolute ethyl alcohol, drying, and determining that the oxygen content of the ingot is 27 ppm; carrying out hot rolling and longitudinal rolling on the cast ingot at the temperature of 1100 ℃, wherein the deformation of single-pass rolling is 12%, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 3%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled base material blank at the temperature of 300 ℃, taking out the blank and air-cooling the blank to obtain a blank, wherein the recrystallization time is 3 h; when the surface of the plate blank is turned or milled to remove 0.5mm, holes visible to naked eyes still exist on the surface, the oxygen content is measured to be 720ppm, the surface layer with the thickness of 2.4mm is removed to realize that the surface has no visible defects to naked eyes, the oxygen content of the obtained target material is 450pm, and the average grain size of the target material is 34.7 mu m.
Comparative example 3
The base material of the sputtering target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 5 wt%, Ni: 95 wt%. Proportioning according to the proportion of Ni and V metals, putting the mixture into a medium-frequency vacuum induction melting furnace, continuously keeping the mixture in a molten state for 3min after the raw materials are completely molten, pouring an alloy melt into a mold, taking out after an ingot is completely cooled, performing ultrasonic cleaning by using absolute ethyl alcohol and drying, and determining the oxygen content of the ingot to be 210 ppm; placing the substrate ingot in a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, performing evaporation coating by taking the easily oxidized Ni metal particles as an evaporation material, wherein the coating current is 50A, and the evaporation coating time is controlled to be 5min to obtain an easily oxidized metal protection coating substrate blank with the thickness of 0.5 mu m; carrying out hot rolling and longitudinal rolling on the coated substrate at the temperature of 1100 ℃, wherein the deformation of single-pass rolling is 12%, the reheating is carried out between passes, the heating time is 10min, and the total rolling deformation is 60%; after the blank is cooled, cold rolling and transverse rolling are carried out, the single-pass rolling deformation is 3%, and the total rolling deformation is 30%; carrying out recrystallization treatment on the rolled base material blank at the temperature of 300 ℃, taking out the base material blank and air-cooling the base material blank to obtain a target material blank, wherein the recrystallization time is 3 hours; when the surface of the plate blank is turned or milled to remove 0.5mm, the surface still has holes visible to naked eyes, the oxygen content is 480ppm, the surface layer with the thickness of 1.6mm is removed to realize that the surface has no visible defects to naked eyes, the oxygen content of the obtained target material is 240pm, and the average grain size is 33.6 mu m.
The magnetron sputtering technology is adopted to carry out coating experiments on the target material, and the film resistance and the oxygen content are measured, and the main results are shown in table 1.
The performance parameters of the example and comparative example targets were compared and the results are shown in table 1.
TABLE 1 evaluation of the properties of the various examples and comparative examples (data)
Note: the sputtering condition is direct current magnetron sputtering, the sputtering power is 500W, the Ar gas pressure is 1.6Pa, the deposition temperature is room temperature, and the substrate is a monocrystalline silicon wafer.
The core technical measure for realizing the purpose of the invention is based on the principle of oxygen control and preferential protection, namely, the oxygen content is controlled and the easy-to-oxidize film is isolated and protected, and the oxygen content and the easy-to-oxidize film are in short supply and complement each other, so that the inner-layer base material is cooperatively inhibited from generating brittle cured objects, and the high-density visible defect-free effect is formed. From the process and results of the examples and comparative examples, the synergy of the two technical measures is the technical key of the invention. The compositions of example 1 and comparative example 1 are the same, except that comparative example 1 neither previously added oxygen scavenger nor plated "easy oxide film" barrier protection, with the result that the target oxygen content is as high as 650 ppm; compared with the prior art, the oxygen scavenger is added firstly, and isolation protection of 'easy oxidation film' is not plated, although the oxygen content of the ingot is not high, the oxygen content of the target material is still up to 455 ppm; comparative example 3 does not add an oxygen scavenger, but plates the isolation protection of the 'easy oxidation film', the oxygen content of the ingot reaches 240ppm, although the oxygen content of the target material is not greatly increased compared with the oxygen content of the ingot, the oxygen content is more than 8 times higher than that of examples 1-8, which is less than 30 ppm. The surface layer stock removal of 3 comparative examples was also several times higher than that of examples 1 to 8. Comprehensive comparison shows that the double technical measures of oxygen content control and easy-oxidation film isolation protection adopted by the technical scheme of the invention achieve excellent technical effects and achieve the technical purposes pursued by the invention: the target has no visible surface defects, high density and low surface layer cutting amount.
Claims (8)
1. A preparation method of a high-density NiV alloy sputtering target material is realized by the processes of base material ingot casting and cleaning treatment, base material film coating, blank material rolling, recrystallization treatment and machining treatment, and is characterized by comprising the following specific process steps:
(1) casting ingots on a base material and cleaning: using Ni and V with the purity of more than or equal to 99.99 wt% as raw materials, and mixing the raw materials according to the ratio of V: 5-8 wt%, Ni: proportioning 92-95 wt%, putting the mixture into a medium-frequency vacuum induction melting furnace, adding an oxygen scavenger according to the weight ratio of 0.01-0.08% after the raw materials are completely melted, continuously keeping the molten state for 3-10 min, erecting a funnel on a casting mold, pouring an alloy melt into the mold, taking out after the cast ingot is completely cooled, and carrying out ultrasonic cleaning and drying by adopting absolute ethyl alcohol to obtain the cast ingot;
(2) coating a film on a substrate: placing the base material ingot into a resistance evaporation coating machine, and vacuumizing to less than or equal to 1x10 -3 Pa, taking easily-oxidizable metal particles as an evaporation material to carry out evaporation coating, controlling the evaporation coating current to be 50-200A and the evaporation coating time to be 5-15 min, and obtaining an easily-oxidizable metal protection coating substrate blank with the required film thickness;
(3) blank rolling: firstly, carrying out hot rolling and longitudinal rolling on a coated substrate at the temperature of 1100-1300 ℃, wherein the deformation of single-pass rolling is 12-30%, the reheating is carried out between passes, the heating time is 5-10 min, and the total rolling deformation is 60%; after cooling the blank, performing cold rolling and transverse rolling, wherein the single-pass rolling deformation is 3-6%, and the total rolling deformation is 30%;
(4) and (3) recrystallization treatment: carrying out recrystallization treatment on the rolled base material blank at the temperature of 300-600 ℃, wherein the recrystallization time is 1-3 h, taking out and air-cooling to obtain a target material plate blank;
(5) and (3) machining treatment: and turning or milling the target material plate blank to obtain the high-density NiV alloy sputtering target material.
2. The method for preparing the high-density NiV alloy sputtering target material according to claim 1, wherein the oxygen scavenger in the step (1) is Mg 2 Ni、MgNi 2 、NiTi 2 、NiTi、Ni 3 Ti、NiAl 3 、Ni 2 Al、NiAl、Ni 5 Al 3 、Ni 3 Al or a mixture of two or more thereof.
3. The method for preparing the high-density NiV alloy sputtering target material according to claim 1, wherein the easily oxidizable metal in the step (1) is one or more of Ni, Al and Ti with the purity of more than or equal to 99.99 wt%.
4. The method for preparing the high-density NiV alloy sputtering target material according to claim 1, wherein the single-pass rolling deformation of the hot rolling in the step (3) is 15-25%, and the time for reheating between passes is 6-8 min.
5. The method for preparing the high-density NiV alloy sputtering target material according to claim 1, wherein the single-pass rolling deformation of the cold rolling in the step (3) in the transverse rolling process is 4-5%.
6. The preparation method of the high-density NiV alloy sputtering target material according to claim 1, wherein the substrate blank in the step (4) is subjected to recrystallization treatment at a temperature of 400-500 ℃, the recrystallization time is 1.5-2.5 h, and the substrate blank is taken out and air-cooled to obtain a target plate blank.
7. The method for preparing the high-density NiV alloy sputtering target material according to claim 1, wherein the surface of the base material is provided with an easily-oxidized metal protective coating film, and the thickness of the coating film is less than or equal to 5 μm; the density of the sputtering target material is more than or equal to 99.5%, the sputtering target material has no visible defects, the purity of the sputtering target material is more than or equal to 99.99 wt%, the oxygen content of the sputtering target material is less than or equal to 30ppm, the grain size of the sputtering target material is uniform, and the average grain size of the sputtering target material is 10-30 mu m; the removing depth of the surface layer of the sputtering target material after machining treatment is less than or equal to 0.5 mm.
8. The preparation method of the high-density NiV alloy sputtering target material according to claim 1, wherein the base material of the target material consists of Ni and V with the purity of more than or equal to 99.99 wt%, wherein V: 6.5-7.5 wt%, Ni: 92.5-93.5 wt%; and an oxygen scavenger with the total weight ratio of 0.03-0.06 percent is added.
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