JP2022048423A - Cu-W-O SPUTTERING TARGET AND OXIDE THIN FILM - Google Patents
Cu-W-O SPUTTERING TARGET AND OXIDE THIN FILM Download PDFInfo
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- 238000005477 sputtering target Methods 0.000 title claims abstract description 59
- 239000010409 thin film Substances 0.000 title claims description 7
- 239000010949 copper Substances 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010937 tungsten Substances 0.000 claims abstract description 5
- 238000004544 sputter deposition Methods 0.000 abstract description 14
- 238000000151 deposition Methods 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 25
- 239000000843 powder Substances 0.000 description 21
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 19
- 238000005245 sintering Methods 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011812 mixed powder Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000011324 bead Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000005401 electroluminescence Methods 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
- 238000005498 polishing Methods 0.000 description 2
- 238000007088 Archimedes method Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 101000892301 Phomopsis amygdali Geranylgeranyl diphosphate synthase Proteins 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
- 230000001133 acceleration Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 230000002706 hydrostatic effect 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
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physical Vapour Deposition (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
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Ｃｕ－Ｗ－Ｏスパッタリングターゲットに関する。 The present invention relates to a Cu—W—O sputtering target suitable for forming an oxide thin film having a high work function.
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。 ITO (indium tin oxide) is used as a transparent electrode (anode) in a light emitting element such as an organic electroluminescence (organic EL) element. The holes injected by applying a voltage to the anode pass through the hole transport layer and combine with electrons in the light emitting layer. In recent years, it has been studied to use an oxide having a higher work function than ITO for the purpose of improving the charge injection efficiency 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 . Those with 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、また、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。また、特許文献１には、酸素供給雰囲気中、ＷＯ3粉末をホットプレスすることで、焼結体の密度を高めることが開示されている。 As shown in Non-Patent Document 1, WO 3 has a relatively high work function. This WO 3 film can be formed by using a sputtering target made of a tungsten oxide sintered body (Patent Documents 1 and 2), but it is difficult to increase the density of the sintered body with the WO 3 single phase. DC sputtering was difficult due to the high volume resistance. Therefore, Patent Document 2 discloses that by adding WO 2 to WO 3 , the high density of the sintered body is achieved, the conductivity is enhanced, and DC sputtering is possible. Further, Patent Document 1 discloses that the density of the sintered body is increased by hot-pressing the WO 3 powder in an oxygen supply atmosphere.
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。高い仕事関数を示す材料としてＷＯ3などが挙げられるが、ＷＯ3などの膜を形成する場合、成膜に使用するスパッタリングターゲットの体積抵抗率が高いため、高速成膜が可能なＤＣスパッタリングができないという問題があった。このようなことから、本発明は、上述の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可能な、体積抵抗率の低い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. WO 3 etc. can be mentioned as a material showing a high work function, but when forming a film such as WO 3 , DC sputtering capable of high-speed film formation cannot be performed because the volume resistivity of the sputtering target used for film formation is high. There was a problem. Therefore, the present invention has been proposed to solve the above-mentioned problems, and provides a sputtering target having a low volume resistivity, which can form a film having a high work function. That is the issue.
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態様は、タングステン（Ｗ）、銅（Ｃｕ）、酸素（Ｏ）及び不可避的不純物からなるスパッタリングターゲットであり、体積抵抗率が１．０×１０3Ω・ｃｍ以下であるＣｕ－Ｗ－Ｏ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 the embodiment of the present invention capable of solving the problems comprises tungsten (W), copper (Cu), oxygen (O) and unavoidable impurities. It is a sputtering target and is a Cu—W—O sputtering target having a volume resistivity of 1.0 × 10 3 Ω · cm or less.
本発明によれば、仕事関数の高い膜を成膜することができるスパッタリングターゲットであって、体積抵抗率が低いため、ＤＣスパッタリングが可能となり、それにより、高速成膜が可能という優れた効果を有する。 According to the present invention, it is a sputtering target capable of forming a film having a high work function, and since it has a low volume resistivity, DC sputtering becomes possible, thereby achieving an excellent effect of enabling high-speed film formation. Have.
上述の通り、ＷＯ3は高い仕事関数を有するが、ＷＯ3単相では、ＤＣスパッタリングが可能な体積抵抗率の低いスパッタリングターゲットを作製することは困難であった。また、他の仕事関数が高い酸化物の材料（例えば、ＣｕＯ単相）を用いた場合も同様に、体積抵抗率が高く、ＤＣスパッタリングが困難であった。このような問題に対して、本発明者らは鋭意研究したところ、ＣｕＯとＷＯ3の混合系を作製することにより、高い仕事関数を維持しつつ、ＤＣスパッタリングが可能な体積抵抗率の低いスパッタリングターゲットを得ることができるとの知見が得られ、本発明に至った。 As described above, WO 3 has a high work function, but it has been difficult to prepare a sputtering target having a low volume resistivity capable of DC sputtering with WO 3 single phase. Further, when another oxide material having a high work function (for example, CuO single phase) is used, the volume resistivity is also high and DC sputtering is difficult. As a result of diligent research on such problems, the present inventors have conducted diligent research, and by producing a mixed system of CuO and WO 3 , sputtering with a low volume resistance capable of DC sputtering while maintaining a high work function. The finding that a target can be obtained has led to the present invention.
本発明の実施形態に係るスパッタリングターゲット（Ｃｕ－Ｗ－Ｏスパッタリングターゲットという。）は、タングステン（Ｗ）、銅（Ｃｕ）、酸素（Ｏ）及び不可避的不純物からなり、体積抵抗率が１．０×１０3Ω・ｃｍ以下である。スパッタリングターゲットの体積抵抗率が１．０×１０3Ω・ｃｍ以下であれば、ＤＣスパッタリングが可能となり、それによる高速成膜が可能となる。好ましくは体積抵抗率が１．０×１０2Ωｃｍ以下である。これにより、さらに安定したＤＣスパッタリングによる高速成膜が可能となる。 The sputtering target (referred to as Cu—W—O sputtering target) according to the embodiment of the present invention is composed of tungsten (W), copper (Cu), oxygen (O) and unavoidable impurities, and has a volume resistance of 1.0. × 10 3 Ω · cm or less. If the volume resistivity of the sputtering target is 1.0 × 10 3 Ω · cm or less, DC sputtering is possible, and high-speed film formation is possible. Preferably, the volume resistivity is 1.0 × 10 2 Ωcm or less. This enables more stable high-speed film formation by DC sputtering.
本実施形態に係るスパッタリングターゲットは、Ｗ、Ｃｕ、Ｏ及び不可避的不純物からなり、ＷとＣｕの含有比率は、原子比でＷ／（Ｃｕ＋Ｗ）≧０．５であることが好ましい。
Ｗ／（Ｃｕ＋Ｗ）＜０．５の場合、体積抵抗率が高くなり、また所望する高い仕事関数が得られないということがある。好ましくは、Ｗ／（Ｃｕ＋Ｗ）≧０．７、より好ましくは、Ｗ／（Ｃｕ＋Ｗ）≧０．８、さらに好ましくはＷ／（Ｃｕ＋Ｗ）≧０．９である。また、ＷＯ3単相であると、上述の通り、スパッタリングターゲットの体積抵抗率が高いため、Ｗ／（Ｃｕ＋Ｗ）＜１とする。なお、前記不可避的不純物は、原料や製造過程などで混入する不純物であって、仕事関数などの特性に特に影響を及ぼさない量を含んでいてもよく、０．１ｗｔ％以下であれば、特に問題はないといえる。
The sputtering target according to the present embodiment is composed of W, Cu, O and unavoidable impurities, and the content ratio of W and Cu is preferably W / (Cu + W) ≧ 0.5 in atomic ratio.
When W / (Cu + W) <0.5, the volume resistivity may be high and the desired high work function may not be obtained. W / (Cu + W) ≧ 0.7, more preferably W / (Cu + W) ≧ 0.8, and even more preferably W / (Cu + W) ≧ 0.9. Further, in the case of WO 3 single phase, since the volume resistivity of the sputtering target is high as described above, W / (Cu + W) <1 is set. The unavoidable impurities are impurities mixed in the raw material, the manufacturing process, etc., and may contain an amount that does not particularly affect the characteristics such as the work function, and if it is 0.1 wt% or less, in particular. It can be said that there is no problem.
本実施形態に係るスパッタリングターゲットは、相対密度が９５％以上であることが好ましい。好ましくは相対密度９８％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Ｃｕの含有比率のほか、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。 The sputtering target according to this embodiment preferably has a relative density of 95% or more. The relative density is preferably 98% or more. Such a high-density sputtering target can prevent cracks and cracks during sputtering, and can reduce particles during film formation. Further, the relative density of the sputtering target is also related to the volume resistivity, and the volume resistivity tends to increase as the value of the relative density decreases. Therefore, in order to reduce the volume resistivity, it is necessary to strictly adjust the W and Cu content ratio of the sputtering target, as well as the manufacturing method and manufacturing conditions of the sputtering target, to increase the relative density.
本発明の一実施形態に係るスパッタリングターゲットは、仕事関数が４．５ｅＶ以上である。このような高い仕事関数を有するスパッタリングターゲットを用いることにより、高い仕事関数を有する膜を作製することができる。そして、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。 The sputtering target according to the embodiment of the present invention has a work function of 4.5 eV or more. By using a sputtering target having such a high work function, a film having a high work function can be produced. A film having such a high work function can improve the charge injection efficiency into the hole transport layer in an organic semiconductor device such as an organic EL or an organic solar cell, and improve the luminous efficiency or the conversion efficiency. Can be expected.
以下に、本実施形態に係る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。 The method for manufacturing the sputtering target according to the present embodiment is shown below. However, the following manufacturing conditions, etc. are not limited to the disclosed scope, and it is clear that some omissions or changes may be made.
原料粉末として、酸化タングステン（ＷＯ3）粉末、酸化銅（ＣｕＯ）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。酸化銅としては、ＣｕＯの他、Ｃｕ2Ｏなどを用いることもできる。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。次に得られた造粒粉をプレス成型する。プレス圧は３００～４００ｋｇｆ／ｃｍ2で行うのが好ましい。その後、冷間静水圧加圧（ＣＩＰ）を行う。ＣＩＰ圧力は１０００～２０００ｋｇｆ／ｃｍ2で行うのが好ましい。次に、得られた成型体を、酸素フロー中、１０～２０時間、常圧焼結を行う。このとき、焼結温度は９００℃以上９５０℃未満とするのが好ましい。９００℃未満であると、高密度の焼結体が得られず、一方、９５０℃以上であると、ＷＯ3とＣｕＯと複合酸化物であるＣｕＷＯ4が、アルミナの焼結部材と反応し、また熔解するため好ましくない。その後は、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。なお、ホットプレス焼結を用いた場合、カーボンの焼結部材によって、ＣｕＯがＣｕに還元されて、部材の消耗が激しいということがある。 Tungsten oxide (WO 3 ) powder and copper oxide (CuO) powder are prepared as raw material powders, and these raw material powders are weighed so as to have a desired composition ratio. As the copper oxide, Cu 2 O or the like can be used in addition to Cu O. 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 becomes 0.1 to 5.0 μm, and then granulation is performed. Next, the obtained granulated powder is press-molded. The press pressure is preferably 300 to 400 kgf / cm 2 . Then, cold hydrostatic pressure pressurization (CIP) is performed. The CIP pressure is preferably 1000 to 2000 kgf / cm 2 . Next, the obtained molded body is subjected to normal pressure sintering for 10 to 20 hours in an oxygen flow. At this time, the sintering temperature is preferably 900 ° C. or higher and lower than 950 ° C. If the temperature is lower than 900 ° C, a high-density sintered body cannot be obtained, while if the temperature is 950 ° C or higher, WO 3 and CuO and Cu WO 4 , which is a composite oxide, react with the sintered member of alumina. Moreover, it is not preferable because it melts. After that, the obtained sintered body can be cut into a target shape, polished, or the like to produce a sputtering target. When hot press sintering is used, CuO may be reduced to Cu by the carbon sintering member, and the member may be heavily consumed.
本願明細書において、スパッタリングターゲット等の各種物性は、以下の測定方法を用いて解析した。
（スパッタリングターゲット及び膜の成分組成）
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）
（膜の成分組成）
装置：ＪＥＯＬ製ＪＸＡ－８５００Ｆ
方法：ＥＰＭＡ(電子線マイクロアナライザー)
加速電圧：５～１０ｋｅＶ
照射電流：２．０×１０-7～２．０～１０-8Ａ
プローブ径：１０μｍ
ゴミ等の付着がなく、基板面がみえていない平滑な成膜部分を５点選択し、点分析を行って、それらの平均組成を算出した。
In the specification of the present application, various physical properties such as a sputtering target were analyzed by using the following measuring methods.
(Sputtering target and film composition)
Equipment: SII SPS3500DD
Method: ICP-OES (High Frequency Inductively Coupled Plasma Emission Analysis)
(Membrane composition)
Equipment: JEOL JXA-8500F
Method: EPMA (Electron Microanalyzer)
Acceleration voltage: 5-10keV
Irradiation current: 2.0 × 10 -7 to 2.0 to 10 -8 A
Probe diameter: 10 μm
Five points of smooth film-forming portions where no dust or the like adhered and the substrate surface was not visible were selected, and point analysis was performed to calculate their average composition.
（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、外周付近４点）測定し、それらの平均値とした。測定には、以下の装置を使用した。
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 (1 point at the center and 4 points near the outer periphery) on the surface of the sputtering target and used as an average value thereof. The following equipment was used for the measurement.
Equipment: NPS resistivity measuring instrument Σ-5 +
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：元素分析からＣｕ、Ｗの原子比を計算し、原子比からＣｕのＣｕＯ換算重量をａ（ｗｔ％）、ＷのＷＯ3換算重量をｂ（ｗｔ％）とし、ＣｕＯ、ＷＯ3の理論密度をそれぞれｄCuO、ｄWO3として、真密度（ｇ／ｃｍ3）＝１００／（ａ／dCuO＋ｂ／dWO3）を計算する。なお、ＣｕＯの理論密度ｄCuO＝６．３１ｇ／ｃｍ3、ＷＯ3の理論密度をｄWO3＝７．１６ｇ／ｃｍ3、とする。
(Relative density of sputtering target)
Relative density (%) = Archimedes density / true density x 100
Archimedes Density: Sputtering Target A small piece is cut out from the target, and the density is calculated from the small piece using the Archimedes method.
True density: The atomic ratios of Cu and W are calculated from the elemental analysis, and the CuO equivalent weight of Cu is a (wt%) and the WO 3 equivalent weight of W is b ( wt%) from the atomic ratio. Let the theoretical densities be d CuO and d WO3 , respectively, and calculate the true density (g / cm 3 ) = 100 / (a / d CuO + b / d WO3 ). The theoretical density of CuO is d CuO = 6.31 g / cm 3 , and the theoretical density of WO 3 is d WO 3 = 7.16 g / cm 3 .
（仕事関数について）
バルク体（スパッタリングターゲット）については、縦：２０ｍｍ、横：１０ｍｍ、厚み：５～１０ｍｍのサンプルを作製した。測定面は番手２０００番の研磨紙を用いて研磨を行った。また、スパッタ膜については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サンプルのサイズに依存しないものである。また、測定面を研磨しない或いは番手の低い研磨紙で研磨し、表面の研磨が不十分な場合には、仕事関数を正確に測定することができず、その値が高く測定されることがある。
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
(About work function)
As for the bulk body (sputtering target), a sample having a length of 20 mm, a width of 10 mm, and a thickness of 5 to 10 mm was prepared. The measurement surface was polished using a polishing paper having a count of 2000. As for the sputtered film, a 20 × 20 mm sample formed on a Si substrate was prepared and measured under the following conditions. The measurement result of the work function does not depend on the size of the sample. In addition, if the measurement surface is not polished or is polished with low-count polishing paper and the surface is not sufficiently polished, the work function cannot be measured accurately, and the value may be measured high. ..
Method: Atmospheric photoelectron spectroscopy Equipment: AC-5 equipment manufactured by RIKEN Keiki Condition: Range of work functions that can be measured: 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, the description will be given based on Examples and Comparative Examples. It should be noted that this embodiment is merely an example, and is not limited by this example. That is, the present invention is limited only by the scope of claims, and includes various modifications other than the examples included in the present invention.
（実施例１）
ＣｕＯ粉とＷＯ3粉を準備し、これらの粉末をＣｕＯ：ＷＯ3＝５０：５０（ｍｏｌ％）で秤量した。次に、３．０ｍｍのジルコニアビーズを用いて２４時間湿式ボール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、この混合粉末を面圧４００ｋｇｆ/ｃｍ2の条件で加圧した後に圧力１８００ｋｇｆ/ｃｍ2の条件でＣＩＰを行い、成型体を作製した。
次に、酸素フロー中、焼結温度９４０℃で１０時間、常圧焼結して焼結体を作製した。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１０３．３％であり、体積抵抗率は１．０×１０3Ω・ｃｍであった。また、スパッタリングターゲットについて仕事関数を測定した結果、４．５ｅＶと高仕事関数のものが得られた。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について成分分析した結果、原料の仕込み時の比率とほとんど変化がないことを確認した。
(Example 1)
CuO powder and WO 3 powder were prepared, and these powders were weighed at CuO: WO 3 = 50: 50 (mol%). Next, wet ball mill mixing and pulverization was carried out using 3.0 mm zirconia beads for 24 hours to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, after pressurizing this mixed powder under the condition of a surface pressure of 400 kgf / cm 2 , CIP was performed under the condition of a pressure of 1800 kgf / cm 2 to prepare a molded body.
Next, a sintered body was prepared by normal pressure sintering for 10 hours at a sintering temperature of 940 ° C. in an oxygen flow. Then, this sintered body was machined to form a sputtering target shape.
As a result of evaluating the sputtering target obtained in Example 1, the relative density was 103.3%, and the volume resistivity was 1.0 × 10 3 Ω · cm. Moreover, as a result of measuring the work function of the sputtering target, the one having a high work function of 4.5 eV was obtained. The above results are shown in Table 1. As a result of component analysis of the sputtering target, it was confirmed that there was almost no change in the ratio at the time of charging the raw materials.
（実施例２～５）
ＣｕＯ粉とＷＯ3粉を準備し、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、３．０ｍｍのジルコニアビーズを用いて２４時間湿式ボール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、この混合粉末を面圧４００ｋｇｆ/ｃｍ2の条件で加圧した後に、圧力１８００ｋｇｆ/ｃｍ2の条件でＣＩＰを行い、成型体を作製した。
次に、酸素フロー中、焼結温度９４０℃で、１０時間、常圧焼結して焼結体を作製した。その後、それぞれ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２～５のスパッタリングターゲットは、いずれも相対密度が９９％以上であり、体積抵抗率は１．０×１０3Ω・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仕事関数を測定した結果、いずれも４．５ｅＶと高仕事関数であった。なお、スパッタリングターゲットについて成分分析した結果、いずれも原料の仕込み時の比率とほとんど変化がないことを確認した。
(Examples 2 to 5)
CuO powder and WO 3 powder were prepared and weighed these powders to the molar ratios shown in Table 1. Next, wet ball mill mixing and pulverization was carried out using 3.0 mm zirconia beads for 24 hours to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, after pressurizing this mixed powder under the condition of a surface pressure of 400 kgf / cm 2 , CIP was performed under the condition of a pressure of 1800 kgf / cm 2 to prepare a molded body.
Next, a sintered body was prepared by normal pressure sintering for 10 hours at a sintering temperature of 940 ° C. in an oxygen flow. After that, each sintered body was machined to form a sputtering target shape.
The sputtering targets of Examples 2 to 5 had a relative density of 99% or more and a volume resistivity of 1.0 × 10 3 Ω · cm or less. Moreover, as a result of measuring the work function for the sputtering target, all of them had a high work function of 4.5 eV. As a result of component analysis of the sputtering target, it was confirmed that there was almost no change in the ratio at the time of charging the raw materials.
（比較例１）
比較例１では、ＣｕＯ粉のみとし、ＷＯ3粉は使用しなかった。Ｃｕ粉を３．０ｍｍのジルコニアビーズを用いて２４時間湿式ボールミル混合粉砕を実施し、メジアン径０．８μｍ以下の混合粉を得た。次に、この混合粉末を面圧４００ｋｇｆ/ｃｍ2の条件で加圧した後に、圧力１８００ｋｇｆ/ｃｍ2の条件でＣＩＰを行い、成型体を作製した。
次に、酸素フロー中、焼結温度９５０℃で、１０時間、常圧焼結して焼結体を作製した。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９８．３％であり、体積抵抗率は３．３×１０5 Ω・ｃｍであった。また、スパッタリングターゲットについて仕事関数を測定した結果、４．２ｅＶであった。なお、スパッタリングターゲットについて成分分析した結果、いずれも原料の仕込み時の比率とほとんど変化がないことを確認した。
(Comparative Example 1)
In Comparative Example 1, only CuO powder was used, and WO 3 powder was not used. The Cu powder was mixed and pulverized with a wet ball mill for 24 hours using 3.0 mm zirconia beads to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, after pressurizing this mixed powder under the condition of a surface pressure of 400 kgf / cm 2 , CIP was performed under the condition of a pressure of 1800 kgf / cm 2 to prepare a molded body.
Next, a sintered body was prepared by normal pressure sintering for 10 hours at a sintering temperature of 950 ° C. in an oxygen flow. Then, this sintered body was machined to form a sputtering target shape.
As a result of evaluating the sputtering target obtained in Comparative Example 1, the relative density was 98.3% and the volume resistivity was 3.3 × 105 Ω · cm. Moreover, as a result of measuring the work function for the sputtering target, it was 4.2 eV. As a result of component analysis of the sputtering target, it was confirmed that there was almost no change in the ratio at the time of charging the raw materials.
（比較例２、３）
比較例２、３では、ＷＯ3粉のみとし、ＣｕＯ粉は使用しなかった。ＷＯ3粉を３．０ｍｍのジルコニアビーズを用いて２４時間湿式ボール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、この混合粉末を面圧４００ｋｇｆ/ｃｍ2の条件で加圧した後に、圧力１８００ｋｇｆ/ｃｍ2の条件でＣＩＰを行い、成型体を作製した。
次に、酸素フロー中、焼結温度を１１００℃（比較例２）、９４０℃（比較例３）とし、１０時間、常圧焼結して焼結体を作製した。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２、３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、いずれも相対密度は９５％未満であり、体積抵抗率は１．０×１０3 Ω・ｃｍ超であった。また、スパッタリングターゲットについて仕事関数を測定した結果、４．４ｅＶであった。なお、スパッタリングターゲットについて成分分析した結果、いずれも原料の仕込み時の比率とほとんど変化がないことを確認した。
(Comparative Examples 2 and 3)
In Comparative Examples 2 and 3, only WO 3 powder was used, and CuO powder was not used. The WO 3 powder was mixed and pulverized with a wet ball mill for 24 hours using 3.0 mm zirconia beads to obtain a mixed powder having a median diameter of 0.8 μm or less. Next, after pressurizing this mixed powder under the condition of a surface pressure of 400 kgf / cm 2 , CIP was performed under the condition of a pressure of 1800 kgf / cm 2 to prepare a molded body.
Next, in the oxygen flow, the sintering temperatures were set to 1100 ° C. (Comparative Example 2) and 940 ° C. (Comparative Example 3), and the sintered body was prepared by normal pressure sintering for 10 hours. Then, this sintered body was machined to form a sputtering target shape.
As a result of evaluating the sputtering targets obtained in Comparative Examples 2 and 3, the relative density was less than 95% and the volume resistivity was more than 1.0 × 10 3 Ω · cm. Moreover, as a result of measuring the work function for the sputtering target, it was 4.4 eV. As a result of component analysis of the sputtering target, it was confirmed that there was almost no change in the ratio at the time of charging the raw materials.
（比較例４）
ＣｕＯ粉とＷＯ3粉を準備し、これらの粉末をＣｕＯ：ＷＯ3＝３０：７０（ｍｏｌ％）で秤量した。次に、３．０ｍｍのジルコニアビーズを用いて２４時間湿式ボール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。この混合粉末を面圧４００ｋｇｆ/ｃｍ2の条件で加圧した後に、圧力１８００ｋｇｆ/ｃｍ2の条件でＣＩＰを行い、成型体を作製した。
次に、酸素フロー中、焼結温度８５０℃で、１０時間、常圧焼結して焼結体を作製した。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４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、体積抵抗率は３．１×１０4Ω・ｃｍであった。
(Comparative Example 4)
CuO powder and WO 3 powder were prepared, and these powders were weighed at CuO: WO 3 = 30: 70 (mol%). Next, wet ball mill mixing and pulverization was carried out using 3.0 mm zirconia beads for 24 hours to obtain a mixed powder having a median diameter of 0.8 μm or less. After pressurizing this mixed powder under the condition of a surface pressure of 400 kgf / cm 2 , CIP was performed under the condition of a pressure of 1800 kgf / cm 2 to prepare a molded body.
Next, a sintered body was prepared by normal pressure sintering for 10 hours at a sintering temperature of 850 ° C. in an oxygen flow. Then, this sintered body was machined to form a sputtering target shape.
As a result of evaluating the sputtering target obtained in Comparative Example 4, the volume resistivity was 3.1 × 10 4 Ω · cm.
次に、実施例３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４．６ｅＶであり、Ａｒガス＋６％Ｏ2下では４.８ｅＶ、と所望の高い仕事関数が得られた。なお、スパッタ膜について成分分析した結果、原料の仕込み時の比率とほとんど変化がないことを確認した。
（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：１．０Ｗ/ｃｍ2
成膜雰囲気：Ａｒ又はＡｒ＋６％Ｏ2
ガス圧：０．５Ｐａ
膜厚：５０ｎｍ
Next, sputter film formation was performed using the sputtering target of Example 3. The film forming conditions were as follows. As a result of measuring the work function of the obtained sputter film, a desired high work function was obtained, which was 4.6 eV under Ar gas and 4.8 eV under Ar gas + 6% O 2 . As a result of component analysis of the sputtered film, it was confirmed that there was almost no change in the ratio at the time of charging the raw materials.
(Film formation conditions)
Equipment: Cannon Anerva SPL-500 Sputtering equipment Substrate: Silicon substrate Film formation power density: 1.0 W / cm 2
Film formation atmosphere: Ar or Ar + 6% O 2
Gas pressure: 0.5Pa
Film thickness: 50 nm
本発明の実施形態に係るＣｕ－Ｗ－Ｏスパッタリングターゲットは、体積抵抗率が低く、ＤＣスパッタリングが可能であり、さらに相対密度が高く、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。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。 The Cu—W—O sputtering target according to the embodiment of the present invention has a low volume resistivity, is capable of DC sputtering, has a high relative density, and does not cause cracks or cracks in the target during film formation. It can be used at a practical and commercial level. The present invention is particularly useful for forming transparent electrodes in light emitting devices such as organic electroluminescence devices.
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| CN202110422866.1A CN114182216A (en) | 2020-09-15 | 2021-04-20 | Cu-W-O sputtering target and oxide thin film |
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