GB2343684A - Target material for spattering - Google Patents
Target material for spattering Download PDFInfo
- Publication number
- GB2343684A GB2343684A GB0001523A GB0001523A GB2343684A GB 2343684 A GB2343684 A GB 2343684A GB 0001523 A GB0001523 A GB 0001523A GB 0001523 A GB0001523 A GB 0001523A GB 2343684 A GB2343684 A GB 2343684A
- Authority
- GB
- United Kingdom
- Prior art keywords
- target material
- sputtering target
- sputtering
- precious metal
- ruthenium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013077 target material Substances 0.000 title claims description 109
- 239000013078 crystal Substances 0.000 claims abstract description 59
- 238000005477 sputtering target Methods 0.000 claims description 83
- 238000004544 sputter deposition Methods 0.000 claims description 52
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 38
- 239000010970 precious metal Substances 0.000 claims description 38
- 229910052707 ruthenium Inorganic materials 0.000 claims description 38
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 150000003839 salts Chemical class 0.000 claims description 22
- 229910052741 iridium Inorganic materials 0.000 claims description 17
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 6
- 239000010409 thin film Substances 0.000 abstract description 19
- 238000005266 casting Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 11
- 230000007547 defect Effects 0.000 abstract description 9
- 238000004663 powder metallurgy Methods 0.000 abstract description 8
- 239000010408 film Substances 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract 2
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 11
- 230000008021 deposition Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000011833 salt mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003746 surface roughness Effects 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- -1 oxygen ions Chemical class 0.000 description 3
- 238000002601 radiography Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000717 platinum sputter deposition Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/04—Alloys based on a platinum group metal
-
- 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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physical Vapour Deposition (AREA)
Abstract
A target for spattering comprising a noble metal, characterized in that it has a columnar crystal texture which grows in the normal direction to a spattering plane. The target is free from the occurrence of the problem that a fine block in a cluster form is missed from a target, which problem is likely to occur in a target for spattering obtained by using the dissolution casting method or the powder metallurgy method, and can be used for producing a thin film having good film properties, and further is a high purity noble metal target for spattering having little internal defect.
Description
PATEENT OFFICE - DERNMVE COPY
Description
Sputtering Target Material Technical Field
The present invention relates to a sputtering target material, and more particularly to a sputtering target material comprising a precious metal.
Background Art
Recently, thin film made of a precious metal such as ruthenium or iridium has frequently been used in a thin-film electrode formed on a wafer of a semiconductor device.
Such thin film is most commonly produced through sputtering, vhich is a physical vapor deposition method. When thin film is produced through sputtering, the characteristics of the formed thin film vary considerably with the characteristics of a sputtering target material, such as purity and microstructure.
Thus, characteristics, such as specific resistance, which are required of a thin-film electrode in practice can be determined simply through control of the purity of a sputtering target material. In this connection, conventionally employed sputtering target materials which have been produced through casting or powder metallurgy have yielded reasonably satisfactory characteristics.
However, during use of a sputtering target produced 1 through casting or powder metallurgy, a minute cluster mass tends to be chipped from the sputtering target and adhere on the formed thin film surface, to thereby cause, for example, a change in electrical resistance, which is detrimental to product quality and results in a reduction in product yield.
Meanwhile, when a sputtering target material is produced through powder metallurgy, the target material is typically hot-shaped under hydrostatic pressure through an HIP method. Particularly, intergranular voids may remain in the thus-produced sputtering target material, and gas may be trapped in the voids. Once the trapped gas is released, the gas affects the stability of vacuum which is required during sputtering, and may deteriorate film characteristics.
In addition, if such a sputtering target material having gas-trapping voids is heated during sputtering, the gas remaining in the sputtering target material expands by heat, to thereby possibly cause damage to the sputtering target per se, in forms such as blow-holes.
Disclosure of the Invention
In order to solve the aforementioned problems involved in the prior art, an object of the present invention is to provide a high-purity precious metal sputtering target material which inhibits chipping of a minute cluster mass; provides excellent film characteristics; and has considerably reduced internal defects.
The present inventors have posited that the 2 crystallographic microstructure which a sputtering target material possesses must carefully be considered so as to prevent chipping of a minute cluster mass, which is one of the conventional problems, to thereby attain the invention. Thus, in describing the present invention, it is very important to have considered the mechanism of chipping a minute cluster mass from a conventional sputtering target material which is produced through casting or powder metallurgy.
Accordingly, a description will first be given of the inventors, understanding of problems involved in a conventional sputtering target material. Then, solution of the problems by use of the sputtering target material of the present invention on the basis of the understanding will be -elucidated. The sputtering target material of the present invention will thus be described hereinbelow.
It is very clear that a conventional sputtering target material which is produced through casting or powder metallurgy comprises innumerable crystals of a constituent metal. Fig. 2 schematically shows a crosssectional view of a crystallographic microstructure of a sputtering target material which is produced through casting.
In the sputtering surface of a sputtering target material having a crystallographic microstructure as shown in Fig. 2, different crystal faces of different crystal orientations are distributed at random. Briefly, the sputtering surface assumes a polycrystalline state. This 3 state is substantiated by the fact that analysis of the X-ray diffraction spectrum of the sputtering target material reveals (100), (002), (110), and (112) faces in proportions approximately the same as those obtained in an X-ray diffraction spectrum of a standard sample.
When sputtering is carried out by use of the sputtering target material having a polycrystalline sputtering surface and sputtering ions such as oxygen ions, nitrogen ions, and argon ions, the sputtering rate varies depending on the species of the sputtering ions and the crystal face orientation of a crystal which is developed to the surface. In other words, in a conventional sputtering target material having a sputtering surface where various crystal faces are developed, different crystal faces exhibit different specific sputtering rates, which justifies existence of a preferential sputtering surface, and crystals of a high sputtering rate and those of a low sputtering rate coexist.
on a microscopic level, as sputtering proceeds, crystal grains developing a crystal face which is easily sputtered are corroded vigorously, whereas those developing a crystal face which is not easily sputtered are corroded slowly, to thereby form depressions of different depths in the surface of the target material, making the surface rough. The phenomenon of roughening the surface of a sputtering target material becomes more remarkable with increasing sputtering rate, although the tendency depends on the employed sputtering ion species. Accordingly, the phenomenon is 4 particularly noticeable when argon, widely used in industry due to its high sputtering rate, is used.
When sputtering is further continued, the surface of the sputtering target material is work-hardened through implantation of sputtering ions. Thus, crystal grains thinned by corrosion during sputtering are removed along a crystal grain boundary embrittled through work hardening, and fall off the surface of the sputtering target material to the surface of a formed thin film. Therefore, the aforementioned minute cluster mass can be regarded as crystal grains per se which are removed and fall off the target material.
Particularly, during roof sputtering; i.e., sputtering by use of a sputtering target disposed above a substrate on which thin film is formed, crystal grains are more liable to adhere on-a substrate, through removal and fall off the grains. Therefore, resistance to chipping of a minute cluster mass from a sputtering target material is a critical quality requirement of a sputtering target material.
In order to solve the aforementioned problems involved in a conventional sputtering target material produced through casting or powder metallurgy, the present inventors have considered that the problems are solved through rendering the crystallographic microstructure of the precious metal sputtering target material of the present invention to a columnar microstructure. Specifically, the precious metal sputtering target material of the present invention is one having a columnar crystallographic microstructure in which crystals are grown in a direction normal to the sputtering surface.
A sputtering target material having a columnar microstructure in which crystals are grown in a direction normal to the sputtering surface has a crystallographic microstructure such that crystals extend continuously in the thickness direction. The microstructure is schematically shown in Fig. 1. Therefore, there rarely arise problems involved in a conventional sputtering target material; i.e., chipping of minute crystal grains from a sputtering target material having a crystallographic microstructure such that crystals do not extend continuously in the thickness direction as shown in Fig. 2.
The columnar microstructure can be regarded as a microstructure in which crystals have been grown to a preferential orientation during crystal growth. Accordingly, through adjustment of the crystallographic microstructure of a material to be a columnar microstructure, a certain level of directional preference in crystal orientation can be provided to crystals constituting the material. Through the arrangement, the crystal orientation of a sputtering target material is aligned, to thereby mitigate microscopic-level local loss of the sputtering target material as much as possible.
As described above, the precious metal sputtering target material of the present invention is characterized in that the target material has a crystallographic 6 microstructure such that columnar crystals are grown in a direction normal to the sputtering surface. Thus, the sputtering target material can serve as a source of precious metal thin film having excellent characteristics without producing a minute cluster mass.
Meanwhile, some sputtering target materials made of a metal such as titanium are known to comprise columnar crystals as does the sputtering target material of the present invention. For example, columnar crystals are produced in a sputtering target material made of a metal such as titanium by regulating the heat flow during a post-melt solidification step in one direction (unidirectional solidification).
However, no research has been conducted for producing a precious metal sputtering target material comprising columnar crystals, and such a precious metal sputtering target material has never been reported. The reason for this is that a precious metal is a high-melting-point material and is difficult to produce through casting as described above. In practice, it is impossible to provide columnar crystals in a crystallographic microstructure of such a high-melting-point material through the aforementioned unidirectional solidification. Therefore, providing columnar crystals in a crystallographic microstructure of a precious metal sputtering target material is not conceivable from the state of the art.
Under such circumstances, the present inventors have 7 conducted further studies in order to obtain a precious metal target material comprising columnar crystals, and have discovered a sputtering target material having a crystallographic microstructure comprising columnar crystals which are electrolytically deposited from a solution containing a precious metal salt.
The columnar crystals can be electrolytically deposited at relatively low temperature from a solution containing a precious metal salt, although the deposition rate is relatively slow. Thus, the above electrolytic method for producing a target material features easier control of production steps and more excellent production efficiency than does a conventional casting method. In addition, the thus-produced target material is advantageously inexpensive.as compared vith a conventional precious metal target material.
Since the electrolytically deposited columnar crystals are produced through selective deposition by use of difference in the deposition potential, which is one characteristic of an electrolysis technique, the columnar crystal of high purity contains low levels of impurities. Accordingly, the target material of the present invention is characterized in that the material of high purity contains very few internal defects.
In addition, in recent years, the diameter of a target material is required to increase in order to enhance productivity of thin film devices. The target material of 8 the present invention can also meet the demand for increasing the diameter of a target material comparatively easily, by appropriately modifying conditions for electrolysis and deposition for producing columnar crystals. Thus, there can be produced a target material having a large diameter and comprising uniform columnar crystals, which material has never been produced through a conventional unidirectional solidification method.
The aforementioned solution containing a precious metal encompasses not only an aqueous solution containing a precious metal salt but also a salt mixture in a molten state incorporated with a precious metal salt.
Particularly, a target material comprising columnar crystals, which material is deposited from the aforementioned molten.--salt-mixture. is preferred in view of purity and directivity of a crystal face. When electrolysis is carried out by use of a molten salt, the composition of the molten salt serving as an electrolyte is easily controlled. In addition, the difference in deposition potential between a precious metal of interest and an impurity can be employed effectively, to thereby selectively deposit high-purity precious metal. Furthermore, molten salt electrolysis enables direct production of a precious metal target material having a desirable shape within a comparatively short period of time as compared with deposition of a precious metal from an aqueous solution containing a precious metal salt, as well as control of the microstructure of a deposited material 9 through appropriate modification of electrolysis conditions. Thus, a sputtering target material in which a columnar microstructure is grown can be produced.
Examples of precious metals which are used in the sputtering target material of the present invention include iridium, ruthenium, platinum, gold, palladium, rhodium, osmium, and rhenium. Of these, platinum, ruthenium, and iridium have considerably poor easiness for physical working as compared with gold also included in precious metals. In practice, these three metals cannot undergo processes such as rolling and forging. Thus, if a target material formed of these three metals is planned to be produced through a method other than casting and powder metallurgy, the method is greatly limited.
Brief Description of the Drawings
Fig. 1 is a schematic diagram of a cross-sectional crystallographic microstructure of a sputtering target material having a columnar crystallographic microstructure. Fig. 2 is a schematic diagram of a crosssectional crystallographic microstructure of a sputtering target material produced through casting.
Fig. 3 is a schematic structural diagram of a molten salt electrolysis apparatus. Fig. 4 shows the microstructure of grains as observed under an optical microscope showing a schematic diagram of a cross-sectional crystallographic microstructure of the ruthenium sputtering target material of the present invention. Fig. 5 shows the microstructure of grains as observed under an optical microscope showing a schematic diagram of a cross-sectional crystallographic microstructure of the indium sputtering target material of the present invention.
Fig. 6 shows the visually observed microstructure of grains at a surface of the ruthenium sputtering target material of the present invention after completion of sputtering. Fig. 7 shows the visually observed microstructure of grains at a surface of a ruthenium sputtering target material produced through casting.
Fig. 8(a) shows the crystallographic microstructure at a surface of the ruthenium sputtering target material of the present invention after completion of sputtering, as observed through Emm- 7ig-' 8(b) shows the surface roughness profile of the sputtering surface after completion of sputtering. Fig. 9(a) shows the crystallographic microstructure at a surface of a ruthenium sputtering target material produced through casting after completion of sputtering, as observed through SEM. Fig. 9(a) shows the surface roughness profile of the sputtering surface after completion of sputtering.
Best Mode for Carrying Out the Invention Rmhodimpnt 1: The precious metal sputtering target of the present invention will be described in more detail. First, in one embodiment, a precious metal target material was produced through electrolysis of an aqueous solution containing platinum.
The solution containing platinum serving as an electrolysis bath had the following composition.
Table 1
Bath component Concentration (g/1) Potassium hexahydroxoplatinate 30 Potassium hydroxide 60 A copper disk (diameter: 130 mm) was used as a cathode for depositing platinum. Prior to electrolysis, the cathode was electrolytically degreased, activated with an acid, and strike-plated with platinum. Subsequently, the cathode was immersed in the above aqueous solution to carry out.elect-rolysis.
Electrodeposition of the molten salt was carried out under the following conditions: bath temperature of 950C, 2 cathodic current density of 3 A/dM, and a deposition time of 125 h, to thereby obtain a platinum deposit having a thickness of 3 mm. The substrate of platinum-deposited cathode; i.e., the copper plate, was dissolved, to thereby obtain disk-shaped platinum plates serving as platinum sputtering target materials. The crystallographic microstructure of theplatinum sputtering target materials was analyzed through X-ray diffraction. The results indicate that the integral intensity of the (200) face is particularly greater than that of another arbitrary crystal face, and the 12 ratio of the integral intensity of the (200) face to that of another arbitrary crystal face is greater for the platinum sputtering target material than for a powder platinum sample. Thus, the target material of the embodiment was proven to have a microstructure strongly oriented in the (200) face.
Fmhodiment 2: Another target material was produced from a molten salt mixture serving as a solution containing a precious metal to be deposited by means of an electrolysis apparatus 1.
As shown in Fig. 3, the electrolysis apparatus 1 comprises a hollow cylindrical vessel 2 having an opening at the top; a flange 3 having an inlet for inserting an electrode and serving as a cap for the cylindrical vessel; a graphite-made electrolytic tank 4; an exhaust chamber 5 for inserting or removing a plated material; and rotating means 6 for rotating a plating substrate.
In the electrolysis apparatus I shown in Fig. 3, ruthenium plates 7 were used as anodes 7 disposed on the side the graphite-made electrolytic tank 4. These ruthenium plates were disposed such that they maintained contact with a bottom portion of the electrolytic tank 4. Electric current was supplied via the electrolytic tank 4 by use of rod-shaped graphite 8 as a cathode, to thereby perform electrolysis of a molten salt. The composition of the molten salt mixture for a ruthenium target material is shown in Table 2.
Table 2
Salt component Weight/g sodium chloride 1577.9 potassium chloride 1241.3 cesium chloride 6894.3 potassium chlororuthenate 765.1 Electrodeposition of the molten salt was carried out under the following conditions: bath temperature of 5200C, 2 cathodic current density of 2 A/dM, and a deposition time of 150 h, to thereby obtain electrolytically deposited ruthenium having a thickness of 3 mm. The deposit was washed with an acid such as hydrochloric acid or sulfuric acid and removed from the graphite electrode, to thereby obtain disk-shaped ruthenium plates serving as ruthenium sputtering target materials.
Finally,.each r)btained ruthenium sputtering material was caused to adhere to a copper plate having a thickness of 3 mm, to thereby fabricate a ruthenium sputtering target. The crystallographic microstructure of the ruthenium target material was observed under a 100-power metallographic microscope. As shown in Fig. 4, a columnar crystallographic microstruct'are was identified. The ruthenium sputtering target materials was analyzed through X-ray diffraction. The results indicate that the integral intensity of the (122) face is particularly greater than that of another arbitrary crystal face, and that the ratio of the integral intensity of the (122) face to that of another arbitrary crystal face is greater for the ruthenium sputtering target material than for 14 a powder ruthenium sample. Thus, the target material of the present embodiment was proven to have a microstructure such that crystals are strongly oriented in the (122) face. The presence of internal defects was investigated through X-ray radiography, and no internal defects were detected.
Rmhn8iment 3, In Embodiment 3, while changing electrolysis conditions, a ruthenium target material was produced by use of the molten salt mixture having a composition shown in Table 2 as employed in Embodiment 2 and the electrolysis apparatus as shown in Fig. 3. Thus, since essential framework of this embodiment is the same as that in Embodiment 1, repetition of the description in relation to the method for production is omitted, and only conditions differing-from'-those employed in Embodiment 1 will be described.
Electrodeposition of the molten salt was carried out under the following conditions: bath temperature of 5600C, cathodic current density of 3 A/dM2, and a deposition time of 100 h, to thereby obtain an electrolytically deposited ruthenium film having a thickness of 3 mm.
The crystallographic microstructure of the ruthenium sputtering target materials was analyzed through X-ray diffraction. The ruthenium target material according to Embodiment 3 was found to show the same tendency as observed in Embodiment 1 for the (001) face, and strong orientation in the (001) face was proven. The presence of internal defects was investigated through X-ray radiography, and no internal defects were detected.
By use of the ruthenium target which had been produced in the aforementioned Embodiments 2 and 3, sputtering was carried out in practice. Sputtering was carried out in a manner of roof sputtering, and the ruthenium target was placed above a substrate to form thin film. The test was repeated (N = 100), and there was observed no case in which crystal grains per se were removed and fell off to affect the performance of the thin film.
Rmhodimpnt 4- In Embodiment 4, an iridium target material was produced by use of the same molten salt electrolysis apparatus -I-shDvm in Fig. 3 as employed in Embodiments 1 and 2. In Embodiment 4, a molten salt mixture having a composition as shown in Table 3 was used.
Table 3
Salt component Weight/g sodium chloride 1420.0 potassium chloride 1643.8 cesium chloride 6894.3 sodium chloroiridate 426.5 Electrodeposition of the molten salt was carried out 0 under the following conditions: bath temperature of 520 C, cathodic current density of 2 A/dm2, and deposition time of 150 h, to thereby obtain an electrolytically deposited 16 iridium film having a thickness of 3 mm. The electrodeposited iridium was washed with an acid such as hydrochloric acid or sulfuric acid and removed from the graphite electrode, to thereby obtain disk-shaped iridium plates serving as iridium sputtering target materials.
Finally, each obtained iridium sputtering target material was caused to adhere to a copper plate having a thickness of 3 mm, to thereby fabricate an iridium sputtering target. The crystallographic microstructure of the iridium target material was observed under a 100-power optical metallographic microscope. As shown in Fig. 5, a columnar crystallographic microstructure was identified. The crystallographic microstructure of the iridium sputtering target materials was analyzed through X-ray diffraction. The zeaults dndicate that the same tendency as observed in Embodiment 1 was identified for the (220) face, and strong orientation in the (220) face was proven. The presence of internal defects was investigated through X-ray radiography, and no internal defects were detected.
Subsequently, sputtering was carried out by use of the iridium target. Sputtering was carried out in a manner of roof sputtering, and the iridium target was placed above a substrate to form a thin film. The test was repeated (N 100), and there was observed no case in which crystal grains per se were removed and fell off to affect the performance of the thin film.
Further, for comparison with the sputtering target 17 material of the present invention, sputtering was carried out by use of a ruthenium sputtering target material produced through casting, whereby the properties were compared with those of the sputtering target of the present invention. Sputtering was carried out in a manner of roof sputtering, and the ruthenium target was placed above a substrate to form a thin film. The test was repeated (N = 100), and there were observed two cases in which crystal grains per se were removed and fell off to possibly affect the performance of the thin film. Although the damage sustained by the two samples was not critical, variation in electric resistance thereof was identified.
However, even though the variation is on the level as described above, it may cause a critical decrease in productionyield.and lower reliability of product quality in the semiconductor industry, where quality control is as fine as on a ppb level.
After completion of sputtering by use of argon as a sputtering gas, the sputtering surfaces of the ruthenium target material of Embodiment 1 and the target material produced through the aforementioned casting method were observed. As is clear from Figs. 6 and 7, as can be seen from even visual observation, the ruthenium target material produced through electrolysis of a molten salt shown in Fig. 6 was corroded more uniformly and had surface roughness lower than that of the ruthenium target material produced through casting shown in Fig. 7.
18 Furthermore, observation of the surfaces through SEM is shown in Fig. 8(a) and Fig. 9(a), and surface roughness profiles obtained by means of a surface roughness meter are shown in Fig. 8(b) and Fig. 9(b). As is clear also qualitatively, the ruthenium target material as shown in Fig. 8 has a uniform sputtering surface.with reduced unevenness, as compared with the ruthenium target material as shown in Fig. 9. As is clear from the results, the sputtering target material produced through electrolysis of a molten salt comprises columnar crystal grains and plays a very important role in realizing constant operation.
Industrial Applicability
The precious metal sputtering target material according to the'-prement invention has a columnar crystallographic microstructure in which crystal orientation is almost uniform at the surface of the material. Therefore, chipping of crystal grains from the sputtering material of the present invention is prevented during a sputtering step, to thereby effectively produce thin film of excellent quality. Use of the sputtering target material of the present invention enables enhanced production yield and reliability of product quality in the semiconductor industry.
19
Claims (8)
1. A precious metal sputtering target material having a crystallographic microstructure containing columnar crystals, in which crystals are grown in a direction normal to a sputtering surface.
2. A sputtering target material according to claim 1, wherein the crystallographic microstructure containing columnar crystals is electrodeposited from a solution containing a precious metal salt.
3. A sputtering target material according to claim 2, wherein the solution containing a precious metal salt is a molten salt admixed with a precious metal.
4. A sputtering target material according to any one of claims 1 through 3, wherein the precious metal is platinum, ruthenium,--oz iridium.
5. A sputtering target material according to any one of claims 1 through 3, wherein the precious metal is platinum, and the ratio of the integral intensity of a (200) face to that of another arbitrary crystal face as determined by X-ray diffractometry is greater than the corresponding ratio as measured for a powder platinum sample.
6. A sputtering target material according to any one of claims 1 through 3, wherein the precious metal is ruthenium, and the ratio of the integral intensity of a (112) face to that of another arbitrary crystal face as determined by X-ray diffractometry is greater than the corresponding ratio as measured for a powder ruthenium sample.
7. A sputtering target material according to any one of claims 1 through 3, wherein the precious metal is ruthenium, and the ratio of the integral intensity of a (001) face to that of another arbitrary crystal face as determined by X-ray diffractometry is greater than the corresponding ratio as measured for a powder ruthenium sample.
8. A sputtering target material according to any one of claims I through 3, wherein the precious metal is iridium, and the ratio of the integral intensity of a (220) face to that of another arbitrary crystal face as determined by X-ray diffractometry is greater than the corresponding ratio as measured for a powder iridium sample.
21
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18571398 | 1998-06-17 | ||
| PCT/JP1999/003194 WO1999066099A1 (en) | 1998-06-17 | 1999-06-16 | Target material for spattering |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB0001523D0 GB0001523D0 (en) | 2000-03-15 |
| GB2343684A true GB2343684A (en) | 2000-05-17 |
| GB2343684B GB2343684B (en) | 2003-04-23 |
Family
ID=16175558
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB0001523A Expired - Fee Related GB2343684B (en) | 1998-06-17 | 1999-06-16 | Sputtering target material |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JP3436763B2 (en) |
| KR (1) | KR100348023B1 (en) |
| DE (1) | DE19981314C2 (en) |
| GB (1) | GB2343684B (en) |
| TW (1) | TW491909B (en) |
| WO (1) | WO1999066099A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3706128B2 (en) * | 2003-06-27 | 2005-10-12 | 株式会社レノメディクス研究所 | Autologous cell delivery support system and method |
| JP4522991B2 (en) * | 2004-03-01 | 2010-08-11 | 日鉱金属株式会社 | Method for producing high purity Ru powder |
| KR100841418B1 (en) * | 2006-11-29 | 2008-06-25 | 희성금속 주식회사 | Preparation of Precious Metal Targets by Discharge Plasma Sintering |
| JP5086452B2 (en) * | 2011-02-09 | 2012-11-28 | Ｊｘ日鉱日石金属株式会社 | Indium target and manufacturing method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4274926A (en) * | 1979-04-12 | 1981-06-23 | Degussa Aktiengesellschaft | Process for the electrolytic deposition of silver and silver alloy coatings and compositions therefore |
| EP0286175A1 (en) * | 1987-04-01 | 1988-10-12 | Shell Internationale Researchmaatschappij B.V. | Process for the electrolytic production of metals |
| JPH04333587A (en) * | 1990-06-29 | 1992-11-20 | Electroplating Eng Of Japan Co | Method and bath for electroforming and plating platinum or platinum alloy and its electro-formed and plated article |
| JPH07332494A (en) * | 1994-06-01 | 1995-12-22 | Honda Motor Co Ltd | High strength inorganic film |
| JPH0867974A (en) * | 1994-08-26 | 1996-03-12 | Mitsubishi Materials Corp | Sputtering target for Pt thin film formation |
| JPH08250427A (en) * | 1995-03-13 | 1996-09-27 | Central Glass Co Ltd | Tungsten target for semiconductor |
| JPH0941131A (en) * | 1995-07-31 | 1997-02-10 | Mitsubishi Materials Corp | Method for producing high-purity Ir or Ru sputtering target |
| JPH11158612A (en) * | 1997-12-01 | 1999-06-15 | Mitsubishi Materials Corp | Dissolved ruthenium sputtering target |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1250155A (en) * | 1984-07-31 | 1989-02-21 | James A. Ruf | Platinum resistance thermometer |
| JPS63262461A (en) * | 1987-04-21 | 1988-10-28 | Mitsubishi Kasei Corp | sputtering target |
-
1999
- 1999-06-16 WO PCT/JP1999/003194 patent/WO1999066099A1/en not_active Ceased
- 1999-06-16 JP JP53819599A patent/JP3436763B2/en not_active Expired - Fee Related
- 1999-06-16 GB GB0001523A patent/GB2343684B/en not_active Expired - Fee Related
- 1999-06-16 DE DE19981314T patent/DE19981314C2/en not_active Expired - Fee Related
- 1999-06-16 KR KR1020007000075A patent/KR100348023B1/en not_active Expired - Fee Related
- 1999-09-02 TW TW088115093A patent/TW491909B/en not_active IP Right Cessation
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4274926A (en) * | 1979-04-12 | 1981-06-23 | Degussa Aktiengesellschaft | Process for the electrolytic deposition of silver and silver alloy coatings and compositions therefore |
| EP0286175A1 (en) * | 1987-04-01 | 1988-10-12 | Shell Internationale Researchmaatschappij B.V. | Process for the electrolytic production of metals |
| JPH04333587A (en) * | 1990-06-29 | 1992-11-20 | Electroplating Eng Of Japan Co | Method and bath for electroforming and plating platinum or platinum alloy and its electro-formed and plated article |
| JPH07332494A (en) * | 1994-06-01 | 1995-12-22 | Honda Motor Co Ltd | High strength inorganic film |
| JPH0867974A (en) * | 1994-08-26 | 1996-03-12 | Mitsubishi Materials Corp | Sputtering target for Pt thin film formation |
| JPH08250427A (en) * | 1995-03-13 | 1996-09-27 | Central Glass Co Ltd | Tungsten target for semiconductor |
| JPH0941131A (en) * | 1995-07-31 | 1997-02-10 | Mitsubishi Materials Corp | Method for producing high-purity Ir or Ru sputtering target |
| JPH11158612A (en) * | 1997-12-01 | 1999-06-15 | Mitsubishi Materials Corp | Dissolved ruthenium sputtering target |
Non-Patent Citations (1)
| Title |
|---|
| JOIS, ECLA, INSPEC * |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010021519A (en) | 2001-03-15 |
| DE19981314T1 (en) | 2002-10-24 |
| TW491909B (en) | 2002-06-21 |
| GB2343684B (en) | 2003-04-23 |
| KR100348023B1 (en) | 2002-08-07 |
| JP3436763B2 (en) | 2003-08-18 |
| WO1999066099A1 (en) | 1999-12-23 |
| GB0001523D0 (en) | 2000-03-15 |
| DE19981314C2 (en) | 2003-07-03 |
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