WO2023186188A1

WO2023186188A1 - Molybdenum alloy target material, and preparation method and application thereof

Info

Publication number: WO2023186188A1
Application number: PCT/CN2023/095633
Authority: WO
Inventors: 王广达; 熊宁; 弓艳飞; 牛曼; 季鹏飞; 王凤权; 常洋
Original assignee: 安泰科技股份有限公司; 安泰天龙钨钼科技有限公司; 安泰天龙(北京)钨钼科技有限公司
Priority date: 2022-05-23
Filing date: 2023-05-22
Publication date: 2023-10-05
Also published as: KR20240087686A; CN114934260B; JP2024530077A; CN114934260A

Abstract

The invention relates to the technical field of rare metal and powder metallurgy, in particular to a molybdenum alloy target material, and a preparation method and application thereof. The target material comprises the following components in percentage by mass: 10-30% of Ni, 5-25% of Ti, 0.5-5% of Re, and the remaining being Mo and inevitable impurities, the mass percentage of Mo ≥ 50%. In the present invention, by adding a specific amount of rhenium to the molybdenum alloy, the grain size can be refined, so that the grains are more uniform, the brittleness of the material is reduced, the plasticity and toughness are improved, the deformation processing capacity is improved, the obtained blank material can be subjected to a rolling process to obtain target materials of different shapes or large sizes, and when same is used as a target material to prepare a film layer, the thickness of the film layer is more uniform and the sputtering speed is higher.

Description

A kind of molybdenum alloy target material and its preparation method and application

Technical field

The invention relates to the technical fields of rare metals and powder metallurgy, and in particular to a molybdenum alloy target material and its preparation method and application.

Background technique

The technological upgrading of flat display devices such as liquid crystal displays and display panels requires lower resistance of wiring films. At the same time, the large screen, high definition, and high-speed response of flat panel displays, as well as the enlargement of flexible panels, also require lower film resistance levels.

Thin film transistors (TFTs) serve as drive elements for display panels and use Al or Cu as the main wiring material. However, if Al or Cu is in direct contact with Si, thermal diffusion will be formed due to thermal processing during the preparation process, deteriorating the performance of the thin film transistor. Mo and molybdenum alloys such as Mo-Nb and Mo-Ti have good corrosion resistance, heat resistance, and good adhesion to the substrate. However, during the preparation process, after the laminated wiring film is formed on the substrate, it may be left in the atmosphere for a long time. When installing signal cables on display panels, they sometimes need to be heated in the atmosphere. In addition, semiconductor films using oxides need to be heated in an aerobic environment to improve performance and stabilize them. Therefore, there is a strong need to enhance oxidation resistance. strong. In addition, the resin film used in portable, lightweight, and flexible display panels is more moisture-permeable than glass substrates, so the laminated wiring film needs to have higher moisture resistance. However, the moisture resistance and oxidation resistance of materials such as pure Mo and Mo-Ti are not sufficient, and oxidation may occur, causing a significant increase in the resistance value of Al or Cu.

The patent "CN2012102930608" discloses a molybdenum alloy target for laminated wiring films. In order to improve the moisture resistance and oxidation resistance of pure molybdenum coatings, a certain amount of Ni and Ti are added to the molybdenum, which helps to stabilize electronic components. manufacturing and improving reliability.

The patent "CN2014100909230" discloses a molybdenum alloy target for electronic components. The oxidation resistance is improved by adding Ni, and the moisture resistance can be improved by adding W element. The patent "CN2014100568166" discloses a molybdenum alloy target for metal film sputtering. The material is made of more than half of the molybdenum element as the matrix, and adding Ni, Ta, Cr, Zr and other elements can improve moisture resistance, oxidation resistance and maintain low resistance value.

The patent "CN2017114460697" discloses a molybdenum alloy target composition containing Ni, Nb, Ti and other elements, which can better improve the moisture resistance and oxidation resistance of pure molybdenum and maintain a low film resistance.

The above-mentioned patent jointly improves the moisture resistance and oxidation resistance of the molybdenum target sputtering film by adding a certain amount of Ni, Ti or Nb and other elements to the molybdenum matrix, and maintains a low resistance value. However, the preparation of targets is mainly through hot isostatic pressing (HIP). As the length of the target increases, the HIP method is seriously limited by the size of the HIP equipment, and it is impossible to mass-produce high-performance molybdenum alloy targets. Moreover, due to the current The alloy is highly brittle and prone to cracking under large deformations, so it is impossible to prepare a series of target products of different lengths through deformation methods such as rolling and forging.

Contents of the invention

The purpose of the present invention is to overcome the shortcomings existing in the prior art and provide a molybdenum alloy target material and its preparation method and application. The molybdenum alloy target material provided by the invention has a low plastic-brittle transition temperature, strong deformation ability, and more uniform grains. When used as a target material to prepare a film layer, the film layer thickness is more uniform and the sputtering speed is faster.

In order to achieve the above objects, the technical solutions adopted by the present invention are:

In a first aspect, the present invention provides a molybdenum alloy target material. In terms of mass percentage, the target material includes 10% to 30% (for example, 15%, 20%, 25%) of Ni, 5% to 25% (for example, 10%, 15%, 20%) Ti and 0.5%~5% (such as 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%) Re, the balance is Mo and unavoidable impurities, and the mass percentage of Mo is ≥50% (such as 55%, 60%, 65%, 70%, 75%, 80%, 85%).

In the above-mentioned molybdenum alloy target material, as a preferred embodiment, in terms of mass percentage, the target material also includes 0.01%-15% (for example, 0.05%, 0.1%, 0.5%, 1%, 3%, 5% , 8%, 11%, 13%) of M, the M is at least one of Cr, Zr, Ta, Nb, and the M is used to replace part of Ti.

In the above molybdenum alloy target, as a preferred embodiment, the target includes 15% to 25% (for example, 18%, 21%, 23%) Ni in mass percentage, 10% to 20% ( For example, 12%, 14%, 16%, 18%) Ti, 1%~5% Re (such as 2%, 3%, 4%), 0%-5% M (such as 1%, 2%, 3%, 4%), the balance is Mo and inevitable impurities, and the mass percentage of Mo is ≥50% (such as 55%, 60%, 65%, 70%).

Ni can improve the oxidation resistance of the film layer formed by the target material of the present invention, and Ti can improve the moisture resistance of the film layer. Adding appropriate amounts of both can not only ensure the oxidation resistance and moisture resistance of the film layer, but also ensure the low performance of the wiring film. Resistance does not affect the etching speed of the etchant.

A small amount of Re element is added to the molybdenum alloy target material of the present invention. The addition of a specific proportion of rhenium element works together with the specific proportion of other elements in the molybdenum alloy to exert the "rhenium effect" in the molybdenum alloy and improve the molybdenum alloy target. Room temperature plasticity of the alloy, lowering the plastic-to-brittle transition temperature, refining the grains, etc. By adding the Re element to the molybdenum alloy target, the deformation performance of the target can be improved, and cracks will not occur during large deformation processing. Since the target structure has fine grains, the target obtained by the optimal molybdenum alloy composition ratio The material has extremely small grain level difference and uniform grains. The film thickness prepared by the target material of the invention is more uniform and the sputtering speed is faster. When the amount of Re element exceeds 5%, on the one hand, the cost increases, and on the other hand, the large addition of Re element will form an alloy phase with other components, causing uneven distribution of tissue components in the target, affecting the subsequent coating effect. When the amount of Re element is less than 0.5%, it cannot effectively refine the grains and enhance the plasticity of the target.

The M element in the present invention has moisture resistance and can be used to partially replace Ti, which also has moisture resistance. However, from the perspective of the interaction of various components in the target, it is preferred that the M element can only partially replace Ti. On the other hand, the addition of M element can not only improve the moisture resistance of the molybdenum alloy target, but also further improve the molybdenum alloy target. of antioxidant properties.

In a second aspect, the present invention provides a method for preparing the above-mentioned molybdenum alloy target, which includes the following steps:

(1) Preparation of raw materials: Weigh the raw materials according to the mass ratio of the above target components and mix them to obtain mixed powder;

(2) Hot isostatic pressing: Put the mixed powder in step (1) into a bag and perform hot isostatic pressing to obtain a hot-pressed green body with a bag;

(3) Hot rolling: hot-rolling the jacketed hot-pressed green body to obtain a rolled piece;

(4) Annealing: anneal the rolled piece to obtain the molybdenum alloy target.

In the preparation method of the above molybdenum alloy target, as a preferred embodiment, the raw material of the component Mo in the target is molybdenum powder with a purity of ≥3N5, and its Fisher particle size range is preferably 2.5 μm ~ 4 μm (for example, 2.8 μm , 3 μm, 3.5 μm, 3.8 μm); preferably, the raw material of the Ni component in the target material is nickel powder with a purity of ≥3N, and its Fisher particle size range is preferably 2 μm ~ 3 μm (for example, 2.2 μm, 2.4 μm, 2.6 μm , 2.8 μm); preferably, the raw material of the Ti component in the target material is titanium powder with a purity of ≥3N, and its Fibonacci particle size range is preferably 2 μm ~ 4 μm (for example, 2.3 μm, 2.6 μm, 3 μm, 3.3 μm, 3.6 μm ); Preferably, the raw material of the target component Re is rhenium powder or ammonium rhenate, the purity of the rhenium powder is ≥ 4N, and the Fisher particle size is preferably 2 μm ~ 4 μm (for example, 2.3 μm, 2.6 μm, 3 μm, 3.3 μm , 3.6 μm), the purity of the ammonium rhenate is ≥ 4N, and the particle size is preferably 150 mesh to 350 mesh (such as 180 mesh, 220 mesh, 260 mesh, 300 mesh, 325 mesh).

Compared with using alloy powders such as molybdenum-titanium alloy powder and molybdenum-nickel alloy powder as raw materials, in the preferred embodiment of the present invention, molybdenum powder, nickel powder and titanium powder whose purity meets relevant standards are used as raw materials for preparing the target material of the present invention. , which can make the distribution of components in the prepared target material more uniform and the coating effect better.

In the above preparation method of the molybdenum alloy target, as a preferred embodiment, when the raw material of the target component Re is ammonium rhenate, after weighing the raw materials in step (1), first take a part of the raw molybdenum powder and rhenium The molybdenum-rhenium alloy powder is obtained by mixing ammonium acid acid and then undergoing reduction treatment, and then the molybdenum-rhenium alloy powder is mixed with the remaining molybdenum powder and other raw materials to obtain a mixed powder.

In the above preparation method of molybdenum alloy target, as a preferred embodiment, the reduction treatment is performed in a hydrogen atmosphere, and the temperature of the reduction treatment is 500°C~900°C (for example, 550°C, 600°C, 650°C , 700℃, 750℃, 800℃, 850℃), the time of the reduction treatment is 2h~8h (such as 3h, 4h, 5h, 6h, 7h); preferably, in the molybdenum-rhenium alloy powder, molybdenum-rhenium The mass ratio is 95:5~50:50 (such as 18:1, 15:1, 12:1, 9:1, 6:1, 3:1).

The gas flow rate in the above hydrogen reduction treatment should be determined according to the size of the reduction furnace, and the pressure should be slightly positive pressure. Ammonium rhenate is selected as the rhenium source and is first prepared with part of the molybdenum into molybdenum-rhenium powder in order to make the rhenium more evenly distributed in the molybdenum; rhenium powder can also be used directly or the ammonium rhenate is reduced to rhenium powder alone as a source for direct mixing. , but the powder uniformity is not as good as the ammonium rhenate-doped molybdenum powder reduction process.

In the above preparation method of molybdenum alloy targets, as a preferred embodiment, in step (1), the mixing method is ball milling, and the ball-to-material ratio of the ball milling is 1: (0.5-2) (for example, 1 :0.8, 1:1.2, 1:1.4, 1:1.6, 1:1.8), preferably 1:1; preferably, the ball milling time is 10h~16h (such as 11h, 12h, 13h, 14h, 15h); Preferably, the ball milling is performed in an inert gas; preferably, the inert gas is argon; preferably, the ball milling speed is 50~300r/min (for example, 100r/min, 150r/min, 200r/min ,250r/min).

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (2), the heat preservation temperature of the hot isostatic pressing is 900°C~980°C (for example, 910°C, 920°C, 930°C, 940°C, 950°C, 960°C, 970°C); preferably, the pressure of the hot isostatic pressing is 100MPa~170MPa (such as 110MPa, 120MPa, 130MPa, 140MPa, 150MPa, 160MPa); preferably, the heat, etc. The holding time of static pressure is 2h~5h (such as 2h, 3h, 4h).

The density of the hot-pressed green body obtained after the hot isostatic pressing process of the present invention can reach 100%.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (2), the mixed powder is put into the bag and then vacuumed and sealed; preferably, the vacuum is pumped until the vacuum degree is 10 ^{- 1} Pa.

In the above method for preparing a molybdenum alloy target, as a preferred embodiment, in step (2), after preparing the hot-pressed green body, it also includes partially trimming the envelope of the hot-pressed green body.

In the present invention, after the hot-pressed green body is obtained through the hot isostatic pressing process, the jacket is partially trimmed to ensure that the large surface of the hot-pressed green body is flat and free of bulges, which is beneficial to subsequent rolling.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (2), the thickness of the hot-pressed green body is 40mm~60mm (for example, 42.5mm, 45mm, 47.5mm, 50mm, 52.5mm, 55mm, 57.5mm).

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (3), the opening temperature of the hot rolling process is 1000°C~1350°C (for example, 1150°C, 1200°C, 1250°C, 1300℃), the final rolling temperature is 900-1100℃ (such as 950℃, 1000℃, 1050℃).

The preferred solution of the present invention is to appropriately lower the rolling temperature of each pass during the rolling process, that is, to control the starting rolling temperature of each pass to be lower than the starting rolling temperature of the adjacent previous pass by more than 0°C and less than or equal to 50°C, which can improve the material quality. Strength and plasticity. If the starting rolling temperature of each pass drops too much based on the starting rolling temperature of the adjacent pass, it will cause the grain resistance to increase, increase the risk of billet cracking, and reduce the yield of hot rolling.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (3), in the hot rolling process, the rolling deformation amount of a single pass is 15%~25% (for example, 17.5%, 20 %, 22.5%), the total deformation amount of the hot rolling process is 40%~80% (such as 45%, 50%, 55%, 60%, 65%, 70%, 75%); preferably, the In the hot rolling process, heating and insulation are performed before each pass of rolling. The insulation temperature is 1000℃~1300℃ (such as 1050℃, 1100℃, 1150℃, 1200℃, 1250℃), and the insulation time is 30 minutes to 120 minutes. (For example, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min); Preferably, the heating and holding temperature before each rolling pass is reduced by more than 0°C and less than or equal to the heating and holding temperature before rolling in the previous pass. 50°C (such as 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C); preferably, the hot rolling is performed in air or argon atmosphere.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (4), before the annealing process of the rolled piece, the steps of removing the cladding and roughing are further included.

The invention can machine the rolled pieces into different sizes before the annealing process, thereby obtaining target materials of different shapes or large sizes, and can meet the market's different specifications of molybdenum alloy target materials.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, in step (4), the annealing treatment is performed in an argon atmosphere; preferably, the annealing temperature is 900°C~1200°C ( For example, 950℃, 1000℃, 1050℃, 1100℃, 1150℃), and the holding time is 60 minutes to 120 minutes (such as 70min, 80min, 90min, 100min, 110min).

In the present invention, controlling the annealing temperature within this range can eliminate the anisotropy of the target material after extrusion and obtain a molybdenum alloy target material with uniform structure and fine grains. If the annealing temperature is lower than 900°C, the target structure is not completely crystallized, and there is a state of grain deformation in some areas. The annealing temperature is higher than 1200°C, which will cause the grains to grow abnormally and mixed crystals to appear, resulting in uneven tissue distribution and affecting the target. The effect of material sputtering coating.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, the grain size of the molybdenum alloy target material prepared in step (4) is ≤100 μm; preferably 60 μm ~ 100 μm (such as 65 μm, 70 μm, 75 μm, 80μm, 85μm, 90μm, 95μm).

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, the grain size of the molybdenum alloy target material prepared in step (4) is 4~5 levels; preferably, the grain size of the molybdenum alloy target material prepared in step (4) is In the same molybdenum alloy target material, the grain size difference is less than or equal to 1, preferably 0.

In the above preparation method of molybdenum alloy target material, as a preferred embodiment, the molybdenum alloy target material is a plate-shaped target material. Preferably, the thickness of the rolled piece is 6mm~24mm (for example, 8mm, 10mm, 12.5mm mm, 15mm, 17.5mm, 20mm, 22mm).

In a third aspect, the present invention also provides the application of the above-mentioned molybdenum alloy target, which is attached to the main conductive layer of the laminated wiring film for electronic components by sputtering to form a metal covering layer; preferably, the The electronic components are displays, semiconductor devices or thin film solar cells.

Due to the adoption of the above technical solutions, the present invention has the following positive effects compared with the prior art:

(1) The addition of rhenium element to the target material of the present invention not only does not affect the heat resistance, oxidation resistance and moisture resistance of the target material after film formation, the present invention can also refine the grains after adding a specific amount of rhenium to the molybdenum alloy. size, reduce the brittleness of the material, increase the plastic toughness, and improve the deformation processing capability, so that the obtained blank can be subjected to the rolling process to obtain targets of different shapes or large sizes. The targets are usually prepared as plates. The price of rhenium is relatively expensive, and the present invention can achieve improvement by using only a small amount of rhenium.

(2) The annealing step of the present invention can further uniformly refine the grains. The molybdenum alloy target prepared by the present invention has a grain size of ≤100 μm and a grain size level of 4 to 5. The difference in grain size among the same molybdenum alloy target materials is Less than or equal to 1, the highest can reach 0.

Description of drawings

Figure 1 is a metallographic structure diagram of the molybdenum alloy target prepared by the method of Example 1 of the present invention.

Implementation

The present invention will be described in further detail below in conjunction with specific embodiments. The examples given are only for illustrating the present invention and are not intended to limit the scope of the present invention. The examples provided below can serve as a basis for further improvements or applications by those of ordinary skill in the art, and do not constitute specific limitations to the present invention in any way.

The test methods in the following examples are all conventional methods unless otherwise specified, and can be carried out according to the techniques or conditions described in literature in the field or according to the product instructions. The materials used in the following examples can be obtained from conventional commercial channels.

The present invention uses the "rhenium effect" exerted by the Re element in molybdenum to improve the room temperature plasticity of the molybdenum alloy, reduce the plastic-to-brittle transition temperature, and refine the grains. By adding Re element to the molybdenum alloy target, the deformation performance of the target is improved, that is, large-sized plate targets can be prepared through deformation methods such as rolling, and targets with uniform fine grains can be obtained through annealing.

Unless otherwise specified, the powder particle sizes mentioned in the following examples are Fisher particle size.

The standard for testing the grain size level in the examples of this application is "GB/T6394 Method for determination of average grain size of metals".

The yield rate referred to in the following examples is the number of qualified rolled pieces obtained after hot rolling treatment/the number of hot-pressed green bodies subjected to hot rolling*100%.

Embodiment 1 A method for preparing molybdenum alloy target material, including the following steps:

Step 1: Mix pure Mo powder with a purity of 3N5 and a particle size of 3.2 μm, Ni powder with a purity of 3N and a particle size of 3.0 μm, Ti powder with a purity of 3N and a particle size of 2.8 μm, and rhenium powder with a purity of 4N and a particle size of 3.2 μm, according to the target materials. Element mass ratio Mo: Ni: Ti: Re=61:20:18:1, configured with 140Kg raw materials;

Step 2: Put the powder obtained in Step 1 into a ball milling tank with a ball-to-material ratio of 1:1, pump the air to negative pressure, fill it with argon to one atmospheric pressure, and conduct ball milling. The ball milling time is 12 hours, and the rotation speed is 200 r/min. ;

Step 3: Put the mixed powder obtained in Step 2 into a bag made of stainless steel, pump air to 10 ^-1 Pa, keep pumping for 3 hours, and seal;

Step 4: HIP the package in Step 3 at a temperature of 950°C, a pressure of 120MPa, and a holding time of 3 hours to obtain a hot-pressed green body;

Step 5: Partially trim the cover of the hot-pressed green body in step 4 to ensure that the hot-pressed green body is flat on the large surface and has no bulges. The thickness of the green body is 56mm;

Step 6: Put the jacketed hot-pressed slab that has been partially trimmed in step 5 into a muffle furnace, and heat it to the opening temperature of 1300°C in an air atmosphere. The holding time is 90 minutes, and the deformation amount in a single pass is 15%. ~25%, before each pass of rolling, it is necessary to return to the furnace for heating and insulation. The heating and insulation temperature before each pass of rolling is lowered by 50°C based on the heating and insulation temperature before each pass of rolling. Each pass of rolling The preheating and holding time is 90 minutes, the rolling passes are 5 times, the final rolling temperature is 1050°C, and the obtained rolled billet size is 20mm×240mm×2900mm (thickness×width×length);

Step 7: Remove the cladding from the rolled billet obtained in Step 6, and machine it to obtain a billet with dimensions of 18mm×230mm×2750mm (thickness×width×length);

Step 8: anneal the green body in Step 7 under an Ar gas atmosphere at an annealing temperature of 1100°C and a holding time of 60 minutes to obtain a uniform fine-grained plate with a grain size of 70 μm to 100 μm. See Figure 1. The grain size level is level 4.

The plate-shaped target material obtained in this example has no cracks, and the yield is 100%.

Embodiment 2 A method for preparing a molybdenum alloy target material, including the following steps:

Step 1: Mix pure Mo powder with a purity of 3N5 and a particle size of 3.5 μm, Ni powder with a purity of 3N and a particle size of 2.6 μm, Ti powder with a purity of 3N and a particle size of 3.0 μm, and ammonium rhenate with a purity of 4N and a particle size of 3.5 μm, according to the target materials. The element mass ratio Mo:Ni:Ti:Re=61:20:18:1, configure 140Kg of raw materials, first prepare molybdenum-rhenium alloy powder, according to the element mass ratio of Mo:Re=7:3 in the molybdenum-rhenium alloy powder, first take the raw materials The middle part of Mo powder is mixed with all the ammonium rhenate in the raw material, and reduced at 600°C for 4 hours in a hydrogen atmosphere to obtain molybdenum-rhenium alloy powder. The reduced molybdenum-rhenium alloy powder is added to the remaining raw material powder;

Step 2: Put the powder obtained in Step 1 into a ball milling tank with a ball-to-material ratio of 1:2. Pump the air to negative pressure, fill it with argon gas to an atmospheric pressure, and conduct ball milling. The ball milling time is 10 hours and the rotation speed is 200 r/min. ;

Step 3: Put the mixed powder obtained in Step 2 into a bag made of stainless steel, pump air to 10 ^-1 Pa, keep pumping for 4 hours, and seal;

Step 4: HIP the package in Step 3 at a temperature of 930°C, a pressure of 150MPa, and a holding time of 3 hours to obtain a hot-pressed green body;

Step 5: Partially trim the cover of the hot-pressed green body in Step 4 to ensure that the large surface of the hot-pressed green body is flat and has no bulges, and the thickness of the green body is 50mm;

Step 6: Put the jacketed hot-pressed slab that has been partially trimmed in step 5 into a muffle furnace and heat it in an air atmosphere to the opening temperature of 1350°C. The holding time is 80 minutes and the deformation amount in a single pass is 15 %~25%, the heating and holding temperature before each rolling pass is lowered by 50°C based on the heating and holding temperature before the previous rolling. The heating and holding time before each rolling pass is 90 minutes, and the rolling passes are 4 times. The final rolling temperature is 1100°C, and the resulting rolled billet size is 24mm×240mm×2900mm (thickness×width×length);

Step 7: Remove the cladding from the rolled billet obtained in Step 6, and machine it to obtain a billet with dimensions of 22mm×230mm×2800mm (thickness×width×length);

Step 8: anneal the green body in Step 7 under an Ar gas atmosphere at an annealing temperature of 1050°C and a holding time of 90 minutes to obtain a uniform fine-grained plate with a grain size of 65 μm to 90 μm, and a grain size level of 4.

Embodiment 3 A method for preparing a molybdenum alloy target material, including the following steps:

Step 1: Mix pure Mo powder with a purity of 3N5 and a particle size of 3.2 μm, Ni powder with a purity of 3N and a particle size of 3.5 μm, Ti powder with a purity of 3N and a particle size of 3.5 μm, and ammonium rhenate with a purity of 4N and a particle size of 3.5 μm, according to the target material. The mass ratio of each element is Mo:Ni:Ti:Re=60:20:18:2. Configure 70Kg of raw materials. First prepare molybdenum-rhenium alloy powder. According to the element ratio of Mo:Re=1:1 in the molybdenum-rhenium alloy powder, first take the raw materials. The middle part of Mo powder is mixed with all the ammonium rhenate in the raw material, and reduced at 700°C for 3 hours in a hydrogen atmosphere to obtain molybdenum-rhenium alloy powder. The reduced molybdenum-rhenium alloy powder is added to the remaining raw material powder;

Step 2: Put the powder obtained in Step 1 into a ball milling tank with a ball-to-material ratio of 1:1, pump the air to negative pressure, fill it with argon to one atmospheric pressure, and perform ball milling. The ball milling time is 16 hours, and the rotation speed is 200 r/min. ;

Step 3: Put the mixed powder obtained in Step 2 into a bag made of stainless steel, pump air to 10 ^-1 Pa, keep pumping for 5 hours, and seal;

Step 4: HIP the package in Step 3 at a temperature of 920°C, a pressure of 170MPa, and a pressure holding time of 4 hours;

Step 5: Partially trim the cover of the hot-pressed plate body in step 4 to ensure that the hot-pressed plate body is flat on the large surface and has no bulges, and the thickness of the slab is 40mm;

Step 6: Put the jacketed hot-pressed plate body that has been partially trimmed in step 5 into a muffle furnace, and heat it in the air atmosphere to the opening temperature of 1300°C. The holding time is 70 minutes, and the deformation amount in a single pass is 15%~ 25%. The heating and holding temperature before each rolling pass is lowered by 50°C based on the heating and holding temperature before the previous rolling. The heating and holding time before each rolling pass is 90 minutes. There are 4 rolling passes and final rolling. The temperature is 1100°C, and the obtained rolled billet size is 18mm×240mm×1450mm (thickness×width×length);

Step 7: Remove the cladding from the rolled billet obtained in Step 6, and machine it to obtain a billet with dimensions of 16mm×230mm×1400mm (thickness×width×length);

Step 8: anneal the green body in Step 7 under an Ar gas atmosphere at an annealing temperature of 1150°C and a holding time of 45 minutes to obtain a uniform fine-grained plate with a grain size of 70 μm to 95 μm, and a grain size level of 4.

Embodiment 4 A method for preparing a molybdenum alloy target material, including the following steps:

Step 1: Mix pure Mo powder with a purity of 3N5 and a particle size of 3.8 μm, Ni powder with a purity of 3N and a particle size of 3.5 μm, Ti powder with a purity of 3N and a particle size of 3.2 μm, and rhenium powder with a purity of 4N and a particle size of 2.8 μm, according to the target materials. The element mass ratio is Mo:Ni:Ti:Re=58:20:18:4, and 140Kg of raw materials are configured;

Step 2: Put the powder obtained in step 1 into a ball milling tank with a ball-to-material ratio of 2:1, pump the air to negative pressure, fill it with argon to one atmospheric pressure, and conduct ball milling. The ball milling time is 14 hours and the rotation speed is 200 r/min. ;

Step 4: HIP the package in Step 3 at a temperature of 920°C, a pressure of 170MPa, and a holding time of 4 hours to obtain a hot pressed plate body;

Step 5: Partially trim the covering of the hot-pressed plate body in step 4 to ensure that the hot-pressed plate body is flat on the large surface and has no bulges. The thickness of the hot-pressed plate body is 54mm;

Step 6: Put the hot pressed plate body that has been partially trimmed in step 5 into a muffle furnace, and heat it to the opening temperature of 1350°C in an air atmosphere. The holding time is 60 minutes, and the deformation amount in a single pass is 15%~25%. , the heating and holding temperature before each rolling pass is lowered by 50°C based on the heating and holding temperature before the previous rolling. The heating and holding time before each rolling pass is 90 minutes. There are 5 rolling passes, and the final rolling temperature is 1100℃, the obtained rolled billet size is 24mm×240mm×2900mm (thickness×width×length);

Step 7: Remove the cladding from the rolled billet obtained in Step 6, and machine it to obtain a billet with dimensions of 22mm×230mm×2750mm (thickness×width×length);

Step 8: anneal the green body in Step 7 under an Ar gas atmosphere at an annealing temperature of 1100°C and a holding time of 60 minutes to obtain a uniform fine-grained plate with a grain size of 65 μm to 95 μm, and a grain size level of 4.

实施例5Example 5

Step 1: Pure Mo powder with a purity of 3N5, a particle size of 3.2 μm, Ni powder with a purity of 3.0 μm, Ti powder with a purity of 3N, a particle size of 2.8 μm, Rhenium powder with a purity of 4N, a particle size of 3.2 μm, and the raw material of Cr is chromium. Powder, according to the mass ratio of each element in the target material Mo:Ni:Ti:Re:Cr=61:20:16:1:2, configure 140Kg of raw materials;

Step 6: Put the jacketed hot-pressed slab that has been partially trimmed in step 5 into a muffle furnace, and heat it to the opening temperature of 1300°C in an air atmosphere. Heating and holding for 90 minutes, the deformation amount in a single pass is 15%. ~25%, the heating and holding temperature of each pass is lowered by 50°C based on the heating and holding temperature of the previous pass, the heating and holding time of each pass is 90 minutes, the rolling passes are 5 times, and the final rolling temperature is 1050°C. The obtained The rolled billet size is 24mm×240mm×2900mm (thickness×width×length);

Step 8: Perform annealing treatment on the green body in Step 7 under an Ar gas atmosphere at an annealing temperature of 1100°C and a holding time of 60 minutes to obtain a uniform fine-grained plate with a grain size of 60 μm-90 μm and a grain size level of 4 to 5. .

对比例1Comparative example 1

Step 1: Mix pure Mo powder with a purity of 3N5 and a particle size of 3.2 μm, Ni powder with a purity of 3N and a particle size of 3.0 μm, Ti powder with a purity of 3N and a particle size of 2.8 μm, and rhenium powder with a purity of 4N and a particle size of 3.2 μm, according to the target materials. Element mass ratio Mo: Ni: Ti: Re=56:20:18:6, configured with 140Kg raw materials;

Step 6: Put the jacketed hot-pressed slab that has been partially trimmed in step 5 into a muffle furnace and heat it to the opening temperature of 1300°C in an air atmosphere. Heating and holding for 90 minutes before each pass of rolling. The deformation amount of each pass is 15%~25%. The heating and holding temperature of each pass is lowered by 50°C based on the previous heating and holding temperature. The rolling passes are 5 times. The final rolling temperature is 1050°C. The resulting rolled billet size is 24mm× 240mm×2900mm (thickness×width×length);

Step 8: Perform annealing treatment on the green body in Step 7 under an Ar gas atmosphere. The annealing temperature is 1100°C and the holding time is 60 minutes. A uniform fine-grained plate with a grain size of 90 μm to 120 μm is obtained. The grain size in the same plate is level 3. , some grain sizes are larger than 100μm.

The plate-shaped target obtained in this comparative example developed cracks, and the yield was 75%.

The cost of the molybdenum alloy target prepared in Comparative Example 1 is increased, and the rhenium content is too high, which increases the difficulty of deformation, and cracks appear on the surface of the blank during the deformation process. At the same time, when the Re content is high, Re can form an alloy phase with other components, affecting the subsequent coating effect.

对比例2Comparative example 2

The same as Example 1, the only difference is that the annealing temperature of this comparative example is 1250°C.

The grain size of the plate-shaped target obtained in this comparative example is 70 μm ~ 110 μm, and some grain sizes are larger than 100 μm.

The plate-shaped target obtained in this comparative example has cracks, and the yield is 90%.

The annealing temperature in this comparative example is too high, causing some grains to grow abnormally. The resulting plate-shaped target has larger grain sizes, mixed crystals, and larger grains in some parts.

对比例3Comparative example 3

The same as Example 1, the only difference is that the deformation amount in the rolling process of this comparative example is 30%.

During the rolling process of this comparative example, edge cracks occurred in the first pass and cracked in the second pass, making it impossible to prepare a plate.

对比例4Comparative example 4

The same as Example 1, the only difference is that in the rolling process of this comparative example, the heating and holding temperature of each pass is lowered by 80°C based on the previous heating and holding temperature.

The grain size of the plate-shaped target obtained in this comparative example is 80 μm ~ 150 μm, with most grain sizes exceeding 100 μm, and the grain uniformity is poor.

The plate-shaped target obtained in this example has cracks, and the yield is 50%. In this comparative example, the heating and holding temperature of each pass during hot rolling dropped too much based on the previous heating and holding temperature, which resulted in an increase in grain resistance, increased the risk of billet cracking, and reduced the yield of hot rolling.

The present invention has been described in detail above. For those skilled in the art, the present invention can be implemented in a wider range under equivalent parameters, proportions and conditions without departing from the spirit and scope of the present invention and without performing unnecessary experiments. Although specific embodiments of the present invention have been shown, it should be understood that further modifications can be made to the invention. In short, based on the principles of the present invention, this application is intended to include any changes, uses, or improvements to the present invention, including changes that depart from the scope disclosed in this application and are made using conventional techniques known in the art. Some essential features may be applied within the scope of the appended claims below.

Claims

A molybdenum alloy target material, characterized in that, in terms of mass percentage, the target material includes 10% to 30% Ni, 5% to 25% Ti and 0.5% to 5% Re, with the balance being Mo and Unavoidable impurities, and the mass percentage of Mo is ≥50%;

The preparation method of the molybdenum alloy target material includes the following steps:

(1) Preparing raw materials: Weigh the raw materials according to the mass ratio of the target components and mix them to obtain mixed powder;

(2) Hot isostatic pressing: Put the mixed powder in step (1) into a bag and perform hot isostatic pressing to obtain a hot-pressed green body with a bag;

(3) Hot rolling: hot-rolling the jacketed hot-pressed green body to obtain a rolled piece;

(4) Annealing: anneal the rolled piece to obtain the molybdenum alloy target;

In step (3), in the hot rolling process, the rolling deformation amount of a single pass is 15~25%, and the total deformation amount of the hot rolling process is 40%~80%; in the hot rolling process, the deformation amount of each pass is 15~25%. Heating and heat preservation is carried out before rolling in a pass. The heat preservation temperature is 1000℃~1300℃ and the heat preservation time is 30 minutes~120 minutes. The heating and heat preservation temperature before each rolling pass is based on the heating and heat preservation temperature before the previous rolling pass. The reduction is greater than 0℃ and less than or equal to 50℃.
The molybdenum alloy target material according to claim 1, characterized in that, in terms of mass percentage, the target material further includes 0.01%-15% M, and the M is at least one of Cr, Zr, Ta, and Nb. species, the M is used to replace part of Ti.
The molybdenum alloy target material according to claim 2, characterized in that, in terms of mass percentage, the target material includes 15%~25% Ni, 10%~20% Ti, 1%~5% Re, 0.01%-5% M, the balance is Mo and inevitable impurities, and the mass percentage of Mo is ≥50%;

And/or, the grain size of the molybdenum alloy target prepared in step (4) is ≤100 μm;

And/or, the molybdenum alloy target prepared in step (4) has a grain size of level 4 to 5;

And/or, in the same molybdenum alloy target prepared in step (4), the grain size difference is less than or equal to 1.
The preparation method of molybdenum alloy target material according to any one of claims 1 to 3, characterized in that it includes the following steps:

(1) Preparation of raw materials: Weigh the raw materials according to the mass ratio of the target components described in any one of claims 1-3 and mix them to obtain mixed powder;

(2) Hot isostatic pressing: Put the mixed powder in step (1) into a bag and perform hot isostatic pressing to obtain a hot-pressed green body with a bag;

(3) Hot rolling: hot-rolling the jacketed hot-pressed green body to obtain a rolled piece;

(4) Annealing: anneal the rolled piece to obtain the molybdenum alloy target;

In step (3), in the hot rolling process, the rolling deformation amount of a single pass is 15~25%, and the total deformation amount of the hot rolling process is 40%~80%; in the hot rolling process, the deformation amount of each pass is 15~25%. Heating and heat preservation is carried out before rolling in a pass. The heat preservation temperature is 1000℃~1300℃ and the heat preservation time is 30 minutes~120 minutes. The heating and heat preservation temperature before each rolling pass is based on the heating and heat preservation temperature before the previous rolling pass. The reduction is greater than 0℃ and less than or equal to 50℃.
The preparation method of molybdenum alloy target material according to claim 4, characterized in that the raw material of the component Mo in the target material is molybdenum powder with a purity of ≥3N5, and its Fisher particle size range is 2.5 μm ~ 4 μm;

The raw material of the Ni component in the target material is nickel powder with a purity of ≥3N, and its Fibonacci particle size range is 2 μm ~ 3 μm;

The raw material of the Ti component in the target material is titanium powder with a purity of ≥3N, and its Fibonacci particle size range is 2 μm ~ 4 μm;

The raw material of the target component Re is rhenium powder or ammonium rhenate. The purity of the rhenium powder is ≥ 4N and the Fisher particle size is 2 μm ~ 4 μm. The purity of the ammonium rhenate is ≥ 4N and the particle size is 150 mesh to 350 mesh. .
The method for preparing a molybdenum alloy target as claimed in claim 4, characterized in that when the raw material of the target component Re is ammonium rhenate, after weighing the raw materials in step (1), first take a part of the raw molybdenum powder and Ammonium rhenate is mixed, and then subjected to reduction treatment to obtain molybdenum-rhenium alloy powder, and then the molybdenum-rhenium alloy powder is mixed with remaining molybdenum powder and other raw materials to obtain mixed powder;

The reduction treatment is performed in a hydrogen atmosphere, the temperature of the reduction treatment is 500°C~900°C, and the time of the reduction treatment is 2h~8h;

In the molybdenum-rhenium alloy powder, the mass ratio of molybdenum-rhenium is 95:5~50:50;

In step (1), the mixing method is ball milling, the ball-to-material ratio of the ball milling is 1: (0.5-2); the ball milling time is 10h~16h; the ball milling is performed in an inert gas, and the The speed of the ball mill is 50~300r/min.
The preparation method of molybdenum alloy target material according to claim 4, characterized in that, in step (2), the insulation temperature of the hot isostatic pressing is 900°C~980°C; the pressure of the hot isostatic pressing is 100MPa~170MPa; the holding time of the hot isostatic pressing is 2h~5h; in step (2), after the hot-pressed green body is obtained, it also includes partial trimming of the envelope of the hot-pressed green body; step (2) ), the thickness of the hot-pressed green body is 40mm~60mm.
The preparation method of molybdenum alloy target material according to claim 4, characterized in that, in step (3), the opening temperature of the hot rolling treatment is 1000°C~1350°C, and the final rolling temperature is 900°C-1100°C. ; The hot rolling is performed in air or argon atmosphere; the molybdenum alloy target is a plate-shaped target, and the thickness of the rolled piece is 6mm~24mm.
The preparation method of molybdenum alloy target material according to claim 4, characterized in that, in step (4), before the annealing treatment of the rolled piece, it also includes the steps of removing the cladding and rough machining; in step (4), the The annealing treatment is performed in an argon atmosphere; the annealing temperature ranges from 900°C to 1200°C, and the holding time ranges from 60 minutes to 120 minutes.
The application of the molybdenum alloy target material according to any one of claims 1 to 3 or the molybdenum alloy target material prepared by the preparation method according to any one of claims 4 to 9, characterized in that the molybdenum alloy target material is produced by sputtering The metal coating layer is formed by attaching to the main conductive layer of the laminated wiring film for electronic components by radiation; the electronic components are displays, semiconductor devices or thin film solar cells.