KR101725535B1 - REFURBISHING METHOD OF WASTE Ru TARGET - Google Patents
REFURBISHING METHOD OF WASTE Ru TARGET Download PDFInfo
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- KR101725535B1 KR101725535B1 KR1020150125032A KR20150125032A KR101725535B1 KR 101725535 B1 KR101725535 B1 KR 101725535B1 KR 1020150125032 A KR1020150125032 A KR 1020150125032A KR 20150125032 A KR20150125032 A KR 20150125032A KR 101725535 B1 KR101725535 B1 KR 101725535B1
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- ruthenium
- powder
- target
- waste
- waste target
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- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 103
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000843 powder Substances 0.000 claims abstract description 88
- 238000011069 regeneration method Methods 0.000 claims abstract description 33
- 238000005245 sintering Methods 0.000 claims abstract description 26
- 230000003746 surface roughness Effects 0.000 claims abstract description 23
- 230000002000 scavenging effect Effects 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 17
- 238000010330 laser marking Methods 0.000 claims description 15
- 239000011858 nanopowder Substances 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 3
- 238000003486 chemical etching Methods 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000001172 regenerating effect Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000005530 etching Methods 0.000 description 13
- 210000004072 lung Anatomy 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 238000004626 scanning electron microscopy Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 230000002685 pulmonary effect Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- -1 KMnO 4 Chemical compound 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009832 plasma treatment Methods 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005542 laser surface treatment Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002493 microarray Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
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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
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
-
- B22F1/0007—
-
- B22F1/0018—
-
- 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
-
- B23K26/0066—
-
- 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
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
Abstract
The present invention relates to a method for regenerating ruthenium waste targets. The regeneration method comprising: controlling the surface roughness of the ruthenium scavenging target; And sintering the surface of the waste target with ruthenium powder. In order to regenerate the ruthenium target having a finely controlled crystal grain size and a high purity through a simple process at a low cost while minimizing the loss of raw material from the waste target It is possible.
Description
The present invention relates to a method for regenerating ruthenium waste targets.
Ruthenium (Ru) is widely used in the next generation semiconductor memory (RAM, MRAM, FeRAM), which is an electronic component in the IT device industry, and is expected to be used in all fields utilizing sputtering target.
On the other hand, in order to control uniform thickness and surface impurities in a film forming process, a target having a fine grain size and a high purity is required, and a recycling method of a target used for cost reduction is emerging.
Conventionally, as a method for recycling ruthenium scavengers, there is known a melt casting method in which a waste target is melted and then cast again. However, there are problems in that the process is complicated and economical is inferior, and research on regeneration methods using powder sintering has been actively conducted.
For example, Korean Patent Laid-Open Publication No. 10-2009-0043522 discloses a method of decomposing a waste target to convert it into a high-purity powder, then sintering the powder to remanufacture it into a target shape, It is not reproduced and is not regenerated in a state in which the lung target circle is maintained or preserved, so that the lung target is not regenerated.
The present invention provides a method for economically reproducing a high quality ruthenium waste target by a simple process based on an environmentally friendly powder sintering process while preserving the original shape of the waste target.
The gist of the present invention based on the recognition of the above problem is as follows.
(1) controlling the surface roughness of the ruthenium scavenging target; And sintering the surface of the waste target with ruthenium powder.
(2) The ruthenium waste target regeneration method according to (1), wherein the surface roughness is controlled to be 0.63 to 0.74 mu m.
(3) The ruthenium waste target regeneration method according to (1), wherein the surface roughness is controlled by a laser marking method after polishing.
(4) The ruthenium waste target regeneration method according to (3), wherein the laser marking is formed by a horizontal pattern or a crosshatch pattern under an output of 10 W or less.
(5) The method for regenerating ruthenium waste target according to (3), further comprising the step of performing chemical etching after the surface roughness control.
(6) The ruthenium waste target regeneration method according to (1), wherein the ruthenium powder has an average particle size of 15 to 20 탆 and is composed of DC-plasma square powder, RF-plasma spherical powder or mixed powder thereof.
(7) The ruthenium waste target regeneration method according to (6), wherein the ruthenium powder has a DC-Plasma square powder and an RF-plasma spherical powder in a weight ratio of 3: 7 to 7: 3.
(8) The ruthenium waste target regeneration method according to (6), wherein the ruthenium powder further comprises a nano powder having an average particle size of 200 nm or less.
(9) The sintering method of
The ruthenium waste target regeneration method according to the present invention can regenerate a ruthenium target having finely controlled crystal grain size and high purity at a low cost through a simple process based on environmentally friendly powder sintering in a state in which loss of raw materials from a waste target is minimized It is possible.
1 is a conceptual diagram of a ruthenium waste target regeneration method according to the present invention.
2 is a flow chart of the process of the ruthenium waste target regeneration method according to the present invention.
3 shows a laser marking pattern for a ruthenium pulsed target surface according to the present invention.
4 is a table showing the process conditions of the laser marking and the surface roughness variation of the waste target according to the embodiment of the present invention.
5 is a SEM and EDS analysis result of a laser-marked waste target according to an embodiment of the present invention.
6 shows SEM and EDS analysis results of a chemically etched waste target according to an embodiment of the present invention.
7 is a table showing the surface roughness variation of a chemically simulated lung target according to an embodiment of the present invention.
8 is a table showing sintering conditions according to an embodiment of the present invention.
9 and 10 are SEM analysis results of a ruthenium waste target sintered at different ratios of the ruthenium powder for regeneration according to an embodiment of the present invention.
11 is a result of ICP analysis of a sintered ruthenium waste target according to an embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Throughout the specification, specific descriptions of known techniques have been omitted to the extent that they do not obscure the gist of the present invention in some cases. Also, throughout the specification, when an element is referred to as " including " an element, it means that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.
1 is a conceptual diagram of a ruthenium waste target regeneration method according to the present invention. Basically, the ruthenium waste target regeneration method according to the present invention comprises the steps of (i) subjecting the surface of a ruthenium waste target to physical / chemical pretreatment, (ii) And bulking it.
The basic concept of this ruthenium pulmonary target regeneration method can be more specifically shown through the process flow chart of the lung target regeneration method of Fig. First, after a sintered body of ruthenium raw material is manufactured (S10), a ruthenium powder for regeneration is prepared from the sintered body through a crushing process for forming a micro-sized ruthenium powder and / or a sphering process (S20, S30) do. Next, a chemical treatment such as etching for oxides or inclusions is performed (S40) together with a physical treatment such as laser processing for controlling the roughness of the ruthenium pulmonary target surface. Next, the previously prepared ruthenium powder is laminated on the surface of the ruthenium waste target and is bulk-formed by hot press sintering (S50).
In the step of preparing the ruthenium powder (S10, S20, S30), the ruthenium raw material may be a 4N-grade ruthenium powder. The ruthenium raw material powder is prepared as a sintered body and then crushed into a square powder having a particle size of several micro units by a DC-plasma and a jet mill process. All or a portion of the angular ruthenium powder whose particle size is controlled by several micros can be spheroidized by an RF-plasma process. On the other hand, it is preferable that the particle size of the powder is controlled to 15 to 20 탆 so as to prevent coarsening of the crystal grains in the bulk during the bulking process by the sintering under pressure and to be controlled to a uniform size of 20 탆 or less Do. When grain boundary coarsening of the regenerated bulk region is suppressed, uniform deposition is possible during the sputtering process using the regenerating target. The average particle size of such powders can be controlled by variables such as the classifier of the jet mill process, time, and the like.
The produced ruthenium powder for waste target regeneration may be any one of (i) a 'square type' powder in which the particle size is controlled after the DC plasma is jet-milled, or (ii) the 'spherical' powder subjected to RF plasma treatment after particle size control, Or in the form of a mixture of both. In the case of the mixed powder, the mixing ratio of the DC-plasma 'square type' powder and the RF-plasma 'spherical' powder is preferably 3: 7 to 7: 3 by weight in order to achieve an excellent relative density after the hot press sintering.
Alternatively, the waste target regenerating ruthenium powder may further include a nano powder having an average particle size of 200 nm or less. The nano powder is added for the purpose of increasing the sintering density by using a packing density effect. In this case, the weight ratio of the micro-powder and the nano powder is preferably in the range of 10: 1 to 5: 1. For example, a relative density of 99.0% can be achieved in hot press sintering at a mixing ratio of 5: 5, and a mixing ratio of nano powder to a micro powder having a mixing ratio of 5: 5 is 10: 1 , And 5: 1, the relative density can be achieved by 99.2% and 99.3% as the ratio of nano powder increases.
In the physical / chemical pretreatment step (S40) of the ruthenium pulsed target surface, the roughness of the surface of the waste target controlled by physical pretreatment such as laser marking is controlled in the subsequent hot pressing sintering process by the carbonization and oxidation of the surface, inclusions, Is controlled to be 0.63 to 0.74 占 퐉 so as to be uniformly bonded to the ruthenium powder for regeneration by inhibiting the generation of the ruthenium powder.
It is preferable that the laser marking as the physical pre-treatment is formed by any one of the horizontal pattern or cross-hatch pattern shown in FIG. 3 under an output of 10 W or less. In this case, the surface of the waste target in the pre-laser marking stage can be polished. The larger the value of the laser output is, the higher the surface roughness can be, with respect to the illuminance of the lung target surface, but oxide and carbonization may occur on the surface when the output exceeds 10 W, which is not preferable. In the case of a horizontal pattern, it is desirable to perform laser processing in the range of 50 to 60% of the lung target surface area and in the range of 60 to 70% of the lung target surface area in the case of a cross hatch pattern, and the pattern interval is performed at 0.1 mm and 0.025 mm .
Optionally, a chemical pretreatment such as etching may be performed to remove surface oxides and / or impurities of the lung target after physical pretreatment for controlling the surface roughness of the ruthenium lung target. The etching solution used may be selected from Ceric Ammonium Nitrate (CAN), KMnO 4 , NaClO.
In the hot press sintering process (S50) for regenerating the ruthenium scavenging target, as described above, the ruthenium powder for regeneration may be any one of micro-sized DC-plasma square powder or RF-plasma spherical powder, Mixed powders may be used, and if necessary, nano powders may be further added in a predetermined weight ratio. The sintering process is preferably carried out at a temperature of 5 to 20 ° C / min and then at a temperature of 1000 to 1550 ° C and a pressure of 20 to 100 MPa for 3 hours.
[Example]
A. Preparation of ruthenium powder for regeneration
The controlled particle size ruthenium (Ru) powder used in the refurbishing process was prepared from 4N ruthenium raw material powder. First, a 4N-grade ruthenium raw material powder is formed into a sintered body, followed by pulverization by a DC-plasma and a Jet-Mill process to prepare powder having a particle size of several micrometers. In this case, DC-plasma was performed under an applied plasma power of 10 to 50 kW or less, N 2 , O 2 gas, gas flow rate of 20 L / min, and degree of vacuum of 10 -3 torr. The particle size of the powders produced according to the parameters such as classifier and time is influenced by the jet-mill process. Specifically, carrier gas N 2 , compressor pressure 7.2 bar, classifier 2000 rpm , And a working time of 24 hours. Subsequently, some of the ruthenium powders whose particle size was controlled in several micrometers were made spherical and high-quality ruthenium powders by RF plasma process. Specifically, torch power was 28 kW, feed rate was 5 g / min, Sheath gas Ar 60 lpm, Reactor pressure 14.7 psi. On the other hand, the ruthenium powder having a particle size of several nanometers was prepared by jet milling, drying fine powder in alcohol, and sinking the powder.
B. Pretreatment of ruthenium pulsed target surface
(a) Physical pretreatment
In order to reliably perform the hot press sintering process for refurbishing the ruthenium waste target, uniform bonding is required between the ruthenium waste target and the ruthenium powder for regeneration. To do this, physical pretreatment was first performed on the surface of the ruthenium waste target. First, for physical pre-treatment, polishing was performed using a 30 mm sintered body sintered from 4N-grade ruthenium powder as a waste target.
After polishing, the surface roughness of the waste target was processed to be in the micrometer range using laser marking, and the change in surface roughness according to the laser marking pattern and the output was measured and shown in FIG. In this case, as shown in FIG. 3, the laser marking pattern was made with two kinds of horizontal patterns (processing area 50 to 60%) and cross hatch pattern (processing area 70 to 80%) and laser output was 10, 0.1 mm in width and 0.025 mm in depth.
Referring to Fig. 4, the horizontal pattern was measured to be 0.6311 mu m at an output of 10W, 1.1442 mu m at 15W, and 2.4357 mu m at 20W. The cross-hatched pattern was measured at 0.8329 탆 at an output of 10 W, at 1.2294 탆 at 15 W, and at 2.7785 탆 at 20 W. As a result of the analysis, the surface roughness was changed more regularly than the treatment method using SiC paper, and the horizontal pattern method showed regular surface roughness more than the cross hatch pattern method, and the surface roughness was increased I could.
5 shows SEM and EDS analysis photographs of the laser-marked waste targets. Specifically, the surface roughness of the ruthenium 30 mm waste target according to the laser marking pattern and the output change is shown. SEM image analysis showed that the ruthenium pulsed target surface was patterned by laser marking and surface treatment was performed. Both horizontal and cross hatch patterns were found to be oxidized and carbonized on the surface due to the detection of element C and O on the surface when the laser output was 15 W or more.
From the results of the above analysis and analysis, it can be seen that, in the post-polishing laser marking as a physical pre-treatment for the waste target surface, the laser pattern has a horizontal pattern, the laser output value is 10 W, the laser interval is 0.1 mm, The physical pretreatment was carried out under the optimum condition in terms of uniform bonding between the ruthenium waste target and the ruthenium powder for regeneration, in which the surface roughness of the waste target was controlled to 0.6311 μm.
(b) chemical pretreatment
After the physical pretreatment described above for the ruthenium scavenging target, a time-varying etch was performed as a chemical pretreatment on a 30 mm scavenging target to remove oxides and impurities from the scavenging target surface.
In this case, the etching solution was selected from Ceric Ammonium Nitrate (CAN), KMnO 4 , and NaClO, and the etching time was 30 seconds, 60 seconds, and 600 seconds. The SEM and EDS analysis results of the chemically etched 30 mm waste target under the above conditions are shown in FIG.
Referring to FIG. 6, SEM image analysis shows that inclusion and oxide are generated on the surface of the waste target as the etching time increases. In the CAN solution, element C was detected on the surface for 60 sec or more, and it was confirmed that the surface was carbonized, and KMnO 4 In the solution, it was confirmed that even if the etching time was increased, the surface was not changed because there was no change in the surface, and the surface was oxidized in the NaClO solution for 600 seconds or more.
Figure 7 shows the surface roughness variation of a chemically sampled lung target. Specifically, the surface roughness of the 30 mm ruthenium scavenging target is shown after 60 seconds of etching time with each of the etching solutions. 0.8516 탆 in the CAN solution, 0.6547 탆 in the KMnO 4 solution and 0.7453 탆 in the NaClO solution, respectively. The surface roughness of the ruthenium waste target after etching was 0.2205 ㎛ for the CAN solution, 0.0236 ㎛ for the KMnO 4 solution and 0.1142 ㎛ for the NaClO solution, respectively, when compared with the chemical pretreatment, that is, the surface roughness before etching.
From the results of the above analysis and analysis, it was found that when the etching solution was NaClO and the etching time was 30 seconds, the ruthenium waste target and the ruthenium powder for regeneration And the chemical pretreatment was carried out with optimal cohesion in terms of uniformity.
3. Bulking of ruthenium waste targets
In order to refurbish the ruthenium waste target by the bulking process, the ruthenium powder for regeneration prepared through the process A was laminated on the surface of the ruthenium waste target subjected to the surface treatment through the B process to perform a hot press sintering process. In this case, the content ratio of any one of the micrometer-unit DC-plasma square powder and the RF-plasma spherical powder obtained from the step A or the mixed powder thereof is controlled, or the content of the nanometer- Was used as a ruthenium powder for regeneration.
Specifically, referring to FIG. 8 showing the hot press process conditions, the ratio of the square-shaped Ru powder of 20 탆 or less jet-mill treated after DC-plasma treatment to the spherical Ru powder of 18.35 탆 or less of RF-plasma treated Ru powder And mixed for 30 minutes using a blender. In the case of mixed micrometer powders, the ratio of the DC-plasma treated square powder to the RF-plasma treated spherical powder was set to 3: 7, 5: 5, 7: 3 by weight ratio (wt%), 100% of powder or 100% of RF-plasma treated spherical powder was prepared as a ruthenium powder for regeneration. The prepared ruthenium powder for regeneration was laminated on the surface of a 30 mm ruthenium waste target subjected to physical / chemical pretreatment, and hot press sintering was performed by maintaining the sintering temperature at 1550 캜 for 3 hours at a heating rate of 5 캜 / min.
Next, reliable hot press sintering process conditions were analyzed in terms of relative density, grain size and target purity of the regenerated ruthenium waste target. In this case, relative density as a numerical value for measuring the sintered density of the target was measured by the Archimedes method, and the grain was etched after mirror polishing and measured by SEM image. Purity was analyzed by ICP. On the other hand, a commercially available target that can be used as a sputtering target requires a relative density of 90% or more, is low in relative density, and microarrays due to micropores may occur, which is not preferable.
FIGS. 9 and 10 show SEM analysis results of sintered titanium waste targets with different ratios of ruthenium powder for regeneration. Specifically, FIG. 9 is a graph showing the relationship between the concentration of the RF-plasma treated spherical powder in terms of micrometer (100% SEM analysis results of hot pressed sintered ruthenium waste targets, respectively. As a result of the analysis, the relative density of the ruthenium scavenging target sintered and regenerated with the DC-plasma treated square powder of (a) was 98%, and the interface boundary between the waste target and the ribbing bulk was hardly observed. However, (B), and the relative density of the ruthenium waste target sintered and regenerated with the RF-plasma treated spherical powder of (b) was 98.5%. As a result, the boundary of the interface did not appear, It can be confirmed that there is no problem.
10 (a), 10 (b) and 10 (c) are graphs showing the relationship between the square-shaped powder of the DC-plasma treated micrometer and the RF-plasma treated spherical powder of the micrometer unit at a weight ratio of 7: 3, 5: : 7 ratio of hot-pressed sintered ruthenium waste target. The optimum density of the ruthenium powder in micrometers was 98.4% in case of 7: 3 in (a), 99.0% in case of 5: 5 of (b) 5: 5. The grain size of the refurbished ruthenium scavenging target was measured to be 17.74 μm in the case of 7: 3 of (a), 18.02 μm in the case of 5: 5 of (b), and 20.11 μm of 3: 7 of (c) , And it was confirmed that as the mixing ratio of the RF-plasma treated spherical powder having an average particle size of 18.35 μm was increased, the grain size was increased.
On the other hand, a micrometer unit powder and a nanometer unit powder mixed at a weight ratio of 5: 5 by weight of the DC-plasma treated square powder and RF-plasma treated spherical powder were mixed at a weight ratio of 10: 1 and 5: 1 The relative density was evaluated by hot press sintering the powder. As a result, the relative density was increased by about 0.3% by adding a nanometer unit of ruthenium powder at a relative density of 99.2% at a ratio of 10: 1 to 99.3% at a ratio of 5: 1.
11 shows the results of ICP analysis of a ruthenium scavenger target. As a result of ICP analysis, the purity of the sintered ruthenium waste target was confirmed to be 99.98%.
From the results of the above analysis and analysis, powders obtained by mixing 5: 5 by weight of DC-plasma treated square powder and RF-plasma treated spherical powder in micrometer units were used and the sintering temperature reached at a heating rate of 5 캜 / The sintering process was carried out at 1550 占 폚 for 3 hours to obtain a regenerated ruthenium waste target with a relative density of 99.0%, a crystal grain size of 18.02 占 퐉 and a target purity of 99.98%.
As described above, in the ruthenium waste target regeneration method according to the present invention, it is possible to regenerate a ruthenium target having finely controlled grain size and high purity at a low cost through a simple process while minimizing the loss of raw materials from the waste target Do.
The foregoing is a description of specific embodiments of the present invention. While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments or constructions. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention. It should be understood that this is possible. It is therefore to be understood that all such modifications and alterations are intended to fall within the scope of the invention as disclosed in the following claims or their equivalents.
Claims (9)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020150125032A KR101725535B1 (en) | 2015-09-03 | 2015-09-03 | REFURBISHING METHOD OF WASTE Ru TARGET |
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