TWI770959B - Composite oxide target and manufacturing method thereof - Google Patents

Abstract

The present invention provides a composite oxide target, which includes magnesium oxide and titanium (II) oxide. Based on a total amount of the composite oxide target, the total amount of the magnesium oxide is from 5 atomic percent to 90 atomic percent, and the total amount of the titanium (II) oxide is from 10 atomic percent to 95 atomic percent. The average grain size of the black phases containing magnesium oxide in the composite oxide target is less than or equal to 2 micrometers and the variance of the grain size of the black phases is smaller than 0.2. The present invention further provides a method of producing the above composite oxide target, which comprises: preparing magnesium oxide powder and titanium(II) oxide powder, wherein the grain size of the magnesium oxide powder is less than or equal to 5 μm and the grain size of the titanium(II) oxide powder is less than or equal to 10 μm; mixing the magnesium oxide powder and the titanium(II) oxide powder to obtain a mixed powder; grinding the mixed powder for more than 48 hours to obtain a fine powder; preforming the fine powder into a green compact; and sintering the green compact at a temperature ranging from 900°C to 1400°C to obtain the composite oxide target.

Description

Composite oxide target and method for producing the same

This creation relates to a composite oxide target and its production method, especially a composite oxide target that can be applied to the barrier layer of a thermally assisted magnetic recording medium and its production method.

All data in a computer is recorded magnetically on the tracks of a magnetic disk. In the past, hard disks were mainly based on horizontal magnetic recording media, but recently they have switched to vertical magnetic recording media to further increase the storage capacity of hard disks. However, the current design of perpendicular magnetic recording media has been developed to approach the limit of theoretical storage capacity under the constraints of thermal stability, writeability and signal-to-noise ratio. In order to continuously increase the storage capacity of hard disks to meet today's demand for mass storage of information, a heat-assisted magnetic recording (HAMR) technology has been developed to improve the above-mentioned key problems.

The thermally assisted magnetic recording medium uses a laser beam to precisely focus the magnetic recording layer for heating. The magnetic composite material in the magnetic recording layer will temporarily lose its magnetism after being heated by the laser to above the Curie temperature. After the data is written, the laser The beam is no longer focused on the magnetic recording layer, causing the magnetic recording layer to cool to stabilize the written data.

The layered structure of the thermally assisted magnetic recording medium includes a substrate, a base layer, a soft magnetic layer, a crystal orientation control layer, a heat dissipation layer, a barrier layer, a magnetic recording layer, a lubricating layer and a cover layer from bottom to top, wherein the magnetic recording layer needs to be like iron The highly stable magnetic composite material of platinum alloy can withstand the focused heating of the laser beam, but the iron-platinum alloy is easily diffused to the layer below the magnetic recording layer in a high temperature environment, so a barrier layer needs to be set under the magnetic recording layer to prevent Slow down or inhibit the diffusion of iron-platinum alloys.

The barrier layer of the thermally assisted magnetic recording medium is usually made of materials with heat resistance such as magnesium monoxide (MgO). Since it has no electrical conductivity, it is usually necessary to use RF magnetron sputtering to form a film. However, the RF magnetron sputtering method has the problems of slow film formation speed and low yield. At present, it is known that titanium monoxide (TiO) can be added to increase the conductivity, and then DC magnetron sputtering method can be used instead. Get a barrier layer. However, when using MgO powder and TiO powder to make a composite oxide target, after sintering, MgO agglomeration is inevitably formed in the composite oxide target, so that the properties of the composite oxide target are deteriorated and the sputtering A large number of particles are easily dropped during the plating process, which affects the properties and yield of the fabricated film.

To overcome the problems faced by the prior art, one of the objectives of the present invention is to inhibit and/or slow down the degree of agglomeration of magnesium monoxide in the composite oxide target.

Another objective of the present invention is to effectively suppress and/or reduce the number of particles dropped from the composite oxide target during the sputtering process.

Another purpose of this creation is to improve the flexural strength and thermal conductivity of the composite oxide target.

In order to achieve the aforementioned purpose, the present invention provides a composite oxide target material, which comprises magnesium monoxide and titanium monoxide. Based on the total number of atoms of the composite oxide target material, the total amount of magnesium monoxide is greater than or equal to 5 atomic percent and less than or equal to 90 atomic percent, and the total amount of the titanium monoxide is greater than or equal to 10 atomic percent and less than or equal to 95 atomic percent; wherein, the composite oxide target has a plurality of blacks containing the magnesium monoxide The average particle size of the black phases can be less than or equal to 2 microns, and the particle size variation of the black phases is less than 0.2.

By controlling the composition of the aforementioned composite oxide target and the average particle size and particle size variation of the black phase in the metallographic microstructure, the composite oxide target of the present invention can inhibit and/or slow down one of the composite oxide targets. The degree of agglomeration of magnesium oxide can effectively inhibit and/or reduce the number of particles dropped by the composite oxide target during the sputtering process, and at the same time improve the flexural strength and thermal conductivity of the composite oxide target.

In one embodiment, the average particle size of the black phases in the composite oxide target of the present invention may be greater than or equal to 0.05 microns and less than or equal to 2 microns. In another embodiment, the average particle size of the black phases in the composite oxide target of the present invention may be greater than or equal to 0.3 micrometers and less than or equal to 2 micrometers.

In one embodiment, the particle size variation of the black phases in the composite oxide target of the present invention may be greater than or equal to 1.00×10 ⁻⁵ and less than 0.2. In another embodiment, the particle size variation of the black phases in the composite oxide target of the present invention may be greater than or equal to 5.00×10 ⁻⁵ and less than 0.2.

In one embodiment, the composite oxide target of the present invention may further include an additive component, and the additive component may be a first additive component, a second additive component, or a combination thereof. Specifically, the first additive component can be selected from the group consisting of aluminum oxide, zirconium dioxide, chromium oxide, silicon dioxide and combinations thereof, and the second additive component can be selected from aluminum, zirconium, A group consisting of chromium, silicon and their combinations. According to the present invention, adding the first additive component and/or the second additive component to the composite oxide target is beneficial to inhibit the growth of the black phase and/or control the particle size variation of the black phase.

In this specification, the total amount of the said additive component is the total amount of the first additive component, the total amount of the second additive component, or the total amount of the first additive component and the total amount of the second additive component. total.

The "total amount of the first additive component" means that when the first additive component is aluminum oxide, zirconium dioxide, chromium oxide and silicon dioxide, the total amount of the first additive component is aluminum oxide. The sum of the individual contents of , zirconium dioxide, chromium dioxide and silicon dioxide; and when the first additive component is separate aluminum oxide, zirconium dioxide, chromium oxide or silicon dioxide, the first addition The total amount of an added component is the individual content of aluminum oxide, the individual content of zirconium dioxide, the individual content of chromium oxide, or the individual content of silicon dioxide.

The "total amount of the second additive component" refers to when the second additive component is aluminum, zirconium, chromium and silicon, the total amount of the second additive component is the sum of the individual contents of aluminum, zirconium, chromium and silicon; When the second additive component is aluminum, zirconium, chromium or silicon alone, the total amount of the second additive component is the individual content of aluminum, the individual content of zirconium, the individual content of chromium, or the individual content of silicon.

In one embodiment, based on the total number of atoms of the composite oxide target of the present invention, the total amount of the additive components is greater than or equal to 1 atomic percent and less than or equal to 6 atomic percent. In another embodiment, based on the total number of atoms of the composite oxide target of the present invention, the total amount of the added components may be greater than or equal to 3 atomic percent and less than or equal to 6 atomic percent; accordingly, the present invention can The average particle size and particle size variation of the black phase in the composite oxide target are further reduced.

According to the present invention, the aforementioned composite oxide target can be applied to a magnetron sputtering process, such as an RF magnetron sputtering process or a DC magnetron sputtering process. By inhibiting and/or slowing down the degree of agglomeration of magnesium monoxide in the composite oxide target, the present invention enables the composite oxide target to drop less than 50 particles during the sputtering process. Preferably, the number of particles dropped when the composite oxide target of the present invention is formed by the DC magnetron sputtering process can be less than 40 particles, less than 30 particles, less than 20 particles, or even less than 10 particles. . Therefore, the thin film sputtered by using the composite oxide target of the present invention can have better film properties and yield, so it can be suitable for heat-assisted magnetic recording media (Heat-Assisted Magnetic Recording media, HAMR media). Barrier layers are used.

In this specification, "flexural strength" refers to the ultimate breaking stress when a target is subjected to a bending load under a unit area, and its unit is expressed in megapascals (MPa). According to the present invention, the flexural strength of the aforementioned composite oxide target is greater than or equal to 100 MPa. Specifically, the flexural strength of the composite oxide target can be greater than or equal to 100 MPa and less than or equal to 200 MPa; preferably, the flexural strength of the aforementioned composite oxide target can be greater than or equal to 110 MPa and less than or equal to 180 MPa; more preferably, the flexural strength of the aforementioned composite oxide target can be greater than or equal to 120 MPa and less than or equal to 170 MPa; even more preferably, the flexural strength of the aforementioned composite oxide target can be greater than or equal to 130 MPa and less than or equal to 170 MPa.

According to the present invention, the thermal conductivity of the aforementioned composite oxide target can be greater than or equal to 10 watts/(meter·Kelvin) (W/m·K); specifically, the thermal conductivity of the aforementioned composite oxide target can be The rate may be greater than or equal to 10 W/m·K and less than or equal to 30 W/m·K. Preferably, the thermal conductivity of the aforementioned composite oxide target can be greater than or equal to 15 W/m·K and less than or equal to 30 W/m·K; more preferably, the thermal conductivity of the aforementioned composite oxide target can be Greater than or equal to 20 W/m·K and less than or equal to 25 W/m·K.

In addition, the present invention provides a method for manufacturing a composite oxide target, which includes the following steps: Prepare magnesium monoxide powder and titanium monoxide powder, the particle size of the magnesium monoxide powder may be less than or equal to 5 microns, and the particle size of the titanium monoxide powder may be less than or equal to 10 microns; Mixing the magnesium monoxide powder and the titanium monoxide powder to obtain a mixed powder, wherein based on the total number of atoms of the mixed powder, the total amount of the magnesium monoxide powder is greater than or equal to 5 atomic percent and less than or equal to 90 atoms percentage, and the total amount of the titanium monoxide powder is greater than or equal to 10 atomic percent and less than or equal to 95 atomic percent; Grinding the mixed powder for more than 48 hours to obtain a fine powder; preforming the refined powder to obtain a target blank; and The target blank is sintered at 900°C to 1400°C to obtain the composite oxide target.

According to the present invention, by controlling the particle size of the raw material powder of the composite oxide target, the mixing ratio of the raw material powder, the grinding time and the sintering temperature, the particles of the black phase in the metallographic microstructure of the composite oxide target can be obtained. The diameter is reduced and the particle size variation is reduced, that is, the present invention can inhibit and/or slow down the agglomeration degree of magnesium monoxide in the composite oxide target, so it can effectively inhibit and/or reduce the composite oxide target in the sputtering process. The number of particles dropped in the medium and at the same time improve the flexural strength and thermal conductivity of the composite oxide target.

In one embodiment, in the aforementioned method of manufacturing a composite oxide target, the particle size of the magnesium monoxide powder may be greater than or equal to 0.5 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 0.5 microns and less than or equal to 10.0 microns. Preferably, the particle size of the magnesium monoxide powder may be greater than or equal to 1.0 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 1.0 microns and less than or equal to 10.0 microns; The particle size of the magnesium powder may be greater than or equal to 2.0 microns and less than or equal to 5 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 2.0 microns and less than or equal to 10.0 microns.

Optionally, the aforementioned method for manufacturing a composite oxide target further comprises preparing an additive powder, and mixing the magnesium monoxide powder, the titanium monoxide powder and the additive powder to obtain the mixed powder; wherein the additive powder comprises a A first additive powder, a second additive powder or a combination thereof, the first additive powder can be selected from the group consisting of aluminum oxide powder, zirconium dioxide powder, chromium oxide powder, silicon dioxide powder and combinations thereof group, and the particle size of the first additive powder may be less than or equal to 3 microns, the second additive powder may be selected from the group consisting of aluminum powder, zirconium powder, chromium powder, silicon powder and combinations thereof, and the second additive powder The particle size of the added powder can be less than or equal to 50 microns; based on the total atomic number of the mixed powder, the total amount of the added powder can be greater than or equal to 1 atomic percent and less than or equal to 6 atomic percent. Specifically, the particle size of the first additive powder may be greater than or equal to 0.1 micrometer and less than or equal to 3 micrometers, and the particle diameter of the second additive powder may be greater than or equal to 1 micrometer and less than or equal to 50 micrometers. Preferably, the particle size of the first additive powder may be greater than or equal to 0.1 micrometer and less than or equal to 1 micrometer, and the particle size of the second additive powder may be greater than or equal to 10 micrometers and less than or equal to 50 micrometers.

In one embodiment, in the aforementioned method of manufacturing a composite oxide target, the particle size of the magnesium monoxide powder may be greater than or equal to 0.5 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 0.5 microns and less than or equal to 10.0 microns, and the particle size of the zirconium dioxide powder may be greater than or equal to 0.1 microns and less than or equal to 1.0 microns. Preferably, the particle size of the magnesium monoxide powder may be greater than or equal to 1.0 μm and less than or equal to 5.0 μm, the particle size of the titanium monoxide powder may be greater than or equal to 1.0 μm and less than or equal to 10.0 μm, and the particle size of the zirconia powder The particle size may be greater than or equal to 0.2 microns and less than or equal to 0.8 microns; more preferably, the particle size of the magnesium monoxide powder may be greater than or equal to 2.0 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 2.0 micrometers and less than or equal to 10.0 micrometers, and the particle size of the zirconium dioxide powder may be greater than or equal to 0.3 micrometers and less than or equal to 0.6 micrometers.

In one embodiment, in the aforementioned method of manufacturing a composite oxide target, the particle size of the magnesium monoxide powder may be greater than or equal to 0.5 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 0.5 micrometers and less than or equal to 10.0 micrometers, and the particle size of the aluminum powder may be greater than or equal to 10 micrometers and less than or equal to 70 micrometers. Preferably, the particle size of the magnesium monoxide powder may be greater than or equal to 1.0 microns and less than or equal to 5.0 microns, the particle size of the titanium monoxide powder may be greater than or equal to 1.0 microns and less than or equal to 10.0 microns, and the particle size of the aluminum powder May be greater than or equal to 20 microns and less than or equal to 60 microns; more preferably, the particle size of the magnesium monoxide powder may be greater than or equal to 2.0 microns and less than or equal to 5.0 microns, and the particle size of the titanium monoxide powder may be greater than or equal to 2.0 microns and less than or equal to 10.0 microns, and the particle size of the aluminum powder may be greater than or equal to 30 microns and less than or equal to 50 microns.

Preferably, in the aforementioned method of manufacturing a composite oxide target, the grinding time may be greater than or equal to 48 hours and less than or equal to 120 hours; in some embodiments, in the aforementioned method of manufacturing a composite oxide target, grinding The time may be greater than or equal to 60 hours and less than or equal to 120 hours.

Optionally, in the aforementioned method of manufacturing a composite oxide target, after grinding the mixed powder for more than 48 hours, it can be sieved with a mesh to obtain the refined powder, and the mesh of the mesh can be 400 meshes. to 600 mesh.

It can be understood that the pre-forming conditions are not particularly limited, as long as the aforementioned refined powder can be pre-shaped into a target blank under appropriate conditions. In one embodiment, the aforementioned refined powder can be uniformly filled in a mold, and the refined powder can be pre-shaped into a target at a pressure of 50 kg/cm 2 (kg/cm ² ) to 100 kg/cm ² embryo.

Preferably, in the aforementioned method of manufacturing a composite oxide target, the sintering temperature of the target blank may be 1000°C to 1300°C.

According to the present invention, the sintering time in the aforementioned method of manufacturing a composite oxide target is 1.5 hours to 5 hours; preferably, the sintering time in the aforementioned method of manufacturing a composite oxide target may be 1.5 hours to 4 hours; more Preferably, the sintering time in the aforementioned method for manufacturing the composite oxide target is 1.5 hours to 3 hours.

According to the present invention, the sintering pressure in the aforementioned method for manufacturing a composite oxide target is 300 kg/cm ² to 510 kg/cm ² ; more preferably, the sintering pressure in the aforementioned method for manufacturing a composite oxide target is 300 kg /cm ² to 400 kg/cm ² .

According to the present invention, the sintering method may be a hot pressing method (Hot Pressing, HP), a spark plasma sintering method (Spark Plasma Sintering, SPS), a hot isostatic pressing method (Hot Isostatic Pressing, HIP), or any of them. combination. In one embodiment, the sintering temperature of the hot pressing method can be 1000°C to 1300°C, and the sintering pressure can be 300 kg/cm ² to 450 kg/cm ² ; The sintering temperature of the plasma sintering method can be 950°C to 1150°C, and the sintering pressure can be 400 kg/cm ² to 510 kg/cm ² ; in another embodiment, the sintering temperature of the hot isostatic pressing method is selected. It can be 1050°C to 1150°C, and the sintering pressure can be 350 kg/cm ² to 510 kg/cm ² .

In order to verify that the technical means of this creation can inhibit and/or slow down the agglomeration of the black phase in the complex oxide target and reduce its particle size and particle size variation, so as to improve the characteristics of the complex oxide target, and inhibit and/or To reduce the number of particles dropped during the sputtering process, several types of composite oxide targets are listed below as examples to illustrate the implementation of the present invention; those skilled in the art can easily understand the advantages that the present invention can achieve through the content of this specification. and effects, and make various modifications and changes without departing from the spirit of this creation to implement or apply the content of this creation.

Example 1 to twenty three : Composite oxide target

First, take an appropriate amount of magnesium monoxide powder (purity 99.99%, particle size 3.0 μm to 4.5 μm), titanium monoxide powder (purity 99.9%, particle size 7.0 μm to 9.5 μm), zirconium dioxide powder (purity 99.9% , particle size 0.5 μm), aluminum powder (purity 99.5%, particle size 45 μm) and other raw materials, of which zirconium dioxide powder can be used as the first additive powder, and aluminum powder can be used as the second additive powder. The amount and particle size of the raw material powder used in each example are shown in Table 1 below.

Next, the above-mentioned raw materials are mixed to obtain a mixed powder. In Table 1 below, the dosage of each raw powder is calculated based on the total atomic amount of the mixed powder, and its unit is expressed in atomic percent (at%).

After that, the aforementioned mixed powder was ground for at least 48 hours according to the grinding time shown in Table 1, and the ground mixed powder was passed through a 400-mesh sieve to obtain a refined powder. In other embodiments, those with ordinary knowledge in the art can also omit the aforementioned sieving step as required, and obtain refined powder after the grinding step is completed.

After that, the above-mentioned refined powder is uniformly filled in the selected mold, and the pressure of 70.31 kg/cm ² is set, and the preform is carried out with a hydraulic press to obtain a target blank.

Finally, continuous sintering is performed at a sintering temperature of 1000°C to 1300°C and a sintering pressure of 400 kg/ ^cm2 by sintering methods such as hot pressing (HP), spark plasma sintering (SPS) or hot isostatic pressing (HIP). 2 hours to prepare the composite oxide targets of Examples 1 to 23.

It can be understood that the amount of the raw material powder shown in Table 1 is substantially equal to or similar to the composition of the composite oxide target prepared by the aforementioned preparation method. Taking Example 1 as an example, according to the amount of the raw material powder, based on the total number of atoms of the composite oxide target of Example 1, the composite oxide target of Example 1 roughly contains 50 at% of magnesium monoxide and 50 at% titanium monoxide.

Comparative example 1 to 9 : Composite oxide target

First, take an appropriate amount of magnesium monoxide powder (purity 99.99%, particle size 12.5 μm to 14.0 μm), titanium monoxide powder (purity 99.9%, particle size 29.5 μm to 38.5 μm), zirconium dioxide powder (purity 99.9% , particle size 1.2 μm), aluminum powder (purity 99.5%, particle size 60 μm) and other raw materials, of which zirconium dioxide powder can be used as the first additive powder, and aluminum powder can be used as the second additive powder. The amount and particle size of the raw material powder used in each comparative example are shown in Table 1 below.

Next, the above-mentioned raw materials are mixed to obtain a mixed powder. In Table 1 below, the dosage of each raw material powder is calculated based on the total number of atoms of the mixed powder, and its unit is expressed in at%.

After that, the aforementioned mixed powder was ground for 24 to 36 hours according to the grinding time shown in Table 1 to obtain a refined powder.

After that, the above-mentioned refined powder is uniformly filled in the selected mold, and the pressure of 70.31 kg/cm ² is set, and the preform is carried out with a hydraulic press to obtain a target blank.

Finally, by sintering methods such as HP, SPS or HIP, the sintering temperature is 1000°C to 1300°C and the sintering pressure is 400 kg/cm ² for 2 hours to obtain the composite oxide targets of Comparative Examples 1 to 9. material. Table 1: Raw material dosage and particle size, process parameters, properties of the composite oxide targets, and drop of the composite oxide targets during sputtering of the composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 number of particles. Sample serial number Raw material powder dosage (at%) Raw material powder particle size (μm) Grinding time (h) Sintering method Sintering temperature (°C) Average particle size of black phase (μm) Black phase particle size variability Flexural strength (MPa) Thermal conductivity (W/m·K) Number of particles dropped (pieces) MgO TiO ZrO ₂ Al MgO TiO ZrO ₂ Al Example 1 50 50 0 0 3.5 7.5 - - 72 HP 1100 1.28 5.35× ^10-2 145 15.06 25 Example 2 54 46 0 0 3.0 7.5 - - 72 HP 1100 1.45 3.04× ^10-3 135 17.25 twenty three Example 3 60 40 0 0 4.0 9.0 - - 60 HP 1100 1.61 7.25× ^10-2 139 18.58 twenty one Example 4 55 45 0 0 4.0 7.5 - - 60 HP 1100 1.39 5.44× ^10-2 140 17.39 twenty one Example 5 70 30 0 0 4.0 9.5 - - 60 HP 1150 1.68 7.73× ^10-2 131 20.51 41 Example 6 90 10 0 0 3.5 8.5 - - 48 HP 1200 1.86 7.35× ^10-2 128 21.23 46 Example 7 65 35 0 0 4.0 9.0 - - 60 HP 1150 1.75 6.57× ^10-2 129 19.34 38 Example 8 40 60 0 0 3.5 7.0 - - 72 HP 1100 0.96 8.73× ^10-3 131 14.87 30 Example 9 35 65 0 0 3.5 8.0 - - 84 HP 1100 1.22 8.26× ^10-3 139 14.84 27 Example 10 20 80 0 0 4.5 9.0 - - 96 HP 1300 1.81 8.66× ^10-4 152 13.21 twenty two Example 11 5 95 0 0 4.0 7.0 - - 120 HP 1000 0.76 9.74× ^10-5 149 10.65 12 Example 12 20 80 0 0 4.0 9.0 - - 96 HP 1100 0.91 9.25× ^10-5 141 14.38 9 Example 13 10 90 0 0 4.0 9.5 - - 120 HP 1100 0.89 7.52× ^10-5 168 13.91 13 Example 14 50 50 0 0 4.0 7.0 - - 72 HP 1000 1.09 4.02× ^10-3 131 16.65 19 Example 15 48.5 48.5 3 0 4.0 8.0 0.5 - 84 HP 1200 1.09 3.05× ^10-3 129 12.22 30 Example 16 47 47 6 0 4.5 9.5 0.5 - 96 HP 1200 0.98 2.18× ^10-3 125 11.84 34 Example 17 50 49 1 0 4.0 9.5 0.5 - 72 HP 1100 1.22 4.74× ^10-3 132 12.89 26 Example 18 48.5 48.5 0 3 4.0 9.0 - 45 96 HP 1100 1.11 1.46× ^10-3 128 18.07 twenty four Example 19 47 47 0 6 4.5 9.5 - 45 120 HP 1100 1.01 6.71× ^10-4 115 19.98 28 Example 20 50 49 0 1 4.0 9.5 - 45 84 HP 1100 1.26 2.94× ^10-3 141 16.12 twenty three Example 21 75 25 0 0 4.0 7.0 - - 60 SPS 1100 1.58 6.36× ^10-2 128 20.15 38 Example 22 50 50 0 0 4.0 7.0 - - 72 SPS 1000 0.97 3.00× ^10-2 143 16.20 42 Example 23 30 70 0 0 3.0 7.0 - - 72 HIP 1100 1.06 5.09× ^10-4 155 14.71 18 Comparative Example 1 50 50 0 0 13.5 33.0 - - 36 HP 1000 4.85 5.01× ^10-1 80 8.07 127 Comparative Example 2 45 55 0 0 13.5 38.5 - - 36 HP 1000 4.75 3.41× ^10-1 79 7.69 105 Comparative Example 3 95 5 0 0 14.0 29.5 - - twenty four HP 1200 6.41 9.84× ^10-1 81 9.27 151 Comparative Example 4 50 50 0 0 14.0 29.5 - - twenty four HP 1300 6.08 7.67× ^10-1 88 9.01 96 Comparative Example 5 3 97 0 0 13.5 31.0 - - twenty four HP 1100 5.11 2.93× ^10-1 97 7.91 78 Comparative Example 6 46 46 8 0 12.5 35.5 1.2 - 36 HP 1150 3.15 8.57× ^10-1 99 8.91 83 Comparative Example 7 46 46 0 8 12.5 33.0 - 60 36 HP 1100 3.67 7.26× ^10-1 89 9.11 91 Comparative Example 8 30 70 0 0 12.5 31.0 - - 36 SPS 1000 4.27 2.19× ^10-1 87 8.31 84 Comparative Example 9 50 50 0 0 14.0 38.5 - - twenty four HIP 1100 5.81 5.52× ^10-1 91 8.48 70

Test example 1 : Black phase average particle size and particle size variation

In this test example, a scanning electron microscope was used to observe the metallographic microstructure of the composite oxide target, supplemented by an energy dispersive X-ray spectrometer to confirm the components of the black phase and the white phase in the metallographic microstructure of the composite oxide target, and the image analysis software was used to analyze the components. The size of the black phase in the composite oxide target.

The composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 were processed by water jet and grinder into a round cake-shaped composite oxide target with a diameter of 152 mm and a thickness of 6 mm, and the above composite oxide targets were prepared. A 10mm*10mm test piece is cut from the center of the target to half of the circumference (ie, half of the radius).

Here, taking the test piece of Example 1 as an example, the composition of the black phase of the composite oxide target of Example 1, and the algorithm of the average particle size and particle size variation of the black phase are described. Other Examples 2 to 23 and For the composite oxide targets of Comparative Examples 1 to 9, the average particle size and particle size variation of the black phase were calculated in the same way.

First, use a scanning electron microscope (brand: HITACHI, model: S-3400N) to observe the metallographic microstructure of the test piece of Example 1 at a magnification of 2000 times; then use an energy dispersive X-ray spectrometer to analyze the composite oxide target material The composition of the medium white and black phases. As shown in Figure 1, two positions were selected respectively in the metallographic microstructure of the test piece of Example 1, and the selected positions were marked with "A" and "B" respectively, to analyze the components of the black phase and the white phase, and to detect the details in detail. The test results are shown in Table 2 below. Table 2: The content of each component in the white phase and the black phase in the composite oxide target of Example 1, the unit is at%. Pick a location Phase description Mg Ti O Example 1 A black phase 37.61 0 62.39 B white phase 0 37.06 62.94

As shown in Table 2 above, the component of the black phase in the composite oxide target of Example 1 is magnesium monoxide, and the white phase is titanium monoxide. Then, according to the analysis results of EDX, the average particle size and particle size variation of the black phase in the composite oxide target of Example 1 were analyzed with image analysis software to evaluate the magnesium monoxide in the composite oxide target of Example 1 degree of agglomeration.

Specifically, the 10 mm*10 mm test piece of the aforementioned Example 1 was first observed with SEM during the analysis, and five SEM metallographic images were obtained by taking pictures at five observation positions. Next, the five SEM metallographic images obtained in Example 1 were processed into high-resolution images by the built-in "Color Threshold" function of the image analysis software Image J. Figures 2A and 2B, 3A and 3B, 4A and 4B, 5A and 5B, 6A and 6B, and 7A and 7B, which are Example 1, Example 8, Example 10, Example 17, Comparative Example 1 and Comparison, respectively The SEM metallographic image and high-resolution image of the composite oxide target of Example 9; comparing Figures 2B, 3B, 4B, and 5B with the high-resolution images of Figures 6B and 7B, it can be seen that Example 1, the implementation of The composite oxide targets of Example 8, Example 10 and Example 17 have a small particle size and a uniform black phase.

In order to objectively evaluate the degree of agglomeration of magnesium monoxide in the composite oxide target of Example 1, the “Analyze Particles” function built into the image analysis software Image J was used to analyze the average particle size of the black phases in each of the above five SEM metallographic images. The results were 1.16 μm, 1.10 μm, 1.61 μm, 1.02 μm and 1.49 μm respectively, and then the average of the above five average particle diameters was taken, that is, the above five numerical values were added and divided by five to obtain the composite of Example 1. The average particle size of the black phase of the oxide target was 1.28 μm, and the results are listed in Table 1 above.

， 即可算出實施例1之複合氧化物靶材之黑色相的粒徑變異度。 After that, follow the formula:

, the particle size variation of the black phase of the composite oxide target of Example 1 can be calculated.

。 Specifically, the detailed formula is as follows:

.

The results of the particle size variation of the black phase of the composite oxide target of Example 1 are listed in Table 1 above. The average particle size of the black phase of the composite oxide targets of Examples 2 to 23 and Comparative Examples 1 to 9 and particle size variability were also analyzed as described above, and the results are listed in Table 1 above.

As shown in Table 1 above, the composite oxide targets of Examples 1 to 23 were mixed with a specific particle size and an appropriate amount of raw material powder, and the appropriate grinding time and sintering temperature were controlled, so Examples 1 to 23 were prepared. The composite oxide target of 23 can have a specific composition, the average particle size of the black phase is all less than or equal to 2 μm, and the particle size variation of the black phase is all less than 0.2.

In contrast to Comparative Examples 1 to 9, since the composite oxide targets of Comparative Examples 1 to 9 did not control the appropriate grinding time, the particle size of the raw material powders of the composite oxide targets of Comparative Examples 1 to 9 was larger, so the composite oxide targets of Comparative Examples 1 to 9 were prepared. The average particle diameters of the black phases of the composite oxide targets of Comparative Examples 1 to 9 are all greater than 3 μm, and the particle diameter variations of the black phases are all greater than 0.2.

It can be seen from the above experimental results that the composite oxide target prepared by the manufacturing method of the present invention can have a black phase with a smaller average particle size and a lower particle size variation.

Looking at Examples 15 to 17 and Examples 18 to 20 again, when the first additive component or the second additive component is added as needed, with the increase of the total amount of the additive components, the average particle size of the black phase of the composite oxide target The particle diameter can be reduced accordingly, and the particle size variability also tends to decrease accordingly.

Test example 2 :Flexural strength

The composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 were processed by water jet and grinder to make round cake-shaped composite oxide targets with a diameter of 152 mm and a thickness of 6 mm. Three test pieces with length, width and height of 50mm*3mm*4mm were cut by line from the center of the pie-shaped composite oxide target to half of the circumference (ie, half of the radius).

Here, the test piece of Example 1 is taken as an example to illustrate the method for analyzing the flexural strength of the composite oxide target of Example 1. The composite oxide targets of other Examples 2 to 23 and Comparative Examples 1 to 9 are The same method was used to derive the respective flexural strengths.

Using a universal testing machine (brand: Instron; model: 3365 series; pressing speed: 0.008 millimeters/second (mm/sec)) to measure the four-point flexural strength of the three test pieces of Example 1 to obtain three data, The average value of the above three data is taken as the mechanical strength of the composite oxide target of Example 1 to be evaluated. The results of the flexural strength of the composite oxide targets of Example 1 are listed in Table 1 above, in megapascals (MPa); while the composite oxide targets of Examples 2 to 23 and Comparative Examples 1 to 9 have Flexural strength was also analyzed as described above and the results are presented in Table 1 above.

As can be seen from Table 1 above, the flexural strengths of the composite oxide targets of Examples 1 to 23 are all greater than 110 MPa; preferably, the composite oxide targets of Examples 1 to 5, 8 to 14, 17, 20, 22 and 23 The flexural strengths of the target targets are all greater than 130 MPa; more preferably, the flexural strengths of the composite oxide targets of Examples 10, 13 and 23 are all greater than 150 MPa.

In contrast, the composite oxide targets of Comparative Examples 1 to 9, their flexural strengths are all less than 100 MPa; in particular, the flexural strengths of the composite oxide targets of Comparative Examples 1 to 4, 7 and 8 are all less than 90 MPa; , the flexural strength of the composite oxide target of Comparative Example 2 did not even reach 80 MPa.

It can be seen from the above experimental results that the composite oxide target prepared by the present invention has excellent flexural strength.

Test example 3 :Thermal conductivity

The composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 were made into pie-shaped composite oxide targets with a diameter of 152 mm and a thickness of 6 mm. Here, take Example 1 as an example to illustrate the calculation method of the thermal conductivity of the composite oxide target of Example 1. The composite oxide targets of other Examples 2 to 23 and Comparative Examples 1 to 9 are all the same method to obtain the respective thermal conductivity.

。 First, from the center of the round cake-shaped composite oxide target of Example 1 to half of the circumference (ie, half of the radius), a line with a length, width and height of 15 mm * 15 mm * 5 mm is cut. The weight of the test piece in air and liquid was measured by Archimedes method, and the actual density of the composite oxide target of Example 1 was calculated according to the following formula (represented by ρ, the unit is kg / Cubic meter (kg/m ³ )):

.

Next, cut a circular pie-shaped test piece with a diameter of 12.7 mm and a height of 2 mm from the center of the pie-shaped composite oxide target of Example 1 to half of the circumference (ie, half of the radius). piece. After that, the thermal diffusivity (Thermal Diffusivity, represented by α, in square meters/second (m ² /s)) was obtained by the Laser Flash Method for this test piece, and the differential scanning amount was used to calculate the thermal diffusivity. Thermal method (Differential Scanning Calorimetry, DSC) to obtain the specific heat capacity (Specific Heat Capacity, expressed in _cp , the unit is Joule/kg·Kelvin (J/kg·K)).

， 即可得到實施例1之複合氧化物靶材的熱導率（k，單位為瓦特/公尺·克耳文（W/m·K）），並將結果列於上表1中。 Finally, substitute the values of thermal diffusivity (α), actual density (ρ) and specific heat capacity (c _p ) obtained above into the following formula:

, the thermal conductivity (k, in watts/meter·Kelvin (W/m·K)) of the composite oxide target of Example 1 can be obtained, and the results are listed in Table 1 above.

The thermal conductivity of the composite oxide targets of Examples 2 to 23 and Comparative Examples 1 to 9 was also analyzed by the method described above, and the results are listed in Table 1 above.

It can be seen from the above Table 1 that the thermal conductivity of the composite oxide targets of Examples 1 to 23 are all greater than 10 W/m·K; preferably, the composite oxide targets of Examples 1 to 7, 14 and 18 to 22 The thermal conductivity of the target materials is greater than 15 W/m·K; more preferably, the thermal conductivity of the composite oxide targets of Examples 5, 6 and 21 are all greater than 20 W/m·K.

In contrast, the thermal conductivity of the composite oxide targets of Comparative Examples 1 to 9 is less than 10 W/m·K; especially the thermal conductivity of the composite oxide targets of Comparative Examples 1, 2, 5, 6, 8 and 9 All are less than 9 W/m·K; what's more, the thermal conductivity of the composite oxide targets of Comparative Examples 2 and 5 does not even reach 8 W/m·K.

It can be seen from the above experimental results that the composite oxide target prepared by the present invention has excellent thermal conductivity.

In addition, by further comparing the results of the composite oxide targets (Examples 1 to 14 and 21 to 23) containing only magnesium monoxide and titanium monoxide in Table 1, it can be seen that with the increase of magnesium monoxide in the composite oxide targets As the content increases, the thermal conductivity generally tends to increase accordingly. Furthermore, observing Examples 18 to 20, when the second additive component is added as needed, the thermal conductivity of the composite oxide target tends to increase as the total amount of the second additive component increases.

Test example 4 : Number of particles dropped

First, the composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 were made into round cake-shaped composite oxide targets with a diameter of 5.08 cm and a thickness of 4 mm, and each composite oxide target was placed in a magnetic In the control sputtering machine, first remove the surface contamination by the pre-sputtering process, then under the vacuum of 10 ^-3 Torr to 10 ^-7 Torr, with a sputtering power of 250 watts/square centimeter (W/cm ² ), A wafer with a size of 2cm*2cm was DC sputtered for 300 seconds, and the number of particles dropped during that time was counted. The sputtering results of the composite oxide targets of Examples 1 to 23 and Comparative Examples 1 to 9 are listed in Table 1 above.

It can be seen from Table 1 above that the number of particles dropped by the composite oxide targets of Examples 1 to 23 after DC sputtering is all less than 50; The number of particles produced by the DC sputtering of the composite oxide targets of 17 to 20 and 23 is less than 30; The number of dropped particles is less than 20; more preferably, the number of dropped particles is even less than 10 after DC sputtering is performed with the composite oxide target of Example 12.

In contrast, in Comparative Examples 1 to 9, the number of particles dropped after DC sputtering with their composite oxide targets was more than or equal to 70; The number of particles dropped after plating is more than 90; what's more, the number of particles dropped after DC sputtering with the composite oxide targets of Comparative Examples 1 to 3 is more than 100, among which Comparative Example 3 The number of particles dropped by the composite oxide targets of Examples 1 to 23 after DC sputtering was even more than 150, and the number of particles dropped by the composite oxide targets of Examples 1 to 23 after DC sputtering. At least three times the number of particles.

It can be seen from the above experimental results that DC sputtering with the composite oxide target prepared in the present invention can significantly reduce the number of particles dropped, thereby improving the properties and yield of the sputtered film.

Based on the above test results, by controlling the particle size of the raw material powder, the mixing ratio of the raw material powder, the grinding time and the sintering temperature, the particle size of the black phase in the metallographic microstructure of the prepared composite oxide target can be made less than or equal to 2. Micron and particle size variation is less than 0.2, so it can effectively suppress and/or reduce the number of particles dropped by the composite oxide target during the sputtering process to less than 50, and make the composite oxide target have a resistance of more than 100 MPa. Folding strength and thermal conductivity above 10 W/m·K.

none.

Fig. 1 shows that in order to use an energy dispersive X-ray spectrometer (Energy Dispersive X-ray Spectrometer, EDS or EDX) to detect the components of the white phase and the black phase in the composite oxide target of Example 1, the composite oxide in Example 1 The selected detection position is marked on the metallographic diagram of the scanning electron microscope (SEM) of the target material.

FIG. 2A is a SEM metallographic image of the composite oxide target of Example 1. FIG.

FIG. 2B is a high-resolution image obtained by processing FIG. 2A with the image analysis software Image J.

FIG. 3A is a SEM metallographic image of the composite oxide target of Example 8. FIG.

FIG. 3B is a high-resolution image obtained by processing FIG. 3A with the image analysis software Image J.

FIG. 4A is a SEM metallographic image of the composite oxide target of Example 10. FIG.

FIG. 4B is a high-resolution image obtained by processing FIG. 4A with the image analysis software Image J.

FIG. 5A is a SEM metallographic image of the composite oxide target of Example 17. FIG.

FIG. 5B is a high-resolution image obtained by processing FIG. 5A with the image analysis software Image J.

FIG. 6A is a SEM metallographic image of the composite oxide target of Comparative Example 1. FIG.

FIG. 6B is a high-resolution image obtained by processing FIG. 6A with the image analysis software Image J.

FIG. 7A is a SEM metallographic image of the composite oxide target of Comparative Example 9. FIG.

FIG. 7B is a high-resolution image obtained by processing FIG. 7A with the image analysis software Image J.

none.

Claims (10)

A composite oxide target, comprising magnesium monoxide and titanium monoxide, and based on the total number of atoms of the composite oxide target, the total amount of magnesium monoxide is greater than or equal to 5 atomic percent and less than or equal to 90 atoms percentage, and the total amount of the titanium monoxide is greater than or equal to 10 atomic percent and less than or equal to 95 atomic percent; wherein, the composite oxide target has a plurality of black phases containing the magnesium monoxide, and the average of the black phases is The particle size is less than or equal to 2 microns, and the particle size variation of the black phases is less than 0.2. The composite oxide target as claimed in claim 1, comprising an additive component, the additive component is a first additive component, a second additive component or a combination thereof, and the first additive component is selected from Al2O3 , zirconium dioxide, chromium dioxide, silicon dioxide and the group consisting of combinations thereof, the second additive component is selected from the group consisting of aluminum, zirconium, chromium, silicon and combinations thereof. The composite oxide target according to claim 2, based on the total number of atoms of the composite oxide target, the total amount of the additive components is greater than or equal to 1 atomic percent and less than or equal to 6 atomic percent. The composite oxide target according to any one of claims 1 to 3, wherein the flexural strength of the composite oxide target is greater than 100 megapascals. The composite oxide target according to any one of claims 1 to 3, wherein the thermal conductivity of the composite oxide target is greater than 10 watts/(m·Kelvin). A method of manufacturing a composite oxide target, comprising the steps of: preparing magnesium monoxide powder and titanium monoxide powder, the magnesium monoxide powder having a particle size greater than or equal to 2 microns and less than or equal to 5 microns, and the one The particle size of the titanium oxide powder is greater than or equal to 2 microns and less than or equal to 10 microns; mixing the magnesium monoxide powder and the titanium monoxide powder to obtain a mixed powder, wherein based on the total number of atoms of the mixed powder, the one The total amount of magnesium oxide powder is greater than or equal to 5 atomic percent and less than or equal to 90 atomic percent, and the total amount of the titanium monoxide powder is greater than or equal to 10 atomic percent and less than or equal to 95 atomic percent; grinding the mixed powder for more than 48 hours to obtain a refined powder; the refinement The powder is preformed to obtain a target blank; and the target blank is sintered at 900° C. to 1400° C. to obtain the composite oxide target material. The method for manufacturing a composite oxide target as claimed in claim 6, wherein after grinding the mixed powder for more than 48 hours, sieving through a mesh to obtain the refined powder, and the mesh number of the mesh is 400 Mesh to 600 mesh. The method for manufacturing a composite oxide target according to claim 7, wherein the sintering time of the target blank is 1.5 hours to 5 hours, and the sintering pressure of the target blank is 300 kg/cm 2 to 510 kg/cm 2 . The method for manufacturing a composite oxide target as claimed in claim 8, wherein the method comprises preparing an additive powder, and mixing the magnesium monoxide powder, the titanium monoxide powder and the additive powder to obtain the mixed powder; wherein, The additive powder comprises a first additive powder, a second additive powder or a combination thereof, the first additive powder is selected from the group consisting of aluminum oxide powder, zirconium dioxide powder, chromium oxide powder, silicon dioxide powder and the like. The group formed by the combination, and the particle size of the first additive powder is less than or equal to 3 microns, the second additive powder is selected from the group consisting of aluminum powder, zirconium powder, chromium powder, silicon powder and combinations thereof, And the particle size of the second added powder is less than or equal to 50 microns; based on the total number of atoms of the mixed powder, the total amount of the added powder is greater than or equal to 1 atomic percent and less than or equal to 6 atomic percent. The method for manufacturing a composite oxide target according to any one of claims 6 to 9, wherein the grinding time of the mixed powder is greater than or equal to 48 hours and less than or equal to 120 hours.

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