CN113423859A - Tungsten oxide sputtering target - Google Patents
Tungsten oxide sputtering target Download PDFInfo
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- CN113423859A CN113423859A CN202080013496.XA CN202080013496A CN113423859A CN 113423859 A CN113423859 A CN 113423859A CN 202080013496 A CN202080013496 A CN 202080013496A CN 113423859 A CN113423859 A CN 113423859A
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- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 title claims description 63
- 229910001930 tungsten oxide Inorganic materials 0.000 title claims description 63
- 238000005477 sputtering target Methods 0.000 title claims description 54
- 238000004544 sputter deposition Methods 0.000 claims abstract description 145
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 13
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 229910052715 tantalum Inorganic materials 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 229910052727 yttrium Inorganic materials 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000010937 tungsten Substances 0.000 claims description 7
- 239000000843 powder Substances 0.000 description 47
- 238000005245 sintering Methods 0.000 description 46
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
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- 150000002697 manganese compounds Chemical class 0.000 description 1
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- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical compound [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- 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
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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Abstract
The present invention is characterized in that W is confirmed by X-ray diffraction analysis of a sputtering surface and a cross section orthogonal to the sputtering surface18O49And W of the sputtering face18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Is 0.57 or more, W of the cross section18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)The W is 0.38 or less and is parallel to the sputtering surface18O49The area ratio of the phase is 37% or more.
Description
Technical Field
The present invention relates to a tungsten oxide sputtering target used for forming a tungsten oxide film.
The present application claims priority based on patent application No. 2019-.
Background
The tungsten oxide film is used in various fields such as an electrochromic display element and a light shielding member. Further, patent document 1 discloses the use of a tungsten oxide film (WO)XFilm) as an anode of the organic EL element.
As described in patent document 1, the tungsten oxide film is formed by a sputtering method using a sputtering target.
As a sputtering target for forming a tungsten oxide film, for example, as shown in patent documents 2 and 3, there is provided a tungsten oxide sputtering target composed of a sintered body obtained by sintering tungsten oxide powder.
Patent document 2 discloses a tungsten oxide sputtering target in which manganese or a manganese compound is added as a sintering aid in order to increase the density of a sintered body.
Further, patent document 3 discloses a tungsten oxide sputtering target using a sputtering target containing WO for DC sputtering2、W18O49And WO3Of at least oneTungsten oxide powder, sintered in vacuum, made of tungsten oxide powder having a chemical composition consisting of WO2Phase sum W18O49A sintered body having a structure constituted of two or more phases.
Patent document 1: japanese laid-open patent publication No. 11-067459
Patent document 2: japanese laid-open patent publication No. 10-259054
Patent document 3: japanese patent laid-open publication No. 2013-076163
Recently, in order to efficiently form a tungsten oxide film, a tungsten oxide sputtering target is subjected to sputtering deposition at a higher power than in the past.
In a tungsten oxide sputtering target composed of a sintered body, when sputtering is performed under high power conditions, cracking may occur on the sputtering surface. Even if cracking does not occur in the initial stage of sputtering, if the depth of the erosion portion increases as sputtering progresses, cracking may easily occur at a high load power.
Disclosure of Invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a tungsten oxide sputtering target which can suppress the occurrence of cracks and can stably perform sputtering deposition for a long period of time even when sputtering is performed under high power conditions.
As a result of intensive studies to solve the above problems, the present inventors have found the following.
By setting the crystal orientation of the sputtering surface and the crystal orientation of the cross section orthogonal to the sputtering surface within a predetermined range, the occurrence of cracks can be suppressed even when a high power is applied, and the occurrence of cracks can be suppressed even in a state where sputtering is progressing. One of the reasons for this is that the hardness of the sputtering surface is improved by setting the crystal orientation of the sputtering surface and the crystal orientation of the cross section perpendicular to the sputtering surface within predetermined ranges.
The present invention has been made in view of the above-mentioned findings, and a tungsten oxide sputtering target of the present invention is characterized in that W is confirmed by X-ray diffraction analysis of a sputtering surface and a cross section orthogonal to the sputtering surface18O49And a peak ofW of the sputtering face18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Is 0.57 or more, W of the cross section18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)The W is 0.38 or less and is parallel to the sputtering surface18O49The area ratio of the phase is 37% or more.
According to the tungsten oxide sputtering target having such a structure, it was confirmed that W was W by X-ray diffraction analysis of the sputtering surface and the cross section orthogonal to the sputtering surface18O49And the W of a plane parallel to the sputtering plane18O49Since the area ratio of the phase is 37% or more, the conductivity can be secured, and DC sputtering can be stably performed. Further, the strength of the tungsten oxide sputtering target can be ensured.
Furthermore, due to the W of the sputtering surface18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)W is 0.57 or more and is a cross section perpendicular to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)W is 0.38 or less on the sputtering surface18O49The (103) plane (a) is strongly oriented, so that the occurrence of cracks can be suppressed even under a high load. Further, even when the erosion portion is formed as the sputtering progresses, the crystal orientation of the sputtering surface can be maintained, and the occurrence of cracking can be suppressed even when a high power is applied.
In the tungsten oxide sputtering target of the present invention, the preferable composition is WOX(2.1≤X≤2.9)。
In this case, the composition is WOX(2.1. ltoreq. X. ltoreq.2.9), thereby suppressing WO2Phase and WO3A large amount of phase is present, and W having excellent conductivity can be sufficiently secured18O49Phase, and further can be stably carried outAnd (6) DC sputtering. Further, the strength of the tungsten oxide sputtering target can be sufficiently ensured.
Further, in the tungsten oxide sputtering target of the present invention, it is preferable that the tungsten oxide sputtering target contains an oxide of an additive metal of one or two or more of Nb, Ta, Ti, Zr, Y, Al, and Si, and when the total content of the additive metals is M (mass%), and the content of tungsten is W (mass%), M/(W + M) is in the range of 0.1 or more and 0.67 or less as the metal component.
In this case, since the oxide of one or two or more kinds of additional metals selected from Nb, Ta, Ti, Zr, Y, Al and Si is contained, and when the total content of the additional metals is M (atomic%), and the content of tungsten is W (atomic%), M/(W + M) is 0.1 or more, the alkali resistance of the oxide film to be formed can be improved. Further, since M/(W + M) is 0.67 or less, the occurrence of abnormal discharge due to the oxide of the additive metal can be suppressed.
According to the present invention, a tungsten oxide sputtering target can be provided which can suppress the occurrence of cracks and can stably perform sputtering film formation for a long period of time even when sputtering is performed under high power conditions.
Drawings
Fig. 1 is a diagram showing the results of X-ray diffraction analysis of the sputtering surface and a cross section perpendicular to the sputtering surface of a tungsten oxide sputtering target according to an embodiment of the present invention.
Fig. 2 is a flowchart showing a method for manufacturing a tungsten oxide sputtering target according to an embodiment of the present invention.
Detailed Description
Hereinafter, a tungsten oxide sputtering target according to an embodiment of the present invention will be described with reference to the drawings.
In the tungsten oxide sputtering target according to the present embodiment, it was confirmed by X-ray diffraction analysis of the sputtering surface and the cross section orthogonal to the sputtering surface that W was formed18O49Peak of (2), W of the plane parallel to the sputtering plane18O49The area ratio of the phase is 37% or more.
As shown in fig. 1, the tungsten oxide sputtering according to the present embodimentIn the target, the result of X-ray diffraction measurement, W of the sputtering surface18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Is 0.57 or more.
And W of a cross section orthogonal to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)Is 0.38 or less.
In the tungsten oxide sputtering target according to the present embodiment, the composition is preferably WOX(2.1≤X≤2.9)。
Further, in the tungsten oxide sputtering target according to the present embodiment, it is preferable that the tungsten oxide sputtering target contains an oxide of one or two or more kinds of additional metals selected from Nb, Ta, Ti, Zr, Y, Al, and Si, and when the total content of the additional metals is M (atomic%), and the content of tungsten is W (atomic%), M/(W + M) is in a range of 0.1 or more and 0.67 or less as the metal component.
In the tungsten oxide sputtering target of the present embodiment, W on the sputtering surface is referred to18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)W of a cross section orthogonal to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)W of a plane parallel to the sputtering plane18O49The reason why the area ratio and composition of the phase are defined as described above will be described.
(diffraction intensity ratio I of sputtering surfaceS(103)/IS(010))
Due to W18O49Since the (103) plane of (a) is harder than the other azimuth plane, the crystal orientation is controlled so that the sputtering plane (103) is strongly oriented, thereby suppressing the occurrence of cracks.
Therefore, in the present embodiment, W of the sputtering surface is set to be W18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Is set to 0.57 or more.
W of sputtering surface18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Preferably 1.2 or more, more preferably 2.02 or more. And, IS(103)/IS(010)The upper limit of (b) is not particularly limited, but is preferably 2.56 or less.
(diffraction intensity ratio I of a cross section orthogonal to the sputtering surface)C(103)/IC(010))
When sputtering progresses, an erosion portion is formed on the sputtering surface. In a cross section orthogonal to the sputtering surface, if W18O49The (103) plane of (2) is low in orientation, so that even when sputtering progresses, a strong orientation state is maintained in the (103) plane of the sputtering surface, and occurrence of cracks can be suppressed even after the sputtering progresses.
Therefore, in the present embodiment, W, which is a cross section orthogonal to the sputtering surface, is defined as18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)The content is set to 0.38 or less.
W of a cross section orthogonal to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)Preferably 0.30 or less, and more preferably 0.18 or less. And, IC(103)/IC(010)The lower limit of (b) is not particularly limited, but is preferably 0.13 or more.
(W of a plane parallel to the sputtering plane18O49Area ratio of the photo)
With respect to W in tungsten oxide18O49Phase W is secured because of high conductivity18O49The area ratio of the phase and the conductivity are improved, and a tungsten oxide film can be stably formed by DC sputtering.
Therefore, in the present embodiment, W of the surface parallel to the sputtering surface18O49The area ratio of the phase is 37% or more. The W of a plane parallel to the sputtering plane can be calculated from an image obtained by EPMA analysis of the observation plane of the observation sample18O49Area fraction of phase. When the sputtering target contains an oxide of an additive metal selected from one or two or more of Nb, Ta, Ti, Zr, Y, Al and Si in addition to tungsten oxide, W is present on the entire surface parallel to the sputtering surface of the oxide containing these additive elements18O49The area ratio of the phase may be 37% or more.
W of a plane parallel to the sputtering plane18O49The area ratio of the phase is preferably 55% or more, and more preferably 85% or more. W of a plane parallel to the sputtering plane18O49The upper limit of the area ratio of the phase is not particularly limited, but is preferably 94% or less.
(composition)
In tungsten oxide, WO exists due to mixing2Phase, WO3Phase, W18O49Equal phases, and thus as WOXThe ratio of tungsten to oxygen is specified.
By setting X to 2.1 or more, WO can be suppressed2The phase ratio of the W-containing compound can sufficiently ensure W with excellent conductivity18O49And (4) phase(s). On the other hand, by setting X to 2.9 or less, WO can be suppressed3The phase ratio of the W-containing compound can sufficiently ensure W with excellent conductivity18O49And (4) phase(s). That is, by setting X to 2.1 or more and 2.9 or less, W18O49The phase becomes a main phase (matrix) and can secure the conductivity of the sputtering target.
The lower limit of X is preferably 2.4 or more. The upper limit of X is preferably 2.82 or less.
(addition of Metal oxide)
In the oxide film formed, an alkali can be used as a resist stripping liquid when patterning by an etching method. The alkali resistance of tungsten oxide can be improved by adding an oxide of an additive metal of any one or two or more of Nb, Ta, Ti, Zr, Y, Al, and Si to tungsten oxide. On the other hand, if the content of the additive metal oxide is too large, there is a possibility that abnormal discharge may occur during sputtering due to the additive metal oxide.
Therefore, in the present embodiment, when the oxide of one or two or more kinds of additional metals of Nb, Ta, Ti, Zr, Y, Al, and Si is contained, when the total content of the additional metals is M (atomic%) and the content of tungsten is W (atomic%), M/(W + M) is defined to be in the range of 0.1 to 0.67.
The lower limit of M/(W + M) is preferably 0.15 or more, more preferably 0.2 or more. On the other hand, the upper limit of M/(W + M) is preferably 0.5 or less, and more preferably 0.4 or less.
Next, a method for manufacturing a tungsten oxide sputtering target according to the present embodiment will be described with reference to fig. 2.
As shown in fig. 2, the method for manufacturing a tungsten oxide sputtering target according to the present embodiment includes: a raw material powder preparation step S01; a sintering step S02 of sintering the raw material powder; and a machining step S03 of machining the obtained sintered body.
(raw material powder preparation step S01)
By subjecting WO to3The powder is subjected to reduction treatment to obtain a powder containing WO2Powder and W18O49WO of powderXAnd (3) powder. The WOXThe powder may comprise WO3And (3) powder. WOXThe purity of the powder is set to 99.9 mass% or more. Controlling WO by adjusting the conditions of the reduction treatmentXX of the powder.
As the above reduction treatment, for example, WO is mentioned3The powder is heated in a hydrogen atmosphere for a predetermined time at a predetermined temperature to perform hydrogen reduction. In the hydrogen reduction, to obtain3To WO2.9、WO2.72、WO2And W is reduced in this order. By controlling the progress of reduction, it is possible to prepare powders having a mixture of the above-mentioned compositions in different reduced states, and to control the state of reduction of WOXThe value of X of the powder varied finely.
And, as control and fine-tuning WOXThe method of X value of the powder may be applied to the powder reduced as described aboveThe powder is suitably mixed with a solvent selected from WO3、WO2.9、WO2.72、WO2And W.
In connection with WOXIn the quantification of X in WOXAfter the weight measurement, heat treatment was performed at 800 ℃ for 1 hour in the atmosphere, and the weight measurement was performed after the heat treatment. Then, it was confirmed by X-ray diffraction analysis that all of them became WO3The amount of W is calculated by the following equation. Then, the proportion of oxygen is calculated as X from the obtained W amount.
Weight of W is weight after heat treatment × MW/MWO3
W (% by mass) is (weight of W/WO before heat treatment)XWeight of) x 100
MW: atomic weight of W (183.85), MWO3：WO3Atomic weight of (231.85)
WO obtained by mixingXAnd (5) obtaining raw material powder. As the mixing method, for example, a dry ball mill using zirconia balls can be used. The mixing method is not limited, and a stirrer or a mixer, specifically, a henschel machine, a swing machine, a scout machine, or the like can be used.
The average particle diameter of the raw material powder is preferably in the range of 1 μm to 30 μm.
When an oxide of an additive metal of one or two or more of Nb, Ta, Ti, Zr, Y, Al and Si is added, various oxide powders are mixed with the above-mentioned WOXThe powders are mixed. As the mixing method, for example, a dry ball mill using zirconia balls can be used. The mixing method is not limited, and a stirrer or a mixer, specifically, a henschel machine, a swing machine, a scout machine (レコン), or the like can be used.
And, in order not to hinder WOXSintering of the powders to each other, the metal-added oxide powder preferably being in proportion to WOXThe particle size of the powder is large.
(sintering step S02)
Next, the raw material powder is pressurized and heated, and sintered to obtain a sintered body. In this embodiment, sintering is performed in vacuum using a hot press apparatus.
The sintering temperature in the sintering step S02 is set to be in the range of 850 ℃ to 1400 ℃, the holding time at the sintering temperature is set to be in the range of 1 hour to 4 hours, and the pressing pressure is set to be in the range of 10MPa to 35 MPa.
In the present embodiment, in the sintering step S02, the crystal orientation in the sintered body is controlled by controlling the temperature as follows.
First, before the temperature rise is started, the pressure is increased at the above-mentioned pressure, and the temperature rise is performed at a temperature rise rate in the range of 5 ℃/min to 20 ℃/min. And is maintained at an intermediate temperature of 586 ℃ to 750 ℃ for 1 hour to 2 hours. Thereafter, the temperature is raised to the sintering temperature and held, thereby performing sintering.
Thereby, W is formed on the pressing surface (the surface orthogonal to the pressing direction)18O49Is strongly oriented, and W is a plane (a plane along the pressing direction) orthogonal to the pressing plane18O49The (010) plane of (A) is strongly oriented.
The lower limit of the intermediate temperature is preferably 600 ℃ or higher, and the upper limit of the intermediate temperature is preferably 700 ℃ or lower.
(machining operation S03)
Next, the obtained sintered body is machined so as to have a predetermined size. At this time, machining is performed so that the pressing surface becomes a sputtering surface.
Thus, the tungsten oxide sputtering target of the present embodiment is manufactured.
According to the tungsten oxide sputtering target of the present embodiment configured as described above, it was confirmed that W was generated by X-ray diffraction analysis of the sputtering surface and the cross section perpendicular to the sputtering surface18O49W of a plane parallel to the sputtering plane18O49Since the area ratio of the phase is 37% or more, the conductivity can be secured, and DC sputtering can be stably performed. Further, the strength of the tungsten oxide sputtering target can be ensured.
In the tungsten oxide sputtering target of the present embodiment, the sputtering surface is W18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)W is 0.57 or more and is a cross section perpendicular to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)W is 0.38 or less on the sputtering surface18O49The (103) plane (b) is strongly oriented, and therefore, even when a high power is applied, the occurrence of cracking can be suppressed. Further, even when the erosion portion is formed as the sputtering progresses, the crystal orientation of the sputtering surface can be maintained, and the occurrence of cracking can be suppressed even when a high power is applied.
In the tungsten oxide sputtering target of the present embodiment, the composition is WOX(2.1. ltoreq. X. ltoreq.2.9) can inhibit WO2Phase and WO3The phase exists in a large amount and sufficiently ensures W18O49Further, DC sputtering can be stably performed. Further, the strength of the tungsten oxide sputtering target can be sufficiently ensured.
Further, in the tungsten oxide sputtering target of the present embodiment, when the oxide of one or two or more kinds of additional metals selected from Nb, Ta, Ti, Zr, Y, Al, and Si is contained and when the total content of the additional metals is M (atomic%) and the content of tungsten is W (atomic%), M/(W + M) is 0.1 or more and 0.67 or less, the alkali resistance of the oxide film to be formed can be improved and the occurrence of abnormal discharge due to the oxide of the additional metal can be suppressed.
The embodiments of the present invention have been described above, but the present invention is not limited to these embodiments, and can be modified as appropriate within a range not departing from the technical spirit of the present invention.
Examples
The results of the evaluation test evaluated with respect to the operational effects of the tungsten oxide sputtering target according to the present invention will be described below.
First, by applying to the above-mentioned WO3The powder is subjected to hydrogen reduction treatment to produce WOXAnd (3) powder. In this example, WO with different x values was prepared by adjusting the degree of reductionXAnd (3) powder. The average particle size of the raw material powder was set to 2.4 μm.
Then, Nb was prepared as oxide powder of various additional metals2O5Powder (purity: 99.9 mass%, particle diameter D50: 4.6 μm), Ta2O5Powder (purity: 99.9 mass%, particle diameter D50: 3.5 μm), TiO2Powder (purity: 99.9 mass%, particle diameter D50: 2.6 μm), ZrO 22Powder (purity: 99.9 mass%, particle diameter D50: 11 μm), Y2O3Powder (purity: 99.9 mass%, particle diameter D50: 2.3 μm), Al2O3Powder (purity: 99.9 mass%, particle diameter D50: 0.2 μm), SiO2The powder (purity: 99.9% by mass, particle diameter D50: 1.9 μm) was blended with WO in the proportions shown in tables 1 and 2XThe powders were mixed.
Using this raw material powder, a sintering step was performed under the apparatus (mode) and conditions shown in tables 1 and 2, and a sintered body was obtained. In tables 1 and 2, "HP" indicates hot pressing in a vacuum atmosphere, "HIP" indicates a hot isostatic pressing method, and "atmosphere firing" indicates uniaxial molding in an atmosphere.
In "HP", sintering was performed under the following sintering conditions a to D.
In the sintering condition a, the temperature was raised at a temperature raising rate of 10 ℃/min in a state of being pressurized at the pressurization pressure described in tables 1 and 2, and the resultant was held at 600 ℃ (intermediate temperature) for 1 hour. Thereafter, the temperature was raised at a rate of 10 ℃/min to the sintering temperatures shown in tables 1 and 2, and the resultant was held at the sintering temperature for 2 hours. After that, the pressure was released and allowed to cool.
In the sintering condition B, the temperature was raised at a temperature raising rate of 10 ℃/min in a state of being pressurized at the pressurization pressure described in table 1 and table 2, and the sintered body was held at 700 ℃ (intermediate temperature) for 1 hour. Thereafter, the temperature was raised at a rate of 10 ℃/min to the sintering temperatures shown in tables 1 and 2, and the resultant was held at the sintering temperature for 2 hours. After that, the pressure was released and allowed to cool.
In the sintering condition C, the temperature was raised to the sintering temperature without being held at the intermediate temperature, and held at the sintering temperature for 2 hours. After that, the pressure was released and allowed to cool.
In the sintering condition D, the temperature was raised at a temperature raising rate of 10 ℃/min in a state of being pressurized at the pressurization pressures shown in tables 1 and 2, and the sintered body was held at 800 ℃ for 1 hour. Thereafter, the temperature was raised at a rate of 10 ℃/min to the sintering temperatures shown in tables 1 and 2, and the resultant was held at the sintering temperature for 2 hours. After that, the pressure was released and allowed to cool.
In "HIP", a metal can filled with a raw material powder and sealed in a vacuum is placed in a pressure vessel of a hot isostatic pressing apparatus which performs a hot isostatic pressing method, and is held at a sintering temperature and a pressure shown in tables 1 and 2 for 2 hours to perform sintering.
In the "atmospheric firing", a mold is filled with a raw material powder, and compression molding is performed by uniaxial molding to obtain a molded body. The molded article was charged into an atmospheric furnace, and was sintered while being held at the sintering temperatures shown in tables 1 and 2 for 20 hours.
Then, the obtained sintered body was machined to produce a tungsten oxide sputtering target having a disk shape of 152.4mm in diameter × 6mm in thickness. In the sintered body manufactured by "HP", machining is performed so that the pressing surface becomes a sputtering surface.
The tungsten oxide sputtering target obtained was evaluated for the following items.
(composition of tungsten oxide sputtering target)
A measurement sample was collected from the obtained tungsten oxide sputtering target, and the measurement sample was pulverized with a mortar, according to the above-mentioned WOXThe method for quantifying X in (1) confirms X. As a result, no change in X was observed from the WOx powder to be blended. The evaluation results are shown in tables 1 and 2.
In the measurement of the degree of oxidation in inventive examples 13 to 20 to which the added metal oxide was added, first, an observation sample was collected from the obtained tungsten oxide sputtering target so that a cross section parallel to the sputtering surface became the observation surfaceAfter the epoxy resin was embedded and the polishing treatment was performed, an element distribution image showing the composition distribution of the elements was observed using an EPMA (field emission electron beam probe micro analyzer). Further, in the observation under EPMA, 0.005mm was photographed2A photograph of the observation field of view (magnification 500 times). Quantitative analysis of a standard sample using W and O was performed at arbitrary 5 points of the region where W was detected in the obtained W element map image, and the average value of the values obtained by measuring the degree of oxidation of W was reported in WO of tables 1 and 2XThe value of (c) is in the column.
In inventive examples 13 to 21 to which the metal-added oxide was added, fragments of the tungsten oxide sputtering target to which the obtained metal-added oxide was added were ground in an agate mortar, the powder was dissolved with acid or alkali, and the content of the added metal was measured by an ICP emission spectrometer.
(X-ray diffraction analysis of sputtering surface and Cross section orthogonal to sputtering surface)
From the obtained tungsten oxide sputtering target, a measurement sample was collected so that the sputtering surface and a cross section orthogonal to the sputtering surface became a measurement surface, and the measurement surface was wet-polished with SiC-Paper (grit 180).
Further, X-ray diffraction analysis was carried out under the following conditions using RINT-ULtima/PC manufactured by Rigaku corporation.
Tube ball: cu
Tube voltage: 40kV
Tube current: 50mA
Scanning range (2 θ): 5-80 degree
The size of the slit is as follows: divergence (DS)2/3 degrees, scattering (SS)2/3 degrees, acceptance (RS)0.8mm
Measuring step length: 0.02 degree in terms of 2 theta
Scanning speed: 2 degree per minute
Rotation speed of sample stage: 30rpm
For the resulting X-ray diffraction peaks, the PDF card number: 1-084-18O49) The face index was confirmed.
Then, W of the sputtering surface was calculated18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)And W in a cross section orthogonal to the sputtering surface18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010). The evaluation results are shown in tables 3 and 4.
(Density)
The density at room temperature was determined from the size and weight of the test specimen. The measurement results are shown in tables 3 and 4.
(W18O49Area ratio of the photo)
An observation sample was collected from the obtained tungsten oxide sputtering target, and after the observation sample was embedded in an epoxy resin and polished so that a cross section parallel to the sputtering surface became an observation surface, an element distribution image showing the composition distribution of elements was observed using an EPMA (field emission electron beam probe micro analyzer). Further, in the observation under EPMA, 5 sheets of the image were taken at 0.005mm2And W observed therein was measured18O49Area of the phase. The measurement results are shown in tables 3 and 4.
W18O49The area ratio of the phases can be measured by the following procedures (a) to (e).
(a) The generated phase on the observation surface of the observation sample was confirmed by the X-ray diffraction analysis under the above conditions.
(b) Identification by elemental analysis of EPMA within the field of view as analyzed as W in (a)18O49Phase of the phases.
(C) 5 photographs of the field of view were taken by EPMA with a COMPO image (60 μm. times.80 μm) at a magnification of 500.
(d) Extracting W identified in (b) by commercially available image analysis software18O49In contrast, the captured image is changed to a monochrome image and binarization processing is performed. As the image analysis software, for example, winroofver.5.6.2 (manufactured by mitanicorroporation) or the like can be used.
(e) Calculating all W according to all binary images18O49The total value of the areas of the phases is divided by the area of the entire region subjected to the binarization processing to calculate W18O49Area ratio with respect to the entire observation region.
(hardness of sputtering surface)
An observation sample was collected from the obtained tungsten oxide sputtering target, and the hardness of the sputtering surface was measured.
Hardness measurement was performed using a Vickers hardness tester under a load of 500gf for 10 seconds. The measurement results are shown in tables 3 and 4.
(occurrence of cracks in sputtering test)
Using a DC magnetron sputtering apparatus, under an ultimate vacuum degree: 5X 10-5Pa below, sputtering Ar pressure: a sputtering test was carried out under the condition of 0.3 Pa.
At this time, the sputtering output was increased by 100W every 10 minutes from DC100W, and it was confirmed that cracking occurred in the sputtering output. The evaluation results are shown in tables 3 and 4.
In tables 3 and 4, "initial" is the result of the sputtering test after the 1 hour press sputtering was performed. The "middle stage" is a result of a sputtering test performed in a state where the depth of the erosion portion reached 1/2, which is the target thickness.
(alkali resistance)
Using a DC magnetron sputtering apparatus, under an ultimate vacuum degree: 5X 10-5Pa below, sputtering Ar pressure: a film of 100nm was formed on the glass substrate under the conditions of 0.3Pa, sputtering output of 300W, Ar gas of 90sccm, and oxygen gas of 10 sccm. The obtained film was immersed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH), and the time until the film disappeared was measured, which is shown in table 3. When the time is 60 seconds or more, it is determined that the film has alkali resistance capable of withstanding a wiring step (development in a photoresist step).
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
In comparative example 1, sintering was performed under sintering condition C by Hot Pressing (HP), but W in a cross section perpendicular to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was observed at 800W in the initial stage and 600W in the middle stage of sputtering.
In comparative example 2, sintering was performed by Hot Isostatic Pressing (HIP), but W in a cross section perpendicular to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was observed at 700W in the middle of sputtering.
In comparative example 3, the atmosphere firing was performed, and as a result, W was not observed18O49Phase, DC sputtering could not be performed.
In comparative example 4, sintering was performed under sintering condition C by Hot Pressing (HP), but W in a cross section perpendicular to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was observed at 600W in the initial stage and 500W in the middle stage of sputtering.
In comparative example 5, sintering was performed under sintering condition C by Hot Pressing (HP), but W of the sputtering surface was18O49Diffraction intensity ratio ofS(103)/IS(010)And W in a cross section orthogonal to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was confirmed at 900W in the initial stage, but cracking was confirmed at 500W in the middle stage of sputtering.
In comparative example 6, WOX(X＝2.06)，W18O49The area ratio of the phase is as low as 28%, and abnormal discharge often occurs during DC sputtering and the discharge is stopped, so that sputtering cannot be performed. Presumably because of WO2The phases are present in large amounts.
In comparative example 7, WOX(X＝2.86)，W18O49The area ratio of the phase is as low as 23%, and abnormal discharge often occurs during DC sputtering and the discharge is stopped, so that sputtering cannot be performed. Presumably because of WO3The phases are present in large amounts.
In comparative example 8, sintering was performed under sintering condition D by Hot Pressing (HP), but the density was low and sufficient sintering could not be performed. And W of a cross section orthogonal to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was confirmed at 400W in the initial stage and at 400W in the middle stage of sputtering.
In comparative example 9, sintering was performed by Hot Isostatic Pressing (HIP), but W in a cross section perpendicular to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Outside the scope of the present invention. In the sputtering test, cracking was observed at 700W in the middle of sputtering.
In comparative example 10, 70 mol% of TiO was contained2W of a plane parallel to the sputtering plane18O49The area ratio of the phase is as low as 27%, and abnormal discharge often occurs during DC sputtering, and the discharge is stopped, so that sputtering cannot be performed.
On the other hand, in inventive examples 1 to 10 and inventive example 12, as a result of sintering under the sintering condition a by Hot Pressing (HP), W on the sputtering surface was obtained18O49Diffraction intensity ratio ofS(103)/IS(010)And W in a cross section orthogonal to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Within the scope of the invention, W18O49The area fraction of the phases is also within the scope of the present invention. Further, in the present invention examples 1 to 4 and the present invention examples 6 to 12, cracking was not observed even when the power was increased to 1000W in the initial and middle stages of the sputtering test. In invention example 5, cracking was confirmed at 900W in both the initial and middle stages of the sputtering test, but the test was sufficiently usable.
In invention example 11, as a result of sintering under sintering condition B by Hot Pressing (HP), W on the sputtering surface was obtained18O49Diffraction intensity ratio ofS(103)/IS(010)And W in a cross section orthogonal to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Within the scope of the invention, W18O49The area fraction of the phases is also within the scope of the present invention. Further, even if the power was increased to 1000W in both the initial and middle stages of the sputtering test, no cracking was observed.
In addition, in inventive examples 13 to 21, the added metal oxide was added, but W on the sputtering surface was W18O49Diffraction intensity ratio ofS(103)/IS(010)And W in a cross section orthogonal to the sputtering surface18O49Diffraction intensity ratio ofC(103)/IC(010)Within the scope of the invention, W18O49The area fraction of the phases is also within the scope of the present invention. In inventive example 13, inventive example 14, and inventive examples 16 to 21, cracking was not observed even when the power was increased to 1000W in the initial and middle stages of the sputtering test. In invention example 15, cracking was confirmed at 900W in both the initial and middle stages of the sputtering test, but the test was sufficiently usable.
Further, the alkali resistance was greatly improved as compared with the examples 1 to 12 of the present invention to which no metal oxide was added.
As described above, it was confirmed that, according to the present invention, a tungsten oxide sputtering target can be provided which can suppress the occurrence of cracks and can stably perform sputter deposition for a long period of time even when sputtering is performed under high power conditions.
Industrial applicability
According to the present invention, a tungsten oxide sputtering target can be provided which can suppress the occurrence of cracks and can stably perform sputtering film formation for a long period of time even when sputtering is performed under high power conditions.
Claims (3)
1. A tungsten oxide sputtering target characterized by comprising,
w was confirmed by X-ray diffraction analysis of the sputtering surface and a cross section perpendicular to the sputtering surface18O49And a peak of
W of the sputtering face18O49Diffraction intensity I of (103) planeS(103)Diffraction intensity with (010) plane IS(010)Ratio of (A to (B))S(103)/IS(010)Is a content of at least 0.57,
w of the cross section18O49Diffraction intensity I of (103) planeC(103)Diffraction intensity with (010) plane IC(010)Ratio of (A to (B))C(103)/IC(010)Is a content of not more than 0.38,
the W of the face parallel to the sputtering face18O49The area ratio of the phase is 37% or more.
2. The tungsten oxide sputtering target according to claim 1, having the composition WOX(2.1≤X≤2.9)。
3. The tungsten oxide sputtering target according to claim 1 or 2,
an oxide containing one or more additional metals selected from Nb, Ta, Ti, Zr, Y, Al and Si,
when the total content of the additive metals is M atomic% and the content of tungsten is W atomic%, M/(W + M) is in the range of 0.1 to 0.67 as the metal component.
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| JP2017025348A (en) * | 2015-07-15 | 2017-02-02 | 三菱マテリアル株式会社 | Mo-W OXIDE SPUTTERING TARGET, AND MANUFACTURING METHOD OF Mo-W OXIDE SPUTTERING TARGET |
| JP2019002064A (en) * | 2017-06-20 | 2019-01-10 | 日立金属株式会社 | MoW target material |
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- 2020-03-06 JP JP2020039257A patent/JP2020153015A/en active Pending
- 2020-03-12 KR KR1020217020166A patent/KR20210139211A/en unknown
- 2020-03-12 CN CN202080013496.XA patent/CN113423859A/en active Pending
- 2020-03-13 TW TW109108313A patent/TW202039900A/en unknown
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Also Published As
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| TW202039900A (en) | 2020-11-01 |
| JP2020153015A (en) | 2020-09-24 |
| KR20210139211A (en) | 2021-11-22 |
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