JP2013076163A - Sputtering target and method for manufacturing the same - Google Patents

Sputtering target and method for manufacturing the same Download PDF

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JP2013076163A
JP2013076163A JP2012195715A JP2012195715A JP2013076163A JP 2013076163 A JP2013076163 A JP 2013076163A JP 2012195715 A JP2012195715 A JP 2012195715A JP 2012195715 A JP2012195715 A JP 2012195715A JP 2013076163 A JP2013076163 A JP 2013076163A
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sputtering target
phase
tungsten oxide
powder
sintered body
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Keita Umemoto
啓太 梅本
Shuhin Cho
守斌 張
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Mitsubishi Materials Corp
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Priority to JP2012195715A priority Critical patent/JP2013076163A/en
Priority to PCT/JP2012/073961 priority patent/WO2013039251A1/en
Priority to TW101133771A priority patent/TWI554622B/en
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    • C04B35/62605—Treating the starting powders individually or as mixtures
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    • 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
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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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    • 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
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    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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Abstract

PROBLEM TO BE SOLVED: To provide a sputtering target that has high electrical conductivity and is capable of forming a WOx film by DC sputtering, and to provide a method for manufacturing the same.SOLUTION: The sputtering target is a sintered body of tungsten oxide having a structure comprising at least two phases including a WOphase and a WOphase, wherein the percentage of the WOphase in the structure is 5% or higher. The method for producing the sputtering target includes a step of preparing a tungsten oxide powder containing WOand at least one of WOand WO, and a step of sintering the tungsten oxide powder in a vacuum by hot pressing to produce the sintered body of tungsten oxide, wherein the content of WOin the tungsten oxide powder is 5-95 mol%.

Description

本発明は、ＤＣスパッタが可能な酸化タングステン（ＷＯｘ）のスパッタリングターゲットおよびその製造方法に関するものである。 The present invention relates to a tungsten oxide (WO x ) sputtering target capable of DC sputtering and a method for manufacturing the same.

従来、エレクトロクロミック表示素子用や遮光部材用としてＷＯｘ膜が用いられており、このＷＯｘ膜を成膜するためにスパッタリングターゲットが使用されている。例えば、特許文献１には、エレクトロクロミック表示素子用のＷＯｘ膜を成膜するスパッタリングターゲットとして、ＷＯ３粉末を大気中でホットプレスにより焼結体とし、ＷＯｘ（Ｘ＝２．０〜３．０）の均一組成からなるターゲットを作製する技術が記載されている。このスパッタリングターゲットを用いて、ＲＦマグネトロンスパッタによりスパッタすることでＷＯｘ膜を成膜している。 Conventionally, a WO x film is used for an electrochromic display element or a light shielding member, and a sputtering target is used to form the WO x film. For example, in Patent Document 1, as a sputtering target for forming a WO x film for an electrochromic display element, WO 3 powder is formed into a sintered body by hot pressing in the atmosphere, and WO x (X = 2.0 to 3). 0.0), a technique for producing a target having a uniform composition is described. Using this sputtering target, a WO x film is formed by sputtering by RF magnetron sputtering.

特許第２６９３５９９号公報Japanese Patent No. 2693599

上記従来の技術には、以下の課題が残されている。
すなわち、従来のＷＯｘスパッタリングターゲットは、高抵抗で導電性が無いためＲＦスパッタにより成膜しており、生産性の高いＤＣスパッタができないという問題があった。なお、ＷＯ２のスパッタリングターゲットは、導電性があるためＤＣスパッタが可能であるのに対し、ＷＯ３のスパッタリングターゲットは、導電性がなくＤＣスパッタが困難である。また、ＷＯ２のスパッタリングターゲットを用いて、透明性の高いＷＯｘ膜（２．０＜ｘ≦３．０）を成膜するには、雰囲気中の含有酸素量を多くした反応性スパッタを行う必要があり、成膜レートが低く不安定なため、高い生産性が得られなかった。 The following problems remain in the conventional technology.
That is, since the conventional WO x sputtering target has high resistance and is not conductive, it is formed by RF sputtering, and there is a problem that DC sputtering with high productivity cannot be performed. The WO 2 sputtering target is conductive and can be DC sputtered, whereas the WO 3 sputtering target is not conductive and DC sputtering is difficult. Also, in order to form a highly transparent WO x film (2.0 <x ≦ 3.0) using a WO 2 sputtering target, reactive sputtering with an increased oxygen content in the atmosphere is performed. It was necessary and the film formation rate was low and unstable, so high productivity could not be obtained.

本発明は、前述の課題に鑑みてなされたもので、高い導電性を有し、ＷＯｘ膜をＤＣスパッタにより成膜可能なスパッタリングターゲットおよびその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a sputtering target having high conductivity and capable of forming a WO x film by DC sputtering and a method for manufacturing the sputtering target.

本発明者らは、ＷＯｘのスパッタリングターゲットについて研究を進めたところ、ＷＯ２とマグネリ相の化合物であるＷ１８Ｏ４９とを含有する酸化タングステン粉（ＷＯｘ粉）あるいはＷＯ３を真空中でホットプレスすることにより、高い導電性を有したスパッタリングターゲットが得られ、このスパッタリングターゲットを用いてＤＣスパッタすることにより、ＷＯｘ膜が得られることを見出した。 As a result of research on the sputtering target of WO x , the present inventors have found that tungsten oxide powder (WO x powder) or WO 3 containing WO 2 and W 18 O 49 , which is a compound of the magnetic phase, can be used in vacuum. It has been found that a sputtering target having high conductivity can be obtained by hot pressing, and a WO x film can be obtained by DC sputtering using this sputtering target.

したがって、本発明は、上記知見から得られたものであり、前記課題を解決するために以下の構成を採用した。すなわち、第１の発明のスパッタリングターゲットは、ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有した酸化タングステンの焼結体であり、前記ＷＯ２相の組織中の割合が、５％以上であることを特徴とする。
このスパッタリングターゲットでは、ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有した酸化タングステンの焼結体であり、ＷＯ２相の組織中の割合が、５％以上であるので、半導体であるＷＯ２相と金属伝導性を示すＷ１８Ｏ４９相とが混在して高い導電性を得ることができる。 Therefore, the present invention has been obtained from the above findings, and the following configuration has been adopted in order to solve the above problems. That is, the sputtering target of the first invention is a tungsten oxide sintered body having a structure composed of two or more phases of WO 2 phase and W 18 O 49 phase, and the proportion of the WO 2 phase in the structure is 5% or more.
This sputtering target is a tungsten oxide sintered body having a structure composed of two or more phases of WO 2 phase and W 18 O 49 phase, and the proportion of the WO 2 phase in the structure is 5% or more. The WO 2 phase, which is a semiconductor, and the W 18 O 49 phase exhibiting metal conductivity can be mixed to obtain high conductivity.

第２の発明のスパッタリングターゲットは、第１の発明において、前記焼結体の密度が、５．０ｇ／ｃｍ３以上であり、前記焼結体の比抵抗が、３００Ｋで１×１０−３Ω・ｃｍ以下であることを特徴とする。
すなわち、このスパッタリングターゲットでは、焼結体の密度が、５．０ｇ／ｃｍ３以上であり、焼結体の比抵抗が、３００Ｋで１×１０−３Ω・ｃｍ以下であるので、高密度および高強度であり、機械加工性が向上すると共に高い導電性も有するため良好なＤＣスパッタが可能になる。 A sputtering target according to a second invention is the sputtering target according to the first invention, wherein the density of the sintered body is 5.0 g / cm 3 or more, and the specific resistance of the sintered body is 1 × 10 −3 Ω at 300K. -It is characterized by being cm or less.
That is, in this sputtering target, the density of the sintered body is 5.0 g / cm 3 or more, and the specific resistance of the sintered body is 1 × 10 −3 Ω · cm or less at 300K. High strength, improved machinability and high electrical conductivity make it possible to perform good DC sputtering.

第３の発明のスパッタリングターゲットは、第１又は第２の発明において、前記ＷＯ２相の組織中の割合が、６０％以下であることを特徴とする。
すなわち、このスパッタリングターゲットでは、ＷＯ２相の組織中の割合が６０％以下であるので、比抵抗の増大を抑制することができる。 The sputtering target of the third invention is characterized in that, in the first or second invention, the proportion of the WO 2 phase in the structure is 60% or less.
That is, in this sputtering target, since the ratio in the structure of the WO 2 phase is 60% or less, an increase in specific resistance can be suppressed.

第３の発明のスパッタリングターゲットは、第１から第３の発明のいずれかにおいて、前記ＷＯ２相と前記Ｗ１８Ｏ４９相との組織中の最大粒径が、５０μｍ未満であることを特徴とする。
すなわち、このスパッタリングターゲットでは、ＷＯ２相とＷ１８Ｏ４９相との組織中の最大粒径が５０μｍ未満であるので、比抵抗の増大を抑制することができる。 The sputtering target of the third invention is characterized in that, in any of the first to third inventions, the maximum particle size in the structure of the WO 2 phase and the W 18 O 49 phase is less than 50 μm. To do.
That is, in this sputtering target, since the maximum particle size in the structure of the WO 2 phase and the W 18 O 49 phase is less than 50 μm, an increase in specific resistance can be suppressed.

第３の発明のスパッタリングターゲットの製造方法は、ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程を有し、前記酸化タングステン粉中の前記ＷＯ２の含有量を、５〜９５ｍｏｌ％とすることを特徴とする。
すなわち、このスパッタリングターゲットの製造方法では、ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程を有しているので、半導体であるＷＯ２相と金属伝導性を示すＷ１８Ｏ４９相とが混在して高い導電性を得ることができる。
なお、ＷＯ２の含有量を、５〜９５ｍｏｌ％とした理由は、５ｍｏｌ％未満である場合又は９５ｍｏｌ％を超える場合、比抵抗が１×１０−３Ω・ｃｍを超えて大きくなってしまうためである。 According to a third aspect of the present invention, there is provided a method for producing a sputtering target, comprising sintering a tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 in a vacuum by hot pressing to sinter tungsten oxide. And the content of the WO 2 in the tungsten oxide powder is 5 to 95 mol%.
That is, in this sputtering target manufacturing method, tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 is sintered in a hot press in a vacuum, and a tungsten oxide sintered body is obtained. Therefore, the WO 2 phase that is a semiconductor and the W 18 O 49 phase exhibiting metal conductivity can be mixed and high conductivity can be obtained.
The reason why the content of WO 2 is set to 5 to 95 mol% is that when it is less than 5 mol% or exceeds 95 mol%, the specific resistance becomes larger than 1 × 10 −3 Ω · cm. It is.

第４の発明のスパッタリングターゲットの製造方法は、第３の発明において、前記ホットプレス時の保持温度を、８５０〜１４００℃とすることを特徴とする。
すなわち、このスパッタリングターゲットの製造方法では、ホットプレス時の保持温度を、８５０〜１４００℃とすることで、比抵抗が低く高強度のターゲットを得ることができる。なお、ホットプレス時の保持温度を上記範囲に設定した理由は、８５０℃未満であると、十分な密度が得られず高強度が得られないためであり、１４００℃を超えると、融点が１４７３℃であるＷＯ２が溶け出すおそれがあるためである。 The sputtering target manufacturing method of the fourth invention is characterized in that, in the third invention, the holding temperature during the hot pressing is 850 to 1400 ° C.
That is, in this sputtering target manufacturing method, by setting the holding temperature at the time of hot pressing to 850 to 1400 ° C., a target with low specific resistance and high strength can be obtained. The reason why the holding temperature at the time of hot pressing is set in the above range is that if it is less than 850 ° C., a sufficient density cannot be obtained and a high strength cannot be obtained. This is because there is a possibility that WO 2 at a temperature may melt.

本発明によれば、以下の効果を奏する。
すなわち、本発明に係るスパッタリングターゲットの製造方法によれば、ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程を有しているので、半導体であるＷＯ２相と金属伝導性を示すＷ１８Ｏ４９相とが混在して高い導電性を得ることができる。したがって、この製法で得られた本発明のスパッタリングターゲットは、ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有した酸化タングステンの焼結体であり、ＷＯ２相の組織中の割合が、５％以上であるので、このターゲットを用いることで、高い導電性により生産性の高いＤＣスパッタができ、良好にＷＯｘ膜を成膜することができる。 The present invention has the following effects.
That is, according to the method for producing a sputtering target according to the present invention, tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 is sintered in a hot press in a vacuum, and tungsten oxide is obtained. Therefore, a high conductivity can be obtained by mixing the WO 2 phase, which is a semiconductor, and the W 18 O 49 phase exhibiting metal conductivity. Therefore, the sputtering target of the present invention obtained in this process is a sintered body of tungsten oxide having a composed of two or more phases structure of WO 2 phase and W 18 O 49 phase, WO 2 phase tissues Therefore, by using this target, DC sputtering with high productivity can be performed due to high conductivity, and a WO x film can be formed satisfactorily.

本発明に係るスパッタリングターゲットおよびその製造方法の実施例３において、作製したスパッタリングターゲットの断面組織を電子線マイクロアナライザ（ＥＰＭＡ）により測定した組成像（ＣＯＭＰ像）に模式的な説明図を追加した図である。In Example 3 of the sputtering target which concerns on this invention, and its manufacturing method, the figure which added typical explanatory drawing to the composition image (COMP image) which measured the cross-sectional structure | tissue of the produced sputtering target with the electron beam microanalyzer (EPMA) It is. 本発明に係るスパッタリングターゲットおよびその製造方法の実施例９において、作製したスパッタリングターゲットの断面組織をＥＰＭＡにより測定した組成像（ＣＯＭＰ像）に模式的な説明図を追加した図である。In Example 9 of the sputtering target which concerns on this invention, and its manufacturing method, it is the figure which added typical explanatory drawing to the composition image (COMP image) which measured the cross-sectional structure | tissue of the produced sputtering target by EPMA. 本発明に係る実施例１〜３において、ホットプレスの保持温度に対する焼結体の密度を示すグラフである。In Examples 1-3 which concern on this invention, it is a graph which shows the density of the sintered compact with respect to the holding temperature of a hot press. 本発明に係る実施例１〜３において、ホットプレスの保持温度に対する焼結体の比抵抗を示すグラフである。In Examples 1-3 which concern on this invention, it is a graph which shows the specific resistance of the sintered compact with respect to the holding temperature of a hot press. 本発明に係る実施例１〜３及び９において、ＥＰＭＡによる組成像（ＣＰ）、タングステン（Ｗ）の元素マッピング像および酸素（Ｏ）の元素マッピング像を示す写真である。In Examples 1-3 and 9 which concern on this invention, it is a photograph which shows the composition image (CP) by EPMA, the elemental mapping image of tungsten (W), and the elemental mapping image of oxygen (O). 本発明に係る実施例３において、作製したスパッタリングターゲットのＸ線回折（ＸＲＤ）結果を示すグラフである。In Example 3 which concerns on this invention, it is a graph which shows the X-ray-diffraction (XRD) result of the produced sputtering target. 本発明に係る実施例９において、作製したスパッタリングターゲットのＸＲＤ結果を示すグラフである。In Example 9 which concerns on this invention, it is a graph which shows the XRD result of the produced sputtering target.

以下、本発明のスパッタリングターゲットおよびその製造方法の一実施形態を、図１を参照して説明する。   Hereinafter, one embodiment of the sputtering target and the manufacturing method thereof of the present invention will be described with reference to FIG.

本実施形態のスパッタリングターゲットの製造方法は、ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を作製する工程と、該酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程とを有している。
また、酸化タングステン粉を作製する工程において、酸化タングステン粉中のＷＯ２の含有量を、５〜９５ｍｏｌ％としている。 The manufacturing method of the sputtering target of this embodiment includes a step of producing tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 , and hot-pressing the tungsten oxide powder in a vacuum. And a step of sintering to form a sintered body of tungsten oxide.
Moreover, in the process of producing the tungsten oxide powder, the content of WO 2 in the tungsten oxide powder is set to 5 to 95 mol%.

すなわち、まずＷＯ３粉を、還元処理して半導体のＷＯ２粉と金属伝導性のＷ１８Ｏ４９粉との混合粉とし、全体としてＷＯ２の含有量が５〜９５ｍｏｌ％となるＷＯｘ粉（酸化タングステン粉：Ｘ＝２〜３）とする。
上記還元処理としては、例えばＷＯ３粉を水素雰囲気中で所定時間、所定温度で加熱して水素化還元を行う。この水素化還元では、ＷＯ３からＷＯ２．９、ＷＯ２．７２（Ｗ１８Ｏ４９）、ＷＯ２、Ｗの順に還元が進行し、その過程でＷＯ２及びＷ１８Ｏ４９も得られる。 That is, the first WO 3 powder, and reduction treatment by a mixed powder of a semiconductor of WO 2 powder and metallic conductivity W 18 O 49 powders, WO x powder content of WO 2 is 5～95Mol% overall (Tungsten oxide powder: X = 2 to 3).
As the reduction treatment, for example, WO 3 powder is heated at a predetermined temperature for a predetermined time in a hydrogen atmosphere to perform hydrogenation reduction. In this hydrogenation reduction, the reduction proceeds in the order of WO 3 to WO 2.9 , WO 2.72 (W 18 O 49 ), WO 2 , W, and WO 2 and W 18 O 49 are also obtained in the process.

なお、このＷＯｘ粉のｘの定量方法は、まずＷＯｘ粉のサンプリングを行い、重量測定をした後、大気中において８００℃で１時間焼成し、再び重量測定を行う。そして、全てＷＯ３粉となっていることをＸ線回折法（ＸＲＤ）で確認し、Ｗ（タングステン）量を以下の式により計算する。そして、求めたＷ量から酸素（Ｏ）の割合をｘとして算出する。
Ｗの重量＝上記焼成後の重量×ＭｗＷ／ＭｗＷＯ３
Ｗ（ｗｔ％）＝（Ｗの重量／焼成前のＷＯｘの重量）×１００
（ＭｗＷ：Ｗの原子量（１８３．８５）、ＭｗＷＯ３：ＷＯ３の原子量（２３１．８５）） In addition, the method of quantifying x in this WO x powder first samples the WO x powder and measures the weight, then calcines it in the atmosphere at 800 ° C. for 1 hour, and then performs the weight measurement again. And it is confirmed by X-ray diffraction method (XRD) that it is all WO 3 powder, and the amount of W (tungsten) is calculated by the following formula. Then, the ratio of oxygen (O) is calculated as x from the obtained amount of W.
W weight = weight after the above baking × Mw W / Mw WO3
W (wt%) = (weight of W / weight of WO x before firing) × 100
(Mw W : atomic weight of W (183.85), Mw WO3 : atomic weight of WO 3 (231.85))

また、ＷＯｘ粉をＸＲＤにて観察することで、ＷＯ２相に帰属する回折ピークとＷ１８Ｏ４９相に帰属する回折ピークとを確認し、ＷＯ２とＷ１８Ｏ４９との含有を確認する。なお、ＷＯ３に帰属する回折ピークが観察されないことが好ましい。 Moreover, by observing the WO x powder with XRD, the diffraction peak attributed to the WO 2 phase and the diffraction peak attributed to the W 18 O 49 phase were confirmed, and the inclusion of WO 2 and W 18 O 49 was confirmed. To do. It is preferable that the diffraction peak assigned to WO 3 is not observed.

次に、得られたＷＯｘ粉とジルコニアボールとをポリ容器（ポリエチレン製ポット）に入れ、例えば乾式ボールミル装置にて混合する。この後、得られた粉末を、所定の目開きの篩にかけて分級し、８５０℃〜１４００℃にて２時間、１００〜３５０ｋｇｆ／ｃｍ２の圧力にて真空中でホットプレスし、スパッタリングターゲットとする。
この製造方法により作製されたＷＯｘのスパッタリングターゲットは、焼結体の密度が、５．０ｇ／ｃｍ３以上となり、焼結体の比抵抗が、３００Ｋで１×１０−３Ω・ｃｍ以下となる。 Next, the obtained WO x powder and zirconia balls are put in a plastic container (polyethylene pot) and mixed, for example, in a dry ball mill apparatus. Thereafter, the obtained powder is classified through a sieve having a predetermined opening, and hot-pressed in vacuum at a pressure of 100 to 350 kgf / cm 2 at 850 ° C. to 1400 ° C. for 2 hours to obtain a sputtering target. .
The sputtering target of WO x produced by this manufacturing method has a sintered body density of 5.0 g / cm 3 or more, and a specific resistance of the sintered body of 1 × 10 −3 Ω · cm or less at 300K. Become.

このように、本実施形態のスパッタリングターゲットの製造方法では、ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程を有しているので、半導体であるＷＯ２相と金属伝導性を示すＷ１８Ｏ４９相とが混在して高い導電性を得ることができる。
また、ホットプレス時の保持温度を、８５０〜１４００℃とすることで、比抵抗が低く高強度のターゲットを得ることができる。 Thus, in the manufacturing method of the sputtering target of this embodiment, tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 is sintered by hot pressing in vacuum, and tungsten oxide is obtained. Therefore, a high conductivity can be obtained by mixing the WO 2 phase, which is a semiconductor, and the W 18 O 49 phase exhibiting metal conductivity.
In addition, by setting the holding temperature during hot pressing to 850 to 1400 ° C., it is possible to obtain a target with low specific resistance and high strength.

このように作製された本実施形態のスパッタリングターゲットでは、上述したように、ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有した酸化タングステンの焼結体であり、ＷＯ２相の組織中の割合が、５％以上であるので、高い導電性により生産性の高いＤＣスパッタができ、良好にＷＯｘ膜を成膜することができる。
特に、焼結体の密度が、５．０ｇ／ｃｍ３以上であり、焼結体の比抵抗が、３００Ｋで１×１０−３Ω・ｃｍ以下であるので、高密度および高強度であり、機械加工性が向上すると共に高い導電性も有するため良好なＤＣスパッタが可能になる。 As described above, the sputtering target of the present embodiment manufactured in this way is a tungsten oxide sintered body having a structure composed of two or more phases of WO 2 phase and W 18 O 49 phase, and WO 2 Since the proportion of the phase in the structure is 5% or more, DC sputtering with high productivity can be performed due to high conductivity, and a WO x film can be formed satisfactorily.
In particular, since the density of the sintered body is 5.0 g / cm 3 or more and the specific resistance of the sintered body is 1 × 10 −3 Ω · cm or less at 300 K, it has high density and high strength, Since the machinability is improved and it has high conductivity, good DC sputtering is possible.

また、ＷＯ２相の組織中の割合を６０％以下とすることで、比抵抗の増大を抑制することができる。
さらに、ＷＯ２相とＷ１８Ｏ４９相との組織中の最大粒径を５０μｍ未満とすることでも、比抵抗の増大を抑制することができる。 Further, the ratio in the tissue of the WO 2 phase by 60% or less, it is possible to suppress an increase in resistivity.
Furthermore, the increase in specific resistance can also be suppressed by setting the maximum particle size in the structure of the WO 2 phase and the W 18 O 49 phase to less than 50 μm.

上記本実施形態に基づいて実際に作製したスパッタリングターゲットおよびその製造方法の実施例について、評価を行った結果を説明する。
まず、上述したＷＯ３粉の還元処理によりＷＯ２粉とＷ１８Ｏ４９粉とからなるＷＯｘ粉を作製した。本実施例では、還元の度合いを調整することにより、表１に示すように、ｘ＝２．６２のＷＯｘ粉（平均粒径２．４μｍ）と、ｘ＝２．５７のＷＯｘ粉（平均粒径１９．０μｍ）とした。また、ＷＯ２粉とＷＯ３粉との乾式混合によりＷＯｘ粉も作製した。混合の度合いを調整することによりｘ＝２．５０のＷＯｘ粉（平均粒径３．２μｍ）を得た。これら３種類を、それぞれホットプレス時の保持温度：８５０，９００，１２００℃で作製した。 The result of having evaluated the sputtering target actually produced based on the said embodiment and the Example of the manufacturing method is demonstrated.
First, WO x powder composed of WO 2 powder and W 18 O 49 powder was produced by the above-described reduction treatment of WO 3 powder. In this example, by adjusting the degree of reduction, as shown in Table 1, x = 2.62 WO x powder (average particle size 2.4 μm) and x = 2.57 WO x powder ( The average particle size was 19.0 μm. Also, to prepare also WO x powder by dry mixing with WO 2 powder and WO 3 powder. By adjusting the degree of mixing, WO x powder (average particle diameter 3.2 μm) of x = 2.50 was obtained. These three types were produced at holding temperatures during hot pressing: 850, 900, and 1200 ° C., respectively.

このＷＯｘ粉を、表１に示すように、ホットプレス時の保持温度を変えた条件において真空中でホットプレスを２時間行い、本発明の実施例１〜９のスパッタリングターゲットを得た。
なお、比較例として、ＷＯ３粉のみ（ｘ＝３．００）又はＷＯ２粉のみ（ｘ＝２．００）の原料粉を用いて、表１に示す条件において真空中でホットプレスを２時間行い、本発明の比較例３〜５のスパッタリングターゲットを得た。 As shown in Table 1, this WO x powder was hot-pressed in vacuum for 2 hours under the conditions of changing the holding temperature at the time of hot pressing to obtain the sputtering targets of Examples 1 to 9 of the present invention.
In addition, as a comparative example, using a raw material powder of only WO 3 powder (x = 3.00) or only WO 2 powder (x = 2.00), hot pressing was performed in a vacuum for 2 hours under the conditions shown in Table 1. It performed and the sputtering target of Comparative Examples 3-5 of this invention was obtained.

＜評価＞
これらの実施例および比較例について、スパッタリングターゲット（焼結体）の密度および比抵抗について測定した結果を表１に示す。また、本発明の実施例１〜３において、ホットプレスの保持温度と得られたターゲットの密度との関係を図３に示すと共に、ホットプレスの保持温度と得られたターゲットの比抵抗との関係を図４に示す。
なお、比抵抗は、温度３００Ｋにおいて三菱ガス化学製四探針抵抗測定計ロレスターで測定することによって求めた。 <Evaluation>
Table 1 shows the results of measuring the density and specific resistance of the sputtering target (sintered body) for these examples and comparative examples. In Examples 1 to 3 of the present invention, the relationship between the holding temperature of the hot press and the density of the obtained target is shown in FIG. 3, and the relationship between the holding temperature of the hot press and the specific resistance of the obtained target. Is shown in FIG.
In addition, the specific resistance was calculated | required by measuring with the four-probe resistance measuring device Lorestar made from Mitsubishi Gas Chemical at the temperature of 300K.

また、組織中のＷＯ２相の割合及び最大粒径については、以下のように測定した。
まず、組織観察をＥＰＭＡ（フィールドエミッション型電子線プローブマイクロアナライザー）を用い、元素の組成分布を示す元素分布像を観察した。また、ＥＰＭＡでの観察において、０．００５ｍｍ２の観察視野の写真（５００倍）を５枚撮影し、その中で観察可能なＷＯ２相の面積を測定し、観察領域全体に対する面積比を計算した。 Further, the ratio of the WO 2 phase in the structure and the maximum particle size were measured as follows.
First, using an EPMA (Field Emission Electron Beam Probe Microanalyzer) for structure observation, an element distribution image showing an element composition distribution was observed. In addition, in the observation with EPMA, five photographs (500 times magnification) of the observation field of 0.005 mm 2 were taken, the area of the WO 2 phase that can be observed was measured, and the area ratio to the entire observation area was calculated. did.

なお、ＷＯ２相の面積比は、例えば、以下（ａ）〜（ｄ）の手順により測定することができる。
（ａ）ＥＰＭＡにより５００倍のＣＯＭＰＯ像（６０μｍ×８０μｍ）１０枚を撮影する。
（ｂ）市販の画像解析ソフトにより、撮影した画像をモノクロ画像に変換すると共に、単一しきい値を使用して二値化する。二値化とは、画像の各画素の輝度（明るさ）に対してある“しきい値”を設け、しきい値以下ならば“０”、しきい値より大きければ“１”として、領域を区別化することである。なお、画像解析ソフトとしては、例えば、ＷｉｎＲｏｏｆ Ｖｅｒ５．６．２（三谷商事社製）などが利用できる。二値化とは、画像の各画素の輝度（明るさ）に対してある“しきい値”を設け、しきい値以下ならば“０”、しきい値より大きければ“１”として、領域を区別化することである。
（ｃ）この画像すべてを選択しない最大のしきい値を１００％とし、３０〜６０％のしきい値を使用しＷＯ２相の領域を選択する。この操作によりＷＯ２相の面積から観察領域全体に対する面積比を算出した。
（ｄ）ＷＯ２相の最大粒径は、撮影した５枚の写真のうち最も面積の大きいＷＯ２相を選び、そのＷＯ２相の最大幅を最大粒径として計測した。 The area ratio of the WO 2 phase can be measured, for example, by the following procedures (a) to (d).
(A) Take ten 500 × COMPO images (60 μm × 80 μm) with EPMA.
(B) Using a commercially available image analysis software, the captured image is converted into a monochrome image and binarized using a single threshold value. In binarization, a certain “threshold value” is set for the luminance (brightness) of each pixel of an image. Is to differentiate. As image analysis software, for example, WinRoof Ver 5.6.2 (manufactured by Mitani Corporation) can be used. In binarization, a certain “threshold value” is set for the luminance (brightness) of each pixel of an image. Is to differentiate.
(C) The maximum threshold value that does not select all of these images is set to 100%, and a threshold value of 30 to 60% is used to select the WO 2 phase region. By this operation, the area ratio with respect to the entire observation region was calculated from the area of the WO 2 phase.
Maximum particle size of (d) WO 2 phase, select the larger WO 2 phases largest area out of five photographs taken, and measured the maximum width of the WO 2 phase as a maximum particle size.

これらの結果からわかるように、ＷＯ３粉のみで作製された比較例３，４では、導電性が無く比抵抗の測定ができなかった。また、ＷＯ２粉のみで作製された比較例５では、比抵抗が３００Ｋで３．１０×１０−３Ω・ｃｍと高かった。これらに対し、本発明の実施例１〜９では、いずれも密度が５．０ｇ／ｃｍ３以上であると共に比抵抗が３００Ｋで１×１０−３Ω・ｃｍ以下となっている。また、ホットプレスの保持温度が高いほど、密度が高くなると共に、比抵抗が低下している。 As can be seen from these results, Comparative Examples 3 and 4 produced using only WO 3 powder had no conductivity and could not be measured for specific resistance. In Comparative Example 5, which is formed using only the WO 2 powder, the specific resistance was as high as 3.10 × 10 -3 Ω · cm at 300K. On the other hand, in Examples 1 to 9 of the present invention, the density is 5.0 g / cm 3 or more and the specific resistance is 300 × K and 1 × 10 −3 Ω · cm or less. In addition, the higher the hot press holding temperature, the higher the density and the lower the specific resistance.

なお、組織中のＷＯ２相の最大粒径が５０μｍ以上である実施例１１と、ＷＯ２相の組織中の割合が６０％を超えている実施例１２とは、どちらも比較例１，２，５よりも比抵抗が低いが、１×１０−３Ω・ｃｍを超えてしまっている。また、組織中のＷＯ２相の割合が５％未満である比較例１，２では、いずれも比抵抗が３×１０−３Ω・ｃｍを超えている。 Incidentally, in Example 11 the maximum particle size of the WO 2 phase in the tissue is 50μm or more, as in Example 12 the ratio in the tissue of the WO 2 phase exceeds 60%, both Comparative Examples 1 and 2 , 5 is lower than the specific resistance, but exceeds 1 × 10 −3 Ω · cm. Moreover, in Comparative Examples 1 and 2 in which the proportion of the WO 2 phase in the structure is less than 5%, the specific resistance exceeds 3 × 10 −3 Ω · cm.

次に、実施例１〜３及び９について、電子線マイクロアナライザ（ＥＰＭＡ）による組成像（ＣＰ）、タングステン（Ｗ）の元素マッピング像および酸素（Ｏ）の元素マッピング像を図５示す。ここで、ＥＰＭＡによる元素マッピング像は、本来カラー像であるが、白黒像に変換して記載しているため、濃淡の淡い部分（比較的白い部分）が所定元素の濃度が高い部分となっている。   Next, for Examples 1 to 3 and 9, a composition image (CP), an element mapping image of tungsten (W), and an element mapping image of oxygen (O) by an electron beam microanalyzer (EPMA) are shown in FIG. Here, the element mapping image by EPMA is originally a color image, but is described by converting it into a black and white image. Therefore, the light and dark portion (relatively white portion) becomes a portion where the concentration of the predetermined element is high. Yes.

図５からわかるように、本発明の実施例１〜３及び９では、ホットプレスの保持温度が高いほど空洞が少なくなっており、これにより密度が向上すると共に、比抵抗も低下していると思われる。特に、ホットプレスの保持温度が１２００℃の実施例３では、Ｗ１８Ｏ４９相が粒状のＷＯ２相の周囲を覆うようにマトリックスとなっている。
なお、実施例３と実施例９とについては、拡大した組成像を、図１および図２に示す。 As can be seen from FIG. 5, in Examples 1 to 3 and 9 of the present invention, the higher the holding temperature of the hot press, the fewer the cavities, thereby improving the density and reducing the specific resistance. Seem. In particular, in Example 3 where the holding temperature of the hot press is 1200 ° C., the W 18 O 49 phase is a matrix so as to cover the periphery of the granular WO 2 phase.
In addition, about Example 3 and Example 9, the enlarged composition image is shown in FIG.1 and FIG.2.

これら図１および図２からわかるように、本発明の実施例３では、金属伝導性を示すマグネリ相のＷ１８Ｏ４９相の素地中に、半導体特性を示す粒状（島状）のＷＯ２相が分散分布している組織となっている。また、本発明の実施例９では、ＷＯ２相とＷ１８Ｏ４９相との間に半導体のＷＯｘ相（Ｘ＝２〜２．７２）が介在した組織となっている。すなわち、実施例３及び実施例９では、共にＷＯ２相間に介在するＷ１８Ｏ４９相によって良好な導電性が得られており、特に実施例９では、ＷＯ２相間により多く介在するＷ１８Ｏ４９相によって十分な電気伝導パスが確保されることで、さらに高い導電性が得られ、比抵抗が大幅に低減されていると考えられる。 As can be seen from FIGS. 1 and 2, in Example 3 of the present invention, a granular (island-like) WO 2 phase exhibiting semiconductor characteristics in a W 18 O 49 phase base material of a magnetic phase exhibiting metal conductivity. Is a distributed organization. Further, Example 9 of the present invention has a structure in which a WO x phase (X = 2 to 2.72) of a semiconductor is interposed between a WO 2 phase and a W 18 O 49 phase. That is, in Example 3 and Example 9, good electrical conductivity is obtained by the W 18 O 49 phase intervening between the WO 2 phases. In particular, in Example 9, W 18 O intervening more between the WO 2 phases. By securing a sufficient electric conduction path by the 49 phases, it is considered that higher conductivity is obtained and the specific resistance is greatly reduced.

なお、文献によれば、ＷＯ３の比抵抗は３００Ｋで２．０×１０−３Ω・ｃｍ（化学大辞典３巻）、ＷＯ２の比抵抗は３００Ｋで２．９×１０−３Ω・ｃｍ（理化学事典第５版）、Ｗ１８Ｏ４９の比抵抗は３００Ｋで２．７５×１０−３Ω・ｃｍ（理化学事典第５版）とされているのに対し、本発明の各実施例では比抵抗が３００Ｋで１×１０−３Ω・ｃｍ以下と低くなるのは、金属−半導体接合による効果が生じていると考えられる。すなわち、ＷＯ２は半導体特性を示し、Ｗ１８Ｏ４９は金属伝導性を示すが、図１に示すように、焼結体の組織がＷＯ２相とＷ１８Ｏ４９相との接合により金属−半導体接合のようになっており、半導体側のエネルギー準位に変化が生じて金属側への電子移動が起こった結果、金属での自由電子が増加して比抵抗が劇的に低下していると考えられる。 According to the literature, the specific resistance of WO 3 is 2.0 × 10 −3 Ω · cm at 300K (Volume of Chemical Dictionary 3), and the specific resistance of WO 2 is 2.9 × 10 −3 Ω · cm at 300K. The specific resistance of cm (physical and chemical encyclopedia 5th edition) and W 18 O 49 is 2.75 × 10 −3 Ω · cm (physical and chemical encyclopedia 5th edition) at 300K, whereas each embodiment of the present invention Then, it is thought that the specific resistance is as low as 1 × 10 −3 Ω · cm or less at 300K because of the effect of metal-semiconductor junction. That is, WO 2 shows semiconductor characteristics and W 18 O 49 shows metal conductivity. However, as shown in FIG. 1, the structure of the sintered body is formed by bonding between the WO 2 phase and the W 18 O 49 phase. It is like a semiconductor junction. As a result of a change in the energy level on the semiconductor side and electron transfer to the metal side, the free electrons in the metal increase and the specific resistance decreases dramatically. it is conceivable that.

次に、実施例３および実施例９について、作製したスパッタリングターゲットのＸ線回折（ＸＲＤ）結果を図６および図７に示す。
なお、このＸ線回折の測定条件は、以下のとおりである。
試料の準備：試料はＳｉＣ−Ｐａｐｅｒ（ｇｒｉｔ １８０）にて湿式研磨、乾燥の後、乳鉢で粉砕後２５０μｍ以下の粉を測定試料とした。
装置：理学電気社製（ＲＩＮＴ−Ｕｌｔｉｍａ／ＰＣ）
管球：Ｃｕ
管電圧：４０ｋＶ
管電流：５０ｍＡ
走査範囲（２θ）：５°〜８０°
スリットサイズ：発散（ＤＳ）２／３度、散乱（ＳＳ）２／３度、受光（ＲＳ）０.８ｍｍ
測定ステップ幅：２θで０.０２度
スキャンスピード：毎分２度
試料台回転スピード：３０ｒｐｍ Next, the X-ray diffraction (XRD) results of the produced sputtering targets for Example 3 and Example 9 are shown in FIGS. 6 and 7.
The measurement conditions for this X-ray diffraction are as follows.
Preparation of sample: The sample was wet-polished with SiC-Paper (grit 180), dried, pulverized with a mortar, and powder of 250 μm or less was used as a measurement sample.
Equipment: Rigaku Electric (RINT-Ultima / PC)
Tube: Cu
Tube voltage: 40 kV
Tube current: 50 mA
Scanning range (2θ): 5 ° -80 °
Slit size: Divergence (DS) 2/3 degree, Scattering (SS) 2/3 degree, Light reception (RS) 0.8mm
Measurement step width: 0.02 degrees at 2θ Scan speed: 2 degrees per minute Sample stage rotation speed: 30 rpm

これらＸ線回折の結果からわかるように、いずれも２θ＝２５．９°の（１１０）面のピークをメインピークとするＷＯ２相に帰属する回折ピークと、２θ＝２３．５°の（０１０）面のピークをメインピークとするＷ１８Ｏ４９相に帰属する回折ピークとがあり、ＷＯ２とＷ１８Ｏ４９とが確認された。
なお、いずれの実施例のスパッタリングターゲットにおいても、ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有していることが確認された。 As can be seen from these X-ray diffraction results, the diffraction peak attributed to the WO 2 phase having the (110) plane peak at 2θ = 25.9 ° as the main peak, and 2θ = 23.5 ° (010). ) And a diffraction peak attributed to the W 18 O 49 phase having a main peak as a peak, and WO 2 and W 18 O 49 were confirmed.
In addition, it was confirmed that the sputtering target of any Example has a structure composed of two or more phases of WO 2 phase and W 18 O 49 phase.

なお、本発明の技術範囲は上記実施形態および上記実施例に限定されるものではなく、本発明の趣旨を逸脱しない範囲において種々の変更を加えることが可能である。   The technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the spirit of the present invention.

Claims (6)

ＷＯ２相とＷ１８Ｏ４９相との２相以上からなる組織を有した酸化タングステンの焼結体であり、
前記ＷＯ２相の組織中の割合が、５％以上であることを特徴とするスパッタリングターゲット。 A tungsten oxide sintered body having a structure composed of two or more phases of a WO 2 phase and a W 18 O 49 phase;
The sputtering target characterized in that the proportion of the WO 2 phase in the structure is 5% or more. 請求項１に記載のスパッタリングターゲットにおいて、
前記焼結体の密度が、５．０ｇ／ｃｍ３以上であり、
前記焼結体の比抵抗が、３００Ｋで１×１０−３Ω・ｃｍ以下であることを特徴とするスパッタリングターゲット。 The sputtering target according to claim 1,
The density of the sintered body is 5.0 g / cm 3 or more,
The specific resistance of the sintered body is 1 × 10 −3 Ω · cm or less at 300K. 請求項１又は２に記載のスパッタリングターゲットにおいて、
前記ＷＯ２相の組織中の割合が、６０％以下であることを特徴とするスパッタリングターゲット。 In the sputtering target according to claim 1 or 2,
The sputtering target, wherein the proportion of the WO 2 phase in the structure is 60% or less. 請求項１から３のいずれか一項に記載のスパッタリングターゲットにおいて、
前記ＷＯ２相と前記Ｗ１８Ｏ４９相との組織中の最大粒径が、５０μｍ未満であることを特徴とするスパッタリングターゲット。 In the sputtering target as described in any one of Claim 1 to 3,
The sputtering target, wherein the maximum particle size in the structure of the WO 2 phase and the W 18 O 49 phase is less than 50 μm. ＷＯ２と、Ｗ１８Ｏ４９及びＷＯ３の少なくとも一方とを含有した酸化タングステン粉を作製する工程と、
該酸化タングステン粉を真空中でホットプレスにて焼結し、酸化タングステンの焼結体とする工程とを有し、
前記酸化タングステン粉中の前記ＷＯ２の含有量を、５〜９５ｍｏｌ％とすることを特徴とするスパッタリングターゲットの製造方法。 Producing a tungsten oxide powder containing WO 2 and at least one of W 18 O 49 and WO 3 ;
Sintering the tungsten oxide powder in a hot press in a vacuum to form a sintered body of tungsten oxide,
Manufacturing method of a sputtering target, wherein a content of the WO 2 of the tungsten oxide powder during, and 5~95mol%. 請求項５に記載のスパッタリングターゲットの製造方法において、
前記ホットプレス時の保持温度を、８５０〜１４００℃とすることを特徴とするスパッタリングターゲットの製造方法。 In the manufacturing method of the sputtering target of Claim 5,
A method for producing a sputtering target, wherein a holding temperature during the hot pressing is 850 to 1400 ° C.
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