CN114411103A - Large-size molybdenum target material and preparation method and application thereof - Google Patents

Large-size molybdenum target material and preparation method and application thereof Download PDF

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Publication number
CN114411103A
CN114411103A CN202210053774.5A CN202210053774A CN114411103A CN 114411103 A CN114411103 A CN 114411103A CN 202210053774 A CN202210053774 A CN 202210053774A CN 114411103 A CN114411103 A CN 114411103A
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China
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hot rolling
molybdenum target
molybdenum
treatment
purity
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Inventor
姚力军
潘杰
郭红波
李伟
王林生
吴庆勇
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Ningbo Molybdenum Material Co ltd
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Ningbo Molybdenum Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/006—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of flat products, e.g. sheets
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/18—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers
    • B22F2003/185—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by using pressure rollers by hot rolling, below sintering temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/247—Removing material: carving, cleaning, grinding, hobbing, honing, lapping, polishing, milling, shaving, skiving, turning the surface

Abstract

The invention provides a large-size molybdenum target material and a preparation method and application thereof, wherein the preparation comprises the steps of sequentially carrying out high-purity molybdenum powder die filling, cold isostatic pressing, sintering, hot rolling, leveling, heat treatment, machining and clean packaging so as to prepare the large-size molybdenum target material; the hot rolling is carried out by adopting a staged hot rolling method, and specifically comprises a first hot rolling treatment, a second hot rolling treatment and a third hot rolling treatment which are sequentially carried out. The preparation method of the large-size molybdenum target material provided by the invention is simple and has strong operability; the prepared large-size molybdenum target realizes the diversity control of crystal grains and meets different sputtering requirements; and the production of large-size high-generation line targets can be realized.

Description

Large-size molybdenum target material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sputtering target preparation, relates to a preparation method of a molybdenum target, and particularly relates to a large-size molybdenum target and a preparation method and application thereof.
Background
Molybdenum is a silvery white metal, hard and tough, with a melting point of 2617 ℃ and a boiling point of 4612 ℃. Molybdenum has good corrosion resistance and stability at normal temperature, and has low specific resistance, good conductivity and good thermal expansion performance. Therefore, molybdenum is widely used in aerospace industry, electronic industry, glass manufacturing industry, solar photovoltaic industry and the like.
In recent years, with the continuous development of technologies in the fields of solar cells, flat panel displays, semiconductor integrated circuits, and the like, films produced by sputtering deposition have been widely used in these fields because of their high density and good adhesion to base materials. Compared with the traditional chromium wiring, the molybdenum wiring can effectively reduce the specific impedance and the film stress of the wiring, so that the molybdenum is used for components of the LCD, the brightness, the contrast and the color of the LCD can be effectively improved, and the service life of the LCD can be prolonged; and the liquid crystal flat panel display and touch screen using molybdenum have the advantages of strong environmental protection performance, small volume, low power consumption and the like.
Early molybdenum targets were obtained by fusion casting, however, the density of molybdenum targets formed by this method was difficult to control. In order to solve the above problems, CN 102392222a discloses a production process method of a large-scale high-purity molybdenum planar target for a display, which comprises the steps of molybdenum powder analysis, powder selection, powder preparation, die filling, pressing, sintering, rolling, annealing, width milling, end face linear cutting, chamfering and grinding machine processing in sequence by adopting a powder metallurgy method to process a molybdenum target, and then obtaining the molybdenum target.
CN 103567445a discloses a method for manufacturing a molybdenum target, which comprises the following steps: carrying out first densification treatment on the molybdenum powder by adopting a static pressure process to form a first molybdenum target blank: putting the first molybdenum target blank into a sheath and vacuumizing; performing secondary densification treatment on the first molybdenum target blank in the jacket by adopting a cold isostatic pressing process to form a second molybdenum target blank; after the second densification treatment, removing the sheath, and performing third densification treatment on the second molybdenum target blank by adopting an induction sintering process to form a third molybdenum target blank; after the third densification treatment, rolling the third molybdenum target blank by adopting a hot rolling process to form a fourth molybdenum target blank: and after the hot rolling process, annealing the fourth molybdenum target blank to form the molybdenum target.
CN 104342619a discloses a method for manufacturing a molybdenum target, which comprises the following steps: the densification treatment of the molybdenum powder is realized through a hot-pressing sintering process to obtain a first molybdenum target blank, and then the further densification treatment of the first molybdenum target blank is gradually realized through a multi-stage hot-rolling treatment process to obtain the molybdenum target.
The molybdenum powder metallurgy method has unique mechanical and physical properties, so that the density of the manufactured molybdenum target material is improved to a certain extent compared with a fusion casting method. However, the uniformity of the internal structure and the grain size of the molybdenum target material manufactured by the existing powder metallurgy process cannot meet the sputtering process with higher and higher requirements; the purity of the molybdenum target material manufactured by the existing powder metallurgy process cannot meet the sputtering process with higher and higher purity requirements; the size of the molybdenum target material manufactured by the existing powder metallurgy process cannot meet the sputtering process with larger and larger size requirements.
With the increasing demand of 55 inches, especially over 65 inches display screens, the existing targets with the specifications of G6 and G8.5 cannot meet the requirements of the production line of the advanced generation line, and the G10.5 cutting large-size televisions have obvious advantages and can effectively improve the cutting efficiency, so the demand of the targets with the specification of G10.5 of the advanced generation line is increasing day by day. However, the high-generation line G10.5 has a single heavy piece and a long length, and thus has higher requirements for controlling the pressing, forming, sintering and rolling processes and the binding process, and has higher difficulty in stabilizing the grain size.
In summary, it is necessary to provide a new method for preparing a molybdenum target, which meets the requirements of the production line of the advanced generation line to meet the market demand.
Disclosure of Invention
The invention aims to provide a large-size molybdenum target material, a preparation method and application thereof, wherein the preparation method realizes the diversity control of crystal grains and meets different sputtering requirements; and the production of large-size high-generation line targets can be realized.
The large-size molybdenum target material is a G10.5 molybdenum target material.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method comprises the steps of sequentially carrying out high-purity molybdenum powder die filling, cold isostatic pressing, sintering, hot rolling, leveling, heat treatment, machining and clean packaging, and further preparing the large-size molybdenum target;
the hot rolling is carried out by adopting a staged hot rolling method, and specifically comprises a first hot rolling treatment, a second hot rolling treatment and a third hot rolling treatment which are sequentially carried out.
The preparation method reduces the pre-sintering process, adopts the hot rolling method for hot rolling, can change the internal organization structure of the molybdenum sintering blank, obtains a processed structure, improves the processing technological property and the service performance of the molybdenum target material, greatly improves the strength and the mechanical property of the molybdenum target material, and can improve the density of the molybdenum blank to 10.15g/cm3The above.
Preferably, the high purity molybdenum powder has a purity of 99.96% or more, such as 99.96%, 99.97%, 99.98%, or 99.99%, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the high purity molybdenum powder has a potassium content of 20ppm or less, such as 20ppm, 19ppm, 18ppm, 17ppm, 16ppm or 15ppm, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
The potassium content in the raw materials used in the process of preparing the molybdenum target material is less than or equal to 20ppm, and the potassium content and the impurity content in the target material can be reduced in the subsequent sintering process.
Preferably, the die filling of the high-purity molybdenum powder comprises the steps of filling the high-purity molybdenum powder into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing.
The material is repeatedly rolled and vibrated to be flat before sealing, so that the powder is uniformly filled, and the integral thickness deviation or the thickness deviation of two sides after sintering is ensured to be small.
Preferably, the cold isostatic pressing adopts a four-stage pressurization mode and a four-stage pressure relief mode.
Preferably, the cold isostatic pressing pressure is 170-250MPa, and may be, for example, 170MPa, 180MPa, 190MPa, 200MPa, 210MPa, 220MPa, 230MPa, 240MPa or 250MPa, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the cold isostatic pressing time is 30-60min, such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
According to the invention, the molybdenum blank is processed by cold isostatic pressing, so that the molybdenum blank can be stressed uniformly and fully and can be shrunk, the problems of breakage and the like in the processing process are prevented, and the size uniformity and the densification degree can be effectively ensured.
Preferably, the sintering temperature is 1800-.
Preferably, the sintering time is 30-60h, for example 30h, 34h, 38h, 42h, 46h, 50h, 54h, 58h or 60h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the molybdenum target blank after sintering has an overall thickness deviation of 4mm or less, for example, 4mm, 3.5mm, 3mm, 2.5mm, 2mm, 1.5mm, 1mm or 0.5mm, but not limited to the values recited, and other values not recited within the range of values are equally applicable; the thickness difference between the two sides is 2mm or less, and may be, for example, 2mm, 1.8mm, 1.6mm, 1.4mm, 1.2mm, 1.0mm, 0.8mm, 0.6mm or 0.4mm, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the density of the sintered molybdenum target blank is 9.8-10g/cm3For example, it may be 9.8cm3、9.9cm3Or 10.0cm3But not limited to the recited values, other values not recited within the numerical range are equally applicable.
Preferably, the hot rolling adopts a one-fire two-pass rolling method.
Preferably, the heating temperature of the first hot rolling treatment is 1200-; the pass deformation is 20 to 30%, for example 20%, 22%, 24%, 26%, 28% or 30%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the hot rolling speed is 30 to 60m/min, and may be, for example, 30m/min, 35m/min, 40m/min, 45m/min, 50m/min, 55m/min or 60m/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the heating temperature of the second hot rolling treatment is 1150-; the pass strain is 15 to 25%, and may be, for example, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24% or 25%, but is not limited to the values recited, and other values not recited in the numerical range are also applicable; the hot rolling speed is 40 to 70m/min, and may be, for example, 40m/min, 45m/min, 50m/min, 55m/min, 60m/min, 65m/min or 70m/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the heating temperature of the third hot rolling treatment is 1100-; the pass deformation is 10 to 20%, and may be, for example, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% or 20%, but is not limited to the values listed, and other values not listed in the numerical range are also applicable; the hot rolling speed is 50 to 80m/min, and may be, for example, 50m/min, 55m/min, 60m/min, 65m/min, 70m/min, 75m/min or 80m/min, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
The invention can effectively prevent the bad problem of abnormal growth of crystal grains caused by continuous high temperature in the hot rolling deformation process of each firing pass of the molybdenum target blank by adopting the one-firing two-pass rolling method, promotes the crystal grains to gradually form fiber crystal grains along with the rolling process, and provides a foundation for controlling the size of the subsequent crystal grains.
Preferably, the levelled molybdenum target blank has a flatness of 1.5mm or less, for example, 1.5mm, 1.4mm, 1.3mm, 1.2mm, 1.1mm, 1.0mm or 0.9mm, but not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the temperature of the heat treatment is 1100-.
Preferably, the heat treatment time is 10-90min, for example, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min or 90min, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the machining comprises sequentially cutting, milling and grinding the molybdenum target blank.
The purpose of the cutting treatment is to obtain the corresponding size of the target material, otherwise, the workload of subsequent milling machine processing is increased.
As a preferred technical solution of the present invention, the preparation method of the large-size molybdenum target provided by the first aspect of the present invention includes the following steps:
(1) filling high-purity molybdenum powder into a mold: filling high-purity molybdenum powder with the purity of more than or equal to 99.96 percent and the potassium content of less than or equal to 20ppm into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing;
(2) cold isostatic pressing: a four-stage pressurizing mode and a four-stage pressure relief mode are adopted; the pressure of the cold isostatic pressing is 170-250MPa, and the time is 30-60 min;
(3) and (3) sintering: sintering the molybdenum target blank subjected to cold isostatic pressing at the temperature of 1800-2000 ℃ for 30-60 h; the density of the sintered molybdenum target blank is 9.8-10g/cm3(ii) a The integral thickness deviation is less than or equal to 4mm, and the thickness difference of the two sides is less than or equal to 2 mm;
(4) hot rolling: sequentially carrying out first hot rolling treatment, second hot rolling treatment and third hot rolling treatment on the sintered molybdenum target blank by adopting a one-fire two-pass rolling method; the heating temperature of the first hot rolling treatment is 1200-1400 ℃, the pass deformation is 20-30%, and the hot rolling speed is 30-60 m/min; the heating temperature of the second hot rolling treatment is 1150-1350 ℃, the pass deformation is 15-25%, and the hot rolling speed is 40-70 m/min; the heating temperature of the fire time of the third hot rolling treatment is 1100-1300 ℃, the deformation of the fire time is 10-20%, and the hot rolling speed is 50-80 m/min;
(5) leveling: leveling the molybdenum target blank subjected to the hot rolling in the step (4) to obtain a molybdenum target blank with the flatness of less than or equal to 1.5 mm;
(6) and (3) heat treatment: heat-treating the leveled molybdenum target blank obtained in the step (5) at the temperature of 1100-1400 ℃ for 10-90 min;
(7) and (3) machining: sequentially carrying out cutting, milling machine machining and grinding machine machining on the molybdenum target blank subjected to heat treatment in the step (6);
(8) cleaning and packaging: and (5) cleaning the molybdenum target blank obtained in the step (7) to obtain the large-size molybdenum target material.
In a second aspect, the invention provides a large-size molybdenum target material, which is prepared by the preparation method provided in the first aspect.
In a third aspect, the invention provides an application of the large-size molybdenum target material prepared by the preparation method provided in the first aspect, and the large-size molybdenum target material can be used for generation-line flat panel displays.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method provided by the invention reduces the pre-sintering process, and the one-fire two-pass rolling method can effectively prevent the adverse problem of abnormal growth of crystal grains caused by continuous high temperature in the hot rolling deformation process of each fire time of the molybdenum target blank;
(2) the large-size molybdenum target material prepared by the preparation method realizes the diversity control of crystal grains and meets different sputtering requirements; and the production of large-size high-generation line targets can be realized.
Drawings
Fig. 1 is a process flow diagram of a preparation method provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a large-size molybdenum target and a preparation method thereof, and the preparation method is shown in fig. 1 and comprises the following steps:
(1) filling high-purity molybdenum powder into a mold: filling high-purity molybdenum powder with the purity of 99.96 percent and the potassium content of 18ppm into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing;
(2) cold isostatic pressing: a four-stage pressurizing mode and a four-stage pressure relief mode are adopted; the pressure of the cold isostatic pressing is 170-250MPa, and the time is 45 min;
(3) and (3) sintering: the molybdenum target after cold isostatic pressingSintering the blank at 1900 ℃ for 45 h; the density of the sintered molybdenum target blank is 10.0g/cm3(ii) a The integral thickness deviation is 3mm, and the thickness difference of two sides is 1.5 mm;
(4) hot rolling: sequentially carrying out first hot rolling treatment, second hot rolling treatment and third hot rolling treatment on the sintered molybdenum target blank by adopting a one-fire two-pass rolling method; the heating temperature of the first hot rolling treatment is 1300 ℃, the pass deformation is 25%, and the hot rolling speed is 45 m/min; the heating temperature of the second hot rolling treatment is 1200 ℃, the pass deformation is 20%, and the hot rolling speed is 50 m/min; the heating temperature of the fire number of the third hot rolling treatment is 1150 ℃, the pass deformation is 15%, and the hot rolling speed is 65 m/min;
(5) leveling: leveling the molybdenum target blank subjected to the hot rolling in the step (4) to obtain a molybdenum target blank with the flatness of 1.0 mm;
(6) and (3) heat treatment: carrying out heat treatment on the leveled molybdenum target blank obtained in the step (5) at 1200 ℃ for 60 min;
(7) and (3) machining: sequentially carrying out cutting, milling machine machining and grinding machine machining on the molybdenum target blank subjected to heat treatment in the step (6);
(8) cleaning and packaging: and (5) cleaning the molybdenum target blank obtained in the step (7) to obtain the large-size molybdenum target material.
Example 2
The embodiment provides a large-size molybdenum target and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) filling high-purity molybdenum powder into a mold: filling high-purity molybdenum powder with the purity of 99.97 percent and the potassium content of 20ppm into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing;
(2) cold isostatic pressing: a four-stage pressurizing mode and a four-stage pressure relief mode are adopted; the pressure of the cold isostatic pressing is 170-250MPa, and the time is 60 min;
(3) and (3) sintering: sintering the molybdenum target blank subjected to cold isostatic pressing at 1800 ℃ for 60 hours; the density of the sintered molybdenum target blank is 9.8g/cm3(ii) a The integral thickness deviation is 4mm, and the thickness difference of two sides is 2 mm;
(4) hot rolling: sequentially carrying out second hot rolling treatment and third hot rolling treatment on the sintered molybdenum target blank by adopting a one-fire two-pass rolling method; the heating temperature of the first hot rolling treatment is 1200 ℃, the pass deformation is 30%, and the hot rolling speed is 60 m/min; the heating temperature of the second hot rolling treatment is 1150 ℃, the pass deformation is 15%, and the hot rolling speed is 70 m/min; the heating temperature of the fire number of the third hot rolling treatment is 1100 ℃, the pass deformation is 20%, and the hot rolling speed is 80 m/min;
(5) leveling: leveling the molybdenum target blank subjected to the hot rolling in the step (4) to obtain a molybdenum target blank with the flatness of 1.5 mm;
(6) and (3) heat treatment: carrying out heat treatment on the leveled molybdenum target blank obtained in the step (5) at the temperature of 1100 ℃ for 90 min;
(7) and (3) machining: sequentially carrying out cutting, milling machine machining and grinding machine machining on the molybdenum target blank subjected to heat treatment in the step (6);
(8) cleaning and packaging: and (5) cleaning the molybdenum target blank obtained in the step (7) to obtain the large-size molybdenum target material.
Example 3
The embodiment provides a large-size molybdenum target and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) filling high-purity molybdenum powder into a mold: filling high-purity molybdenum powder with the purity of 99.96 percent and the potassium content of 20ppm into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing;
(2) cold isostatic pressing: a four-stage pressurizing mode and a four-stage pressure relief mode are adopted; the pressure of the cold isostatic pressing is 170-250MPa, and the time is 30 min;
(3) and (3) sintering: sintering the molybdenum target blank subjected to cold isostatic pressing at the temperature of 2000 ℃ for 30 hours; the density of the sintered molybdenum target blank is 10.1g/cm3(ii) a The integral thickness deviation is 2mm, and the thickness difference of two sides is 2 mm;
(4) hot rolling: sequentially carrying out second hot rolling treatment and third hot rolling treatment on the sintered molybdenum target blank by adopting a one-fire two-pass rolling method; the heating temperature of the fire number of the first hot rolling treatment is 1400 ℃, the pass deformation is 20%, and the hot rolling speed is 30 m/min; the heating temperature of the second hot rolling treatment is 1350 ℃, the pass deformation is 15%, and the hot rolling speed is 40 m/min; the heating temperature of the fire number of the third hot rolling treatment is 1300 ℃, the pass deformation is 10%, and the hot rolling speed is 50 m/min;
(5) leveling: leveling the molybdenum target blank subjected to the hot rolling in the step (4) to obtain a molybdenum target blank with the flatness of 1.2 mm;
(6) and (3) heat treatment: carrying out heat treatment on the leveled molybdenum target blank obtained in the step (5) at the temperature of 1400 ℃ for 10 min;
(7) and (3) machining: sequentially carrying out cutting, milling machine machining and grinding machine machining on the molybdenum target blank subjected to heat treatment in the step (6);
(8) cleaning and packaging: and (5) cleaning the molybdenum target blank obtained in the step (7) to obtain the large-size molybdenum target material.
Example 4
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: the purity of the high-purity molybdenum powder in the step (1) is changed to 90.6%, and the potassium content is changed to 25 ppm.
Example 5
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: and (3) changing the pressure of the cold isostatic pressing in the step (2) to 120 MPa.
Example 6
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: the sintering temperature in the step (3) is changed to 1500 ℃.
Example 7
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: the sintering temperature in the step (3) is changed to 2200 ℃.
Example 8
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: and (1) filling high-purity molybdenum powder into a rubber sleeve, directly sealing, and then carrying out cold isostatic pressing.
Example 9
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: the temperature of the heat treatment in the step (4) is changed to 800 ℃.
Example 10
The present embodiment provides a large-sized molybdenum target and a preparation method thereof, and the preparation method is different from embodiment 1 only in that: the temperature of the heat treatment in the step (4) is changed to 1500 ℃.
Comparative example 1
The present comparative example provides a large-size molybdenum target and a preparation method thereof, and the preparation method differs from example 1 only in that: and (4) changing the hot rolling into primary hot rolling treatment, wherein the heating temperature of the primary hot rolling treatment is 1200 ℃, the pass deformation is 20%, and the hot rolling speed is 50 m/min.
Comparative example 2
The present comparative example provides a large-size molybdenum target and a preparation method thereof, and the preparation method differs from example 1 only in that: the hot rolling is changed into a first hot rolling treatment and a second hot rolling treatment which are sequentially carried out; the heating temperature of the first hot rolling treatment is 1300 ℃, the pass deformation is 25%, and the hot rolling speed is 45 m/min; the heating temperature of the second hot rolling treatment is 1200 ℃, the pass deformation is 20%, and the hot rolling speed is 50 m/min.
The large-size molybdenum targets provided in examples 1 to 10 and comparative examples 1 to 2 were subjected to the following performance tests:
density: the measurement is carried out according to the basket hanging method disclosed in the national standard GB/T3850-2015 Density measurement method for dense sintered metal materials and hard alloys;
purity: according to a measuring method disclosed in the series national standard GB/T4325 molybdenum chemical analysis method, GDMS and ICP-OES are adopted to detect the impurity content of a molybdenum target material sample;
average grain size: the measurement is carried out according to a cross-section method disclosed in the national standard GB/T6394-2017 method for measuring average metal grains.
TABLE 1
Density/% Purity/%) Average grain size/. mu.m
Example 1 10.15 99.96 80
Example 2 10.15 99.97 70
Example 3 10.15 99.96 150
Example 4 10.15 99.96 82
Example 5 10.15 99.96 78
Example 6 9.6 99.96 Not recrystallized
Example 7 10.15 99.96 85
Example 8 10.15 99.96 76
Example 9 10.15 99.96 Not recrystallized
Example 10 10.15 99.96 140
Comparative example 1 10.15 99.96 80
Comparative example 2 10.15 99.96 90
As can be seen from the analysis of examples 1 and 7, the sintering temperature is increased, the sintered grains grow large, the sintered density is increased, and the grains and density of the target material are increased; as can be seen from the analysis of examples 1 and 6, the sintering temperature is too low, which makes the blank not easy to be formed and the final target material cannot be obtained.
It can be seen from the analysis of examples 1 and 9 that the growth of target grains is affected by the excessively low temperature of the heat treatment; analysis of examples 1 and 10 revealed that the increase in the heat treatment temperature resulted in the growth of the crystal grains of the target material.
It can be seen from the analysis of example 1 and comparative examples 1-2 that the variation of temperature in the rolling process acts on the target grains, and the temperature is increased, so that the target grains are increased.
In conclusion, the preparation method of the large-size molybdenum target material provided by the invention is simple and has strong operability; the prepared large-size molybdenum target realizes the diversity control of crystal grains and meets different sputtering requirements; and the production of large-size high-generation line targets can be realized.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The preparation method of the large-size molybdenum target is characterized by comprising the steps of sequentially carrying out high-purity molybdenum powder die filling, cold isostatic pressing, sintering, hot rolling, leveling, heat treatment, machining, cleaning and packaging, and further preparing to obtain the large-size molybdenum target;
the hot rolling is carried out by adopting a staged hot rolling method, and specifically comprises a first hot rolling treatment, a second hot rolling treatment and a third hot rolling treatment which are sequentially carried out.
2. The preparation method according to claim 1, wherein the purity of the high-purity molybdenum powder is more than or equal to 99.96%;
preferably, the content of potassium in the high-purity molybdenum powder is less than or equal to 20 ppm;
preferably, the die filling of the high-purity molybdenum powder comprises the steps of filling the high-purity molybdenum powder into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing.
3. The method of claim 1 or 2, wherein the cold isostatic pressing is performed in a four-stage pressurization mode and a four-stage pressure release mode;
preferably, the pressure of the cold isostatic pressing is 170-250 MPa;
preferably, the time of the cold isostatic pressing is 30-60 min.
4. The method as claimed in any one of claims 1 to 3, wherein the sintering temperature is 1800-2000 ℃;
preferably, the sintering time is 30-60 h;
preferably, the integral thickness deviation of the sintered molybdenum target blank is less than or equal to 4mm, and the thickness difference of two sides is less than or equal to 2 mm;
preferably, the density of the sintered molybdenum target blank is 9.8-10g/cm3。
5. The production method according to any one of claims 1 to 4, wherein the hot rolling is performed by a one-pass two-pass rolling method;
preferably, the heating temperature of the fire times of the first hot rolling treatment is 1200-1400 ℃, the pass deformation is 20-30%, and the hot rolling speed is 30-60 m/min;
preferably, the heating temperature of the second hot rolling treatment is 1150-1350 ℃, the pass deformation is 15-25%, and the hot rolling speed is 40-70 m/min;
preferably, the heating temperature of the fire pass of the third hot rolling treatment is 1100-1300 ℃, the pass deformation is 10-20%, and the hot rolling speed is 50-80 m/min.
6. The method of any one of claims 1-5, wherein the leveled molybdenum target blank has a flatness of 1.5mm or less;
preferably, the temperature of the heat treatment is 1000-1400 ℃;
preferably, the time of the heat treatment is 10-90 min.
7. The production method according to any one of claims 1 to 6, wherein the machining includes sequentially performing cutting, milling and grinding on the molybdenum target blank.
8. The production method according to any one of claims 1 to 7, characterized by comprising the steps of:
(1) filling high-purity molybdenum powder into a mold: filling high-purity molybdenum powder with the purity of more than or equal to 99.96 percent and the potassium content of less than or equal to 20ppm into a rubber sleeve, rolling, vibrating, repeatedly rolling, repeatedly vibrating, flattening, and sealing;
(2) cold isostatic pressing: a four-stage pressurizing mode and a four-stage pressure relief mode are adopted; the pressure of the cold isostatic pressing is 170-250MPa, and the time is 30-60 min;
(3) and (3) sintering: sintering the molybdenum target blank subjected to cold isostatic pressing at the temperature of 1800-2000 ℃ for 30-60 h; the density of the sintered molybdenum target blank is 9.8-10g/cm3(ii) a The integral thickness deviation is less than or equal to 4mm, and the thickness difference of the two sides is less than or equal to 2 mm;
(4) hot rolling: sequentially carrying out second hot rolling treatment and third hot rolling treatment on the sintered molybdenum target blank by adopting a one-fire two-pass rolling method; the heating temperature of the first hot rolling treatment is 1200-1400 ℃, the pass deformation is 20-30%, and the hot rolling speed is 30-60 m/min; the heating temperature of the second hot rolling treatment is 1150-1350 ℃, the pass deformation is 15-25%, and the hot rolling speed is 40-70 m/min; the heating temperature of the fire time of the third hot rolling treatment is 1100-1300 ℃, the deformation of the fire time is 10-20%, and the hot rolling speed is 50-80 m/min;
(5) leveling: leveling the sintered molybdenum target blank in the step (4) to obtain a molybdenum target blank with the flatness of less than or equal to 1.5 mm;
(6) and (3) heat treatment: heat-treating the leveled molybdenum target blank obtained in the step (5) at the temperature of 1100-1400 ℃ for 10-90 min;
(7) and (3) machining: sequentially carrying out cutting, milling machine machining and grinding machine machining on the molybdenum target blank subjected to heat treatment in the step (6);
(8) cleaning and packaging: and (5) cleaning the molybdenum target blank obtained in the step (7) to obtain the large-size molybdenum target material.
9. A large-size molybdenum target obtained by the production method according to any one of claims 1 to 8.
10. The use of the large molybdenum target according to claim 9, wherein the large molybdenum target is used for advanced line flat panel displays.
CN202210053774.5A 2022-01-18 2022-01-18 Large-size molybdenum target material and preparation method and application thereof Pending CN114411103A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060042728A1 (en) * 2004-08-31 2006-03-02 Brad Lemon Molybdenum sputtering targets
CN105568236A (en) * 2016-03-14 2016-05-11 洛阳高新四丰电子材料有限公司 Preparation method for high-purity high-compactness and large-dimension molybdenum-titanium alloy sputtering target material
CN108950494A (en) * 2018-07-30 2018-12-07 常州苏晶电子材料有限公司 The production method of strip molybdenum target material
CN109778126A (en) * 2019-03-13 2019-05-21 安泰天龙（天津）钨钼科技有限公司 A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material
CN111850495A (en) * 2020-07-24 2020-10-30 宁波江丰钨钼材料有限公司 Semiconductor molybdenum target material and preparation method and application thereof
CN113061851A (en) * 2021-03-16 2021-07-02 宁波江丰电子材料股份有限公司 Solar molybdenum target blank and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060042728A1 (en) * 2004-08-31 2006-03-02 Brad Lemon Molybdenum sputtering targets
CN105568236A (en) * 2016-03-14 2016-05-11 洛阳高新四丰电子材料有限公司 Preparation method for high-purity high-compactness and large-dimension molybdenum-titanium alloy sputtering target material
CN108950494A (en) * 2018-07-30 2018-12-07 常州苏晶电子材料有限公司 The production method of strip molybdenum target material
CN109778126A (en) * 2019-03-13 2019-05-21 安泰天龙（天津）钨钼科技有限公司 A kind of preparation method of high-densit Ultra-fine Grained large scale molybdenum target material
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