JP2022131665A - Oxide sputtering target, manufacturing method of the same, and oxide thin film - Google Patents
Oxide sputtering target, manufacturing method of the same, and oxide thin film Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 71
- 239000010409 thin film Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 13
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 9
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010937 tungsten Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- 239000011812 mixed powder Substances 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 abstract description 4
- 238000002441 X-ray diffraction Methods 0.000 description 21
- 239000010408 film Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000002994 raw material Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 239000011324 bead Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 230000002950 deficient Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/083—Oxides of refractory metals or yttrium
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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
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3256—Molybdenum oxides, molybdates or oxide forming salts thereof, e.g. cadmium molybdate
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- 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
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3258—Tungsten oxides, tungstates, or oxide-forming salts thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/541—CuInSe2 material PV cells
Abstract
Description
本発明は、仕事関数の高い酸化物薄膜を成膜するのに適した、酸化物スパッタリングターゲット及びその製造方法並びに酸化物薄膜に関する。 The present invention relates to an oxide sputtering target suitable for forming an oxide thin film having a high work function, a method for producing the same, and an oxide thin film.
有機エレクトロルミネッセンス（有機ＥＬ）素子などの発光素子における透明電極（陽極）としてＩＴＯ（インジウム・スズ酸化物）が用いられている。陽極に電圧を印加することで注入された正孔は、正孔輸送層を経由して、発光層で電子と結合する。近年、正孔輸送層への電荷注入効率を向上させる目的で、ＩＴＯよりも仕事関数が高い酸化物を用いることが研究されている。たとえば、非特許文献１には、有機半導体デバイスにおける酸化物薄膜として、ＴｉＯ2、ＭｏＯ2、ＣｕＯ、ＮｉＯ、ＷＯ3、Ｖ2Ｏ5、ＣｒＯ3、Ｔａ2Ｏ5、Ｃｏ3Ｏ4などの高い仕事関数のものが報告されている。 BACKGROUND ART ITO (indium tin oxide) is used as a transparent electrode (anode) in a light-emitting element such as an organic electroluminescence (organic EL) element. Holes injected by applying a voltage to the anode combine with electrons in the light emitting layer via the hole transport layer. In recent years, research has been conducted on using an oxide having a higher work function than ITO for the purpose of improving the efficiency of charge injection into the hole transport layer. For example, Non-Patent Document 1 describes oxide thin films in organic semiconductor devices such as TiO 2 , MoO 2 , CuO, NiO, WO 3 , V 2 O 5 , CrO 3 , Ta 2 O 5 and Co 3 O 4 . High work functions have been reported.
非特許文献１に示されるように、ＷＯ3は比較的高い仕事関数を有する。このＷＯ3膜は酸化タングステン焼結体からなるスパッタリングターゲットを用いて成膜することができるが（特許文献１、２）、ＷＯ3単相では焼結体の高密度化が困難であり、体積抵抗率が高いために、ＤＣスパッタリングが困難であった。そのため、特許文献２には、ＷＯ3にＷＯ2を添加することで、焼結体の高密度化を達成し、導電性を高めてＤＣスパッタリングを可能とすることが開示されている。なお、特許文献３、４には、ＷとＭｏの酸化物を含む酸化物スパッタリングターゲットが開示されている。 As shown in Non-Patent Document 1 , WO3 has a relatively high work function. This WO3 film can be formed using a sputtering target made of a tungsten oxide sintered body (Patent Documents 1 and 2 ), but with a WO3 single phase, it is difficult to increase the density of the sintered body, and the volume DC sputtering was difficult due to the high resistivity. Therefore, Patent Literature 2 discloses that by adding WO2 to WO3 , the density of the sintered body is increased and the electrical conductivity is increased to enable DC sputtering. Patent Documents 3 and 4 disclose oxide sputtering targets containing oxides of W and Mo.
上述の通り、有機ＥＬなどの有機半導体デバイスを構成する膜として、仕事関数の高い酸化物膜が求められている。ＷＯ3、ＭｏＯ3は、ともに高い仕事関数を有する材料として知られているが、両材料とも単相で高密度なスパッタリングターゲットを製造することが困難であった。このようなことから本発明は、上述課題を解決するために提案されたものであって、仕事関数の高い膜を成膜することができる高密度のスパッタリングターゲットを提供することを課題とする。 As described above, an oxide film having a high work function is required as a film constituting an organic semiconductor device such as an organic EL. Both WO 3 and MoO 3 are known as materials having a high work function, but it is difficult to produce single-phase, high-density sputtering targets from both materials. In view of the above, the present invention has been proposed to solve the above problems, and an object of the present invention is to provide a high-density sputtering target capable of forming a film having a high work function.
本発明は、上記課題を解決するために提案されたものであって、その課題を解決できる本発明の一態様は、タングステン（Ｗ）、モリブデン（Ｍｏ）、及び、酸素（Ｏ）からなる酸化物スパッタリングターゲットであって、相対密度が９０％以上であることを特徴とする酸化物スパッタリングターゲットである。 The present invention has been proposed to solve the above problems, and one aspect of the present invention that can solve the problems is an oxide containing tungsten (W), molybdenum (Mo), and oxygen (O) An oxide sputtering target characterized by having a relative density of 90% or more.
本発明によれば、相対密度が高い酸化物スパッタリングターゲットを製造することができ、このような酸化物スパッタリングターゲットを用いて仕事関数の高い酸化物薄膜を製造することができるという優れた効果を有する。 According to the present invention, an oxide sputtering target having a high relative density can be produced, and an oxide thin film having a high work function can be produced using such an oxide sputtering target. .
本発明の実施形態に係る酸化物スパッタリングターゲットは、タングステン（Ｗ）、モリブデン（Ｍｏ）、及び、酸素（Ｏ）からなる。但し、当該スパッタリングターゲットには、原料や製造過程などから混入する不純物が含まれる場合があり、成膜した薄膜の仕事関数などに特別な影響を及ぼさない量の不純物を含んでいてもよく、不純物の合計含有量が０．１ｗｔ％以下であれば、特に問題ないといえる。 An oxide sputtering target according to embodiments of the present invention consists of tungsten (W), molybdenum (Mo), and oxygen (O). However, the sputtering target may contain impurities mixed in from raw materials and manufacturing processes, and may contain impurities in an amount that does not have a particular effect on the work function of the thin film formed. If the total content of is 0.1 wt% or less, it can be said that there is no particular problem.
本発明の実施形態に係る酸化物スパッタリングターゲットは、相対密度が９０％以上であることを特徴とするものである。より好ましくは９２％以上、さらに好ましくは９４％以上である。このような高密度のスパッタリングターゲットは、スパッタリングの際にクラックや割れ等を防ぐことができ、成膜時のパーティクルを低減することができる。
また、スパッタリングターゲットの相対密度は、体積抵抗率とも関連し、相対密度の値が低くなると、体積抵抗率が高くなる傾向にある。そのため、体積抵抗率を下げるためには、スパッタリングターゲットのＷとＭｏの含有比率の他、スパッタリングターゲットの製造方法や製造条件を厳格に調整して、相対密度を高める必要がある。
An oxide sputtering target according to an embodiment of the present invention is characterized by having a relative density of 90% or more. More preferably 92% or more, still more preferably 94% or more. Such a high-density sputtering target can prevent cracks, cracks, and the like during sputtering, and can reduce particles during film formation.
The relative density of the sputtering target is also related to volume resistivity, and the lower the relative density value, the higher the volume resistivity. Therefore, in order to lower the volume resistivity, it is necessary to increase the relative density by strictly adjusting the content ratio of W and Mo in the sputtering target as well as the manufacturing method and manufacturing conditions of the sputtering target.
本発明の実施形態に係る酸化物スパッタリングターゲットは、モリブデンの酸化物を含有し、前記モリブデン酸化物はＭｏＯ2として存在していることが好ましい。モリブデン酸化物には、ＭｏＯ2とＭｏＯ3があるが、ＭｏＯ2はＭｏＯ3に比べて、密度が高く、導電性も高いため、ＭｏＯ3ではなく、ＭｏＯ2として存在させることが、高密度、且つ、低抵抗の酸化物スパッタリングターゲットを製造する上で重要である。
好ましい実施形態は、ＭｏＯ2相の（１１０）面に帰属するＸＲＤピーク強度をＩMoO2とし、バックグランドのＸＲＤ平均強度をＩBGとしたときに、ＩMoO2／ＩBGが３．０以上とすることである。
本願明細書おいて、ＭｏＯ2相の（１１０）面に帰属するＸＲＤピーク強度ＩMoO2、バックグランドのＸＲＤ平均強度ＩBGは以下のように定義される。
ＩMoO2：２５．８°≦２θ≦２６．３°の範囲におけるＸＲＤピーク強度
ＩBG：２０.０°≦２θ＜２２.０°の範囲におけるＸＲＤ平均強度
An oxide sputtering target according to embodiments of the present invention comprises an oxide of molybdenum, said molybdenum oxide preferably being present as MoO2 . Molybdenum oxide includes MoO 2 and MoO 3 , but MoO 2 has a higher density and higher conductivity than MoO 3 , so it is possible to have MoO 2 instead of MoO 3 to have a high density and a high conductivity. Moreover, it is important in manufacturing a low resistance oxide sputtering target.
In a preferred embodiment, I MoO2 /I BG is 3.0 or more, where I MoO2 is the XRD peak intensity attributed to the (110) plane of the MoO 2 phase and I BG is the XRD average intensity of the background. That is.
In the present specification, the XRD peak intensity I MoO2 attributed to the (110) plane of the MoO 2 phase and the background XRD average intensity I BG are defined as follows.
I MoO2 : XRD peak intensity in the range of 25.8°≦2θ≦26.3° I BG : XRD average intensity in the range of 20.0°≦2θ<22.0°
本発明の実施形態に係る酸化物スパッタリングターゲットは、タングステン酸化物を含有し、タングステン酸化物はＷＯ3として存在していることが好ましい。タングステン酸化物は、ＷＯ3が安定酸化物であるが、酸素欠損した、ＷＯ2、ＷＯ2.72～2.75、ＷＯ2.9などが存在する。酸素欠損したタングステン酸化物では、ターゲットの相対密度が上がり難く、また、仕事関数が低下する可能性が高いことから、ターゲットの高密度化、かつ、薄膜の高仕事関数を得るためには、ＷＯ3として存在していることが望ましい。
好ましい実施形態は、ＷＯ3相の（２０２）面に帰属するＸＲＤピーク強度をＩWO3とし、バックグランドのＸＲＤ平均強度をＩBGとしたときに、ＩｗO3／ＩBGが３．０以上である。本願明細書において、ＷＯ3相の（２０２）面に帰属するＸＲＤピーク強度ＩWO3、バックグランドのＸＲＤ平均強度ＩBGは以下のように定義される。
ＩWO3：３３．５°≦２θ≦３４．５°の範囲におけるＸＲＤピーク強度
ＩBG：２０.０°≦２θ＜２２.０°の範囲におけるＸＲＤ平均強度
The oxide sputtering targets according to embodiments of the present invention contain tungsten oxide , which is preferably present as WO3. Among tungsten oxides, WO 3 is a stable oxide, but oxygen-deficient WO 2 , WO 2.72 to 2.75 and WO 2.9 exist. With oxygen-deficient tungsten oxide, it is difficult to increase the relative density of the target and the work function is likely to decrease. It is desirable to exist as 3 .
In a preferred embodiment, when the XRD peak intensity attributed to the (202) plane of the WO3 phase is IWO3 and the background XRD average intensity is IBG , IwO3 / IBG is 3.0 or more. . In the present specification, the XRD peak intensity I WO3 attributed to the (202) plane of the WO 3 phase and the background XRD average intensity I BG are defined as follows.
I WO3 : XRD peak intensity in the range of 33.5°≦2θ≦34.5° I BG : XRD average intensity in the range of 20.0°≦2θ<22.0°
本発明の実施形態に係る酸化物スパッタリングターゲットは、ＷとＭｏの含有比率が原子％で０．１０≦Ｗ／（Ｗ＋Ｍｏ）＜１.０を満たすことが好ましい。ＷとＭｏの含有比率が原子％でＷ／（Ｗ＋Ｍｏ）が０．１０未満であると、本実施形態に係る酸化物スパッタリングターゲットを用いて形成した酸化物膜において、所望の仕事関数が得られないことがある。一方、Ｗ／（Ｗ＋Ｍｏ）＝１．０（ＷＯ3単相）であると、高密度の酸化物スパッタリングターゲットが得ることが困難となる。より好ましくは、ＷとＭｏの含有比率が原子％で０．１５≦Ｗ／（Ｗ＋Ｍｏ）≦０．８５である In the oxide sputtering target according to the embodiment of the present invention, the content ratio of W and Mo preferably satisfies 0.10≦W/(W+Mo)<1.0 in terms of atomic %. When the content ratio of W and Mo is atomic % and W/(W+Mo) is less than 0.10, the oxide film formed using the oxide sputtering target according to the present embodiment has a desired work function. sometimes not. On the other hand, when W/(W+Mo)=1.0 ( WO3 single phase), it becomes difficult to obtain a high-density oxide sputtering target. More preferably, the content ratio of W and Mo is 0.15 ≤ W / (W + Mo) ≤ 0.85 in atomic %
本発明の実施形態に係る酸化物スパッタリングターゲットは、体積抵抗率が１Ω・ｃｍ以下であることが好ましい。より好ましくは０．５Ω・ｃｍ以下、さらに好ましくは０．１Ω・ｃｍ以下である。これにより、高速成膜が可能なＤＣスパッタリングを安定して実施することができる。上述の通り、本実施形態に係る酸化物スパッタリングターゲット中、酸化モリブデンはＭｏＯ2となっており、ＭｏＯ2はＭｏＯ3に比べて酸素欠損しているため体積抵抗率を低くすることができる。なお、Ｍｏの含有比率によって、体積抵抗率は変動し、Ｍｏの含有比率が増えると、体積抵抗率が低くなる傾向にある。 The oxide sputtering target according to the embodiment of the present invention preferably has a volume resistivity of 1 Ω·cm or less. It is more preferably 0.5 Ω·cm or less, still more preferably 0.1 Ω·cm or less. As a result, DC sputtering capable of high-speed film formation can be stably performed. As described above, in the oxide sputtering target according to the present embodiment, molybdenum oxide is MoO 2 , and MoO 2 has more oxygen deficiency than MoO 3 , so the volume resistivity can be lowered. Note that the volume resistivity varies depending on the content of Mo, and tends to decrease as the content of Mo increases.
本発明の別の実施形態に係る酸化物薄膜は、上記酸化物スパッタリングターゲットを用いて成膜される薄膜であって、仕事関数が４．５ｅＶ以上であることを特徴とする。このような仕事関数が高い膜は、例えば、有機ＥＬ、有機太陽電池などの有機半導体デバイスにおいて正孔輸送層への電荷注入効率を向上させることができ、発光効率あるいは変換効率などの向上が期待できる。 An oxide thin film according to another embodiment of the present invention is a thin film formed using the above oxide sputtering target, and is characterized by having a work function of 4.5 eV or more. A film with such a high work function can, for example, improve the efficiency of charge injection into the hole transport layer in organic semiconductor devices such as organic EL and organic solar cells, and is expected to improve luminous efficiency or conversion efficiency. can.
（酸化物スパッタリングターゲットの製造方法）
以下に、本実施形態に係る酸化物スパッタリングターゲットの製造方法を示す。但し、以下の製造条件等は開示した範囲に限定するものではなく、いくらかの省略や変更を行ってもよいことは明らかである。
(Method for producing oxide sputtering target)
A method for manufacturing an oxide sputtering target according to this embodiment will be described below. However, it is clear that the following manufacturing conditions and the like are not limited to the disclosed range, and that some omissions and changes may be made.
原料粉末として、酸化タングステン（ＷＯ3）粉末、酸化モリブデン（ＭｏＯ2）粉末を準備し、これらの原料粉末を所望の組成比となるように秤量する。このとき、酸化モリブデンはＭｏＯ3ではなく、ＭｏＯ2を使用すること好ましい。次に、ボール径が０．５～３．０ｍｍのジルコニアビーズを用いて、湿式粉砕を行う。そして、粒径の中央値が０．１～５．０μｍとなるまで粉砕を行い、その後、造粒を行う。 Tungsten oxide (WO 3 ) powder and molybdenum oxide (MoO 2 ) powder are prepared as raw material powders, and these raw material powders are weighed so as to have a desired composition ratio. At this time, it is preferable to use MoO 2 instead of MoO 3 as molybdenum oxide. Next, wet pulverization is performed using zirconia beads having a ball diameter of 0.5 to 3.0 mm. Then, pulverization is performed until the median particle size reaches 0.1 to 5.0 μm, and then granulation is performed.
次に、得られた造粒混合粉を真空又は不活性ガス（Ａｒなど）雰囲気、８００℃以上１０００℃以下でホットプレス焼結を行う。焼結温度が８００℃未満であると、高密度の焼結体が得られず、一方、１０００℃超であると、粒が粗大化し、クラックが発生するため好ましくない。また、焼結時間は、１～１０時間とすることが好ましい。その後、得られた焼結体をターゲット形状に切削、研磨などして、スパッタリングターゲットを作製することができる。 Next, the obtained granulated mixed powder is subjected to hot press sintering at 800° C. or higher and 1000° C. or lower in a vacuum or an inert gas (such as Ar) atmosphere. If the sintering temperature is less than 800° C., a high-density sintered body cannot be obtained. Also, the sintering time is preferably 1 to 10 hours. After that, the obtained sintered body is cut into a target shape, polished, or the like, so that a sputtering target can be produced.
本願明細書において、スパッタリングターゲット及び薄膜の各種物性の分析方法等を以下に示す。
（スパッタリングターゲットの成分組成）
スパッタリングターゲットの成分組成の分析は、以下の装置を用いることができる。
装置：ＳＩＩ社製ＳＰＳ３５００ＤＤ
方法：ＩＣＰ-ＯＥＳ（高周波誘導結合プラズマ発光分析法）
なお、スパッタリングターゲットの成分組成は、原料の組成比率と同じとみなすことができる。本実施形態に係るスパッタリングターゲットの製造プロセスにおいて、特定の酸化物のみをロスするような工程はなく、組成比率の変化が少ないと考えられるためである。
In the specification of the present application, methods for analyzing various physical properties of sputtering targets and thin films are shown below.
(Component composition of sputtering target)
The following equipment can be used to analyze the composition of the sputtering target.
Device: SPS3500DD manufactured by SII
Method: ICP-OES (Inductively Coupled Plasma Emission Spectrometry)
In addition, the composition of the sputtering target can be considered to be the same as the composition ratio of the raw material. This is because, in the manufacturing process of the sputtering target according to the present embodiment, there is no process in which only a specific oxide is lost, and the change in the composition ratio is thought to be small.
（スパッタリングターゲットのＸ線回折分析について）
スパッタリングターゲットのＸ線回折分析（ＸＲＤ）は、以下の方法により行う。
装置：リガク社製ＳｍａｒｔＬａｂ
管球：Ｃｕ－Ｋα線
管電圧：４０ｋＶ
電流：３０ｍＡ
測定方法：２θ－θ反射法
スキャン速度：２０．０°／ｍｉｎ
サンプリング間隔：０．０１°
(About X-ray diffraction analysis of sputtering target)
X-ray diffraction analysis (XRD) of the sputtering target is performed by the following method.
Apparatus: SmartLab manufactured by Rigaku
Tube: Cu-Kα ray Tube voltage: 40 kV
Current: 30mA
Measurement method: 2θ-θ reflection method Scanning speed: 20.0°/min
Sampling interval: 0.01°
（スパッタリングターゲットの体積抵抗率）
スパッタリングターゲットの体積抵抗率は、スパッタリングターゲットの表面を５点（中心１点、半径の１／２の箇所を９０度間隔で４点）測定し、それらの平均値とした。測定には、以下の装置を使用する。
装置：ＮＰＳ社製 抵抗率測定器 Σ－５＋
方式：定電流印加方式
方法：直流４探針法
(Volume resistivity of sputtering target)
The volume resistivity of the sputtering target was measured at 5 points on the surface of the sputtering target (1 point at the center and 4 points at half the radius at 90 degree intervals), and the average value thereof was taken. The following equipment is used for the measurement.
Apparatus: Resistivity measuring instrument Σ-5+ manufactured by NPS
Method: Constant current application method Method: DC 4-probe method
（スパッタリングターゲットの相対密度について）
相対密度（％）＝アルキメデス密度／真密度×１００
アルキメデス密度：スパッタリングターゲットターゲットから小片を切り出して、その小片からアルキメデス法を用いて密度を算出する。
真密度：原料の組成比率から計算したＷ、Ｍｏの原子比を、スパッタリングターゲットのＷ、Ｍｏの原子比とみなし、その原子比から、ＷのＷＯ3換算重量をａ（ｗｔ％）、ＭｏのＭｏＯ2換算重量をｂ（ｗｔ％）を求め、ＷＯ3、ＭｏＯ2の理論密度をそれぞれｄWO3、ｄMoO2として、真密度（ｇ／ｃｍ3）＝１００／（ａ／dWO3＋ｂ／dMoO2）を計算する。なお、ＷＯ3の理論密度をｄWO3＝７．１６ｇ／ｃｍ3、ＭｏＯ2の理論密度ｄMoO2＝６．４７ｇ／ｃｍ3、とする。
(Regarding the relative density of the sputtering target)
Relative density (%) = Archimedes density / true density x 100
Archimedes Density: A small piece is cut from the sputtering target and the density is calculated from the piece using the Archimedes method.
True density: The atomic ratio of W and Mo calculated from the composition ratio of the raw material is regarded as the atomic ratio of W and Mo of the sputtering target, and from that atomic ratio , the WO3 equivalent weight of W is a (wt%), and the weight of Mo is b (wt%) is obtained as the MoO 2 equivalent weight, and the theoretical densities of WO 3 and MoO 2 are d WO3 and d MoO2 , respectively, and the true density (g/cm 3 ) = 100/(a/d WO3 +b/d MoO2 ). The theoretical density of WO 3 is d WO3 =7.16 g/cm 3 , and the theoretical density of MoO 2 is d MoO2 = 6.47 g/cm 3 .
（酸化物薄膜の仕事関数について）
酸化物薄膜の仕事関数の測定は、ガラス基板もしくはＳｉ基板上に成膜した２０×２０ｍｍのサンプルを作製し、以下の条件で測定を実施した。なお、仕事関数の測定結果は、通常、サンプルのサイズに依存しない。
方式：大気中光電子分光法
装置：理研計器製 ＡＣ－５装置
条件：測定可能な仕事関数の範囲：３．４ｅＶ～６．２ｅＶ
光源パワー:２０００Ｗ
(Work function of oxide thin film)
For the measurement of the work function of the oxide thin film, a sample of 20×20 mm formed on a glass substrate or a Si substrate was prepared, and the measurement was carried out under the following conditions. It should be noted that the measurement result of the work function usually does not depend on the size of the sample.
Method: Atmospheric photoelectron spectroscopy Apparatus: Riken Keiki AC-5 apparatus Conditions: Measurable work function range: 3.4 eV to 6.2 eV
Light source power: 2000W
以下、実施例および比較例に基づいて説明する。なお、本実施例はあくまで一例であり、この例によって何ら制限されるものではない。すなわち、本発明は特許請求の範囲によってのみ制限されるものであり、本発明に含まれる実施例以外の種々の変形を包含するものである。 Hereinafter, description will be made based on examples and comparative examples. It should be noted that this embodiment is merely an example, and the present invention is not limited by this example. That is, the present invention is limited only by the scope of the claims, and includes various modifications other than the examples included in the present invention.
（実施例１）
ＷＯ3粉とＭｏＯ2粉とを準備し、これらの粉末をＷＯ3：ＭｏＯ2＝８５：１５（ｍｏｌ％）で秤量した。次に、０．５ｍｍのジルコニアビーズを用いて３時間湿式ビーズミル混合粉砕を実施し、メジアン径０．８μｍ以下の混合粉末を得た。次に、この混合粉末を焼結温度：８２５℃、最高圧力：２５０ｋｇｆ／ｃｍ2、保持時間：６時間、雰囲気：アルゴン、の条件でホットプレス焼結を行い、焼結体を作製した。その後、この焼結体を機械加工してスパッタリングターゲット形状に仕上げた。
実施例１で得られたスパッタリングターゲットについて評価した結果、相対密度は、９４．４％であり、体積抵抗率は７５．５ｍΩ・ｃｍであった。また、スパッタリングターゲットについてＸ線回折分析（ＸＲＤ）を行った結果、ＩMoO2／ＩBGは７．１であった。以上の結果を表１に示す。なお、スパッタリングターゲットの成分組成は、原料の組成比率と同じとみなして計算した。
(Example 1)
WO 3 powder and MoO 2 powder were prepared, and these powders were weighed at WO 3 :MoO 2 =85:15 (mol %). Next, wet bead mill mixing pulverization was performed using 0.5 mm zirconia beads for 3 hours to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, this mixed powder was subjected to hot press sintering under the following conditions: sintering temperature: 825° C., maximum pressure: 250 kgf/cm 2 , holding time: 6 hours, atmosphere: argon to produce a sintered body. After that, this sintered body was machined and finished into a sputtering target shape.
As a result of evaluating the sputtering target obtained in Example 1, the relative density was 94.4% and the volume resistivity was 75.5 mΩ·cm. As a result of X-ray diffraction analysis (XRD) of the sputtering target, I MoO2 /I BG was 7.1. Table 1 shows the above results. The composition of the sputtering target was calculated assuming that it was the same as the composition ratio of the raw material.
（実施例２～４）
ＷＯ3粉とＭｏＯ2粉とを準備し、これらの粉末を表１に記載するモル比となるように秤量した。次に、０．５ｍｍのジルコニアビーズを用いて３時間湿式ビーズミル混合粉砕し、メジアン径０．８μｍ以下の混合粉末を得た。次に、この混合粉末を焼結温度：８５０℃～８７５℃、最高圧力：２５０ｋｇｆ／ｃｍ2、保持時間：６時間、雰囲気：アルゴンの条件でホットプレス焼結を行い、焼結体を作製した。その後、この焼結体を機械加工してスパッタリングターゲット形状に仕上げた。
実施例２～４のスパッタリングターゲットは、いずれも相対密度が９４％以上であり、体積抵抗率は１．０Ω・ｃｍ以下であった。また、スパッタリングターゲットについてＸ線回折分析（ＸＲＤ）を行った結果、ＩMoO2／ＩBGは３．０以上であった。なお、スパッタリングターゲットの成分組成は、原料の組成比率と同じとみなして計算した。
(Examples 2-4)
WO 3 powder and MoO 2 powder were prepared, and these powders were weighed so as to have the molar ratios shown in Table 1. Next, the mixed powder was mixed and pulverized in a wet bead mill for 3 hours using 0.5 mm zirconia beads to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, this mixed powder was subjected to hot press sintering under the conditions of sintering temperature: 850° C. to 875° C., maximum pressure: 250 kgf/cm 2 , holding time: 6 hours, and atmosphere: argon to produce a sintered body. . After that, this sintered body was machined and finished into a sputtering target shape.
The sputtering targets of Examples 2 to 4 all had a relative density of 94% or more and a volume resistivity of 1.0 Ω·cm or less. As a result of X-ray diffraction analysis (XRD) of the sputtering target, I MoO2 /I BG was 3.0 or more. The composition of the sputtering target was calculated assuming that it was the same as the composition ratio of the raw material.
（比較例１）
比較例１では、ＷＯ3粉のみとした。ＷＯ3粉を０．５ｍｍのジルコニアビーズを用いて３時間湿式ビーズミル混合粉砕し、メジアン径０．８μｍ以下の混合粉末を得た。次に、この混合粉末を焼結温度：９４０℃、最高圧力：２５０ｋｇｆ／ｃｍ2、保持時間：１０時間、雰囲気：酸素の条件で、常圧焼結を行い、焼結体を作製した。その後、この焼結体を機械加工してスパッタリングターゲット形状に仕上げた。
比較例１のスパッタリングターゲットは、相対密度が９４％であり、体積抵抗率は１．６×１０4Ω・ｃｍであった。また、スパッタリングターゲットについてＸ線回折分析（ＸＲＤ）を行った結果、ＩMoO2／ＩBGは１．９であった。なお、スパッタリングターゲットの成分組成は、原料の組成比率と同じとみなして計算した。
(Comparative example 1)
In Comparative Example 1 , only WO3 powder was used. The WO 3 powder was mixed and pulverized in a wet bead mill using 0.5 mm zirconia beads for 3 hours to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, this mixed powder was sintered at normal pressure under conditions of sintering temperature: 940° C., maximum pressure: 250 kgf/cm 2 , holding time: 10 hours, atmosphere: oxygen, and a sintered body was produced. After that, this sintered body was machined and finished into a sputtering target shape.
The sputtering target of Comparative Example 1 had a relative density of 94% and a volume resistivity of 1.6×10 4 Ω·cm. As a result of X-ray diffraction analysis (XRD) of the sputtering target, I MoO2 /I BG was 1.9. The composition of the sputtering target was calculated assuming that it was the same as the composition ratio of the raw material.
次に、実施例１～４のスパッタリングターゲットを用いて、スパッタ成膜を行った。なお、成膜条件は以下の通りとした。得られたスパッタ膜について、仕事関数を測定した結果、Ａｒガス下では４．６２～４．７６ｅＶであり、Ａｒガス＋２％Ｏ2下では４．７１～４．７６ｅＶであり、Ａｒガス＋６％Ｏ2下では４．７４～４．７７ｅＶであり、所望の高い仕事関数が得られた。以上の結果を表１に示す。なお、スパッタ膜の成分組成は、原料比率と同じとみなして計算した。
（成膜条件）
装置：キャノンアネルバ製 ＳＰＬ－５００スパッタ装置
基板：シリコン基板
成膜パワー密度：２．７４Ｗ/ｃｍ2
成膜雰囲気：Ａｒ、Ａｒ＋２％Ｏ2、Ａｒ＋６％Ｏ2
ガス圧：０．５Ｐａ
膜厚：５０ｎｍ
Next, using the sputtering targets of Examples 1 to 4, sputtering film formation was performed. The film formation conditions were as follows. As a result of measuring the work function of the obtained sputtered film, it was 4.62 to 4.76 eV under Ar gas, 4.71 to 4.76 eV under Ar gas + 2% O 2 , and Ar gas + 6%. 4.74 to 4.77 eV under O 2 , yielding the desired high work function. Table 1 shows the above results. The component composition of the sputtered film was calculated assuming that it was the same as the raw material ratio.
(Deposition conditions)
Apparatus: SPL-500 sputtering apparatus manufactured by Canon ANELVA Substrate: Silicon substrate Deposition power density: 2.74 W/cm 2
Deposition atmosphere: Ar, Ar+2% O2 , Ar+6% O2
Gas pressure: 0.5 Pa
Film thickness: 50 nm
本発明の実施形態に係る酸化物スパッタリングターゲットは、相対密度が高く、成膜時にターゲットに割れやクラックが発生することがなく、実用的、商業的レベルで使用することができる。さらに、体積抵抗率が低く、ＤＣスパッタリングが可能である。本発明は、特に有機エレクトロルミネッセンス素子などの発光素子における透明電極を形成するために有用である。 INDUSTRIAL APPLICABILITY The oxide sputtering target according to the embodiment of the present invention has a high relative density, does not generate cracks or breakage in the target during film formation, and can be used on a practical and commercial level. Furthermore, the volume resistivity is low and DC sputtering is possible. INDUSTRIAL APPLICABILITY The present invention is particularly useful for forming transparent electrodes in light-emitting devices such as organic electroluminescence devices.
Claims (10)
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| JP2021030722A JP7436409B2 (en) | 2021-02-26 | 2021-02-26 | Oxide sputtering target, its manufacturing method, and oxide thin film |
| KR1020210150402A KR20220122465A (en) | 2021-02-26 | 2021-11-04 | Oxide sputtering target and production method thereof, and oxide thin film |
| CN202111358250.9A CN114959594A (en) | 2021-02-26 | 2021-11-16 | Oxide sputtering target, method for producing same, and oxide thin film |
| TW110143455A TW202233867A (en) | 2021-02-26 | 2021-11-23 | Oxide sputtering target, method for producing the same, and oxide thin film an oxide sputtering target, which is composed of tungsten (W), molybdenum (Mo) and oxygen (O) |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004190120A (en) * | 2002-12-13 | 2004-07-08 | Sony Corp | Method of producing sputtering target, and sputtering target |
| JP2007092089A (en) * | 2005-09-27 | 2007-04-12 | Japan New Metals Co Ltd | Method for producing high-purity molybdenum-tungsten alloy powder used for raw powder for sputtering target |
| WO2008088076A1 (en) * | 2007-01-17 | 2008-07-24 | Sony Corporation | Developing solution and method for production of finely patterned material |
| CN101550535A (en) * | 2009-05-07 | 2009-10-07 | 上海交通大学 | Method for preparing compound metal sulfide diamond composite membrane |
| JP2016017224A (en) * | 2014-07-11 | 2016-02-01 | パナソニックＩｐマネジメント株式会社 | Method of reactive sputtering formation and cylindrical media deposited by reactive sputtering formation method |
| JP2020536174A (en) * | 2017-10-06 | 2020-12-10 | プランゼー エスエー | Target material for depositing molybdenum oxide layer |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2693599B2 (en) | 1989-11-06 | 1997-12-24 | 日本タングステン株式会社 | Target and its manufacturing method |
| JP4066101B2 (en) * | 1997-10-17 | 2008-03-26 | 旭硝子株式会社 | Low emissivity laminate manufacturing method |
| JP2013076163A (en) | 2011-09-15 | 2013-04-25 | Mitsubishi Materials Corp | Sputtering target and method for manufacturing the same |
| 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 |
| KR20200020855A (en) * | 2018-08-09 | 2020-02-26 | 제이엑스금속주식회사 | Oxide thin film formed using the oxide sputtering target, its manufacturing method, and this oxide sputtering target |
-
2021
- 2021-02-26 JP JP2021030722A patent/JP7436409B2/en active Active
- 2021-11-04 KR KR1020210150402A patent/KR20220122465A/en not_active Application Discontinuation
- 2021-11-16 CN CN202111358250.9A patent/CN114959594A/en active Pending
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004190120A (en) * | 2002-12-13 | 2004-07-08 | Sony Corp | Method of producing sputtering target, and sputtering target |
| JP2007092089A (en) * | 2005-09-27 | 2007-04-12 | Japan New Metals Co Ltd | Method for producing high-purity molybdenum-tungsten alloy powder used for raw powder for sputtering target |
| WO2008088076A1 (en) * | 2007-01-17 | 2008-07-24 | Sony Corporation | Developing solution and method for production of finely patterned material |
| CN101550535A (en) * | 2009-05-07 | 2009-10-07 | 上海交通大学 | Method for preparing compound metal sulfide diamond composite membrane |
| JP2016017224A (en) * | 2014-07-11 | 2016-02-01 | パナソニックＩｐマネジメント株式会社 | Method of reactive sputtering formation and cylindrical media deposited by reactive sputtering formation method |
| JP2020536174A (en) * | 2017-10-06 | 2020-12-10 | プランゼー エスエー | Target material for depositing molybdenum oxide layer |
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| KR20220122465A (en) | 2022-09-02 |
| TW202233867A (en) | 2022-09-01 |
| JP7436409B2 (en) | 2024-02-21 |
| CN114959594A (en) | 2022-08-30 |
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