CN111499381B - Preparation method of high-compactness conductive zirconia ceramic target for magnetron sputtering - Google Patents

Preparation method of high-compactness conductive zirconia ceramic target for magnetron sputtering Download PDF

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CN111499381B
CN111499381B CN202010336636.9A CN202010336636A CN111499381B CN 111499381 B CN111499381 B CN 111499381B CN 202010336636 A CN202010336636 A CN 202010336636A CN 111499381 B CN111499381 B CN 111499381B
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powder
compactness
target material
sintering
magnetron sputtering
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CN111499381A (en
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康明生
崔娜
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Hebei East With Photoelectronic Technology Co ltd
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Abstract

The invention discloses a preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering, which comprises the following steps: doping and pretreating zirconia powder to obtain stable tetragonal crystal form powder; carrying out atmosphere sintering treatment on the powder to obtain conductive zirconia powder; conducting primary pressing molding on the conductive powder through isostatic pressing equipment according to the size of a die to obtain a rough blank; loading the rough blank into a graphite mold, then loading the graphite mold into a vacuum hot-pressing sintering furnace for sintering, and after sintering, carrying out stepped temperature reduction, pressure relief and discharging to obtain a rough target; and finally, performing finish machining to obtain the high-compactness conductive zirconia ceramic target special for magnetron sputtering. The preparation method disclosed by the invention is simple in preparation process, easy to operate, safe and pollution-free, and the prepared zirconia target material is good in conductivity, compactness and stability, completely meets the requirements of the target material for the magnetron sputtering process, and provides a reliable guarantee for realizing industrialized coating.

Description

Preparation method of high-compactness conductive zirconia ceramic target for magnetron sputtering
Technical Field
The invention relates to the technical field of target preparation, in particular to a preparation method of a special target for a magnetron sputtering coating process.
Background
The zirconia film is a novel high-transparency hard functional film material, is applied to the fields of high-end mobile phones, watches, household appliances and the like, has the protective effect of scratch prevention and abrasion prevention on the appearance of a product, and is transparent and does not influence the appearance of the product. With the progress of science and technology, the market demand of the hard high-transparency film is larger and larger, so that the application field in the future is wider and wider. At present, two forming processes exist in the market, but the produced target has low compactness and is not conductive, and industrialization is not formed.
Chemical Vapor Deposition (CVD) and electroplating processes in the film forming process are heavily contaminated, and the development space is limited. The physical vapor deposition coating process has no pollution, and the film produced by the process has the characteristics of strong adhesive force, uniform film layer and the like, so the process has wide future development space. The substrate required by the physical vapor deposition coating process is a carrier in the form of a blocky zirconia target material, and the coating is finished after the zirconia is bombarded; at present, no zirconia target suitable for the process exists in the market, so that the research and development of the high-quality zirconia target can realize industrialization and is beneficial to future wide application.
The technical requirements of the physical vapor deposition process on the zirconia target material are high compactness, conductivity and stable performance. Because the crystal forms of the zirconia are complex and various, generally have three monoclinic crystal forms, tetragonal crystal forms and cubic crystal forms, and the crystal form conversion can change along with the temperature change, the qualified target material can not be obtained by adopting the traditional forming process mode, therefore, Chinese patent CN103936415B discloses a stable zirconia ceramic target material for electron beam physical vapor deposition and a preparation method thereof, the stability of the target material is improved by adding Nb, Ta, Sm or Gd oxide into the components of the zirconia and the yttrium oxide, but the prepared target material has no conductivity, so the stable zirconia ceramic target material can only be suitable for an EB-PVD process, and the requirement of the physical vapor deposition process on the target material can not be met.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a high-compactness conductive zirconia ceramic target special for a magnetron sputtering process, wherein the prepared target has high compactness, conductivity and stability by adding powder and forming through a hot pressing process, and a required substrate is provided for the magnetron sputtering coating process.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows.
A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering comprises the following steps:
A. doping zirconia powder: zirconium oxide (ZrO)2) Mixing the powder with stabilizer Yttrium oxide (Y)2O3) Magnesium oxide (MgO) capable of changing the brittleness of the target material and metal niobium (Nb) or tantalum (Ta) with the function of electric conduction are doped according to the proportion, and the prepared powder is put into a ball mill to be mixed uniformly;
B. powder treatment: calcining the mixed material obtained in the step A in a hydrogen atmosphere at 850-900 ℃ for 5-8 h, wherein the amount of single calcined powder is 40-42 Kg;
C. b, isostatic pressing is carried out on the powder obtained in the step B, the isostatic pressing pressure is 100-150 MPa, the pressure maintaining time is 1-2 h, the thickness of the rough blank is pressed according to the thickness of the finished product, and the density of the rough blank is controlled to be 50% -60% of the relative density;
D. c, placing the rough blank obtained in the step C into a graphite mold, and placing the mold with the rough blank into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering to obtain a rough target;
E. finish machining: and D, cutting and carrying out plane grinding on the coarse target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target with the relative density of more than 98% and the target resistance of less than 300 omega.
The preparation method of the high-compactness conductive zirconia ceramic target material for magnetron sputtering comprises the step of preparing ZrO in zirconia powder2The mass fraction of (A) is 88-90%; y is2O38 to 9 percent of the total amount of the Nb or Ta, 1 to 1.5 percent of MgO and 1 to 1.5 percent of the total amount of the Nb or Ta.
The preparation method of the high-compactness conductive zirconia ceramic target material for magnetron sputtering comprises the step of preparing ZrO2The purity of the powder is more than or equal to 99.95 percent, the content of iron impurities is less than or equal to 30ppm, and the content of cobalt impurities is less than or equal to 40 ppm; ZrO (ZrO)2The particle size D50 is 0.2-0.3 micron; y is2O3The purity is more than or equal to 99.9 percent; the purity of MgO is more than or equal to 99.9 percent; the purity of Nb or Ta is more than or equal to 99.9 percent.
According to the preparation method of the high-compactness conductive zirconia ceramic target material for magnetron sputtering, balls used in the ball mill in the step A are zirconia balls, and the sizes of the balls are divided into three types: the phi 40mm balls account for one third of the total number of the balls, the phi 20mm balls account for one third of the total number of the balls, the phi 10mm balls account for one third of the total number of the balls, and the single ball milling time is 4-5 hours.
The preparation method of the high-compactness conductive zirconia ceramic target material for magnetron sputtering comprises the following vacuum hot-pressing sintering conditions in the step D: the vacuum degree is less than 10Pa, the sintering temperature is 1650-1750 ℃, the heating rate is controlled at 6-8 ℃/min, the sintering pressure is 38-46 MPa, and the heat preservation and pressure maintaining are carried out for 7-9 h; and after sintering, cooling to 500 ℃, relieving the pressure to normal pressure, and discharging when the temperature is continuously reduced to below 100 ℃ to obtain the coarse target.
Due to the adoption of the technical scheme, the technical progress of the invention is as follows.
According to the invention, a stabilizer for controlling crystal form, a stabilizer for reducing target brittleness and a metal additive with a conductive effect are added into zirconia powder, and the conversion rate of the zirconia crystal form is controlled, so that the cubic crystal form ratio of the zirconia target reaches more than 98.5%; the zirconia ceramic target material prepared by the method is simple in preparation process and easy to operate, and the prepared zirconia ceramic target material is used as a magnetron sputtering coating substrate, so that the zirconia hard film can be coated on the surface of electronic products such as mobile phones and household appliances, and the surface of the electronic products is protected on the basis of realizing conductivity.
In the process of preparing the target material, the brittleness of the target material is reduced by adding MgO; by adding appropriate amount of niobium (Nb) or tantalum (Ta) and using H2Atmosphere sintering, namely replacing part of oxygen by combining with the control of hydrogen replacement time and temperature, and replacing the oxygen with Nb or Ta to obtain multi-valence Nb or Ta atoms with electrons, so that the purposes of conductivity and controllable resistance are achieved, and the conductivity of the target material is realized; the high compactness of the target is ensured by adopting a hot pressing process and controlling the pressure, and the density of the target is more than or equal to 5.7g/cm3And the relative density reaches more than 98 percent. The high-compactness conductive zirconia ceramic target material special for the magnetron sputtering process, prepared by the invention, has the advantages of resistance less than or equal to 300 omega, good stability, no target cracking and no peculiar smell when the target material is heated in a metallization way at 200 ℃, can meet the coating requirement of the magnetron sputtering process, has a smooth sputtering runway without nodules, and provides a reliable guarantee for realizing the industrialized coating of zirconia.
Detailed Description
A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering comprises the steps of adding a stabilizer and a Nb or Ta metal material with a conductive effect into zirconia powder, carrying out ball milling and mixing, calcining in a hydrogen atmosphere to obtain conductive powder, and pressurizing under the conditions of high temperature and high vacuum to ensure the target material forming and the target material compactness. The preparation method specifically comprises the following steps.
A. Doping of zirconia powder: zirconium oxide (ZrO)2) Mixing the powder with stabilizer Yttrium oxide (Y)2O3) Magnesium oxide (MgO) capable of changing the brittleness of the target material and metal niobium (Nb) or tantalum (Ta) with the conductive function are doped according to the proportion. The doping proportion is as follows: ZrO (ZrO)288 to 90 percent of Y2O3Has a mass fraction of8 to 9 percent of MgO, 1 to 1.5 percent of Nb or Ta, and putting the prepared powder into a ball mill for ball milling and mixing uniformly.
Zirconia generally has three crystal forms, namely monoclinic, tetragonal and cubic, at normal temperature, zirconia only has monoclinic phase, when the temperature reaches 1100-1200 ℃, monoclinic and tetragonal crystal forms are mutually transformed, and along with the change of volume, a target material is easy to deform and become unstable; when the temperature reaches 2370 ℃, the tetragonal crystal form is converted to the cubic fluorite structure, and Y is added2O3The purpose of (1) is to prevent the cubic crystal form from being reversed; at ZrO2During the transformation of the crystal form with increasing temperature, Y3+Replacing Zr in Zr lattice4+Filled with ZrO2Medium lattice defect, suppression of ZrO2Twist of when ZrO2When the cubic crystal proportion of the target material reaches more than 98.5 percent, the performance of the target material becomes stable, and the target is not cracked in the process of raising the temperature to 200 ℃ by metallization. The addition of MgO can reduce the brittleness of the target material, so that the target material cannot crack in the processing process and the coating process. The addition of the metal Nb or Ta can make the target material conductive, and can control the resistance of the target material without influencing the coating quality.
As the excessive impurity content of Fe and Co in the zirconium oxide can influence the uniformity of the appearance of the target material film, the ZrO2The too large particle size affects the activity reduction of the powder, consumes more electricity and time and increases the production cost, while the too small particle size and the too high activity are difficult to control the conductivity and the stability, so the ZrO powder has the advantages of small particle size, high activity and difficult control of the conductivity and the stability2The purity of the powder is more than or equal to 99.95 percent, the content of iron (Fe) impurities is less than or equal to 30ppm, the content of cobalt (Co) impurities is less than or equal to 40ppm, and ZrO is formed2The particle size D50 is controlled to be 0.2-0.3 micron; y is2O3The purity is more than or equal to 99.9 percent; the purity of MgO is more than or equal to 99.9 percent; the purity of Nb or Ta is more than or equal to 99.9 percent.
In the ball milling process of the mixture, balls used in the ball mill are zirconia balls, and the sizes of the balls are divided into three types: the phi 40mm balls account for one third of the total number of the balls, the phi 20mm balls account for one third of the total number of the balls, the phi 10mm balls account for one third of the total number of the balls, and the single ball milling time is 4-5 hours, so that the particle size of the zirconia can be effectively controlled.
B. Powder partProcessing: mixing the mixed powder obtained in the step A in the presence of hydrogen2Calcining in the atmosphere, wherein the calcining temperature is 850-900 ℃, the calcining time is 5-8 h, and the single calcining amount is 40-42 kg.
In the invention, the metal is conductive, but the target resistance is uneven due to the doping uniformity, and H is adopted2Substituted ZrO2And the metal and the oxygen react to generate multi-valence Nb or Ta, so that the zirconium and the metal both have partial electrons, and the uniformity of the target resistance is ensured.
C. B, conducting isostatic pressing on the conductive powder obtained in the step B to form a rough blank, and keeping the isostatic pressing pressure at 100-150 MPa for 1-2 hours; the thickness of the rough blank is pressed according to the thickness of the finished product, and the density of the rough blank is controlled to be 50-60% of the relative density.
D. And D, placing the rough blank obtained in the step C into a graphite mold, and conveying the rough blank into a vacuum sintering furnace for vacuum hot-pressing sintering. The conditions of the vacuum hot-pressing sintering are as follows: the vacuum degree is less than 10Pa, the sintering temperature is 1650-1700 ℃, the heating rate is controlled at 6-8 ℃/min, the sintering pressure is 38-46 MPa, and the heat preservation and pressure maintaining are carried out for 7-9 h; and after sintering, cooling to 500 ℃, relieving the pressure to normal pressure, and discharging when the temperature is continuously reduced to below 100 ℃ to obtain the coarse target.
After the target sintering, the temperature need slowly reduce, this stage is the target design shaping stage, if be higher than 500 ℃ pressure release, the target is crooked easily, so should cool down to 500 ℃ after again the pressure release, after the pressure release was accomplished, continue cooling to 100 ℃ and go out of the stove, the setting of this temperature is because the furnace material is graphite products, the mould is graphite mold, if it is too high to go out of the stove temperature, oxidation phenomenon can appear in furnace and mould, reduce the life of furnace and mould.
E. Finish machining: and D, cutting and carrying out plane grinding on the rough target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target material special for magnetron sputtering, wherein the relative density of the target material is more than 98%, and the target material resistance is less than 300 omega.
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering specifically comprises the following steps.
A. Pretreatment of zirconia powder: and ball-milling and uniformly mixing the zirconium oxide powder with a stabilizer and a metal powder ball mill in a certain proportion to obtain a mixed material. In this example, yttrium oxide (Y) was used as the stabilizer2O3) The metal powder is metal niobium (Nb); wherein, wt% ZrO2＝89％，Y2O3In wt% Y2O38%, 1.5% by weight of MgO and 1.5% by weight of Nb. And putting the prepared powder into a ball mill for ball milling and mixing for 4 hours, and weighing 40 kg.
B. Putting 40kg of mixed powder obtained in the step A into H2Calcining in an atmosphere sintering furnace at 850 ℃ for 5 h.
C. B, carrying out isostatic pressing on the conductive mixed material obtained in the step B, wherein the isostatic pressure is 125MPa, and the pressure maintaining time is 1 h; pressing into a block-shaped rough blank with the relative density of 52 percent.
D. And D, putting the massive rough blank obtained in the step C into a graphite mold, conveying the massive rough blank into a vacuum sintering furnace for vacuum hot-pressing sintering, wherein the vacuum degree is 8Pa, the sintering temperature is 1650 ℃, the heating rate is 6 ℃/min, the sintering pressure is 40MPa, the pressure is increased for 1h, the heat preservation and pressure maintaining are carried out for 7h, after the sintering is finished, the power is cut off and the temperature is reduced, the pressure is released to normal pressure when the temperature is reduced to 500 ℃, the rough blank is continuously reduced to below 100 ℃, and then the rough blank is discharged out of the furnace by breaking the air to obtain the rough target.
E. Finish machining: and D, performing linear cutting and plane grinding on the coarse target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target material special for magnetron sputtering.
Through detection, the density of the zirconia ceramic target material prepared by the embodiment is 5.73g/cm3The relative density was 98.8%, and the target resistance was 201 Ω.
Example 2
A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering specifically comprises the following steps.
A. Pretreatment of zirconia powder: and ball-milling and uniformly mixing the zirconium oxide powder with a stabilizer and a metal powder ball mill in a certain proportion to obtain a mixed material. In this example, the stabilizer was usedYttrium oxide (Y)2O3) The metal powder is metal tantalum (Ta); wherein, wt% ZrO2＝90％，Y2O3In wt% Y2O38%, 1% of MgO and 1% of Ta. And ball-milling and mixing the proportioned powder for 4 hours, and weighing 40 kg.
B. Putting 40kg of mixed powder obtained in the step A into H2Calcining in an atmosphere sintering furnace at 880 ℃ for 6 h.
C. B, carrying out isostatic pressing on the conductive mixed material obtained in the step B, wherein the isostatic pressure is 140MPa, and the pressure maintaining time is 1.5 h; pressing into a block-shaped rough blank with the relative density of 56 percent.
D. And D, putting the massive rough blank obtained in the step C into a graphite mold, conveying the massive rough blank into a vacuum sintering furnace for vacuum hot-pressing sintering, wherein the vacuum degree is 9Pa, the sintering temperature is 1680 ℃, the heating rate is 7 ℃/min, the sintering pressure is 46MPa, the pressure is applied for 1h, the heat preservation and pressure maintaining are carried out for 8h, after the sintering is finished, the power is cut off and the temperature is reduced, the pressure is released to normal pressure when the temperature is reduced to 500 ℃, the rough blank is continuously reduced to below 100 ℃, and then the rough blank is discharged out of the furnace after being broken to the air, so that the rough target is obtained.
E. Finish machining: and D, performing linear cutting and plane grinding on the coarse target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target material special for magnetron sputtering.
The density of the zirconia ceramic target material prepared by the embodiment is detected to be 5.77g/cm3The relative density was 99.5%, and the target resistance was 158 Ω.
Example 3
A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering specifically comprises the following steps.
A. Pretreatment of zirconia powder: and ball-milling and uniformly mixing the zirconium oxide powder with a stabilizer and a metal powder ball mill in a certain proportion to obtain a mixed material. In this example, yttrium oxide (Y) was used as the stabilizer2O3) The metal powder is metal niobium (Nb); wherein, wt% ZrO2＝88％，Y2O3In wt% Y2O39%, 1.5% by weight of MgO, and 1.5% by weight of Nb. The prepared powder was ball milled and mixed for 4 hours and weighed 40 kg.
B. Putting 40kg of mixed powder obtained in the step A into H2Calcining in an atmosphere sintering furnace at 880 ℃ for 5 h.
C. B, carrying out isostatic pressing on the conductive mixed material obtained in the step B, wherein the isostatic pressure is 125MPa, and the pressure maintaining time is 2 h; pressing into a block-shaped rough blank with the relative density of 60 percent.
D. And D, putting the block rough blank obtained in the step C into a graphite die, and conveying the block rough blank into a vacuum sintering furnace for vacuum hot-pressing sintering. The conditions of the vacuum hot-pressing sintering are as follows: the vacuum degree is 8Pa, the sintering temperature is 1700 ℃, the heating rate is 8 ℃/min, the sintering pressure is 46MPa, the pressure is 1h, the heat preservation and pressure maintaining are carried out for 9h, after the sintering is finished, the power is cut off and the temperature is reduced, the pressure is released to the normal pressure when the temperature is reduced to 500 ℃, the temperature is continuously reduced to below 100 ℃, and then the coarse target is obtained by breaking the air and discharging.
E. Processing: and D, performing linear cutting and plane grinding on the coarse target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target material special for magnetron sputtering.
Through detection, the density of the zirconia ceramic target material prepared by the embodiment is 5.78g/cm3The relative density was 99.7%, and the target resistance was 132 Ω.
The above-described embodiments are only preferred embodiments of the present invention, and do not limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.

Claims (4)

1. A preparation method of a high-compactness conductive zirconia ceramic target material for magnetron sputtering is characterized by comprising the following steps:
A. doping zirconia powder: zirconium oxide (ZrO)2) Mixing the powder with stabilizer Yttrium oxide (Y)2O3) Magnesium oxide (MgO) capable of changing the brittleness of the target material and metal niobium (Nb) or tantalum (Ta) with the function of electric conduction are doped according to the proportion, and the prepared powder is put into a ball mill to be mixed uniformly;
B. powder treatment: calcining the mixed material obtained in the step A in a hydrogen atmosphere at the calcining temperature of 850-900 DEG CThe calcination time is 5-8 h, and the amount of powder calcined once is 40-42 Kg; by means of H2Substituted ZrO2The metal and oxygen react to generate multi-valence Nb or Ta, so that zirconium and the metal both have partial electrons;
C. b, isostatic pressing is carried out on the powder obtained in the step B, the isostatic pressing pressure is 100-150 MPa, the pressure maintaining time is 1-2 h, the thickness of the rough blank is pressed according to the thickness of the finished product, and the density of the rough blank is controlled to be 50% -60% of the relative density;
D. c, placing the rough blank obtained in the step C into a graphite mold, and placing the mold with the rough blank into a vacuum hot-pressing sintering furnace for vacuum hot-pressing sintering to obtain a rough target; the conditions of the vacuum hot-pressing sintering in the step D are as follows: the vacuum degree is less than 10Pa, the sintering temperature is 1650-1750 ℃, the heating rate is controlled at 6-8 ℃/min, the sintering pressure is 38-46 MPa, and the heat preservation and pressure maintaining are carried out for 7-9 h; after sintering, cooling to 500 ℃, decompressing to normal pressure, and discharging when the temperature is continuously reduced to below 100 ℃ to obtain a coarse target;
E. finish machining: and D, cutting and carrying out plane grinding on the coarse target obtained in the step D to obtain the high-compactness conductive zirconia ceramic target with the relative density of more than 98% and the target resistance of less than 300 omega.
2. The method for preparing a high-compactness conductive zirconia ceramic target material for magnetron sputtering according to claim 1, wherein ZrO in the zirconia powder2The mass fraction of (A) is 88-90%; y is2O38 to 9 percent of the total amount of the Nb or Ta, 1 to 1.5 percent of MgO and 1 to 1.5 percent of the total amount of the Nb or Ta.
3. The method for preparing the high-compactness conductive zirconia ceramic target material for magnetron sputtering according to claim 2, wherein ZrO is ZrO2The purity of the powder is more than or equal to 99.95 percent, the content of iron impurities is less than or equal to 30ppm, and the content of cobalt impurities is less than or equal to 40 ppm; ZrO (ZrO)2The particle size D50 is 0.2-0.3 micron; y is2O3The purity is more than or equal to 99.9 percent; the purity of MgO is more than or equal to 99.9 percent; the purity of Nb or Ta is more than or equal to 99.9 percent.
4. The method for preparing the high-compactness conductive zirconia ceramic target material for magnetron sputtering according to claim 1, wherein the balls used in the ball mill in the step A are zirconia balls, and the sizes of the balls are divided into three types: the phi 40mm balls account for one third of the total number of the balls, the phi 20mm balls account for one third of the total number of the balls, the phi 10mm balls account for one third of the total number of the balls, and the single ball milling time is 4-5 hours.
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