CN111235536A - Iridium sputtering target with high oriented crystal grains and preparation method thereof - Google Patents
Iridium sputtering target with high oriented crystal grains and preparation method thereof Download PDFInfo
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- CN111235536A CN111235536A CN202010186255.7A CN202010186255A CN111235536A CN 111235536 A CN111235536 A CN 111235536A CN 202010186255 A CN202010186255 A CN 202010186255A CN 111235536 A CN111235536 A CN 111235536A
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- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 57
- 239000013078 crystal Substances 0.000 title claims abstract description 42
- 238000005477 sputtering target Methods 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 71
- 238000007731 hot pressing Methods 0.000 claims abstract description 31
- 239000000843 powder Substances 0.000 claims abstract description 27
- 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 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 29
- 238000010438 heat treatment Methods 0.000 claims description 25
- 238000009768 microwave sintering Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 abstract description 20
- 239000013077 target material Substances 0.000 abstract description 17
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000012298 atmosphere Substances 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 16
- 239000010408 film Substances 0.000 description 12
- 238000004321 preservation Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 229910000575 Ir alloy Inorganic materials 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000007547 defect Effects 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229910001264 Th alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009694 cold isostatic pressing Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005242 forging Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- WLTSUBTXQJEURO-UHFFFAOYSA-N thorium tungsten Chemical compound [W].[Th] WLTSUBTXQJEURO-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000203 mixture Substances 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
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
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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
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
-
- 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
- B22F3/02—Compacting only
-
- 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
-
- 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
-
- 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
- B22F3/24—After-treatment of workpieces or articles
-
- 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
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
-
- 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
-
- 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
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
The invention discloses an iridium sputtering target with high oriented crystal grains and a preparation method thereof, wherein the iridium sputtering target has high oriented (111) 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 (111) crystal face to the (200) crystal face is not lower than 4. The preparation method comprises the following steps: selecting iridium 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 iridium sputtering target material has excellent performance, high density and (111) crystal face high-orientation are beneficial to obtaining the iridium film with high sputtering rate and uniform thickness, the preparation process is simple and convenient, the condition is mild, the operation and the 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 an iridium sputtering target with high oriented orientation and high density of crystal grains for electronic information industry and a preparation method thereof.
Background
Iridium (Ir) is a platinum group metal with a face-centered cubic structure, has a melting point as high as 2443 ℃, is a noble metal with the highest melting point, and has high density (22.65 g/cm)3) The high-temperature-resistant alloy has stable chemical properties, high hardness and good high-temperature performance, is one of the metals with the best heat strength and heat stability at high temperature, and is also a metal with extremely high melting point and strong oxidation resistance. In addition, it is one of the most corrosion resistant metals, able to withstand many melting agents and high temperature silicic acidSalt attack, which is capable of resisting corrosion at high temperatures by almost all acids, aqua regia, molten metals, and even silicates.
Due to its excellent physical and chemical stability, iridium thin films are increasingly used in the electronic information industry. For example, in a Micro Electro Mechanical System (MEMS), a pure iridium thin film is used as an upper electrode layer (for an extraction electrode) and a lower electrode layer (for a connection substrate layer), an Ir-Ta-O composite thin film is used as an electrode layer of a ferroelectric capacitor in an integrated circuit, and the like; the pure iridium film is directly obtained by taking an iridium sputtering target as a source material and performing magnetron sputtering in an argon atmosphere; and the Ir-Ta-O composite film is obtained by adopting an iridium target and a tantalum target to perform reactive co-sputtering in an oxygen atmosphere. In order to form a high-quality film, the preparation of an iridium target is very critical, and generally, requirements on an iridium sputtering target material are high purity (4N), high density (reaching more than 99% of theoretical density), and fine crystal grains (1-10 μm), so that an iridium film with low defect density and uniform thickness is obtained in a sputtering process. 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 of the coating equipment such as the improved design of a sputtering magnetic field; 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.
The retrieval of the current patents mainly relates to the processing and forming of iridium wires and iridium plates, and the preparation patents of iridium targets are few.
For example, chinese patent application, a high-density iridium alloy billet and a method for preparing the same (CN102168200A, published 2011/8/31/h), discloses a high-density iridium alloy billet and a method for preparing the same. The invention focuses on uniform mixing of iridium alloy raw materials and compactness of the alloy, and the preparation method comprises the steps of performing high-energy activation on tungsten powder, tungsten-thorium alloy powder and iridium powder by a high-energy ball mill according to the component requirements of a final iridium alloy blank, uniformly mixing the tungsten powder, the tungsten-thorium alloy powder and the iridium powder, then placing the mixture in a vacuum oven for drying to obtain high-energy activated mixed powder, then performing compression molding on the high-energy activated mixed powder in a mould pressing or cold isostatic pressing mode to obtain a powder compact, then placing the powder compact in a high-temperature sintering furnace for sintering (2200-2290 ℃), and performing furnace cooling to obtain a high-density iridium alloy blank, wherein the relative density reaches more than 95%.
For another example, in chinese patent application, a method for processing an iridium alloy bar or plate (CN102205486A, published 2011/10/5/h), which aims to improve the compactness of iridium alloy, includes selecting a hot-rolled metal molybdenum plate as a sheathing material, cladding the iridium alloy to be processed, welding, heating, processing into a bar or plate, annealing, and finally soaking the bar or plate in aqua regia to remove the clad hot-rolled metal molybdenum plate, thereby obtaining the iridium alloy bar or plate. The invention uses molybdenum plate coating technology to make iridium alloy smoothly finish processing without being influenced by environmental conditions. The invention also fails to control crystal plane orientation.
In summary, the iridium target material preparation methods in the prior art include hot forging/hot rolling, cold isostatic pressing and sintering, die pressing and sintering, etc., and although the target material with high density can be obtained by adjusting the process parameters, the grain orientation of the target material is difficult to control. According to the knowledge of materials science, the grain orientation of the target is known to have a significant influence on sputtering film formation, such as the highest atomic density on metal close-packed surfaces, the largest spacing between the close-packed surfaces and the relatively weakest bonding force between the close-packed surfaces. The closely-arranged plane of iridium is a (111) crystal plane, so that a method for adjusting the orientation of iridium target crystal grains to be a (111) crystal plane high-orientation is needed, and the sputtering deposition rate is favorably improved under the condition of certain sputtering power.
Disclosure of Invention
A first object of the present invention is to provide an iridium sputtering target having a crystal grain orientation high with respect to a (111) crystal plane.
The invention also aims to provide a preparation method of the iridium sputtering target with high oriented crystal grains.
The first purpose of the invention is realized by that the iridium sputtering target material presents a (111) crystal face highly-oriented structure 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 iridium 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 1x10-2～1x10-3Introducing high-purity hydrogen to 1-10 Pa, then heating to a sintering temperature of 400-800 ℃ 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 400-900 ℃, 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 1x10-3～1x10-4Pa, 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 iridium target with the preferred orientation of the (111) crystal face is obtained by effectively controlling the sintering temperature and the sintering time. The scheme has the advantages that: compared with the traditional high-temperature forging/rolling or high-temperature sintering method (1500-2300 ℃), the low sintering temperature (400-900 ℃) 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 that the iridium target with high density and preferred orientation of the (111) crystal face can be obtained by the two-step method, the iridium film with high sputtering rate and uniform film thickness is obtained in the subsequent sputtering process of the preferred orientation of the (111) close-packed face, 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 iridium sputtering target material with the high oriented crystal grains is characterized by exhibiting the high oriented (111) crystal face, the density of the iridium sputtering target material is not lower than 99.5%, the size of the crystal grains is 1-10 mu m, and the oxygen content is within 100 ppm.
The integral intensity ratio of the (111) crystal face to the (200) crystal face is not lower than 4.
The invention discloses a method for preparing an iridium 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 iridium 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: first, vacuum was applied to 1X10-2～1x10-3Pa, introducing high-purity hydrogen to 1-10 Pa, and then heating to the sintering temperature of 400-800 ℃ 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 400-900 ℃, and the heating rate is 10-30 ℃/min, 100-300 MPa of hot pressing pressure, 30-60 min of sintering time and 1x10 of vacuum degree-3～1x10-4Pa, 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 an iridium sputtering target with high oriented crystal grains, (1) selecting iridium powder with 4N purity, 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 cold-pressed ingot blank is sintered by microwave, the microwave frequency is 2.45GHz, and the ingot blank is firstly vacuumized to 8x10- 3Introducing high-purity hydrogen to 3Pa, then heating to the sintering temperature of 400 ℃ 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 500 ℃, the hot-pressing pressure is 180MPa, the heat preservation time is 35min after reaching the temperature, and the vacuum degree is 1x10-3Pa, 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 iridium 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 iridium sputtering target with highly oriented crystal grains, (1) selecting 4N 5-purity iridium powder, wherein the powder granularity is 1-10 mu m, and the average particle size is 5 mu mm; (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 vacuum-pumping to 1x10- 3Pa, introducing high-purity hydrogen to 1Pa, then heating to the sintering temperature of 500 ℃ at the speed of 40 ℃/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 20 ℃/min, the sintering temperature is 550 ℃, the hot-pressing pressure is 100MPa, the heat preservation time is 30min after reaching the temperature, and the vacuum degree is 1x10-3Pa, 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 iridium 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 an iridium sputtering target with high oriented crystal grains, (1) selecting iridium powder with 5N purity, 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 vacuum-pumping to 1x10- 3Pa, introducing high-purity hydrogen to 5Pa, then heating to the sintering temperature of 600 ℃ 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 650 ℃, the hot-pressing pressure is 210MPa, the heat preservation time is 40min after reaching the temperature, and the vacuum degree is 1x10-4Pa, 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 iridium 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 iridium sputtering target with high oriented crystal grains, (1) selection of 4N5The iridium powder has a purity of 1-10 μm in powder particle size and an average particle diameter of 7 μm; (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 vacuum to 6x10- 3Pa, introducing high-purity hydrogen to 7Pa, then heating to the sintering temperature of 700 ℃ 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 800 ℃, the hot-pressing pressure is 250MPa, the heat preservation time is 50min after reaching the temperature, and the vacuum degree is 1x10-3Pa, 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 iridium 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 an iridium sputtering target with high oriented crystal grains, (1) selecting 4N8 iridium 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) the cold-pressed ingot blank is sintered by microwave, the microwave frequency is 2.45GHz, and the ingot blank is firstly vacuumized to 1x10-3Introducing high-purity hydrogen to 10Pa, heating to the sintering temperature of 800 ℃ 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 900 ℃, the hot-pressing pressure is 300MPa, the sintering time is 60min, and the vacuum degree is 1x10-4Pa, 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 iridium 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
Preparation of iridium sputtering target material, comparative example 1 and example 1In contrast, steps 1-3 are all the same, lacking step 4 in example 1: selecting iridium powder with the purity of 4N, wherein 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; then the cold-pressed ingot blank is sintered by microwave, the microwave frequency is 2.45GHz, and the ingot blank is firstly vacuumized to 8x10-3Introducing high-purity hydrogen to 3Pa, then heating to the sintering temperature of 400 ℃ 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 an iridium sputtering target product with a required size, wherein the performance indexes are shown in table 1.
Comparative example 2
Compared with the preparation method of the example 1, the steps 1, 2 and 4 of the comparative example 2 are the same, and the step 3 in the example 1 is lacked in the comparative example 2: selecting iridium powder with the purity of 4N, wherein the powder granularity is 1-10 mu m, and the average particle size is 5 mu m; (ii) a 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 500 ℃, the hot-pressing pressure is 180MPa, the heat preservation time is 35min after reaching the temperature, and the vacuum degree is 1x10-3Pa, 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 an iridium sputtering target product with a required size, wherein the performance indexes are shown in table 1.
Comparative example 3
Compared with the embodiment 5, the steps 1, 2 and 3 of the comparative example 3 are the same, and the vacuum hot-pressing temperature in the step 4 in the comparative example 3 is 1000 ℃: selecting iridium powder of 4N8, wherein 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 vacuum-pumping to 1x10-3Pa, introducing high-purity hydrogen to 10Pa, heating to 800 deg.C at a rate of 50 deg.C/min, sintering for 30min, and sinteringAfter the setting time is up, cooling the ingot blank along with the furnace, cooling to room temperature, closing 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 1000 ℃, the hot-pressing pressure is 300MPa, the sintering time is 60min, and the vacuum degree is 1x10-4Pa, 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 an iridium sputtering target product with a 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: 1. the sputtering condition is direct current magnetron sputtering, the sputtering power is 400W, the Ar gas pressure is 5Pa, the deposition temperature is room temperature, and the substrate is a monocrystalline silicon wafer.
As can be seen from table 1, the sputtering rate of the sputtered iridium thin film obtained in comparative example 1 is not much different from that of example 1, but significant grain/void defects are observed; the sputtering rate of the target iridium film obtained in the comparative example 2 is obviously lower than that of the target iridium film obtained in the example 1, and obvious particle/hole defects can be observed; comparative example 3 although no obvious holes and defects were formed by sputtering, the grain size increased and the preferred orientation of the (111) crystal plane decreased due to the vacuum hot-pressing temperature of 1000 ℃, so that the sputtering rate was significantly lower than that of example 5; the iridium thin films obtained by sputtering the target products in examples 1-5 have high sputtering rate, no obvious particle/hole defects are observed, the (111) crystal plane orientation is obviously superior to that of a comparative example, the film thickness uniformity of all examples is 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 (7)
1. The iridium sputtering target with high oriented crystal grains is characterized by exhibiting (111) crystal face high oriented structure orientation, having the density of not less than 99.5 percent, the crystal grain size of 1-10 mu m and the oxygen content within 100 ppm.
2. The grain-highly oriented iridium sputtering target according to claim 1, wherein the integrated intensity ratio of the (111) crystal plane to the (200) crystal plane is not less than 4.
3. The method for preparing the iridium sputtering target with the high oriented grain size according to claim 1 or 2, which is characterized by comprising the following steps:
(1) preparing raw materials: selecting iridium 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 1x10-2～1x10-3Pa, introducing high-purity hydrogen to 1-10 Pa, and then heating to 400-800 ℃ 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 iridium target ingot blank after microwave sintering, wherein the sintering temperature is 400-900 ℃, 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 1x10-3～1x10-4Pa, 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.
4. The method for preparing the iridium sputtering target with the highly oriented crystal grains according to claim 3, wherein the temperature rise rate in the step 3 is 10-50 ℃/min.
5. The method for preparing the iridium sputtering target with the highly oriented crystal grains according to claim 3, wherein the sintering time in the step 3 is 10-30 min.
6. The method for preparing the iridium sputtering target with the grain oriented in the high orientation according to claim 3, 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, the hydrogen is turned off, and the ingot blank is taken out.
7. The method for preparing the iridium sputtering target with highly oriented crystal grains according to claim 3, wherein the sintering temperature in the step 4 is 50-200 ℃ higher than that in the step 3.
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