CN111270210B - Ruthenium sputtering target with high oriented crystal grains and preparation method thereof - Google Patents
Ruthenium sputtering target with high oriented crystal grains and preparation method thereof Download PDFInfo
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- CN111270210B CN111270210B CN202010186065.5A CN202010186065A CN111270210B CN 111270210 B CN111270210 B CN 111270210B CN 202010186065 A CN202010186065 A CN 202010186065A CN 111270210 B CN111270210 B CN 111270210B
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 68
- 238000005477 sputtering target Methods 0.000 title claims abstract description 46
- 239000013078 crystal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005245 sintering Methods 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000007731 hot pressing Methods 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 238000003754 machining Methods 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims description 28
- 238000009768 microwave sintering Methods 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 5
- 238000004544 sputter deposition Methods 0.000 abstract description 18
- 239000013077 target material Substances 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 17
- 238000004321 preservation Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 230000007547 defect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1054—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by microwave
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
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Abstract
The invention discloses a ruthenium sputtering target with high oriented crystal grains and a preparation method thereof, wherein the ruthenium sputtering target has high oriented (002) crystal face, the density is not lower than 99.5%, the crystal grain size is 1-10 mu m, and the oxygen content is within 100 ppm; the integral intensity ratio of the (002) crystal face to the (101) crystal face is not lower than 3. The preparation method comprises the following steps: selecting ruthenium powder with purity of 4N or above and granularity of 1-10 μm; then carrying out cold press molding on the powder; then the ingot blank formed by cold pressing is sintered by low temperature microwave; then the ingot blank is subjected to low-temperature vacuum hot-pressing sintering to further improve the density; and finally, machining to obtain the target material. The invention adopts lower sintering temperature, low-temperature vacuum hot-pressing technology and hydrogen filling gas to form reducing atmosphere, so that the ruthenium sputtering target material has excellent performance, high density and (002) crystal face high-orientation are beneficial to obtaining the ruthenium film with high sputtering rate and uniform thickness, the preparation process is simple and convenient, the condition is mild, the operation and control are easy, the production efficiency can be greatly improved, and the preparation cost is greatly saved.
Description
Technical Field
The invention belongs to the technical field of powder metallurgy, further belongs to the technical field of precious metal sputtering targets, and particularly relates to a high-orientation and high-density ruthenium sputtering target for electronic information industry and a preparation method thereof.
Background
The ruthenium film is widely applied to the field of electronic information industry, and is mainly used as a middle transition layer in a high-density perpendicular magnetic recording medium in a mechanical hard disk; the diffusion barrier layer and the seed crystal layer in the process of seedless Cu electroplating are mainly used in the integrated circuit. The ruthenium thin film is generally obtained by magnetron sputtering with a ruthenium sputtering target as a source material. The main requirements for ruthenium sputtering targets in general are high purity (4N), high densification (up to a theoretical density of 12.45 g/cm)3More than 99%) and fine grains (1 to 10 μm), thereby obtaining a ruthenium thin film having a low defect density and a uniform thickness during sputtering. With the miniaturization and complicated structure of modern microelectronic devices, the number of layers of films to be sputtered is gradually increased, and the corresponding sputtering process becomes more complicated and time-consuming. Therefore, if the film sputtering deposition rate can be increased, the production efficiency can be improved, and the cost can be greatly saved. Therefore, the improvement can be divided into two directions, one is the improvement on coating equipment, such as the improved design of a sputtering magnetic field and the like; it is directed to improvements in the microstructure of the sputtering target such as control of grain orientation. The improved design of the sputtering magnetic field is relatively complex, and the microstructure of the target is relatively simple to adjust.
For example, chinese patent application, a method for preparing a ruthenium metal sputtering target (CN102485378A, published as 6.6.2012) discloses a method for preparing a ruthenium metal sputtering target, which is a method for preparing a ruthenium metal sputtering target by direct hot pressing, and the method focuses on controlling and improving the grain size, density, and oxygen content, and the obtained ruthenium metal target has a density of more than 98%, an average grain size of less than 20 μm, and an oxygen content of 200ppm, but the method of the present invention is difficult to control the grain orientation of the target.
Further, as shown in the chinese patent application, a method for preparing a ruthenium sputtering target (CN107805789A, published 2018, 3/16) discloses a method for preparing a ruthenium sputtering target, and the invention aims to increase the density of the ruthenium target, so that the relative density of the prepared ruthenium sputtering target is greater than 99.5%, but the invention is also difficult to control the grain orientation.
Also, as in the chinese patent application, a ruthenium alloy sputtering target, (CN101198717A, published 2008, 6/11) discloses a ruthenium alloy sputtering target. The method also aims to improve the density, the grain size and the impurity control of the ruthenium target, such as the control of parameters such as oxygen content and the like. Not only is the process complicated, but also it is difficult to control the grain orientation.
In summary, the ruthenium target preparation methods in the prior art include vacuum hot pressing, hot isostatic pressing, Spark Plasma Sintering (SPS), etc., and although a high-density target can be obtained by adjusting process parameters, it is difficult to control the grain orientation of the target. According to the knowledge of materials science, the grain orientation of the target has a significant influence on sputtering film formation, such as the highest atomic density on metal dense-arranged surfaces, the largest spacing between the dense-arranged surfaces and the relatively weakest bonding force between the dense-arranged surfaces. The dense arrangement surface of ruthenium is (002) crystal surface, so a method for adjusting the ruthenium target material crystal grain to be oriented to the (002) crystal surface high orientation needs to be provided, and the sputtering deposition rate is favorably improved under the condition of certain sputtering power.
Disclosure of Invention
The first object of the present invention is to provide a ruthenium sputtering target having a crystal grain exhibiting a highly oriented (002) crystal plane.
The invention also aims to provide a preparation method of the ruthenium sputtering target with high oriented crystal grains.
The first purpose of the invention is realized by that the ruthenium sputtering target material presents (002) crystal face high orientation, the compactness is not less than 99.5%, the grain size is 1-10 μm, and the oxygen content is within 100 ppm.
The other purpose of the invention is realized by the following steps of raw material preparation, cold press molding, low-temperature microwave sintering and low-temperature vacuum hot pressing:
(1) preparing raw materials: selecting ruthenium powder with purity of 4N or more, wherein the powder granularity is 1-10 mu m;
(2) cold press molding: putting the powder into a die for cold press molding, wherein the cold press pressure is 100-300 MPa, and the pressure maintaining time is 10-60 min;
(3) low-temperature microwave sintering: and (3) performing microwave sintering on the cold-pressed ingot blank: firstly, vacuumizing to 1 × 10-2～1×10-3Introducing high-purity hydrogen to 1-10 Pa, then heating to a sintering temperature of 300-600 ℃ for sintering, wherein the microwave frequency is 2.45GHz, the heating rate is 10-50 ℃/min, the sintering time is 10-30 min, after the sintering time is up, cooling the ingot blank along with the furnace, cooling to room temperature, closing the hydrogen, and taking out the ingot blank;
(4) low-temperature vacuum hot pressing: carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the sintering temperature is 300-800 ℃, the heating rate is 10-30 ℃/min, the hot-pressing pressure is 100-300 MPa, the sintering time is 30-60 min, and the vacuum degree is 1 multiplied by 10-3～1×10-4Pa, after the sintering time is up, reducing the pressure at a pressure reduction rate of 10-30 MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to room temperature;
(5) machining: and (5) carrying out machining treatment to obtain a target product with a required size.
The invention adopts a two-step combined technical scheme of low-temperature microwave sintering and low-temperature vacuum hot pressing technology, namely, the compact ruthenium target with (002) crystal face preferred orientation is obtained by effectively controlling the sintering temperature and the sintering time. The scheme has the advantages that: compared with the traditional high-temperature vacuum hot pressing or hot isostatic pressing method (1300-1700 ℃), the low sintering temperature (300-800 ℃) of the scheme effectively limits the growth of crystal grains; secondly, the low-temperature vacuum hot-pressing technology is adopted, so that the preferred orientation result formed by microwave sintering is not changed, and the density of the target material is further improved; thirdly, hydrogen is filled in the microwave sintering process to form a reducing atmosphere, which is beneficial to controlling the oxygen content in the target material. The three points are the reasons that the ruthenium target with high density and (002) crystal face preferred orientation can be obtained by the two-step method, the ruthenium film with high sputtering rate and uniform film thickness is obtained by the (002) dense-arranged face preferred orientation in the subsequent sputtering process, the production efficiency is greatly improved, and the cost is greatly saved.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The ruthenium sputtering target with the high oriented crystal grains is characterized by exhibiting the high oriented (002) crystal face orientation, having the density not lower than 99.5%, having the crystal grain size of 1-10 mu m and having the oxygen content within 100 ppm.
The integral intensity ratio of the (002) crystal face to the (101) crystal face is not lower than 3.
The invention discloses a method for preparing a ruthenium sputtering target with high oriented crystal grains, which comprises the following steps of raw material preparation, cold press molding, low-temperature microwave sintering and low-temperature vacuum hot pressing:
(1) preparing raw materials: selecting ruthenium powder with purity of 4N or more, wherein the powder granularity is 1-10 mu m;
(2) cold press molding: putting the powder into a die for cold press molding, wherein the cold press pressure is 100-300 MPa, and the pressure maintaining time is 10-60 min;
(3) low-temperature microwave sintering: and (3) performing microwave sintering on the cold-pressed ingot blank: firstly, vacuumizing to 1 × 10-2～1×10-3Pa, introducing high-purity hydrogen to 1-10 Pa, and then heating to the sintering temperature of 300-600 ℃ for sintering, wherein the microwave frequency is 2.45 GHz;
(4) low-temperature vacuum hot pressing: carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the sintering temperature is 300-800 ℃, the heating rate is 10-30 ℃/min, the hot-pressing pressure is 100-300 MPa, the sintering time is 30-60 min, and the vacuum degree is 1 multiplied by 10-3～1×10-4Pa, after the sintering time is up, reducing the pressure at a pressure reduction rate of 10-30 MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to room temperature;
(5) machining: and (5) carrying out machining treatment to obtain a target product with a required size.
And in the step 3, the heating rate is 10-50 ℃/min.
And the sintering time in the step 3 is 10-30 min.
And in the step 3, after the sintering time is up, cooling the ingot blank along with the furnace, cooling to room temperature, closing hydrogen, and taking out the ingot blank.
The sintering temperature in the step 4 is 50-200 ℃ higher than that in the step 3.
Example 1
Preparation of a ruthenium sputtering target with high oriented crystal grains, (1) selecting 4N-purity ruthenium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 5 mu m; (2) putting the powder into a die for cold press molding, wherein the cold press pressure is 150MPa, and the pressure maintaining time is 30 min; (3) the ingot blank formed by cold pressing is sintered by microwave, the microwave frequency is 2.45GHz, and the ingot blank is firstly vacuumized to 8 multiplied by 10- 3Introducing high-purity hydrogen to 3Pa, then heating to the sintering temperature of 300 ℃ at the heating rate of 30 ℃/min for sintering for 10min, cooling the ingot blank along with the furnace after the sintering time is up, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; (4) carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 10 ℃/min, the sintering temperature is 400 ℃, the hot-pressing pressure is 180MPa, the heat preservation time is 35min after reaching the temperature, and the vacuum degree is 1 multiplied by 10-3Pa, after the heat preservation time is up, reducing the pressure at a pressure reduction rate of 18MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to room temperature; (5) the ruthenium sputtering target material product with the required size is obtained by machining treatment, and the performance indexes are shown in table 1.
Example 2
Preparation of a ruthenium sputtering target with high oriented crystal grains, (1) selecting 4N 5-purity ruthenium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 5 mu m; (2) putting the powder into a die for cold press molding, wherein the cold press pressure is 100MPa, and the pressure maintaining time is 10 min; (3) and (3) performing microwave sintering on the cold-pressed ingot blank: microwave frequency of 2.45GHz, first evacuating to 1 × 10- 3Pa, introducing high-purity hydrogen to 1Pa, and introducing at 40 deg.C/minHeating to the sintering temperature of 400 ℃ at a speed rate for sintering for 10min, cooling the ingot blank along with the furnace after the sintering time is reached, cooling to the room temperature, closing hydrogen, and taking out the ingot blank; (4) carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 20 ℃/min, the sintering temperature is 450 ℃, the hot-pressing pressure is 100MPa, the heat preservation time is 30min after reaching the temperature, and the vacuum degree is 1 multiplied by 10-3Pa, after the heat preservation time is up, reducing the pressure at the pressure reduction rate of 10MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to the room temperature; (5) the ruthenium sputtering target material product with the required size is obtained by machining treatment, and the performance indexes are shown in table 1.
Example 3
Preparation of a ruthenium sputtering target with high oriented crystal grains, (1) selecting 5N-purity ruthenium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 6 mu m; (2) putting the powder into a die for cold press molding, wherein the cold press pressure is 210MPa, and the pressure maintaining time is 20 min; (3) and (3) performing microwave sintering on the cold-pressed ingot blank: microwave frequency of 2.45GHz, first evacuating to 1 × 10- 3Pa, introducing high-purity hydrogen to 5Pa, then heating to the sintering temperature of 500 ℃ at the speed of 20 ℃/min for sintering, wherein the sintering time is 20min, cooling the ingot blank along with the furnace after the sintering time is reached, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; (4) carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 15 ℃/min, the sintering temperature is 550 ℃, the hot-pressing pressure is 210MPa, the heat preservation time is 40min after reaching the temperature, and the vacuum degree is 1 multiplied by 10-4Pa, after the heat preservation time is up, reducing the pressure at the pressure reduction rate of 30MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to the room temperature; (5) the ruthenium sputtering target material product with the required size is obtained by machining treatment, and the performance indexes are shown in table 1.
Example 4
Preparation of a ruthenium sputtering target with high oriented crystal grains, (1) selecting 4N 5-purity ruthenium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 7 mu m; (2) putting the powder into a die for cold press molding, wherein the cold press pressure is 250MPa, and the pressure maintaining time is 20 min; (3) and (3) performing microwave sintering on the cold-pressed ingot blank: microwave frequency of 2.45GHz, first evacuating to 6 × 10- 3Pa, introducing high-purity hydrogen to 7Pa, then heating to the sintering temperature of 600 ℃ at the speed of 30 ℃/min, sintering for 25min, cooling the ingot blank along with the furnace after the sintering time is reached, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; (4) carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 15 ℃/min, the sintering temperature is 700 ℃, the hot-pressing pressure is 250MPa, the heat preservation time is 50min after reaching the temperature, and the vacuum degree is 1 multiplied by 10-3Pa, after the heat preservation time is up, reducing the pressure at the pressure reduction rate of 25MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to the room temperature; (5) the ruthenium sputtering target material product with the required size is obtained by machining treatment, and the performance indexes are shown in table 1.
Example 5
Preparation of a ruthenium sputtering target with high oriented crystal grains, (1) selecting 4N8 ruthenium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 8 mu m; (2) putting the powder into a die for cold press molding, wherein the cold press pressure is 300MPa, and the pressure maintaining time is 60 min; (3) and (3) performing microwave sintering on the cold-pressed ingot blank: microwave frequency of 2.45GHz, first evacuating to 1 × 10-3Pa, introducing high-purity hydrogen to 10Pa, then heating to the sintering temperature of 600 ℃ at the speed of 50 ℃/min for sintering for 30min, cooling the ingot blank along with the furnace after the sintering time is up, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; (4) carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 20 ℃/min, the sintering temperature is 800 ℃, the hot-pressing pressure is 300MPa, the sintering time is 60min, and the vacuum degree is 1 multiplied by 10-4Pa, after the heat preservation time is up, reducing the pressure at the pressure reduction rate of 15MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to the room temperature; (5) the ruthenium sputtering target material product with the required size is obtained by machining treatment, and the performance indexes are shown in table 1.
Comparative example 1
A preparation method of a ruthenium sputtering target material is provided, wherein a comparative example 1 is the same as the steps 1-3 of the example 1, and the step 4 of the example 1 is omitted, namely 4N purity ruthenium powder is selected, the powder particle size is 1-10 mu m, and the average particle size is 5 mu m; then putting the powder into a die for cold press molding, wherein the cold press pressure is 150MPa, and the pressure maintaining time is 30 min; subsequently cold-press forming the ingot blankMicrowave sintering at 2.45GHz under vacuum of 8 × 10-3Introducing high-purity hydrogen to 3Pa, then heating to the sintering temperature of 300 ℃ at the heating rate of 30 ℃/min for sintering for 10min, cooling the ingot blank along with the furnace after the sintering time is up, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; and finally, machining to obtain a ruthenium sputtering target product with the required size, wherein the performance indexes are shown in table 1.
Comparative example 2
A preparation method of a ruthenium sputtering target material is provided, wherein a comparative example 2 is the same as steps 1, 2 and 4 of an example 1, and the comparative example 2 lacks a step 3 of the example 1, namely 4N purity ruthenium powder is selected, the powder granularity is 1-10 mu m, and the average particle size is 5 mu m; then putting the powder into a die for cold press molding, wherein the cold press pressure is 150MPa, and the pressure maintaining time is 30 min; carrying out vacuum hot-pressing sintering treatment on the ingot blank, wherein the heating rate is 10 ℃/min, the sintering temperature is 400 ℃, the hot-pressing pressure is 180MPa, the heat preservation time is 35min after reaching the temperature, and the vacuum degree is 1 multiplied by 10-3Pa, after the heat preservation time is up, reducing the pressure at a pressure reduction rate of 18MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to room temperature; and finally, machining to obtain a ruthenium sputtering target product with the required size, wherein the performance indexes are shown in table 1.
Comparative example 3
A preparation method of a ruthenium sputtering target material comprises the steps of 1, 2 and 3 of a comparative example 3 and an example 5, wherein the vacuum hot pressing temperature in the step 4 of the comparative example 3 is 900 ℃, namely 4N8 ruthenium powder is selected, the powder granularity is 1-10 mu m, and the average particle size is 8 mu m; putting the powder into a die for cold press molding, wherein the cold press pressure is 300MPa, and the pressure maintaining time is 60 min; and (3) performing microwave sintering on the cold-pressed ingot blank: microwave frequency of 2.45GHz, first evacuating to 1 × 10-3Pa, introducing high-purity hydrogen to 10Pa, then heating to the sintering temperature of 600 ℃ at the speed of 50 ℃/min for sintering for 30min, cooling the ingot blank along with the furnace after the sintering time is up, cooling to the room temperature, closing the hydrogen, and taking out the ingot blank; carrying out vacuum hot-pressing sintering treatment on the ingot blank after microwave sintering, wherein the heating rate is 20 ℃/min, the sintering temperature is 900 ℃, the hot-pressing pressure is 300MPa, the sintering time is 60min, and the vacuum degree is 1 multiplied by 10-4Pa, after the heat preservation time is up, reducing the pressure at the pressure reduction rate of 15MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to the room temperature; and finally, machining to obtain a ruthenium sputtering target product with the required size, wherein the performance indexes are shown in table 1.
The performance parameters of the example and comparative example targets were compared and the results are shown in table 1.
TABLE 1 evaluation of the properties of the various examples and comparative examples (data)
Note: the sputtering condition is direct current magnetron sputtering, the sputtering power is 300W, the Ar gas pressure is 3Pa, the deposition temperature is room temperature, and the substrate is a monocrystalline silicon wafer.
As can be seen from Table 1, the sputtering rates of the target ruthenium thin films obtained in comparative example 1 and example 1 are almost the same, but significant grain/void defects were observed in the thin film in the comparative example; the sputtering rate of the target ruthenium film obtained in the comparative example 2 is obviously lower than that of the target ruthenium film obtained in the example 1, and obvious particle/hole defects can be observed; comparative example 3 although no obvious holes and defects are formed in the sputtering film, the grain size is increased and the preferred orientation of the (002) crystal face is weakened due to the fact that the vacuum hot-pressing temperature reaches 900 ℃, and the sputtering rate is obviously lower than that of example 5; in the examples 1-5, no obvious particle/hole defect is observed in the ruthenium thin film obtained by sputtering the target product, the film thickness uniformity of all the examples is superior to that of the comparative example, the (002) crystal face directionality is obviously superior to that of the comparative example, and the performance of the obtained material is far superior to that of the comparative example and the prior art.
Claims (5)
1. A preparation method of a ruthenium sputtering target with high oriented crystal grains is characterized in that the ruthenium sputtering target is in (002) crystal face high oriented orientation, the density is not lower than 99.5%, the crystal grain size is 1-10 mu m, the oxygen content is within 100ppm, the integral intensity ratio of (002) crystal face to (101) crystal face is not lower than 3, and the ruthenium sputtering target is prepared according to the following steps:
(1) preparing raw materials: selecting ruthenium powder with purity of 4N or more, wherein the powder granularity is 1-10 mu m;
(2) cold press molding: putting the powder into a die for cold press molding, wherein the cold press pressure is 100-300 MPa, and the pressure maintaining time is 10-60 min;
(3) low-temperature microwave sintering: microwave sintering the cold-pressed ingot blank, firstly vacuumizing to 1 × 10-2～1×10-3Pa, introducing high-purity hydrogen to 1-10 Pa, and then heating to 300-600 ℃ for sintering, wherein the microwave frequency is 2.45 GHz;
(4) low-temperature vacuum hot pressing: carrying out vacuum hot-pressing sintering treatment on the ruthenium target ingot blank subjected to microwave sintering, wherein the sintering temperature is 300-800 ℃, the heating rate is 10-30 ℃/min, the hot-pressing pressure is 100-300 MPa, the sintering time is 30-60 min, and the vacuum degree is 1 multiplied by 10-3～1×10-4Pa, after the sintering time is up, reducing the pressure at a pressure reduction rate of 10-30 MPa/min, cooling the ingot blank along with the furnace, and taking out the ingot blank after the temperature is reduced to room temperature;
(5) machining: and (5) carrying out machining treatment to obtain a target product with a required size.
2. The method for preparing a ruthenium sputtering target with highly oriented crystal grains according to claim 1, wherein the temperature rise rate in the step 3 is 10-50 ℃/min.
3. The method for preparing the ruthenium sputtering target with highly oriented crystal grains according to claim 1, wherein the sintering time in the step 3 is 10-30 min.
4. The method for preparing a ruthenium sputtering target with highly oriented crystal grains according to claim 1, wherein in the step 3, after the sintering time is up, the ingot blank is cooled along with the furnace, and after the temperature is reduced to room temperature, hydrogen is turned off, and the ingot blank is taken out.
5. The method for preparing the ruthenium sputtering target with highly oriented crystal grains according to claim 1, wherein the sintering temperature in the step 4 is 50-200 ℃ higher than that in the step 3.
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