CN113149633A - Preparation method of secondary phase controllable zinc-aluminum oxide sputtering target material - Google Patents
Preparation method of secondary phase controllable zinc-aluminum oxide sputtering target material Download PDFInfo
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Abstract
The preparation method of the secondary phase controllable zinc-aluminum oxide sputtering target material comprises the following steps: uniformly mixing zinc oxide powder and alumina powder in a molar ratio of 1:1 to obtain first mixed powder, and calcining the first mixed powder in an oxygen atmosphere to generate zinc aluminate powder; wherein the calcining temperature is set to be 1000-1400 ℃, and the calcining treatment time is set to be 2-20 hours; mixing the generated zinc aluminate powder and zinc oxide powder in a molar ratio of 0.015-0.02 to obtain second mixed powder, and mixing the second mixed powder with water, a dispersant and a binder in a set ratio to obtain zinc-aluminum oxide slurry with the solid content of more than 80% and the viscosity of less than 100mPa & s; performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent; drying the zinc-aluminum oxide target biscuit; and (3) degreasing and sintering the dried zinc-aluminum oxide target biscuit to obtain the secondary phase controllable zinc-aluminum oxide sputtering target.
Description
Technical Field
The application belongs to the technical field of photoelectric materials, and particularly relates to a sputtering target material, in particular to a preparation method of a secondary phase controllable zinc-aluminum oxide sputtering target material.
Background
Transparent conductive oxide films (TCO) are a material with a special function, have good optical properties and electrical conductivity, and are widely used in the fields of electronic screens, touch screen panels, Light Emitting Diodes (LEDs), solar cells, and the like. Such materials can be prepared using chemical vapor deposition, magnetron sputtering, spray pyrolysis, and like techniques. The TCO most commonly used at present is tin-doped indium oxide, i.e. indium tin oxide, ITO, but since indium is expensive and scarce, the cost of ITO sputtering target materials in industrial production is too high. The TCO film of ZnO has been widely studied due to its excellent electrical and optical properties, low price, low manufacturing cost, and the like. Addition of Al2O3The ZnO of (1), namely the aluminum-doped zinc oxide AZO, is considered as a potential substitute of ITO (indium tin oxide) due to the advantages of low resistivity, high visible light transmittance, low cost, lower deposition temperature and the like. With the rapid development of heterojunction solar cells, the demand on TCO films is rapidly increased, and the demand on further optimizing the photoelectric properties of AZO films and preparing higher-performance AZO targets is increasing day by day.
The performance of the AZO film depends on the performance of the AZO sputtering target to a great extent, and in order to obtain an AZO film with good performance, the AZO sputtering target is often required to have high purity, high density, and a uniform and fine phase structure. ZnAl in AZO sputtering targets in general2O4The spinel phase is preferentially formed in a ZnO crystal boundary in the sintering process, so that abnormal growth of ZnO crystal grains is inhibited, the sintering driving force of the Al-doped ZnO composite material is reduced, the crystal grains can be refined, and the strength of the AZO sputtering target material is increased. Secondary phase ZnAl in AZO sputtering target material in prior art2O4Less content and uneven distribution of secondary phaseAnd (4) homogenizing.
Disclosure of Invention
In view of this, some embodiments disclose a method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target, the method comprising:
uniformly mixing zinc oxide powder and alumina powder in a molar ratio of 1:1 to obtain first mixed powder, and calcining the first mixed powder in an oxygen atmosphere to generate zinc aluminate powder; wherein the calcining temperature is set to be 1000-1400 ℃, and the calcining treatment time is set to be 2-20 hours;
mixing the generated zinc aluminate powder and zinc oxide powder in a molar ratio of 0.015-0.02 to obtain second mixed powder, and mixing the second mixed powder with water, a dispersant and a binder in a set ratio to obtain zinc-aluminum oxide slurry with the solid content of more than 80% and the viscosity of less than 100mPa & s;
performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent;
drying the zinc-aluminum oxide target biscuit;
and (3) degreasing and sintering the dried zinc-aluminum oxide target biscuit, wherein zinc aluminate powder in the zinc-aluminum oxide target biscuit forms a secondary phase, zinc oxide powder forms a main phase, and the secondary phase is uniformly dispersed among the main phases to obtain the secondary phase controllable zinc-aluminum oxide sputtering target.
Further, in some embodiments, the zinc oxide powder and the aluminum oxide powder in the first mixed powder are nanoparticles, and the particle size distribution is between 100 nm and 300 nm.
Some embodiments disclose a method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target, wherein in a zinc-aluminum oxide slurry, a mass ratio of a dispersant to second mixed powder is 1.2-1.8: 100, a mass ratio of a binder to the second mixed powder is 0.3-1.0: 100, and a mass ratio of water to the second mixed powder is 16-20: 100.
In some embodiments, in the preparation method of the secondary phase controllable zinc-aluminum oxide sputtering target material disclosed in the embodiments, in the calcination treatment process of the first mixed powder, the temperature rise rate of raising the temperature to the calcination temperature is set to 10-20 ℃/min.
Some embodiments disclose a method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target, wherein a biscuit of the zinc-aluminum oxide sputtering target is dried at a constant temperature and humidity, and the method specifically comprises the following steps:
drying for the first time for 24-36 hours under the conditions that the first drying temperature is 25-35 ℃ and the first humidity is 70-80% RH;
and then drying for a second time for 36-48 hours under the conditions that the second drying temperature is 35-45 ℃ and the second humidity is 70-80% RH.
Some embodiments disclose a method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target, wherein a zinc-aluminum oxide target biscuit is subjected to degreasing and sintering integrated treatment, wherein:
the degreasing temperature is set to be 500-800 ℃, the degreasing temperature rise rate is 0.5-1.5 ℃/min, and the degreasing heat preservation time is 5-24 h;
the sintering process is carried out according to the following step variable temperature sintering procedure:
heating the degreasing temperature to a first step temperature T1 at a speed of 2-4 ℃/min, and keeping the temperature for 10-20 hours;
heating to a second step temperature T2 at a speed of 5-10 ℃/min, and keeping the temperature;
cooling to a third step sintering temperature T3 at a speed of 10-20 ℃/min, and preserving heat for 10-30 hours;
cooling to 600 ℃ at a speed of 1-2 ℃/min, and naturally cooling;
wherein T1 is 900-1100 deg.C, T2 is 1400-1500 deg.C, and T3 is 1000-1300 deg.C.
Some embodiments disclose a method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target material, wherein zinc-aluminum oxide slurry is subjected to vacuum defoaming treatment before pressure grouting forming, and the vacuum pressure is less than 0.1 Pa.
In some embodiments, the method for preparing the secondary phase controllable zinc-aluminum oxide sputtering target material disclosed in the embodiments comprises the steps of crushing the generated zinc aluminate powder to form nano-particles with a particle size equivalent to that of the zinc oxide powder, and then mixing the nano-particles to obtain a second mixed powder.
In some embodiments, the zinc oxide powder and the aluminum oxide powder are nanoparticles, and the particle size distribution is 100-200 nm.
Some embodiments disclose a preparation method of a secondary phase controllable zinc-aluminum oxide sputtering target material, wherein a dispersant is polyacrylic acid or polycarboxylic acid dispersant, and a binder is polyvinyl alcohol or Arabic gum.
The preparation method of the secondary phase controllable zinc-aluminum oxide sputtering target material disclosed by the embodiment of the application comprises the steps of firstly, adopting zinc oxide powder and alumina powder to generate zinc aluminate powder, then mixing the zinc aluminate powder with the zinc oxide powder, and then carrying out degreasing sintering, wherein the zinc aluminate powder preferentially forms spinel phase zinc aluminate secondary phase in a zinc oxide crystal interface, so that abnormal growth of zinc oxide crystal grains is inhibited, the crystal grains can be refined, the zinc-aluminum oxide sputtering target material with uniformly refined structure and controllable secondary phase is obtained, the relative density can reach more than 99%, and the bulk resistivity is less than 3m omega cm.
Drawings
FIG. 1 XRD pattern of zinc-aluminum oxide target in example 1
FIG. 2 scanning electron microscope image of cross section of the zinc-aluminum oxide target material in example 1
FIG. 3 is a distribution diagram of the grain structure of the zinc-aluminum oxide target material in example 1
FIG. 4 is a distribution diagram of the grain structure of a zinc-aluminum oxide target material in comparative example 1
Reference numerals
1 zinc oxide bulk phase crystal grain 2 zinc aluminate secondary phase crystal grain
Detailed Description
The word "embodiment" as used herein, is not necessarily to be construed as preferred or advantageous over other embodiments, including any embodiment illustrated as "exemplary". Performance index tests in the examples of this application, unless otherwise indicated, were performed using routine experimentation in the art. It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs; other test methods and techniques not specifically mentioned in the present application are those commonly employed by those of ordinary skill in the art.
The terms "substantially" and "about" are used herein to describe small fluctuations. For example, they may mean less than or equal to ± 5%, such as less than or equal to ± 2%, such as less than or equal to ± 1%, such as less than or equal to ± 0.5%, such as less than or equal to ± 0.2%, such as less than or equal to ± 0.1%, such as less than or equal to ± 0.05%. Numerical data represented or presented herein in a range format is used merely for convenience and brevity and thus should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a numerical range of "1 to 5%" should be interpreted to include not only the explicitly recited values of 1% to 5%, but also include individual values and sub-ranges within the indicated range. Thus, included in this numerical range are individual values, such as 2%, 3.5%, and 4%, and sub-ranges, such as 1% to 3%, 2% to 4%, and 3% to 5%, etc. This principle applies equally to ranges reciting only one numerical value. Moreover, such an interpretation applies regardless of the breadth of the range or the characteristics being described.
In this document, including the claims, all conjunctions such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" containing, "and the like are to be understood as being open-ended, i.e., to mean" including but not limited to. Only the conjunctions "consisting of … …" and "consisting of … …" are closed conjunctions.
In the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present disclosure. It will be understood by those skilled in the art that the present application may be practiced without some of these specific details. In the examples, some methods, means, instruments, apparatuses, etc. known to those skilled in the art are not described in detail in order to highlight the subject matter of the present application.
On the premise of no conflict, the technical features disclosed in the embodiments of the present application may be combined arbitrarily, and the obtained technical solution belongs to the content disclosed in the embodiments of the present application.
In some embodiments, a method of preparing a secondary phase controlled zinc aluminum oxide sputtering target comprises:
(1) uniformly mixing zinc oxide powder and alumina powder in a molar ratio of 1:1 to obtain first mixed powder, and calcining the first mixed powder in an oxygen atmosphere to generate zinc aluminate powder; wherein the calcining temperature is set to be 1000-1400 ℃, and the calcining treatment time is set to be 2-20 hours;
(2) mixing the generated zinc aluminate powder and zinc oxide powder in a molar ratio of 0.015-0.02 to obtain second mixed powder, and mixing the second mixed powder with water, a dispersant and a binder in a set ratio to obtain zinc-aluminum oxide slurry with the solid content of more than 80% and the viscosity of less than 100mPa & s;
(3) performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent;
(4) drying the zinc-aluminum oxide target biscuit;
(5) and (3) degreasing and sintering the dried zinc-aluminum oxide target biscuit, wherein zinc aluminate powder in the zinc-aluminum oxide target biscuit forms a secondary phase, zinc oxide powder forms a main phase, and the secondary phase is uniformly dispersed among the main phases to obtain the secondary phase controllable zinc-aluminum oxide sputtering target.
Typically, the molar ratio of zinc oxide ZnO to aluminum oxide Al is 1:12O3After mixing, the mixture is calcined in oxygen atmosphere to generate zinc aluminate ZnAl2O4Powder, can adopt high-efficient blender to mix zinc oxide powder and alumina powder usually, form the first mixed powder of two kinds of powder homogeneous mixings of zinc oxide and alumina, be favorable to first mixed powder to form homogeneous zinc aluminate spinel structure in calcining the in-process, and then have the zinc aluminate powder of spinel crystal structure and zinc oxide mix and carry out the follow-up technology of sintering, zinc aluminate spinel can keep its spinel structure and atomic composition, the secondary crystalline phase ZnAl of preferentially forming zinc aluminium oxide in the main phase that zinc oxide powder formed2O4Can realize the secondary phase Z of the zinc aluminate in the zinc-aluminum oxide target materialnAl2O4The zinc-aluminum atoms in the zinc aluminate secondary phase are kept stable, so that the zinc-aluminum oxide target with controllable secondary phase can be obtained.
As an optional implementation mode, the high-efficiency mixer adopted for mixing the zinc oxide powder and the alumina powder can select an air flow mill, a common ball mill and the like; the first mixed powder calcination process is carried out in oxygen atmosphere, which is favorable for inhibiting the generation of oxygen vacancy and forming spinel ZnAl with complete crystal structure2O4。
As an optional embodiment, a temperature programming mode can be adopted in the process of calcining the first mixed powder, the temperature is raised to the calcining temperature of 1000-1400 ℃ at the temperature raising rate of 10-20 ℃/min, the calcining time is controlled to be 2-20 hours, the complete reaction of zinc oxide and an alumina solid phase is facilitated, and the alumina and the zinc oxide can be completely converted into a secondary phase ZnAl2O4To obtain optimized ZnAl2O4A spinel crystal structure.
In an optional embodiment, the zinc oxide powder and the aluminum oxide powder in the first mixed powder are nanoparticles, and the particle size distribution is between 100 nm and 300 nm.
In a more preferred embodiment, the zinc oxide powder and the aluminum oxide powder have a particle size distribution of 100 to 200 nm.
Generally, the zinc aluminate powder obtained by calcination needs to be crushed into smaller particles through crushing treatment, and then is subjected to classification treatment to obtain zinc aluminate powder particles with appropriate particle size distribution, and the particle size of the zinc aluminate powder particles is generally equal to that of the zinc oxide powder particles, so that the zinc aluminate powder particles and the zinc oxide powder particles are favorably and uniformly mixed to form uniformly mixed second mixed powder.
As an optional embodiment, the zinc aluminate powder generated by calcination is crushed and then mixed with a set amount of zinc oxide powder to obtain a second mixed powder, the second mixed powder is subjected to ball milling, and then deionized water, a dispersant and a binder in a certain proportion are added to prepare zinc-aluminum oxide slurry; the zinc-aluminum oxide slurry with high solid content and low viscosity can be prepared by controlling the content and the proportion of the components and the types of the components. For example, the powder can be pulverized in a jet mill to obtain uniform zinc aluminate powder particles.
As an alternative embodiment, the secondary phase of zinc aluminate ZnAl in the zinc-aluminum oxide target material is adopted2O4The zinc aluminate powder ZnAl in the second mixed powder2O4The molar ratio of the aluminum atoms to the zinc oxide is controlled to be 0.015-0.02, and the molar ratio of the aluminum atoms to the zinc atoms is correspondingly 0.03-0.04.
In an optional embodiment, in the zinc-aluminum oxide slurry, the mass ratio of the dispersant to the second mixed powder is 1.2-1.8: 100, the mass ratio of the binder to the second mixed powder is 0.3-1.0: 100, and the mass ratio of the water to the second mixed powder is 16-20: 100.
In the preparation process of the zinc-aluminum oxide slurry, a Zeta potential value of the slurry along with the change of the pH value of the slurry can be detected by adopting a nano-particle size potentiometer, the slurry is ensured to be in an optimal dispersing device, and the zinc-aluminum oxide slurry with high solid content and low viscosity is obtained. For example, the zinc-aluminum oxide slurry has a solid content of more than 80% and a viscosity of less than 100 mPas.
As an alternative embodiment, the zinc-aluminum oxide slurry is further subjected to grinding treatment to obtain a slurry with uniform powder particle distribution, and the sintering activity of the powder particles in the slurry is increased. As an optional embodiment, the zinc-aluminum oxide slurry is subjected to high-energy sanding treatment in a high-energy sanding machine, the rotating speed of the sanding machine is set to be 1000-2400 rpm, and the sanding dispersion time is 30-120 min.
As an alternative embodiment, the dispersant is polyacrylic acid or polycarboxylic acid dispersant, and the binder is polyvinyl alcohol or gum arabic.
Usually, the zinc-aluminum oxide slurry is prepared into a zinc-aluminum oxide target biscuit in a mould by adopting a novel pressure grouting forming process, and the relative density of the target biscuit is more than 60%. The material of the mould is high-strength water-absorbing gypsum, and the mould is made of high-strength water-absorbing gypsum powder. The grouting pressure of the pressure grouting forming is usually set to be 0.01-0.4 MPa. In the preparation process of the AZO sputtering target material, powder forming methods mainly comprise die forming, cold isostatic pressing forming, slip casting forming and the like. Generally, the die forming and the cold isostatic pressing are difficult to prepare sputtering target biscuit with larger size, the precision requirement on a die is higher during the die forming, the die is damaged more greatly, the pressure slip casting operation is simple and convenient, and the preparation of the sputtering target biscuit with larger size is facilitated.
As an alternative embodiment, the zinc-aluminum oxide slurry is subjected to vacuum defoaming treatment before pressure grouting forming, and the vacuum pressure is less than 0.1 Pa.
Generally, the zinc-aluminum oxide target biscuit can be dried at constant temperature and humidity. As an optional implementation mode, the constant-temperature and constant-humidity drying process can be carried out in two stages in a constant-temperature and constant-humidity box, and finally a target biscuit with constant weight is obtained; the two-stage constant-temperature constant-humidity drying process specifically comprises the following steps: drying for the first time for 24-36 hours under the conditions that the first drying temperature is 25-35 ℃ and the first humidity is 70-80% RH; and then drying for a second time for 36-48 hours under the conditions that the second drying temperature is 35-45 ℃ and the second humidity is 70-80% RH. Reference herein to humidity is to relative humidity.
As an optional embodiment, the zinc-aluminum oxide target biscuit is subjected to integrated degreasing and sintering treatment, wherein the zinc-aluminum oxide target is degreased at a degreasing temperature, and then the temperature is directly increased to a sintering temperature for sintering; wherein the degreasing temperature is set to be 500-800 ℃, the degreasing temperature rise rate is 0.5-1.5 ℃/min, and the degreasing heat preservation time is 5-24 h; the sintering process is carried out according to a step temperature-changing sintering procedure, firstly, the temperature is increased from the degreasing temperature to a first step temperature T1 at the speed of 2-4 ℃/min, and the temperature is kept for 10-20 hours; then heating to a second step temperature T2 at a speed of 5-10 ℃/min, and keeping the temperature; then, cooling to a third step sintering temperature T3 at a speed of 10-20 ℃/min, and preserving heat for 10-30 hours; finally, cooling to 600 ℃ at a speed of 1-2 ℃/min, and cooling to normal temperature; wherein T1 is 900-1100 deg.C, T2 is 1400-1500 deg.C, and T3 is 1000-1300 deg.C.
As an alternative embodiment, the degreasing sintering of the zinc-aluminum oxide target biscuit is carried out in air, oxygen or nitrogen atmosphere, and a flowing atmosphere can be generally selected, for example, the gas flow rate is set to be 5-15L/min.
The technical details are further illustrated in the following examples.
Example 1
In embodiment 1, a method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target specifically includes:
(1) mixing zinc oxide powder with the granularity of 2-5 mu m and aluminum oxide powder in a molar ratio of 1:1, uniformly mixing in a high-efficiency mixer to obtain 500g of first mixed powder, and calcining the first mixed powder in an oxygen atmosphere to generate zinc aluminate powder; wherein the calcining temperature is 1200 ℃, and the calcining treatment time is 10 hours;
(2) crushing and grading the generated zinc aluminate powder by using a jet mill, and mixing the treated zinc aluminate powder with micron-sized zinc oxide powder according to a molar ratio of 0.015 to obtain 1000g of second mixed powder, wherein the zinc oxide powder is 980g, and the zinc aluminate powder is 20 g; 200g of deionized water, 12g of polyacrylic acid and 5g of polyvinyl alcohol are added into the second mixed powder to prepare zinc-aluminum oxide slurry with the solid content of 82.17% and the viscosity of 90mPa & s; performing high-energy sanding dispersion on the prepared zinc-aluminum oxide slurry, wherein the rotating speed of a sanding machine is 1800rpm, the time is 50min, and performing vacuum-pumping defoaming treatment on the sanded zinc-aluminum oxide AZO slurry;
(3) performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent; wherein, the grouting pressure is 0.2MPa, and the pressure maintaining time is 5 hours;
(4) drying the zinc-aluminum oxide target biscuit; the drying treatment adopts a secondary constant temperature and humidity drying process, wherein the primary drying is carried out for 24 hours at a first drying temperature of 25 ℃ and a first humidity of 80% RH; then drying for the second time for 36 hours under the conditions of a second drying temperature of 45 ℃ and a second humidity of 70% RH;
(5) carrying out degreasing sintering treatment on the dried zinc-aluminum oxide target biscuit, wherein the degreasing sintering adopts an integrated process, the degreasing temperature is set to 600 ℃, the degreasing heating rate is 0.5 ℃/min, and the degreasing heat preservation time is 18 h; then, sintering process is carried out according to the following step variable temperature sintering procedure:
heating from the degreasing temperature to 1000 ℃ of the first step at the speed of 3 ℃/min, and preserving the heat for 15 hours; then heating to 1450 ℃ of the second step at the speed of 8 ℃/min, and keeping the temperature, namely, cooling to 1200 ℃ of the third step at the speed of 18 ℃/min, and keeping the temperature for 20 hours; then the temperature is reduced to 600 ℃ at the speed of 2 ℃/min, and then the temperature is naturally reduced and cooled.
The obtained zinc-aluminum oxide target is tested, wherein an XRD diffraction pattern of secondary-phase zinc aluminate is shown in figure 1, a scanning electron microscope pattern of a target section is shown in figure 2, and crystal grains are in close contact and completely densified; the structure distribution diagram of the target crystal grains is shown in fig. 3, the main phase crystal grains 1 in the zinc-aluminum oxide sputtering target are zinc oxide, and zinc aluminate secondary phase crystal grains 2 are discretely and uniformly distributed among the zinc oxide main phase crystal grains 1; the secondary phase crystal grains 2 are completely filled between the main phase crystal grains 1, the crystal grains are in close contact, the structure compactness degree is high, the relative density of the target material is 99.1 percent, and the volume resistivity is 3m omega cm.
Therefore, the zinc aluminate powder in the zinc-aluminum oxide target biscuit forms a secondary phase through the degreasing and sintering process, the zinc oxide powder forms a main phase, and the secondary phase is uniformly dispersed among the main phase to obtain the secondary phase-controllable zinc-aluminum oxide sputtering target.
Example 2
Example 2 a method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target was carried out according to example 1;
wherein the sintering temperature of the third step is 1300 ℃.
The obtained zinc-aluminum oxide target material has the relative density of 99.5 percent and the volume resistivity of 2.8m omega cm.
Example 3
Example 3 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
the particle sizes of the zinc oxide powder and the aluminum oxide powder are nano-scale and are distributed between 100 nm and 200nm, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, and the rotating speed of the high-energy sand mill is 2000 rpm;
the obtained zinc-aluminum oxide target had a relative density of 99.5% and a bulk resistivity of 1m Ω · cm.
Example 4
Example 4 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
the particle sizes of the zinc oxide powder and the aluminum oxide powder are nano-scale and are distributed between 100 nm and 200nm, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, the rotating speed of the high-energy sand mill is 2000rpm, and the temperature of a second step is 1400 ℃;
the obtained zinc-aluminum oxide target had a relative density of 99.1% and a bulk resistivity of 1.3m Ω · cm.
Example 5
Example 5 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
the particle sizes of the zinc oxide powder and the alumina powder are nano-scale and are distributed between 100 nm and 200nm, the molar ratio of the zinc aluminate powder to the zinc oxide powder is 0.02, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, and the rotating speed of the high-energy sand mill is 2000 rpm;
the obtained zinc-aluminum oxide target had a relative density of 99.3% and a volume resistivity of 0.8m Ω · cm.
Example 6
Example 6 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
the particle sizes of the zinc oxide powder and the alumina powder are nano-scale and are distributed between 100 nm and 200nm, the molar ratio of the zinc aluminate powder to the zinc oxide powder is 0.0175, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, and the rotating speed of the high-energy sand mill is 2000 rpm;
the obtained zinc-aluminum oxide target had a relative density of 99.6% and a volume resistivity of 0.6m Ω · cm.
Example 7
Example 7 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
wherein the particle sizes of the zinc oxide powder and the alumina powder are nano-scale and are distributed between 100-200 nm, the molar ratio of the zinc aluminate powder to the zinc oxide powder is 0.0175, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, the rotating speed of the high-energy sand mill is 2000rpm, and the temperature of a third step is 1100 ℃;
the obtained zinc-aluminum oxide target had a relative density of 99.2% and a bulk resistivity of 0.9m Ω · cm.
Example 8
Example 8 a method for preparing a secondary phase controlled zinc aluminum oxide sputtering target was carried out according to example 1;
wherein the particle sizes of the zinc oxide powder and the alumina powder are nano-scale and are distributed between 100-200 nm, the molar ratio of the zinc aluminate powder to the zinc oxide powder is 0.0175, the viscosity of the zinc-aluminum oxide slurry is 100mPa & s, the rotating speed of the high-energy sand mill is 2000rpm, and the temperature of a third step is 1000 ℃;
the obtained zinc-aluminum oxide target had a relative density of 99.0% and a bulk resistivity of 1.5 m.OMEGA.cm.
Comparative example 1
In comparative example 1, the method for preparing a zinc-aluminum oxide sputtering target specifically includes:
(1) mixing alumina powder and micron-sized zinc oxide powder in a molar ratio of 0.0175, wherein 1000g of first mixed powder is prepared, 980g of zinc oxide powder is prepared, and 20g of zinc aluminate powder is prepared; 200g of deionized water, 12g of polyacrylic acid and 5g of polyvinyl alcohol are added into the first mixed powder to prepare zinc-aluminum oxide slurry with the solid content of 82.17% and the viscosity of 200mPa & s; performing high-energy sanding dispersion on the prepared zinc-aluminum oxide slurry, wherein the rotating speed of a sand mill is 2000rpm, the time is 50min, and performing vacuum-pumping defoaming treatment on the sanded zinc-aluminum oxide AZO slurry;
(3) performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent; wherein, the grouting pressure is 0.2MPa, and the pressure maintaining time is 5 hours;
(4) drying the zinc-aluminum oxide target biscuit; the drying treatment adopts a secondary constant temperature and humidity drying process, wherein the primary drying is carried out for 24 hours at a first drying temperature of 25 ℃ and a first humidity of 70% RH; then drying for the second time for 36 hours under the conditions of a second drying temperature of 45 ℃ and a second humidity of 70% RH;
(5) carrying out degreasing sintering treatment on the dried zinc-aluminum oxide target biscuit, wherein the degreasing sintering adopts an integrated process, the degreasing temperature is set to 600 ℃, the degreasing heating rate is 0.5 ℃/min, and the degreasing heat preservation time is 18 h; then, sintering process is carried out according to the following step variable temperature sintering procedure:
heating from the degreasing temperature to 1000 ℃ of the first step at the speed of 3 ℃/min, and preserving the heat for 15 hours; then raising the temperature to 1450 ℃ of the second step at the speed of 8 ℃/min, and keeping the temperature, namely lowering the temperature to 1000 ℃ of the third step at the speed of 18 ℃/min, and keeping the temperature for 20 hours; then the temperature is reduced to 600 ℃ at the speed of 2 ℃/min, and then the temperature is naturally reduced and cooled.
Testing the obtained zinc-aluminum oxide target, wherein the texture distribution diagram of the target crystal grains is shown in fig. 4, the main phase crystal grains 1 in the zinc-aluminum oxide sputtering target are zinc oxide, and zinc aluminate secondary phase crystal grains 2 are discretely and randomly distributed among the main phase crystal grains 1 of the zinc oxide; the secondary phase crystal grains are irregular in shape, incomplete in structure, irregular in shape and distribution position and random in distribution, are mainly located on the surface of the main phase and the grain boundary of the main phase, and have gap flaws in the internal structure, the relative density of the target material is 98.1%, and the bulk resistivity is 6m omega cm.
The preparation method of the secondary phase controllable zinc-aluminum oxide sputtering target material disclosed by the embodiment of the application firstly adopts zinc oxide powder and alumina powder to generate zinc aluminate powder, then mixing the zinc aluminate powder with the zinc oxide powder, then carrying out degreasing sintering, wherein the zinc aluminate powder preferentially forms spinel phase zinc aluminate secondary phase in a zinc oxide crystal interface, thus inhibiting abnormal growth of zinc oxide crystal grains, the grain can be refined, the zinc-aluminum oxide sputtering target material with uniformly refined structure and controllable secondary phase is obtained, the grains of the internal structure of the target material are in close contact and are completely densified, the zinc aluminate secondary phase grains are discretely and uniformly distributed among the zinc oxide of the main phase grains, the secondary phase grains are completely filled among the main phase grains, the grains are in close contact, the structure densification degree is high, the relative density can reach more than 99 percent, and the volume resistivity is less than 3m omega cm.
The technical solutions and the technical details disclosed in the embodiments of the present application are only examples to illustrate the inventive concept of the present application, and do not constitute a limitation on the technical solutions of the present application, and all the conventional changes, substitutions, combinations, and the like made to the technical details disclosed in the present application have the same inventive concept as the present application and are within the protection scope of the claims of the present application.
Claims (10)
1. The preparation method of the secondary phase controllable zinc-aluminum oxide sputtering target is characterized by comprising the following steps:
uniformly mixing zinc oxide powder and alumina powder in a molar ratio of 1:1 to obtain first mixed powder, and calcining the first mixed powder in an oxygen atmosphere to generate zinc aluminate powder; wherein the calcining temperature is set to be 1000-1400 ℃, and the calcining treatment time is set to be 2-20 hours;
mixing the generated zinc aluminate powder and zinc oxide powder according to a molar ratio of 0.015-0.02 to obtain second mixed powder, and mixing the second mixed powder with water, a dispersing agent and a binding agent according to a set proportion to obtain zinc-aluminum oxide slurry with a solid content of more than 80% and a viscosity of less than 100mPa & s;
performing pressure slip casting on the generated zinc-aluminum oxide slurry to obtain a zinc-aluminum oxide target biscuit with the relative density of more than 60 percent;
drying the zinc-aluminum oxide target biscuit;
and (3) degreasing and sintering the dried zinc-aluminum oxide target biscuit, wherein zinc aluminate powder in the zinc-aluminum oxide target biscuit forms a secondary phase, zinc oxide powder forms a main phase, and the secondary phase is uniformly dispersed among the main phases to obtain the secondary phase controllable zinc-aluminum oxide sputtering target.
2. The method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein the zinc oxide powder and the aluminum oxide powder in the first mixed powder are nanoparticles, and the particle size distribution is 100-300 nm.
3. The preparation method of a secondary phase controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein in the zinc-aluminum oxide slurry, the mass ratio of the dispersant to the second mixed powder is 1.2-1.8: 100, the mass ratio of the binder to the second mixed powder is 0.3-1.0: 100, and the mass ratio of the water to the second mixed powder is 16-20: 100.
4. The method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein in the calcination treatment process of the first mixed powder, the temperature rise rate of raising the temperature to the calcination temperature is set to 10-20 ℃/min.
5. The method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target according to claim 1, wherein the zinc-aluminum oxide target biscuit is dried at a constant temperature and humidity, and specifically comprises:
drying for the first time for 24-36 hours under the conditions that the first drying temperature is 25-35 ℃ and the first humidity is 70-80% RH;
and then drying for a second time for 36-48 hours under the conditions that the second drying temperature is 35-45 ℃ and the second humidity is 70-80% RH.
6. The method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target according to claim 1, wherein the zinc-aluminum oxide target biscuit is subjected to integrated degreasing and sintering treatment, wherein:
the degreasing temperature is set to be 500-800 ℃, the degreasing temperature rise rate is 0.5-1.5 ℃/min, and the degreasing heat preservation time is 5-24 h;
the sintering process is carried out according to the following step variable temperature sintering procedure:
heating the degreasing temperature to a first step temperature T1 at a speed of 2-4 ℃/min, and keeping the temperature for 10-20 hours;
heating to a second step temperature T2 at a speed of 5-10 ℃/min, and keeping the temperature;
cooling to a third step sintering temperature T3 at a speed of 10-20 ℃/min, and preserving heat for 10-30 hours;
cooling to 600 ℃ at a speed of 1-2 ℃/min, and naturally cooling;
wherein T1 is 900-1100 deg.C, T2 is 1400-1500 deg.C, and T3 is 1000-1300 deg.C.
7. The method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein the zinc-aluminum oxide slurry is subjected to vacuum defoaming treatment before pressure grouting forming, and the vacuum pressure is less than 0.1 Pa.
8. The method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein the generated zinc aluminate powder is pulverized to form nano particles with a particle size equivalent to that of the zinc oxide powder, and then the nano particles are mixed to obtain a second mixed powder.
9. The method for preparing a secondary phase controllable zinc-aluminum oxide sputtering target material according to claim 2, wherein the zinc oxide powder and the aluminum oxide powder are nanoparticles, and the particle size distribution is 100-200 nm.
10. The method for preparing a secondary phase-controllable zinc-aluminum oxide sputtering target material according to claim 1, wherein the dispersant is polyacrylic acid or polycarboxylic acid dispersant, and the binder is polyvinyl alcohol or gum arabic.
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