CN108517498B - Preparation method of integrated tubular molybdenum target for magnetron sputtering - Google Patents
Preparation method of integrated tubular molybdenum target for magnetron sputtering Download PDFInfo
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- CN108517498B CN108517498B CN201810341952.8A CN201810341952A CN108517498B CN 108517498 B CN108517498 B CN 108517498B CN 201810341952 A CN201810341952 A CN 201810341952A CN 108517498 B CN108517498 B CN 108517498B
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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
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- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
Abstract
A preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises a molybdenum powder or molybdenum alloy powder sieving treatment step, a cold isostatic pressing step, a sintering step, a hollow forging processing step, a forging step, an annealing treatment step, a machining step, a sand blasting treatment step, an atomization spraying step, a cleaning step and a drying step, and the integrated tubular molybdenum target is prepared. The invention adopts the process of combining large-deformation forging processing and recrystallization heat treatment, realizes the refinement of the grain structure and good uniformity, replaces extrusion forming with a hollow forging processing mode, and reduces the processing equipment requirement and the processing cost.
Description
Technical Field
The invention relates to the technical field of rotary targets, in particular to a preparation method of an integrated tubular molybdenum target for magnetron sputtering.
Background
In the production process of a CIGS thin-film solar cell or a TFT-LCD flat panel display, a molybdenum-containing layer is deposited with a thin film by a magnetron sputtering mode through a tubular target made of pure molybdenum and molybdenum alloy such as molybdenum niobium.
During the sputtering process of the tubular molybdenum target, various performance indexes of the tubular molybdenum target have key influence on the quality of a sputtering deposition film. At present, the main foreign tubular molybdenum target material manufacturers use the process routes of powder metallurgy forming, extruding, machining and binding. Wherein, the extrusion process has high requirement on equipment condition and high cost; the quality control of the binding process is greatly improved as the length of the tubular molybdenum target material is increased.
The heat generated by magnetron sputtering can not be dissipated in time, which has great influence on the sputtering effect of the product. In the industry, the temperature of the molybdenum tube is reduced by cooling water, but the cooling water corrodes the inner wall of the tubular molybdenum target to a certain extent, so that the sputtering quality of the tubular molybdenum target is affected, and molybdenum metal in a cooling water system is polluted. Therefore, metals such as indium are often used in industry to bind the stainless steel tube and the molybdenum tube inside the molybdenum tube, and after binding, circulating cooling water is introduced into the stainless steel tube to reduce the use temperature of the molybdenum tube target. However, through application, after the length of the pipe is increased, the original binding mode is easy to generate defects in the production process, the control of the binding welding rate and the area index of the maximum independent non-welded area is increasingly difficult, and the off-target is easy to generate in the using process of a client, so that the quality and the stable production of the client product are influenced; and the binding technology has the reasons of high cost, complex process, uneven heat dissipation effect and the like, thereby limiting the use of the molybdenum tube target. Therefore, the method for improving the corrosion resistance of the molybdenum tube in the cooling water by means of spraying the coating on the inner wall of the molybdenum tube and the like becomes a reliable way for improving the service performance of the molybdenum tube at present.
The foreign tubular molybdenum target material is processed by extrusion, so that the equipment requirement is high, and the production cost is high, so that the hollow forging and sintering molybdenum tube becomes a substitute process with low equipment requirement and low production cost.
Disclosure of Invention
The invention provides a preparation method of an integrated tubular molybdenum target for magnetron sputtering, aiming at solving the problems that the requirement on target extrusion processing equipment is high, the cost is high, the large-size tubular molybdenum target is difficult to bind, and the inner wall of the tubular molybdenum target without a back lining pipe is easy to be corroded by industrial cooling water in the prior art.
The technical scheme adopted by the invention for solving the problems is as follows: a preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises the following steps:
step one, selecting molybdenum powder or molybdenum alloy powder, and sieving for later use;
step two, molybdenum powder or molybdenum alloy powder is filled into a tubular flexible die with a flexible steel core, and a powdery molybdenum tube blank is manufactured by cold isostatic pressing;
step three, putting the powdery molybdenum tube blank into a sintering furnace, and sintering in a hydrogen or vacuum environment to obtain a sintered molybdenum tube with the density of more than 95%, wherein the sintering temperature is 1800-2200 ℃, and the sintering time is 6-8 h;
heating the sintered molybdenum tube, and then adopting a hollow forging processing mode, forging the sintered molybdenum tube by using a die to produce the target tube, wherein the heating temperature is 1000-1500 ℃, and the forging section shrinkage rate is 5-50%;
step five, annealing the forged target tube, and naturally cooling; wherein the annealing temperature is 800-1300 ℃, and the annealing heat preservation time is 1-5 h;
step six, machining the target tube after heat treatment to a target required size, and then performing defect detection and crystallization scanning detection;
step seven, performing sand blasting treatment on the inner wall surface of the target pipe to realize that the inner wall surface of the target pipe is a uniform sand blasting surface, and the surface sand blasting grade is Sa 3; cleaning the inner wall of the target tube after sand blasting treatment, and airing;
step eight, mixing the mixed slurry and the thinner according to the proportion of 5: 1, uniformly mixing, and uniformly spraying the mixture on the inner wall surface of a target tube by an atomization spraying device;
step nine, placing the target tube after atomization spraying in a vacuum furnace for drying treatment to achieve the drying effect and optimize the bonding quality of the coating and the inner wall of the target tube;
step ten, using hot water of 80-100 ℃ to the dried target tube, washing the atomized spray coating, removing floating stains on the surface of the inner wall, drying, and carrying out vacuum packaging to obtain the integrated tubular molybdenum target.
In the first step, when the molybdenum powder and the molybdenum alloy powder are screened, the screen is selected to be 160-200 meshes, oversize materials are treated as waste materials, and undersize molybdenum powder and molybdenum alloy powder are reserved. Before and after use, the screen is checked for damage, and impurities or large powder aggregates are screened out.
In the second step, the pressing pressure of cold isostatic pressing is 150-250 MPa, the pressure maintaining time is 2-10 min, and the specific execution process is adjusted within the range according to the specification of the prepared tube target and the technical index of molybdenum powder; the cold isostatic pressing is the automatic pressure increase of the equipment, and the pressure increase speed is not limited.
In the fourth step of the invention, the sintered molybdenum tube blank is placed into a muffle furnace to be heated, the heating temperature is 1000-1500 ℃, the heating time is 60-80 min, the specification of the selected die is the target size requirement, according to the designed forging die, the external diameter size of the sintered molybdenum tube with three fifths of length is forged to the specification of the target size requirement by the first fire, then the sintered molybdenum tube with the rest length is forged to the specification of the target size requirement after going back to the furnace for compensation heating for 60-80 min, and the target tube is manufactured by hollow forging processing for two times. When hollow forging, the outer forging mould applies force to the outer surface of the molybdenum tube to reduce the outer diameter of the molybdenum tube and synchronously change the inner diameter.
In the seventh step of the invention, white corundum or steel balls with the specification and size of 0.5-2 mm are adopted as the materials for sand blasting; the process for cleaning the inner wall of the target tube after sand blasting comprises the following steps: and (4) washing the inner wall of the target tube subjected to sand blasting for multiple times by using tap water, and cleaning the inner wall of the target tube by using deionized water or distilled water again after the inner wall is washed clean.
In the sixth step of the invention, water immersion type ultrasonic C scanning is used, no pore defect with the average diameter larger than 0.5mm exists in the machined target tube, the intensity of the crystal scanning bottom wave is not smaller than 75%, and the average grain diameter is smaller than 50 um. The water immersion type ultrasonic C scanning is divided into two times, different models are respectively selected to detect physical defects and grain structure uniformity, and detection results are expressed by color difference of color pictures.
In the eighth step of the invention, before atomization spraying, the pipeline of the atomization spraying device is washed once by using thinner; in the atomization spraying process, the spray head moves from one end of the inner wall surface of the target pipe to the other end at a constant speed, and after the primary spraying is finished, the spray head is naturally dried for 24-120 hours; and (4) spraying again after drying, carrying out 1-10 times of atomization spraying according to the coating thickness required by the target, wherein the spraying is finished every time, and naturally drying for 24-120 h. In the air drying process after each atomization spraying, the tube target is placed in a clean environment without dust deposition, so that the next spraying quality is ensured. The total thickness of the coating is designed to be 10-200 um according to the application of a customer, 1-10 times of atomization spraying can be carried out, and natural drying is carried out after each spraying is finished;
and step eight, after atomization spraying once, naturally airing for 24 hours at the ambient temperature of 25 ℃ in relation to production site conditions, wherein the airing time is 120 hours at the ambient temperature of 0 ℃.
In the ninth step of the present invention, the vacuum degree is continuously maintained less than 10-2Pa, and the drying temperature is 20-60 ℃.
In the ninth step, the gradient temperature zone treatment process in the vacuum furnace under the vacuum environment comprises the following steps: heating for 2h at 0-20 ℃, and keeping the temperature for 5 h; raising the temperature for 2 hours at the temperature of 20-40 ℃, and preserving the temperature for 5 hours; heating for 2h at 40-60 ℃, and keeping the temperature for 5 h.
In the eighth step, the mixed slurry is formed by mixing a macromolecular compound, a metal oxide, a rare earth element and ceramic micro powder, and the mass fraction ratio of the macromolecular compound, the metal oxide, the rare earth element and the ceramic micro powder in the mixed slurry is 12: 5: 1: 2; wherein the macromolecular compound is methyl ethyl ketone, cyclohexenone, isopropyl alcohol or epoxy resin; the rare earth element is , erbium or samarium; the metal oxide is K, Ca, Na, Mg, Fe, Sn, Ag or Pt metal oxide; the thinner is acetone cyclohexanone or n-butanol.
The tubular flexible mold in the second step of the invention can be a rubber mold, a silica gel mold and the like.
And in the seventh step, high-pressure air blowing cannot be adopted, because factory high-pressure air is prepared by a compressor and contains a small amount of oil stain, and the oil stain is introduced into the inner wall of the blowing target tube to influence the combination effect of the atomized spraying coating and the inner wall of the target tube.
Has the advantages that: the invention adopts the process of combining large-deformation forging processing and recrystallization heat treatment, realizes the refinement of the grain structure and good uniformity, replaces extrusion forming with a hollow forging processing mode, and reduces the processing equipment requirement and the processing cost.
The water corrosion resistant coating on the inner wall is sprayed by atomization by using a mixture of a macromolecular compound, a metal oxide, a rare earth element and ceramic micro powder, and a back tube binding process is replaced, so that the performance of the tubular molybdenum target material in the magnetron sputtering use process is more stable.
The tubular molybdenum target material prepared by the method is made of molybdenum or molybdenum alloy; the density is more than 98.5 percent of the theoretical density, and the average grain diameter is less than 50 um.
Detailed Description
The invention will be further described with reference to specific examples for the purpose of facilitating an understanding of the technical means, the inventive features and the objectives obtained, but the scope of the invention as claimed should not be limited to the scope described in the detailed description.
A preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises the following steps: step one, selecting molybdenum powder or molybdenum alloy powder, and sieving the molybdenum powder or molybdenum alloy powder by a sieve of 160-200 meshes for later use;
step two, molybdenum powder or molybdenum alloy powder is put into a tubular rubber mould with a flexible steel core, and is subjected to cold isostatic pressing under the pressure of 150MPa to 250MPa to prepare a powdery molybdenum tube blank;
step three, putting the powdery molybdenum tube blank into a sintering furnace, and sintering the powdery molybdenum tube blank in a hydrogen or vacuum environment to obtain a sintered molybdenum tube with the density of more than 95%, wherein the sintering temperature is 1800-2200 ℃;
step four, heating the sintered molybdenum tube, and then forging the tube target by using a die, wherein the heating temperature is 1000-1500 ℃, and the forging section shrinkage is 5-50%;
step five, annealing the forged tube target at the annealing temperature of 800-1300 ℃ for 1-5 h;
and step six, machining the target tube after heat treatment to the size required by a customer drawing, then carrying out defect flaw detection and crystal scanning detection, checking whether the inside of the target tube has defects such as cracks, air holes and the like by the defect flaw detection, and detecting and analyzing the uniformity of the grain structure inside the target tube by the crystal scanning detection. No pore defect with the average diameter larger than 0.5m exists in the tube target, the intensity of the crystal scanning bottom wave is not less than 75%, and the average grain diameter is less than 50 um;
step seven, performing sand blasting treatment on the inner wall of the target tube to realize a uniform sand blasting surface on the inner wall surface, wherein the sand blasting grade of the surface is Sa3 to realize good bonding strength with a coating material after atomization spraying, and cleaning the inner wall of the target tube after sand blasting treatment by using deionized water or distilled water after the inner wall of the target tube needs to be washed clean by tap water for many times, and drying the target tube;
step eight, uniformly spraying the mixed slurry of the macromolecular compound and the metal oxide on the inner wall of the target tube through an atomization spraying device;
in the atomization spraying process, the spray head runs from one end of the inner wall of the target pipe to the other end at a constant speed, after one-time spraying is finished, the spray head is naturally dried, the drying time is 24-120 h, the spray head can be sprayed again after being dried, the total thickness of the coating is designed to be 10-200 um according to the application of a customer, the atomization spraying can be carried out for 1-10 times, and the spray head is naturally dried after each time of spraying;
and step nine, putting the atomized and sprayed tube target into a vacuum furnace for drying treatment, and performing gradient temperature zone treatment in a vacuum environment, wherein the temperature is increased for 2 hours at 0-20 ℃, the temperature is maintained for 5 hours, the temperature is increased for 2 hours at 20-40 ℃, the temperature is maintained for 5 hours, the temperature is increased for 2 hours at 40-60 ℃ and the temperature is maintained for 5 hours. The drying effect is achieved, and the bonding quality of the coating and the inner wall of the target tube is optimized.
Step ten, after the tube target is dried, the atomized spray coating needs to be washed by hot water at the temperature of 80-100 ℃, and floating stains on the surface of the inner wall are removed; and drying and then carrying out vacuum packaging to obtain the integrated tubular molybdenum target.
Example 1
A preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises the following steps:
selecting molybdenum powder with the Fisher size of 4.0 mu m, sampling molybdenum powder in batches to analyze that various physical and chemical performance indexes meet application requirements, screening by using a 200-mesh screen, treating oversize materials as waste materials, and keeping the undersize molybdenum powder for later use;
selecting a tubular rubber mold with the specification of phi 230mm multiplied by 2000mm, cleaning the interior, matching with a phi 130mm flexible steel core, uniformly adding molybdenum powder, and filling the powder with the weight of 180 kg; after sealing, carrying out cold isostatic pressing, wherein the pressing pressure is 220MPa, and the pressure maintaining time is 5 min; demolding for later use after pressing is finished;
step three, putting the powdery molybdenum tube blank into a medium-frequency induction sintering furnace, introducing hydrogen as a protective and reducing atmosphere, cooling along with the furnace, discharging, and sintering at the density of 9.8-10.0 g/cm3；
Step four, putting the sintered molybdenum tube blank into a muffle furnace with a hydrogen protective atmosphere for heating at 1200 ℃, keeping the temperature for 60min, forging the length and the outer diameter of about three fifths of one end to 160mm by using a die with the specification of phi 160mm through a first fire, turning around, returning to the furnace, performing compensation heating for 60min, and forging the rest length to the size;
step five, carrying out recrystallization annealing at 1250 ℃ by using an annealing furnace, preserving heat for 2 hours, and naturally cooling;
step six, machining the molybdenum tube after the annealing treatment by using a lathe, performing defect flaw detection and crystal scanning detection after the inner diameter and the outer diameter are exposed to light, confirming that no physical defects such as cracks, air holes and the like exist, ensuring that the size consistency of internal crystal grains is good, and continuously machining the inner diameter and the outer diameter and the shape of a port interface according to a drawing;
step seven, performing sand blasting treatment on the molybdenum tube with the machining size qualified through rough inspection, selecting 1mm white corundum as a sand blasting material, continuously moving and blasting sand by using a spray head through a roller from one end of the molybdenum tube, repeatedly blasting sand for 5 times back and forth, obtaining a uniform rough surface on the inner surface of the molybdenum tube, and cleaning the inner wall of the molybdenum tube by using distilled water after the molybdenum tube is washed clean by tap water to ensure the cleanliness of the inner wall;
step eight, mixing the mixed slurry (solution A) and the thinner (solution B) according to the proportion of 5: 1, uniformly mixing, heating by using a hot water bath at 30-40 ℃ in winter, before atomization spraying, washing a spraying system pipeline once by using a thinner (liquid B), adjusting air pressure and spray head moving speed, wherein the spraying thickness is about 20 mu m each time, naturally airing for 48h after spraying once, then spraying for the second time, naturally airing for 48h, and coating the thickness of the coating after two atomization spraying times is about 40-50 mu m; wherein the macromolecular compound is methyl ethyl ketone, cyclohexenone, isopropyl alcohol or epoxy resin; the metal oxide is K, Ca, Na, Mg, Fe, Sn, Ag or Pt metal oxide; wherein the mixed slurry is prepared from the following components in percentage by mass: 5: 1: 2, mixing the macromolecular compound, the metal oxide, the rare earth element and the ceramic micro powder;
step nine, placing the target tube subjected to atomization spraying in a vacuum furnace for drying treatment, performing gradient temperature zone treatment in a vacuum environment, heating to 0-20 ℃ for 2 hours, preserving heat for 5 hours, heating to 20-40 ℃ for 2 hours, preserving heat for 5 hours, heating to 40-60 ℃ for 2 hours, preserving heat for 5 hours, and enabling the vacuum degree to be less than 10-2Pa；
Step ten, using hot water of 80 ℃ to the dried target tube, washing the atomized spraying coating of the target tube, drying and then carrying out vacuum packaging to obtain the integrated tubular molybdenum target material.
The density of the integrated tubular pure molybdenum target material prepared by the embodiment is greater than 98.5% of theoretical density, and the average particle size is less than 50um, so that the integrated tubular pure molybdenum target material can be used in the photovoltaic solar industry.
Example 2
A preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises the following steps:
step one, selecting molybdenum alloy powder, and sieving the molybdenum alloy powder for later use; selecting a screen with 160 meshes, treating oversize materials as waste materials, and screening molybdenum powder and molybdenum alloy powder for later use;
step two, loading molybdenum alloy powder into a tubular flexible die with a flexible steel core, and carrying out cold isostatic pressing to prepare a powdery molybdenum tube blank, wherein the pressing pressure of the cold isostatic pressing is 250MPa, and the pressure maintaining time is 3 min;
step three, putting the powdery molybdenum tube blank into a sintering furnace, and sintering in a hydrogen or vacuum environment to obtain a sintered molybdenum tube with the density of more than 95%, wherein the sintering temperature is 1800 ℃ and the sintering time is 8 hours;
step four, putting the sintered molybdenum tube blank into a muffle furnace for heating, and adopting a hollow forging processing mode, wherein the heating temperature is 100 ℃, the heating time is 80min, and the forging section shrinkage rate is 5-50%; selecting a mold with the specification as a target dimension requirement, forging the outer diameter of the sintered molybdenum tube with three fifths of the length to the specification of the target dimension requirement by using a first fire, then performing remelting compensation heating for 70min, forging the outer diameter of the sintered molybdenum tube with the rest length to the specification of the target dimension requirement, and performing hollow forging processing twice to obtain the target tube.
Step five, annealing the forged target tube, and naturally cooling; wherein the annealing temperature is 1300 ℃, and the annealing heat preservation time is 1 h;
step six, machining the target tube after heat treatment to a target required size, and then performing defect detection and crystal scanning detection: by using water immersion type ultrasonic C scanning, no pore defect with the average diameter larger than 0.5mm exists in the machined target tube, the intensity of the bottom wave of crystal scanning is not less than 75%, and the average grain diameter is less than 50 um;
step seven, performing sand blasting treatment on the inner wall surface of the target pipe, wherein the sand blasting material adopts white corundum with the specification and size of 0.5mm, so that the inner wall surface of the target pipe is a uniform sand blasting surface, and the surface sand blasting grade is Sa 3; then, washing the inner wall of the target tube subjected to sand blasting for multiple times by using tap water, washing the inner wall of the target tube by using deionized water or distilled water again after the inner wall is washed clean, and drying the target tube;
step eight, mixing the mixed slurry and the thinner according to the proportion of 5: 1, uniformly mixing, and uniformly spraying the mixture on the inner wall surface of a target tube by an atomization spraying device; before atomization spraying, a pipeline of the atomization spraying device is washed once by using a thinner; in the atomization spraying process, the spray head moves from one end of the inner wall surface of the target pipe to the other end at a constant speed, and after the primary spraying is finished, the spray head is naturally dried for 50 hours; and (4) spraying again after drying, carrying out 1-10 times of atomization spraying according to the coating thickness required by the target, wherein the natural drying is carried out for at least 50h after each spraying is finished. After the atomization spraying is carried out once, the natural air drying time is related to the production field conditions, the air drying time is 120h when the ambient temperature is 0 ℃, and the air drying time is 24h when the ambient temperature is 25 ℃.
Wherein the rare earth element is , erbium or samarium; the thinner is acetone cyclohexanone or n-butanol; wherein the mixed slurry is prepared from the following components in percentage by mass: 5: 1: 2, mixing the macromolecular compound, the metal oxide, the rare earth element and the ceramic micro powder;
step nine, placing the target tube after the atomization spraying in a vacuum furnace for drying treatment, and continuously keeping the vacuum degree to be less than 10-2Pa, drying temperature is 40 ℃; the gradient temperature zone treatment process in the vacuum furnace under the vacuum environment comprises the following steps: heating for 2h at 0-20 ℃, and keeping the temperature for 5 h; raising the temperature for 2 hours at the temperature of 20-40 ℃, and preserving the temperature for 5 hours;
step ten, using 90 ℃ hot water to the dried target tube, washing the atomized spraying coating of the target tube, drying and then carrying out vacuum packaging to obtain the integrated tubular molybdenum target material.
Example 3
A preparation method of an integrated tubular molybdenum target for magnetron sputtering comprises the following steps:
step one, selecting molybdenum alloy powder, and sieving the molybdenum alloy powder for later use; selecting a screen with 180 meshes, treating oversize materials as waste materials, and screening molybdenum powder and molybdenum alloy powder for later use;
step two, loading molybdenum alloy powder into a tubular flexible die with a flexible steel core, and carrying out cold isostatic pressing to prepare a powdery molybdenum tube blank, wherein the pressing pressure of the cold isostatic pressing is 150MPa, and the pressure maintaining time is 10 min;
step three, putting the powdery molybdenum tube blank into a sintering furnace, and sintering in a hydrogen or vacuum environment to obtain a sintered molybdenum tube with the density of more than 95%, wherein the sintering temperature is 2200 ℃, and the sintering time is 7 hours;
step four, putting the sintered molybdenum tube blank into a muffle furnace for heating, and adopting a hollow forging processing mode, wherein the heating temperature is 1500 ℃, the heating time is 75min, and the forging section shrinkage rate is 5-50%; selecting a mold with the specification as a target dimension requirement, forging the outer diameter of the sintered molybdenum tube with three fifths of the length to the specification of the target dimension requirement by using a first fire, then returning to the furnace for compensation heating for 80min, forging the outer diameter of the sintered molybdenum tube with the rest length to the specification of the target dimension requirement, and performing hollow forging processing twice to obtain the target tube.
Step five, annealing the forged target tube, and naturally cooling; wherein the annealing temperature is 800 ℃, and the annealing heat preservation time is 5 h;
step six, machining the target tube after heat treatment to a target required size, and then performing defect detection and crystal scanning detection: by using water immersion type ultrasonic C scanning, no pore defect with the average diameter larger than 0.5mm exists in the machined target tube, the intensity of the bottom wave of crystal scanning is not less than 75%, and the average grain diameter is less than 50 um;
performing sand blasting treatment on the inner wall surface of the target pipe, wherein the sand blasting material adopts a steel ball with the specification and size of 2mm, so that the inner wall surface of the target pipe is a uniform sand blasting surface, and the surface sand blasting grade is Sa 3; then, washing the inner wall of the target tube subjected to sand blasting for multiple times by using tap water, washing the inner wall of the target tube by using deionized water or distilled water again after the inner wall is washed clean, and drying the target tube;
step eight, mixing the mixed slurry and the thinner according to the proportion of 5: 1, uniformly mixing, and uniformly spraying the mixture on the inner wall surface of a target tube by an atomization spraying device; before atomization spraying, a pipeline of the atomization spraying device is washed once by using a thinner; in the atomization spraying process, the spray head moves from one end of the inner wall surface of the target pipe to the other end at a constant speed, and after the primary spraying is finished, the spray head is naturally dried for 120 hours; and (4) spraying again after drying, carrying out 1-10 times of atomization spraying according to the coating thickness required by the target, wherein the natural drying is carried out for 120h after each spraying is finished. After the atomization spraying is carried out once, the natural air drying time is related to the production field conditions, the air drying time is 120h when the ambient temperature is 0 ℃, and the air drying time is 24h when the ambient temperature is 25 ℃.
Wherein the macromolecular compound is methyl ethyl ketone, cyclohexenone, isopropyl alcohol or epoxy resin; the rare earth element is , erbium or samarium; the metal oxide is K, Ca, Na, Mg, Fe, Sn, Ag or Pt metal oxide; the thinner is acetone cyclohexanone or n-butanol; wherein the mixed slurry is prepared from the following components in percentage by mass: 5: 1: 2, mixing the macromolecular compound, the metal oxide, the rare earth element and the ceramic micro powder;
step nine, placing the target tube after the atomization spraying in a vacuum furnace for drying treatment, and continuously keeping the vacuum degree to be less than 10-2Pa, drying temperature is 60 ℃; the gradient temperature zone treatment process in the vacuum furnace under the vacuum environment comprises the following steps: heating for 2h at 0-20 ℃, and keeping the temperature for 5 h; raising the temperature for 2 hours at the temperature of 20-40 ℃, and preserving the temperature for 5 hours; heating for 2h at 40-60 ℃, and keeping the temperature for 5 h.
Step ten, using hot water of 100 ℃ to the dried target tube, washing the atomized spraying coating of the target tube, drying and then carrying out vacuum packaging to obtain the integrated tubular molybdenum target material.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The above examples are intended to illustrate the technical solutions of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, but not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (8)
1. A preparation method of an integrated tubular molybdenum target material for magnetron sputtering is characterized by comprising the following steps:
step one, selecting molybdenum powder or molybdenum alloy powder, and sieving for later use;
step two, molybdenum powder or molybdenum alloy powder is filled into a tubular flexible die with a flexible steel core, and a powdery molybdenum tube blank is manufactured by cold isostatic pressing;
step three, putting the powdery molybdenum tube blank into a sintering furnace, and sintering in a hydrogen or vacuum environment to obtain a sintered molybdenum tube with the density of more than 95%, wherein the sintering temperature is 2000-2200 ℃, and the sintering time is 6-8 h;
heating the sintered molybdenum tube, and then adopting a hollow forging processing mode, forging the sintered molybdenum tube by using a die to produce the target tube, wherein the heating temperature is 1000-1500 ℃, and the forging section shrinkage rate is 5-50%;
step five, annealing the forged target tube, and naturally cooling; wherein the annealing temperature is 800-1300 ℃, and the annealing heat preservation time is 1-5 h;
step six, machining the target tube after heat treatment to a target required size, and then performing defect detection and crystallization scanning detection;
step seven, performing sand blasting treatment on the inner wall surface of the target pipe to realize that the inner wall surface of the target pipe is a uniform sand blasting surface, and the surface sand blasting grade is Sa 3; cleaning the inner wall of the target tube after sand blasting treatment, and airing;
step eight, mixing the mixed slurry and the thinner according to the proportion of 5: 1, uniformly mixing, and uniformly spraying the mixture on the inner wall surface of a target tube by an atomization spraying device; the mixed slurry is formed by mixing a macromolecular compound, a metal oxide, a rare earth element and ceramic micro powder, wherein the mass fraction ratio of the macromolecular compound, the metal oxide, the rare earth element and the ceramic micro powder in the mixed slurry is 12: 5: 1: 2; wherein the macromolecular compound is methyl ethyl ketone, cyclohexenone, isopropyl alcohol or epoxy resin; the rare earth element is , erbium or samarium; the metal oxide is K, Ca, Na, Mg, Fe, Sn, Ag or Pt metal oxide; the thinner is acetone cyclohexanone or n-butanol;
step nine, placing the target tube after atomization spraying in a vacuum furnace for drying treatment;
step ten, using hot water of 80-100 ℃ to the dried target tube, washing the atomized spray coating of the dried target tube, drying and then carrying out vacuum packaging to obtain the integrated tubular molybdenum target material, wherein the vacuum degree is continuously kept to be less than 10-2Pa, drying temperature is 20-60 ℃; wherein, the gradient temperature in the vacuum furnace is passed through the vacuum environmentThe zone treatment process comprises the following steps: heating for 2h at 0-20 ℃, and keeping the temperature for 5 h; raising the temperature for 2 hours at the temperature of 20-40 ℃, and preserving the temperature for 5 hours; heating for 2h at 40-60 ℃, and keeping the temperature for 5 h.
2. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: in the first step, when the molybdenum powder and the molybdenum alloy powder are screened, a screen is selected to be 160-200 meshes, oversize materials are treated as waste materials, and undersize molybdenum powder and molybdenum alloy powder are reserved.
3. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: and in the second step, the pressing pressure of the cold isostatic pressing is 150-250 MPa, and the pressure maintaining time is 2-10 min.
4. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: and in the fourth step, the sintered molybdenum tube blank is placed into a muffle furnace to be heated, the heating temperature is 1000-1500 ℃, the heating time is 60-80 min, the specification of a die is selected as the target dimension requirement, the outer diameter dimension of the sintered molybdenum tube with the length of three fifths of the tube blank is forged to the specification of the target dimension requirement by the first fire, then the tube blank is returned to the furnace to be heated for compensation for 60 min-80 min, the outer diameter dimension of the sintered molybdenum tube with the residual length is forged to the specification of the target dimension requirement, and the target tube is manufactured by hollow forging processing twice.
5. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: in the seventh step, white corundum or steel balls with the specification and size of 0.5-2 mm are adopted as the materials for sand blasting; the process for cleaning the inner wall of the target tube after sand blasting comprises the following steps: and (4) washing the inner wall of the target tube subjected to sand blasting for multiple times by using tap water, and cleaning the inner wall of the target tube by using deionized water or distilled water again after the inner wall is washed clean.
6. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: and step six, performing water immersion type ultrasonic C scanning, wherein no pore defect with the average diameter larger than 0.5mm exists in the machined target tube, the intensity of the bottom wave of the crystal scanning is not smaller than 75%, and the average grain diameter is smaller than 50 um.
7. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: step eight, before atomization spraying, the pipeline of the atomization spraying device is washed once by using a thinner; in the atomization spraying process, the spray head moves from one end of the inner wall surface of the target pipe to the other end at a constant speed, and after the primary spraying is finished, the spray head is naturally dried for 24-120 hours; and (4) spraying again after drying, carrying out 1-10 times of atomization spraying according to the coating thickness required by the target, wherein the spraying is finished every time, and naturally drying for 24-120 h.
8. The preparation method of the integrated tubular molybdenum target for magnetron sputtering according to claim 1, wherein the preparation method comprises the following steps: and step eight, after atomization spraying once, naturally airing for 24 hours at the ambient temperature of 25 ℃ in relation to production site conditions, wherein the airing time is 120 hours at the ambient temperature of 0 ℃.
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