JPWO2009028641A1 - Zinc sulfide molding and method for producing the same - Google Patents

Zinc sulfide molding and method for producing the same Download PDF

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JPWO2009028641A1
JPWO2009028641A1 JP2009530191A JP2009530191A JPWO2009028641A1 JP WO2009028641 A1 JPWO2009028641 A1 JP WO2009028641A1 JP 2009530191 A JP2009530191 A JP 2009530191A JP 2009530191 A JP2009530191 A JP 2009530191A JP WO2009028641 A1 JPWO2009028641 A1 JP WO2009028641A1
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sulfide
zinc
zinc sulfide
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JP5451393B2 (en
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伸彦 木村
伸彦 木村
真人 岡本
真人 岡本
一真 井上
一真 井上
雅 白波瀬
雅 白波瀬
一彦 前川
一彦 前川
岩崎　秀治
秀治 岩崎
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Kuraray Co Ltd
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Abstract

本発明の課題は、工業的に容易な方法で、1に近い硫黄／亜鉛比を有する硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物を含む複合硫化物の成型体およびその製造方法を提供することにあり、かかる課題は、硫黄／亜鉛の比が０．９以上である硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物からなる成型体とその製造方法によって解決することができる。An object of the present invention is to provide a composite sulfide containing zinc sulfide or zinc sulfide having a sulfur / zinc ratio close to 1 and a sulfide containing at least one element of silver, copper, manganese and rare earth in an industrially easy manner. It is an object of the present invention to provide a molded article and a method for producing the same, and the problem is that zinc sulfide or zinc sulfide having a sulfur / zinc ratio of 0.9 or more and at least one element of silver, copper, manganese, and rare earth This can be solved by a molded article made of a composite sulfide containing sulfide containing sulfur and a manufacturing method thereof.

Description

本発明は、無機ＥＬ素子形成用ターゲット材としての硫化亜鉛成型体およびその製造方法に関する。更に詳しくは、硫黄／亜鉛の比が０．９以上である硫化亜鉛を主成分とする成型体およびその製造方法に関する。  The present invention relates to a zinc sulfide molded body as a target material for forming an inorganic EL element and a method for producing the same. More specifically, the present invention relates to a molded body mainly composed of zinc sulfide having a sulfur / zinc ratio of 0.9 or more and a method for producing the same.

これまでＥＬ素子の発光層の形成には、スパッタリング法や電子ビーム蒸着法といった製膜技術が一般的に使用されてきた。そしてこれらの製膜技術によって発光層を形成する際のターゲット材となる硫化亜鉛成型体の製造方法として、硫化亜鉛粉末に発光性元素を混合した硫化亜鉛粉末をホットプレス法にて成型する方法、または冷間プレス法にて成型した後、焼成炉によって焼結させる方法などが開発されてきた。  Until now, film formation techniques such as sputtering and electron beam evaporation have generally been used to form a light emitting layer of an EL element. And as a method for producing a zinc sulfide molded body that becomes a target material when forming a light emitting layer by these film forming techniques, a method of molding zinc sulfide powder in which a luminescent element is mixed with zinc sulfide powder by a hot press method, Alternatively, a method of forming by a cold press method and then sintering in a firing furnace has been developed.

しかしながら、硫化亜鉛粉末は、結晶性が悪く、成型体の相対密度（嵩密度と理論密度との比）を高めることが難しい。例えば単純にホットプレス法で成型するだけの場合や、冷間プレスで予備成型し、単純に焼結するだけの成型方法では、得られる成型体の相対密度が６０〜７０％程度にしかならない。そのような相対密度の低い成型体を使用して電子ビーム蒸着などの方法で製膜する場合、硫化亜鉛成型体からガスが放出し、真空度の低下のみならず、発光層を構築できないなどの問題があった。  However, zinc sulfide powder has poor crystallinity and it is difficult to increase the relative density (ratio of bulk density to theoretical density) of the molded body. For example, in the case of simply molding by the hot press method or the molding method of simply performing the preliminary molding by the cold press and simply sintering, the relative density of the obtained molded body is only about 60 to 70%. When forming a film by a method such as electron beam vapor deposition using such a molded article having a low relative density, gas is released from the zinc sulfide molded article, and not only the degree of vacuum is lowered, but also a light emitting layer cannot be constructed. There was a problem.

そこで、硫化亜鉛と酸化ケイ素を混合し、ホットプレスすることで嵩密度を向上させる方法（特許文献１参照）や、バリウム成分を添加した硫化亜鉛粉末を用いて冷間プレスにより成型し、硫化水素ガス中で焼成成型する方法（特許文献２参照）が改良法として提案されている。更に、冷間プレスした成型体をホットプレスする方法（特許文献３参照）が知られている。  Therefore, a method of improving the bulk density by mixing zinc sulfide and silicon oxide and hot pressing (see Patent Document 1), or forming by cold pressing using zinc sulfide powder to which a barium component is added, and hydrogen sulfide. A method of firing and molding in gas (see Patent Document 2) has been proposed as an improved method. Furthermore, a method of hot pressing a cold pressed molded body (see Patent Document 3) is known.

しかしながら、特許文献１記載の方法では、多量の酸化ケイ素を入れて成型するため、相対密度は向上するが、ケイ素が製膜時に混入する。また、特許文献２においては、バリウムが混入するという問題が生じる。更に、特許文献２では、硫化水素中で焼成成型するために特殊な装置が必要になるという問題も生じる。また、特許文献3では特殊な材質の装置等は必要ないが、２つの装置を使用せねばならず、工数も多く煩雑であるという問題は解決できていない。
特開平１０−３２４９６８号公報 特開平２−５９４６３号公報 特開平５−３１０４６７号公報 However, in the method described in Patent Document 1, since a large amount of silicon oxide is added and molded, the relative density is improved, but silicon is mixed during film formation. Moreover, in patent document 2, the problem that barium mixes arises. Further, in Patent Document 2, there arises a problem that a special apparatus is required for firing and molding in hydrogen sulfide. Patent Document 3 does not require a special material device or the like, but two devices must be used, and the problem that the number of man-hours is complicated is not solved.
Japanese Patent Laid-Open No. 10-324968 JP-A-2-59463 JP-A-5-310467

したがって、本発明の目的は、工業的に有利な方法で、硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物を含む複合硫化物の成型体およびその製造方法を提供することにある。  Accordingly, an object of the present invention is to provide a composite sulfide molded article containing zinc sulfide or zinc sulfide and a sulfide containing at least one element of silver, copper, manganese and rare earth, and production thereof in an industrially advantageous manner. It is to provide a method.

本発明者らは、鋭意検討を重ね、1に近い硫黄／亜鉛比を有する硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物を含む複合硫化物の成型体とその製造方法によって上記目的を達成することを見出し、本発明に至った。すなわち、本発明は、以下のものを提供する。  The inventors of the present invention have made extensive studies and formed a composite sulfide containing zinc sulfide or zinc sulfide having a sulfur / zinc ratio close to 1 and a sulfide containing at least one element of silver, copper, manganese, and rare earth. It has been found that the above object can be achieved by the body and its production method, and the present invention has been achieved. That is, the present invention provides the following.

[１] 硫黄／亜鉛の比が０．９以上である硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物からなる成型体。  [1] A molded article made of a composite sulfide containing zinc sulfide or zinc sulfide having a sulfur / zinc ratio of 0.9 or more and a sulfide containing at least one element of silver, copper, manganese and rare earth.

[２] 該成型体の相対密度が０．９以上である[１]記載の成型体。  [2] The molded article according to [1], wherein the molded article has a relative density of 0.9 or more.

[３] 該成型体に含有される水分が５０ｐｐｍ以下である[１]または[２]記載の成型体。  [3] The molded product according to [1] or [2], wherein the molded product has a water content of 50 ppm or less.

[４] 該成型体に含有される硫酸イオンが５００ｐｐｍ以下である[１]〜[３]いずれかに記載の成型体。  [4] The molded body according to any one of [1] to [3], wherein sulfate ions contained in the molded body are 500 ppm or less.

[５] 粒径が１００μｍ以下であり、比表面積測定において、０．２ｍ２／ｇ〜５０ｍ２／ｇである硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物を７００℃以上１１００℃以下の温度下に加圧成型することを特徴とする硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物からなる成型体の製造方法。[5] the particle size is at 100μm or less, including the specific surface area measurement, 0.2m 2 / g~50m 2 / g and a zinc sulfide or zinc sulfide and silver, copper, at least one element of manganese, and rare earth A sulfide containing zinc sulfide or zinc sulfide and at least one element of silver, copper, manganese and rare earth, characterized in that a composite sulfide containing sulfide is pressure-molded at a temperature of 700 ° C. to 1100 ° C. The manufacturing method of the molded object which consists of composite sulfide containing a thing.

[６] 該硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物の、Ｘ線結晶解析における、２θ＝３３°の回折ピークの半値幅が０．２°〜１．５°である[５]記載の成型体の製造方法。  [6] Half of the diffraction peak at 2θ = 33 ° in the X-ray crystal analysis of the composite sulfide containing zinc sulfide or zinc sulfide and a sulfide containing at least one element of silver, copper, manganese and rare earth The method for producing a molded article according to [5], wherein the value range is 0.2 ° to 1.5 °.

[７] 硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物が水溶液下で調製される[５]または[６]記載の成型体の製造方法。  [7] The molded article according to [5] or [6], wherein zinc sulfide or a composite sulfide containing zinc sulfide and a sulfide containing silver, copper, manganese, and a rare earth element is prepared in an aqueous solution. Manufacturing method.

本発明の成型体は、1に近い硫黄／亜鉛比を有する硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物とを含む複合硫化物の成型体であり、発光層を形成する際のターゲット材となる高い成型性を有する硫化亜鉛を提供することができる。以下、記載を簡潔にするために「硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物とを含む複合硫化物」を単に「複合硫化物」、「硫化物複合体」などと示すことがある。  The molded body of the present invention is a composite sulfide molded body containing zinc sulfide or zinc sulfide having a sulfur / zinc ratio close to 1 and a sulfide containing at least one element of silver, copper, manganese and rare earth. It is possible to provide zinc sulfide having a high moldability as a target material when forming a light emitting layer. Hereinafter, in order to simplify the description, “composite sulfide containing zinc sulfide or zinc sulfide and sulfide containing at least one element of silver, copper, manganese and rare earth” is simply referred to as “composite sulfide”, “sulfurization”. It may be indicated as “composite complex”.

本発明において、硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物とを含む複合硫化物としては、好ましくは、水溶液下で調製された硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物とを含む複合硫化物、または、水溶液下に調製された硫化亜鉛に銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物を混合して得られる複合硫化物を使用する。  In the present invention, the composite sulfide containing zinc sulfide or zinc sulfide and a sulfide containing at least one element of silver, copper, manganese and rare earth is preferably zinc sulfide or zinc sulfide prepared in an aqueous solution. And a composite sulfide containing at least one element of silver, copper, manganese and rare earth, or at least one element of silver, copper, manganese and rare earth in zinc sulfide prepared in an aqueous solution The composite sulfide obtained by mixing the sulfide containing is used.

水溶液下での調製方法としては、特に制限されるものではなく、亜鉛を含有する塩と硫化剤を反応させる方法であれば、塩基性、酸性何れの条件で作製されたものでも構わない。例えば、硝酸亜鉛の水溶液と硫化ナトリウム水溶液を室温下で混合することによって調製することもできるし、硝酸亜鉛の水溶液にチオアセトアミドを添加して、１００℃程度の温度下に反応させて調製することもできる。  The preparation method under an aqueous solution is not particularly limited, and any preparation method may be used as long as it is a method in which a zinc-containing salt and a sulfurizing agent are reacted. For example, it can be prepared by mixing an aqueous solution of zinc nitrate and an aqueous solution of sodium sulfide at room temperature, or by adding thioacetamide to an aqueous solution of zinc nitrate and reacting at a temperature of about 100 ° C. You can also.

液相下調製に使用する亜鉛を含有する塩としては、塩化亜鉛、臭化亜鉛などのハロゲン化物、硫酸亜鉛、亜硫酸亜鉛、りん酸亜鉛、硝酸亜鉛、炭酸亜鉛などの鉱酸塩、または、ギ酸亜鉛、酢酸亜鉛、シュウ酸亜鉛などの有機酸塩を使用することができる。これらは、無水塩であっても含水塩であっても構わない。これらは、単一で使用しても混合して使用しても差し支えない。使用する塩の純度としては、特に制限されるものではなく高いほど好ましいが、特に鉄、ニッケル、コバルト、クロム、タングステンなどの金属不純物を含まないものを使用することが、得られる成型体を蛍光体の製造に使用する場合に好ましい。  Salts containing zinc used in the preparation in the liquid phase include halides such as zinc chloride and zinc bromide, mineral salts such as zinc sulfate, zinc sulfite, zinc phosphate, zinc nitrate and zinc carbonate, or formic acid. Organic acid salts such as zinc, zinc acetate, and zinc oxalate can be used. These may be anhydrous salts or hydrated salts. These may be used alone or in combination. The purity of the salt to be used is not particularly limited and is preferably as high as possible. However, it is particularly preferable to use a salt that does not contain metal impurities such as iron, nickel, cobalt, chromium, and tungsten. Preferred for use in the production of body.

液相下に複合硫化物を調製する場合、銀、銅、マンガンおよび希土類の塩を少なくとも１種、亜鉛を含有する塩に添加して、複合硫化物を調製する。必要に応じて、アクセプターとしての銀、銅、マンガンおよび希土類元素に対して、ドナーとして作用する、アルミニウム、ガリウム、インジウム、塩素、臭素などの元素を液相中に存在させて、このようなドナー元素が複合硫化物中に取り込まれるようにする。  When preparing a composite sulfide under a liquid phase, a composite sulfide is prepared by adding at least one silver, copper, manganese and rare earth salt to a salt containing zinc. If necessary, elements such as aluminum, gallium, indium, chlorine and bromine that act as donors for silver, copper, manganese and rare earth elements as acceptors are present in the liquid phase, and such donors The element is incorporated into the complex sulfide.

銀、銅、マンガンおよび希土類の塩ならびにドナー元素の塩としては、上述のハロゲン塩、鉱酸塩、有機酸塩を使用することができ、これらは、無水塩であっても含水塩であっても構わない。これらは、単一で使用しても混合して使用しても差し支えない。使用する塩の純度としては、特に制限されるものではなく高いほど好ましいが、特に鉄、ニッケル、コバルト、クロム、タングステンなどの金属不純物を含まないものを使用することが、得られる成型体を蛍光体の製造に使用する場合に好ましい。  As the salt of silver, copper, manganese and rare earth, and the salt of the donor element, the above-mentioned halogen salts, mineral acid salts, and organic acid salts can be used, and these are anhydrous salts or hydrated salts. It doesn't matter. These may be used alone or in combination. The purity of the salt to be used is not particularly limited and is preferably as high as possible. However, it is particularly preferable to use a salt that does not contain metal impurities such as iron, nickel, cobalt, chromium, and tungsten. Preferred for use in the production of body.

複合硫化物中に含まれる銀、銅、マンガンおよび希土類元素並びにアクセプターとしての銀、銅、マンガンおよび希土類元素に対してドナーとして作用する元素の量としては、特に制限されるものではないが、多すぎる量は、励起子同士の相互作用により蛍光収率を低下させるため好ましくなく、少なすぎる量は、取り出せる蛍光量が低下するため好ましくない。従って、５０〜５０，０００ｐｐｍ、好ましくは、１００〜４０，０００ｐｐｍ、より好ましくは、３００〜３０，０００ｐｐｍの範囲で含有することが好ましい。  The amount of silver, copper, manganese, and rare earth elements contained in the composite sulfide and the element that acts as a donor for silver, copper, manganese, and rare earth elements as acceptors is not particularly limited. An excessive amount is not preferable because it reduces the fluorescence yield due to the interaction between excitons, and an excessive amount is not preferable because the amount of fluorescence that can be extracted decreases. Therefore, it is preferably contained in the range of 50 to 50,000 ppm, preferably 100 to 40,000 ppm, more preferably 300 to 30,000 ppm.

本発明において使用される硫化剤としては、硫化水素、硫化リチウム、硫化ナトリウム、硫化カリウムなどのアルカリ金属硫化物、チオホルムアミド、チオアセトアミドなどのチオアミド類、チオ尿素などを使用することができる。これらの硫化剤の使用量としては、その適用方法によって異なることは言うまでもないが、通常、使用する亜鉛塩に対して、０．１〜５当量の範囲、硫化物の生成効率、経済性を考慮して、０．５〜３当量、より好ましくは、０．８〜２当量を使用することが好ましい。  As the sulfurizing agent used in the present invention, hydrogen sulfide, lithium sulfide, sodium sulfide, alkali metal sulfides such as potassium sulfide, thioamides such as thioformamide and thioacetamide, thiourea and the like can be used. Needless to say, the amount of these sulfiding agents to be used varies depending on the application method, but usually the range of 0.1 to 5 equivalents, the formation efficiency of sulfide, and the economy are taken into account with respect to the zinc salt used. Thus, it is preferable to use 0.5 to 3 equivalents, more preferably 0.8 to 2 equivalents.

本発明において、液相調製は、水中で実施するのが好ましい。得られた硫化物を蛍光体として使用するためには、必要とする金属以外を含まないことが好ましい。従って、使用する水は、イオン交換水を使用することが好ましく、鉄、ニッケル、コバルトなどの重金属は各々５０ｐｐｍ以下、好ましくは１０ｐｐｍ以下、ナトリウム、カリウム、カルシウム、マグネシウムなどの典型金属は各々５００ｐｐｍ以下、好ましくは１００ｐｐｍ以下のものを使用する。  In the present invention, the liquid phase preparation is preferably carried out in water. In order to use the obtained sulfide as a phosphor, it is preferable not to contain other than the required metal. Therefore, it is preferable to use ion-exchanged water as the water to be used. Heavy metals such as iron, nickel and cobalt are each 50 ppm or less, preferably 10 ppm or less, and typical metals such as sodium, potassium, calcium and magnesium are each 500 ppm or less. Preferably, the one with 100 ppm or less is used.

液相調製の際に、液相中に硫酸マグネシウムなどの粒径調整剤（電解質による凝集効果を利用）として使用する金属塩を存在させることができる。このような金属は、洗浄などによって最終的には、硫化物中には取り込まれないようにする。  During the preparation of the liquid phase, a metal salt used as a particle size adjusting agent (utilizing the coagulation effect by the electrolyte) such as magnesium sulfate can be present in the liquid phase. Such a metal is finally prevented from being taken into the sulfide by washing or the like.

液相調製における反応温度は使用する硫化剤によって異なるが、低すぎる温度では、反応の進行が著しく遅くなるので好ましくなく、高すぎる温度では、発生する硫化水素の液中濃度が低下し、硫化剤効率が低下するため好ましくない。通常、５℃〜１２０℃、より好ましくは、１０℃〜１００℃の範囲で実施される。反応の方式も特に限定されるものではなく、バッチ式、連続式何れの方法を採用しても構わない。  The reaction temperature in the liquid phase preparation varies depending on the sulfiding agent used. However, if the temperature is too low, the progress of the reaction is remarkably slow, which is not preferable. If the temperature is too high, the concentration of hydrogen sulfide generated in the liquid decreases, and the sulfiding agent. Since efficiency falls, it is not preferable. Usually, it is carried out in the range of 5 ° C to 120 ° C, more preferably 10 ° C to 100 ° C. The reaction method is not particularly limited, and either a batch method or a continuous method may be adopted.

液相調製において得られた硫化物は、デカンテーションや遠心分離などの方法で水と分離しながら、イオン交換水による洗浄を繰り返し、水洗層のｐＨが６〜８になるまで洗浄する。  The sulfide obtained in the liquid phase preparation is repeatedly washed with ion-exchanged water while being separated from water by a method such as decantation or centrifugation, and washed until the pH of the washing layer becomes 6-8.

洗浄された硫化物は、真空乾燥または１５０℃以下の熱風乾燥などの方法で水を除去、乾燥することができる。乾燥時間としては、含んでいる水の量に依存することは言うまでもないが、通常、１時間〜５０時間、乾燥の効率を考慮して、１．５時間〜２０時間の範囲で実施される。  The washed sulfide can be dried by removing water by a method such as vacuum drying or hot air drying at 150 ° C. or lower. Needless to say, the drying time depends on the amount of water contained, but is usually in the range of 1 hour to 50 hours and 1.5 hours to 20 hours in consideration of the efficiency of drying.

本発明で得られる成型体に含有される水分量は５０ｐｐｍ以下であることが好ましい。水分量が多いと、スパッタリング法などに用いた場合、金属硫化物が酸化されるため好ましくない。よって、好ましくは１〜３０ｐｐｍ、より好ましくは、１〜２０ｐｐｍである。そのため、乾燥終了時（加圧成型前）の硫化物複合体中の水分は、１ｐｐｍ〜２０００ｐｐｍの範囲、より好ましくは、１０〜１０００ｐｐｍである。  The amount of water contained in the molded product obtained in the present invention is preferably 50 ppm or less. If the amount of moisture is large, the metal sulfide is oxidized when used in a sputtering method or the like, which is not preferable. Therefore, it is preferably 1 to 30 ppm, more preferably 1 to 20 ppm. Therefore, the moisture in the sulfide composite at the end of drying (before pressure molding) is in the range of 1 ppm to 2000 ppm, more preferably 10 to 1000 ppm.

本発明で得られる成型体に含有される硫酸イオン濃度としては、５００ｐｐｍ以下であることが好ましい。硫酸イオンが多いと、スパッタリング法などに用いた場合、金属硫化物が酸化されたり、薄膜中に混入し、腐食や分解の原因になるため好ましくない。よって、成型体中の硫酸イオン濃度としては１〜２００ｐｐｍの範囲、より好ましくは、１〜１００ｐｐｍの範囲である。そのため、洗浄、乾燥終了時（加圧成型前）の硫化物複合物中の硫酸イオン濃度としては、１ｐｐｍ〜２０００ｐｐｍの範囲が好ましく、安定して硫酸イオン濃度を目的の範囲とするためには、１〜６００ｐｐｍの範囲にあることがより好ましい。  The concentration of sulfate ions contained in the molded product obtained in the present invention is preferably 500 ppm or less. A large amount of sulfate ions is not preferable when used in a sputtering method or the like because the metal sulfide is oxidized or mixed into the thin film, causing corrosion or decomposition. Therefore, the sulfate ion concentration in the molded body is in the range of 1 to 200 ppm, more preferably in the range of 1 to 100 ppm. Therefore, the sulfate ion concentration in the sulfide composite at the end of washing and drying (before pressure molding) is preferably in the range of 1 ppm to 2000 ppm, and in order to stably set the sulfate ion concentration to the target range, More preferably, it is in the range of 1 to 600 ppm.

硫化亜鉛中に、銀、銅、マンガンおよび希土類塩を少なくとも1種の金属を添加して、混合硫化物を調製する場合には、各々の金属硫化物を使用することができる。これらは、単一で使用しても混合して使用しても差し支えない。使用する硫化物の純度としては、特に制限されるものではなく高ければ高いほど好ましいが、特に鉄、ニッケル、コバルト、クロム、タングステンなどの金属不純物を含まないものを使用することが、得られる成型体を蛍光体の製造に使用する場合に好ましい。  When preparing a mixed sulfide by adding at least one kind of metal such as silver, copper, manganese and rare earth salt to zinc sulfide, each metal sulfide can be used. These may be used alone or in combination. The purity of the sulfide to be used is not particularly limited and is preferably as high as possible. In particular, it is possible to obtain a molded product that does not contain metal impurities such as iron, nickel, cobalt, chromium, and tungsten. It is preferable when the body is used for the production of a phosphor.

得られた硫化物の比表面積は０．２ｍ２／ｇ〜５０ｍ２／ｇであるのが好ましい。比表面積が小さ過ぎると、成型時に融着するに十分な硫黄蒸気圧を発生することができず、結着しないため高い温度または長時間の成形を必要とするため、結果として硫黄成分の欠落が起こり、欠損してしまうため好ましくない。また、広すぎる比表面積を有すると、成型時の温度上昇と共に、著しく硫黄蒸気圧が上がる一方で、結着できる温度に到達していないため、所定温度到達以前に、硫黄の欠損が起こり、結果として、硫黄の欠落が起こるため好ましくない。The specific surface area of the resulting sulfide is preferably 0.2m 2 / g~50m 2 / g. If the specific surface area is too small, a sulfur vapor pressure sufficient for fusing at the time of molding cannot be generated, and a high temperature or long-time molding is required because it does not bind, resulting in a lack of sulfur component. It is not preferable because it occurs and is lost. Also, if the specific surface area is too large, the sulfur vapor pressure will rise significantly with the temperature rise at the time of molding, but since it has not reached the temperature at which it can be bound, sulfur deficiency occurs before the predetermined temperature is reached. Since sulfur loss occurs, it is not preferable.

また、得られた硫化物は、Ｘ線結晶解析で分析し、２θ＝３３°に観測されるシグナルの半値幅が０．２°〜１．５°の範囲内にあるものを使用するとさらに好ましい。０．２°以下では、結晶性が高すぎ、加熱・加圧成型での成形性が悪化することがあるため好ましくない。また、１．５°を越えると、結晶性が低すぎ、焼結時に分解などを併発することがあり、結晶性を向上させる処理が必要になることがある。  Further, it is more preferable to use the obtained sulfide which is analyzed by X-ray crystal analysis and has a half-value width of a signal observed at 2θ = 33 ° within a range of 0.2 ° to 1.5 °. . If it is 0.2 ° or less, the crystallinity is too high, and the moldability in heating / pressing molding may deteriorate, which is not preferable. If it exceeds 1.5 °, the crystallinity is too low, and decomposition may occur at the time of sintering, which may require treatment for improving the crystallinity.

本発明において、得られた硫化物は、必要に応じて、加熱焼成される。この焼成によって、複合硫化物中に含まれる水分の除去や、硫酸イオンの分解を促進することができる。一方で、硫化物結晶化度が向上するが、必要以上に向上させると、比表面積が著しく低下し、結晶化を促すため加圧成形できなくなるため留意が必要である。また、余りに低いと、加熱の効果を得ることができず、工程が複雑化するだけである。加熱の温度は、液相調製時の方法にもよるため特定されないことは言うまでもないが、通常２００℃〜８００℃の範囲、好ましくは、３００℃〜６００℃の範囲で実施する。  In the present invention, the obtained sulfide is heated and fired as necessary. By this firing, removal of moisture contained in the composite sulfide and decomposition of sulfate ions can be promoted. On the other hand, although the degree of sulfide crystallinity is improved, if it is improved more than necessary, the specific surface area is significantly reduced, and crystallization is promoted, so that pressure molding cannot be performed. On the other hand, if it is too low, the effect of heating cannot be obtained, and the process is only complicated. It goes without saying that the heating temperature is not specified because it depends on the method for preparing the liquid phase, but it is usually in the range of 200 ° C to 800 ° C, preferably in the range of 300 ° C to 600 ° C.

焼成の時間も特に制限されるものではなく、目的に応じて変化するが、通常０．５〜１０時間の範囲、装置の加熱、冷却能力を考慮して、１〜８時間の範囲で実施される。通常、焼成は、不活性雰囲気下または還元雰囲気下で実施されることは言うまでもない。方法としても、バッチ式、連続式何れの方法を採用しても構わない。  The firing time is not particularly limited and varies depending on the purpose, but it is usually carried out in the range of 0.5 to 10 hours and in the range of 1 to 8 hours in consideration of the heating and cooling capabilities of the apparatus. The Needless to say, firing is usually performed in an inert atmosphere or a reducing atmosphere. As a method, either a batch method or a continuous method may be adopted.

本発明では、焼成の雰囲気としては、特に限定されるものではないが、酸素の存在は、複合硫化物の表面酸化を起こすために好ましくなく、不活性ガス雰囲気下、または還元雰囲気下で実施する。還元雰囲気下としては、硫化水素存在下、複合硫化物中に硫黄を添加して焼成することができる。焼成炉の構造にもよるが、安全性を考慮して、硫黄を複合硫化物中に添加して焼成することが好ましい。これにより、複合硫化物中に含まれる水分や、硫酸イオンの除去効率を更に向上させることができる。  In the present invention, the firing atmosphere is not particularly limited, but the presence of oxygen is not preferable because it causes surface oxidation of the composite sulfide, and is performed in an inert gas atmosphere or a reducing atmosphere. . As the reducing atmosphere, sulfur can be added to the composite sulfide and fired in the presence of hydrogen sulfide. Although depending on the structure of the firing furnace, in consideration of safety, it is preferable to add sulfur to the composite sulfide for firing. Thereby, the removal efficiency of the water | moisture content contained in composite sulfide and a sulfate ion can be improved further.

焼成時の硫黄添加量としては特に限定されるものではないが、通常、複合硫化物１００重量部に対して、０．１〜２０重量部、操作性、機器安定性を考慮して、０．２〜１５重量部、より好ましくは、０．３〜１０重量部を添加することができる。添加の方法としては、固体同士を混合してもかまわないし、硫黄を二硫化炭素などの溶媒に溶解して、複合硫化物と混合し、乾燥させたものでも構わない。  Although it does not specifically limit as sulfur addition amount at the time of baking, Usually, 0.1-20 weight part with respect to 100 weight part of composite sulfides, operativity, and apparatus stability are considered, and it is set to 0. 2 to 15 parts by weight, more preferably 0.3 to 10 parts by weight can be added. As a method of addition, solids may be mixed, or sulfur may be dissolved in a solvent such as carbon disulfide, mixed with a composite sulfide, and dried.

更に、本発明では、焼成を真空下に実施しても構わない。真空下に付する温度としては、特に限定されないが、高すぎる温度では、添加した硫黄の気散や、複合硫化物の表面硫黄の欠損を助長するため好ましくなく、通常１００〜４００℃の範囲、より好ましくは、１００℃〜３００℃の範囲で実施することができる。これにより、複合硫化物に付着した酸素、水分を効率よく除去することが可能となり、焼成中の酸化による硫酸イオン増加を抑止することができる。減圧度としては、特に限定されるものではないが、通常、１〜６０ＫＰａの範囲で実施する。  Furthermore, in the present invention, firing may be performed under vacuum. The temperature to be applied under vacuum is not particularly limited, but a temperature that is too high is not preferable because it promotes the diffusion of added sulfur and the loss of surface sulfur of the composite sulfide, and is usually in the range of 100 to 400 ° C. More preferably, it can implement in the range of 100 to 300 degreeC. Thereby, it becomes possible to efficiently remove oxygen and moisture adhering to the composite sulfide, and an increase in sulfate ions due to oxidation during firing can be suppressed. Although it does not specifically limit as a pressure reduction degree, Usually, it implements in the range of 1-60 KPa.

得られた焼成物は、必要に応じて、破砕分級し、成型に使用するが、必要に応じて、酸、イオン交換水などで洗浄し、表面に生成した酸化物を除去することができる。このような洗浄を行った場合には、あらためて、真空、熱風などの方法で乾燥される。  The obtained fired product is crushed and classified as necessary, and used for molding. If necessary, it can be washed with an acid, ion-exchanged water or the like to remove oxides generated on the surface. When such cleaning is performed, it is dried again by a method such as vacuum or hot air.

本発明において、成型する前に、硫化物は予め成型時の流動性、圧縮性を向上するために粉体にされる。粉体の粒度としては、成型時の流動性を維持できる範囲であれば良く、通常１００μｍ以下、より好ましくは７０μｍ以下、成型機への負荷を考慮すると５０μｍ以下、特に４０μｍ以下であることが好ましい。粉砕の方法としては特に限定されるものではなく、乳鉢による粉砕、ボールミル、ターボミル、サイクロンミルなどの方法を用いても構わない。  In the present invention, before molding, the sulfide is powdered in advance to improve fluidity and compressibility during molding. The particle size of the powder may be in a range that can maintain the fluidity at the time of molding, and is usually 100 μm or less, more preferably 70 μm or less, and considering the load on the molding machine, it is preferably 50 μm or less, particularly preferably 40 μm or less. . The pulverization method is not particularly limited, and a mortar pulverization method, a ball mill, a turbo mill, a cyclone mill, or the like may be used.

本発明において、得られた硫化物は、ホットプレス成形型（モールド）に入れ、圧力と温度をかけて成型する。本発明において、加熱、加圧成型の方法としては、ホットプレス法、放電焼結法などいずれの方法を用いても構わない。ホットプレスの成形型の材質としては、カーボン、アルミナ、サイアロンなどを使用することができる。特に、硫化物との反応が顕著な場合には、サイアロン、カーボンなどの表面をガラスなどの非反応物でコーティングしたものを用いても構わない。  In the present invention, the obtained sulfide is put into a hot press mold (mold) and molded by applying pressure and temperature. In the present invention, any method such as a hot press method or a discharge sintering method may be used as the heating and pressure molding method. Carbon, alumina, sialon, etc. can be used as the material for the hot press mold. In particular, when the reaction with sulfide is remarkable, the surface of sialon, carbon or the like coated with a non-reacted material such as glass may be used.

本発明において、ホットプレス成型の際に加圧する圧力としては、特に限定されないが、相対密度向上のため、１００Ｋｇ／ｃｍ２〜５００Ｋｇ／ｃｍ２で加圧して成型体を構築する。低すぎる圧力は、相対密度が向上しないため、好ましくなく、高すぎる圧力は、粒子強度を損なうため好ましくない。In the present invention, the pressure applied during the hot press molding is not particularly limited, because of the relative density increase, to construct the molded body under pressure at 100Kg / cm 2 ~500Kg / cm 2 . A pressure that is too low is not preferable because the relative density does not improve, and a pressure that is too high is not preferable because the particle strength is impaired.

本発明において、ホットプレス成型の際に加熱する温度をしては、６００℃〜１１００℃の範囲で実施される。低すぎる温度では、粒子の結着が起こらないため好ましくなく、高すぎる温度では、粒子の結晶化が大きく、成形体内のボイドの発生が多くなるため好ましくない。よって、７００℃〜１０５０℃の範囲、より好ましくは、８００℃〜１０００℃の範囲で実施することが好ましい。  In the present invention, the heating is performed in the range of 600 ° C. to 1100 ° C. in the hot press molding. If the temperature is too low, particle binding will not occur, which is not preferable. If the temperature is too high, crystallization of the particles will be large and voids in the molded body will increase, which is not preferable. Therefore, it is preferable to carry out in the range of 700 ° C to 1050 ° C, more preferably in the range of 800 ° C to 1000 ° C.

本発明において、成形の手順としては、特に制限されるものではない。例えば、モールドに硫化物、必要に応じて硫黄を添加して入れ、成形冶具を装着し、一旦、１４０Ｐａ程度に減圧する。減圧をアルゴンで開放し、この操作を繰り返し、硫化物複合体内に含まれる酸素、および硫化物複合体表面に付着した水分を除去する。  In the present invention, the molding procedure is not particularly limited. For example, sulfide and sulfur as required are added to the mold, a forming jig is attached, and the pressure is once reduced to about 140 Pa. The decompression is released with argon, and this operation is repeated to remove oxygen contained in the sulfide complex and water adhering to the surface of the sulfide complex.

次に、硫化物を減圧中に置いた状態で機械的に加圧を開始し、硫化物に所定の機械的な圧力（プレス圧）がかかったところで、１分〜１時間程度保持する。そこで、硫化物に対する減圧をアルゴンで開放し、硫化物にプレス圧がかかった状態で昇温を開始する。  Next, pressurization is started mechanically in a state where the sulfide is placed under reduced pressure, and when a predetermined mechanical pressure (pressing pressure) is applied to the sulfide, the sulfide is held for about 1 minute to 1 hour. Therefore, the pressure reduction for the sulfide is released with argon, and the temperature rise is started in a state where the press pressure is applied to the sulfide.

所定の温度で、１分〜１時間保持した後、降温を開始し、室温に戻った段階で、プレス圧を解除して、目的の成型体を得ることもできるし、昇温後に減圧を開放する方法、降温時にプレス圧を解除して冷却する方法を採用しても構わない。得られた成型体は、モールドから取り外した後、必要に応じて、研磨などの処置を施すことで、容易にスパッタ用ターゲットとして使用することができる。以下、実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例に限定されるものではない。  After holding at a predetermined temperature for 1 minute to 1 hour, the temperature lowering is started, and when the temperature returns to room temperature, the press pressure can be released to obtain the desired molded body. A method of cooling by releasing the press pressure when the temperature is lowered may be adopted. The obtained molded body can be easily used as a sputtering target by removing it from the mold and then performing a treatment such as polishing as necessary. EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to a following example.

実施例１
２Lセパラブルフラスコに、硝酸亜鉛六水和物２３２．２ｇ、硫酸マグネシウム４．５ｇ、硝酸銅三水和物１．３９ｇ、硝酸ガリウム八水和物３．３５ｇを取り、イオン交換水７５０ｇを加えて溶解した。そこに硝酸１．５ｇを添加して、系中のｐHを２程度に調整し、そのフラスコに、攪拌器、温度計、還流管を装着し、ｐＨを調整した液を攪拌しながら、９０℃まで昇温した。所定の温度に到達したところで、チオ尿素８４．５ｇを固体で添加した。添加終了後、２時間攪拌した後、反応停止のため、系内を３０℃まで冷却した。冷却中、窒素を流気し、系内の硫化水素を排気した。Example 1
In a 2 L separable flask, take 232.2 g of zinc nitrate hexahydrate, 4.5 g of magnesium sulfate, 1.39 g of copper nitrate trihydrate and 3.35 g of gallium nitrate octahydrate, and add 750 g of ion-exchanged water. And dissolved. Nitric acid (1.5 g) was added thereto, the pH in the system was adjusted to about 2, and the flask was equipped with a stirrer, thermometer and reflux tube, and the pH adjusted liquid was stirred while stirring at 90 ° C. The temperature was raised to. When the predetermined temperature was reached, 84.5 g of thiourea was added as a solid. After completion of the addition, the mixture was stirred for 2 hours, and then the system was cooled to 30 ° C. to stop the reaction. During cooling, nitrogen was passed and the hydrogen sulfide in the system was exhausted.

得られた反応液からデカンテーションで反応液を除き、更にイオン交換水にて残りの固体の洗浄を行い、洗液のｐＨが６程度になるまで洗浄を行なった。洗浄が終了した固体を、１５０℃にて１２時間熱風乾燥し、更に、１２０℃で真空乾燥し、銅がドーピングされた硫化亜鉛複合体５８．５ｇを得た。  The reaction solution was removed from the obtained reaction solution by decantation, and the remaining solid was washed with ion-exchanged water, and washing was performed until the pH of the washing solution reached about 6. The solid after the washing was dried with hot air at 150 ° C. for 12 hours and further dried under vacuum at 120 ° C. to obtain 58.5 g of a zinc sulfide composite doped with copper.

得られた硫化亜鉛複合体は粒径Ｄ５０（中心粒径）が１２μｍの粉末であった。ここで粒度分布は株式会社堀場製作所製ＬＡ−９５０を用い、水溶媒に分散させて測定した。得られた粉末を、日本ベル株式会社製ＢＥＬＳＯＲＰ１８を使用し、窒素吸着により比表面積測定したところ、４０．２ｍ２／ｇであった。また、得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は１．２７３°であった。The obtained zinc sulfide composite was a powder having a particle size D50 (center particle size) of 12 μm. Here, the particle size distribution was measured by using LA-950 manufactured by HORIBA, Ltd. and dispersing it in an aqueous solvent. When the specific surface area of the obtained powder was measured by nitrogen adsorption using BELSORP18 manufactured by Nippon Bell Co., Ltd., it was 40.2 m 2 / g. Moreover, when the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 1.273 °.

水分量は、電量滴定法カールフィッシャー水分計（三菱化成株式会社製：型式ＶＡ−０６）を用いて測定した結果、得られた水分量は、８９２ｐｐｍであった。  The moisture content was measured using a coulometric titration Karl Fischer moisture meter (manufactured by Mitsubishi Kasei Co., Ltd .: Model VA-06). As a result, the obtained moisture content was 892 ppm.

硫酸イオン分析は、イオンクロマト法（島津製作所製：型式ＨＩＣ−ＳＰ）により実施した。２０ｍｇのサンプルを５．０ｇの塩酸に溶解し、完全に溶解させた後、窒素ガスを通じて、塩酸を揮発させ、イオン交換水を加えて、１０．０ｇとした。検出された硫酸イオン量は５６２ｐｐｍであった。  The sulfate ion analysis was carried out by ion chromatography (manufactured by Shimadzu Corporation: model HIC-SP). A 20 mg sample was dissolved in 5.0 g of hydrochloric acid and completely dissolved, and then the hydrochloric acid was volatilized through nitrogen gas, and ion exchanged water was added to make 10.0 g. The amount of sulfate ion detected was 562 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、減圧をアルゴンにて常圧に開放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧力を解除し、２時間で室温まで冷却した。モールドから成型体をはずし、３０ｍｍφ、厚さ５．４９ｍｍの円筒形ターゲット材を得た。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The pressure inside the mold was reduced to 130 Pa, held for 10 minutes, and the reduced pressure was released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours. The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.49 mm.

得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、エチレンジアミン四酢酸（ＥＤＴＡ）溶液で滴定し、金属含量を定量した。定量した結果、硫黄／亜鉛＝０．９７であった。得られたターゲットの嵩密度は３．８８ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比。理論密度として硫化亜鉛本来の密度４．０ｇ／ｃｍ３を使用した。）は０．９７であった。水分量は、４１ｐｐｍであった。硫酸イオン量は、２２ｐｐｍであった。A portion of the obtained target material was taken, dissolved in 1N hydrochloric acid, and titrated with an ethylenediaminetetraacetic acid (EDTA) solution to quantify the metal content. As a result of quantification, it was sulfur / zinc = 0.97. The obtained target had a bulk density of 3.88 g / cm 3 and a relative density (ratio of bulk density to theoretical density. The original density of zinc sulfide of 4.0 g / cm 3 was used as the theoretical density). 97. The water content was 41 ppm. The amount of sulfate ion was 22 ppm.

実施例２
実施例１で得た液相調製した銅がドーピングされた硫化亜鉛３０ｇに硫黄６ｇを添加して、窒素下にて、５００℃で３時間加熱焼成し、室温まで冷却した。得られた硫化亜鉛複合体は粒径Ｄ５０が１８μｍの粉末であった。得られた粉末を比表面積測定したところ、０．６５ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．４１５°であった。また、水分量は１２８ｐｐｍ、硫酸イオン量は、２５５ｐｐｍであった。Example 2
6 g of sulfur was added to 30 g of zinc sulfide doped with copper prepared in the liquid phase obtained in Example 1, heated and calcined at 500 ° C. for 3 hours under nitrogen, and cooled to room temperature. The obtained zinc sulfide composite was a powder having a particle size D50 of 18 μm. When the specific surface area of the obtained powder was measured, it was 0.65 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.415 °. The water content was 128 ppm, and the sulfate ion content was 255 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に開放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released and the temperature was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ５．３７ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９５であった。得られたターゲットの嵩密度は３．７５ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．９５であった。また、水分量は４９ｐｐｍ、硫酸イオン量は４１ｐｐｍであった。The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.37 mm. A portion of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.95. The obtained target had a bulk density of 3.75 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.95. The water content was 49 ppm and the sulfate ion content was 41 ppm.

実施例３
実施例２において、８００℃で焼成した以外は、実施例２と同様に行った。得られた硫化亜鉛複合体は粒径Ｄ５０が２８μｍの粉末であった。得られた粉末を比表面積測定したところ、０．２２ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．３７５°であった。また、水分量は１１８ｐｐｍ、硫酸イオン量は２２１ｐｐｍであった。Example 3
In Example 2, it carried out like Example 2 except having baked at 800 degreeC. The obtained zinc sulfide composite was a powder having a particle size D50 of 28 μm. When the specific surface area of the obtained powder was measured, it was 0.22 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.375 °. The water content was 118 ppm and the sulfate ion content was 221 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に開放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the reduced pressure in the mold was released with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ５．２０ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９２であった。得られたターゲットの嵩密度は３．７３ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．９４であった。また、水分量は３３ｐｐｍ、硫酸イオン量は５１ｐｐｍであった。The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.20 mm. A part of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.92. The obtained target had a bulk density of 3.73 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.94. The water content was 33 ppm and the sulfate ion content was 51 ppm.

実施例４
実施例１において、金属塩として硝酸亜鉛六水和物２３２．２ｇのみを使用した以外は、実施例１と同様に実施し、硫化亜鉛５７．１ｇを得た。得られた硫化亜鉛は粒径Ｄ５０が１６μｍの粉末であった。得られた粉末を比表面積測定したところ、４０．３ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は１．３７１°であった。また、水分量は９９４ｐｐｍ、硫酸イオンは５５７ｐｐｍであった。Example 4
In Example 1, it implemented similarly to Example 1 except having used only 232.2 g of zinc nitrate hexahydrate as a metal salt, and obtained 57.1 g of zinc sulfide. The obtained zinc sulfide was a powder having a particle size D50 of 16 μm. When the specific surface area of the obtained powder was measured, it was 40.3 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 1.371 °. Further, the water content was 994 ppm and the sulfate ion was 557 ppm.

上記で得られた硫化亜鉛粉末２０ｇに、硫化マンガン０．０５ｇを混合し、株式会社シンキー製混合機ＡＲＥ−２５０にて、２０００回転３０秒間混合した。３０ｍｍφのモールドに、得られた硫化亜鉛混合物１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。To 20 g of the zinc sulfide powder obtained above, 0.05 g of manganese sulfide was mixed and mixed for 2000 seconds for 30 seconds with a mixer ARE-250 manufactured by Sinky Corporation. 12 g of the obtained zinc sulfide mixture was put in a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ５．２６ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９４であった。得られたターゲットの嵩密度は３．７２ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．９３であった。また、水分量は２７ｐｐｍ、硫酸イオン量は３２ｐｐｍであった。The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.26 mm. A part of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.94. The obtained target had a bulk density of 3.72 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.93. The water content was 27 ppm and the sulfate ion content was 32 ppm.

実施例５
実施例４で得た硫化亜鉛混合物３０ｇに硫黄６ｇを添加して、窒素下にて、６００℃で３時間加熱焼成し、室温まで冷却した。得られた硫化亜鉛は粒径Ｄ５０が３２μｍの粉末であった。得られた粉末を比表面積測定したところ、０．２２ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．２６５°であった。また、水分量は１１３ｐｐｍ、硫酸イオン量は２４５ｐｐｍであった。Example 5
6 g of sulfur was added to 30 g of the zinc sulfide mixture obtained in Example 4, heated and calcined at 600 ° C. for 3 hours under nitrogen, and cooled to room temperature. The obtained zinc sulfide was a powder having a particle size D50 of 32 μm. When the specific surface area of the obtained powder was measured, it was 0.22 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.265 °. The water content was 113 ppm, and the sulfate ion content was 245 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ５．１５ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９３であった。得られたターゲットの嵩密度は３．６６ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．９１であった。また、水分量は４４ｐｐｍ、硫酸イオン量は５７ｐｐｍであった。The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.15 mm. A portion of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.93. The obtained target had a bulk density of 3.66 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.91. The water content was 44 ppm and the sulfate ion content was 57 ppm.

実施例６
実施例２において、硫化亜鉛複合体を４００℃で焼成し、加熱成型を８５０℃で実施した以外は、実施例２と同様に行った。得られた硫化亜鉛複合体粉末を比表面積測定したところ、０．８９ｍ２／ｇであった。得られた硫化亜鉛複合体は粒径Ｄ５０が１６μｍの粉末であった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．６６５°であった。また、水分量は１２８ｐｐｍ、硫酸イオン量は２５５ｐｐｍであった。Example 6
In Example 2, the same procedure was performed as in Example 2 except that the zinc sulfide composite was fired at 400 ° C. and the heat molding was performed at 850 ° C. It was 0.89 m < 2 > / g when the specific surface area of the obtained zinc sulfide composite powder was measured. The obtained zinc sulfide composite was a powder having a particle size D50 of 16 μm. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.665 °. The water content was 128 ppm, and the sulfate ion content was 255 ppm.

得られた円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝１．０５であった。得られたターゲットの嵩密度は３．８７ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．９６であった。また、水分量は３５ｐｐｍ、硫酸イオン量は５５ｐｐｍであった。A part of the obtained cylindrical target material was taken, dissolved with 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 1.05. The obtained target had a bulk density of 3.87 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.96. The water content was 35 ppm, and the sulfate ion content was 55 ppm.

実施例７
実施例２において、硫化亜鉛複合体を７００℃で焼成し、加熱成型を７５０℃で実施した以外は、実施例２と同様に行った。得られた硫化亜鉛複合体粉末を比表面積測定したところ、０．１８ｍ２／ｇであった。得られた硫化亜鉛複合体は粒径Ｄ５０が１９μｍの粉末であった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．２２４°であった。また、水分量は９６ｐｐｍ、硫酸イオン量は１３８ｐｐｍであった。Example 7
In Example 2, the same procedure was performed as in Example 2 except that the zinc sulfide composite was fired at 700 ° C. and the heat molding was performed at 750 ° C. When the specific surface area of the obtained zinc sulfide composite powder was measured, it was 0.18 m 2 / g. The obtained zinc sulfide composite was a powder having a particle size D50 of 19 μm. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.224 °. The water content was 96 ppm, and the sulfate ion content was 138 ppm.

得られた円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９１であった。得られたターゲットの嵩密度は３．５６ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．８９であった。また、水分量は２１ｐｐｍ、硫酸イオン量は４４ｐｐｍであった。 A part of the obtained cylindrical target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was determined. As a result, sulfur / zinc = 0.91 was obtained. The obtained target had a bulk density of 3.56 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.89. The water content was 21 ppm, and the sulfate ion content was 44 ppm.

比較例１
実施例３において、実施例１で得た液相調製した銅がドーピングされた硫化亜鉛複合体３０ｇに硫黄６ｇおよび塩化ナトリウム１．５ｇを添加した以外は、実施例３と同様に行なった。得られた硫化亜鉛複合体は粒径Ｄ５０が２８μｍの粉末であった。得られた粉末を比表面積測定したところ、０．１２ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．１８３°であった。また、水分量は８８ｐｐｍ、硫酸イオン量は８９ｐｐｍであった。Comparative Example 1
In Example 3, the same procedure as in Example 3 was performed, except that 6 g of sulfur and 1.5 g of sodium chloride were added to 30 g of the zinc sulfide composite doped with copper prepared in the liquid phase obtained in Example 1. The obtained zinc sulfide composite was a powder having a particle size D50 of 28 μm. When the specific surface area of the obtained powder was measured, it was 0.12 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.183 °. The water content was 88 ppm, and the sulfate ion content was 89 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ４．９２ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．８７であった。得られたターゲット材の嵩密度は３．４１ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．８５であった。また、水分量は２２ｐｐｍ、硫酸イオン量は４１ｐｐｍであった。The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 4.92 mm. A part of the obtained target material was taken, dissolved with 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.87. The obtained target material had a bulk density of 3.41 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.85. The water content was 22 ppm and the sulfate ion content was 41 ppm.

比較例２
５Ｌ三つ口フラスコに、攪拌器、還流管、温度計を装着し、硝酸亜鉛６水和物１４９．１ｇ、硝酸銅３水和物０．０９２６ｇ、硝酸ガリウム５水和物０・１２４６ｇを取り、１Ｌのイオン交換水を添加し溶解させ、窒素気流下とした。そこに、硫化ナトリウム９水和物１４５．５ｇをイオン交換水１Ｌに溶解した水溶液を２０分間で添加した。反応温度は２７℃であり、更に２時間攪拌した。Comparative Example 2
A 5 L three-necked flask is equipped with a stirrer, reflux tube, and thermometer, and 149.1 g of zinc nitrate hexahydrate, 0.0926 g of copper nitrate trihydrate, and 0.1246 g of gallium nitrate pentahydrate are taken. 1 L of ion exchange water was added and dissolved, and the mixture was placed under a nitrogen stream. Thereto was added an aqueous solution in which 145.5 g of sodium sulfide nonahydrate was dissolved in 1 L of ion-exchanged water over 20 minutes. The reaction temperature was 27 ° C., and the mixture was further stirred for 2 hours.

得られた反応液からデカンテーションで反応液を除き、更にイオン交換水にて洗浄を行い、洗液のｐＨが６程度になるまで洗浄を行なった。洗浄が終了した固体を、１５０℃にて１２時間熱風乾燥し、銅がドーピングされた硫化亜鉛４１．１ｇを得た。得られた硫化亜鉛複合体は粒径Ｄ５０が３０μｍの粉末であった。得られた粉末を比表面積測定したところ、１０５．２ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は２．２２°であった。また、水分量は２４５０ｐｐｍ、硫酸イオンは１２６６ｐｐｍであった。The reaction solution was removed from the obtained reaction solution by decantation, and further washed with ion-exchanged water until the pH of the washing solution reached about 6. The washed solid was dried with hot air at 150 ° C. for 12 hours to obtain 41.1 g of zinc sulfide doped with copper. The obtained zinc sulfide composite was a powder having a particle size D50 of 30 μm. When the specific surface area of the obtained powder was measured, it was 105.2 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 2.22 °. Moreover, the moisture content was 2450 ppm and the sulfate ion was 1266 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。モールドから成型体をはずしたが、モールドに固着し、目的物を得ることはできなかった。水分量は８９９ｐｐｍ、硫酸イオン量は４４７ｐｐｍであった。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was decompressed to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours. Although the molded body was removed from the mold, it was fixed to the mold and the target product could not be obtained. The amount of water was 899 ppm, and the amount of sulfate ions was 447 ppm.

比較例３
実施例１で得た液相調製した銅がドーピングされた硫化亜鉛複合体３０ｇに硫黄６ｇを添加して窒素下にて、２５０℃で３時間加熱焼成し、室温まで冷却した。得られた硫化亜鉛複合体は粒径Ｄ５０が６２μｍの粉末であった。得られた粉末を比表面積測定したところ、５０．３３ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は１．８１°であった。また、水分量は１２２７ｐｐｍ、硫酸イオン量は７２３ｐｐｍであった。Comparative Example 3
6 g of sulfur was added to 30 g of the zinc sulfide composite doped with copper prepared in the liquid phase obtained in Example 1, and heated and fired at 250 ° C. for 3 hours under nitrogen, and then cooled to room temperature. The obtained zinc sulfide composite was a powder having a particle size D50 of 62 μm. It was 50.33 m < 2 > / g when the specific surface area of the obtained powder was measured. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 1.81 °. Further, the water content was 1227 ppm and the sulfate ion content was 723 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。モールドから成型体をはずしたが、成型体の一部がモールド壁面に固着し、ターゲットを取り出す際に、固着部分から剥離が起こり、目的のターゲットの形状を維持することは出来なかった。水分量は１０１１ｐｐｍ、硫酸イオン量は５１２ｐｐｍであった。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours. Although the molded body was removed from the mold, a part of the molded body was fixed to the mold wall surface, and when the target was taken out, peeling occurred from the fixed portion, and the target target shape could not be maintained. The amount of water was 1011 ppm and the amount of sulfate ions was 512 ppm.

比較例４
実施例４で得た硫化亜鉛混合物３０ｇに硫黄６ｇ、塩化ナトリウム１．５ｇを添加、混合して、窒素下にて、１０００℃で３時間加熱焼成し、室温まで冷却した。得られた硫化亜鉛複合体は粒径Ｄ５０が３５μｍの粉末であった。得られた粉末を比表面積測定したところ、０．０９ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．１８３°であった。また、水分量は６４ｐｐｍ、硫酸イオン量は６６ｐｐｍであった。Comparative Example 4
6 g of sulfur and 1.5 g of sodium chloride were added to 30 g of the zinc sulfide mixture obtained in Example 4 and mixed, heated and fired at 1000 ° C. for 3 hours under nitrogen, and cooled to room temperature. The obtained zinc sulfide composite was a powder having a particle size D50 of 35 μm. When the specific surface area of the obtained powder was measured, it was 0.09 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.183 °. The water content was 64 ppm and the sulfate ion content was 66 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ３ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．８６であった。得られたターゲット材の嵩密度は３．４１ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．８５であった。また、水分量は３５ｐｐｍ、硫酸イオン量は３１ｐｐｍであった。 The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 3 mm. A part of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.86. The obtained target material had a bulk density of 3.41 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.85. The water content was 35 ppm, and the sulfate ion content was 31 ppm.

比較例５
実施例２において、複合硫化物を７００℃で焼成し、加熱成型を１０００℃で実施した以外は、実施例２と同様に行った。得られた硫化亜鉛複合体は粒径Ｄ５０が２２μｍの粉末であった。得られた粉末を比表面積測定したところ、０．１８ｍ２／ｇであった。得られた粉末をＸＲＤ測定したところ、２θ＝３３°の半値幅は０．２２３°であった。また、水分は９６ｐｐｍ、硫酸イオンは１３８ｐｐｍであった。Comparative Example 5
In Example 2, it carried out like Example 2 except having baked the composite sulfide at 700 degreeC and heat-molding at 1000 degreeC. The obtained zinc sulfide composite was a powder having a particle size D50 of 22 μm. When the specific surface area of the obtained powder was measured, it was 0.18 m 2 / g. When the obtained powder was measured by XRD, the half width at 2θ = 33 ° was 0.223 °. The water content was 96 ppm, and the sulfate ion was 138 ppm.

成型した後、円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．８８であった。得られたターゲットの嵩密度は３．７６ｇ／ｃｍ３であり、相対密度（実測密度と理論密度との比）は０．９４であった。また、得られた成型体の水分量は１９ｐｐｍ、硫酸イオン量は３７ｐｐｍであった。After molding, a part of the cylindrical target material was taken, dissolved with 1N hydrochloric acid, titrated with EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.88. The obtained target had a bulk density of 3.76 g / cm 3 and a relative density (ratio of measured density to theoretical density) of 0.94. Further, the obtained molded body had a water content of 19 ppm and a sulfate ion content of 37 ppm.

比較例６
比較例４において、硫化亜鉛複合体を１１００℃で加熱焼成した以外は、比較例４と同様に実施した。得られた硫化亜鉛複合体は粒径Ｄ５０が３８μｍの粉末であった。得られた硫化亜鉛複合体粉末を比表面積測定したところ、０．０８ｍ２／ｇであった。２θ＝３３°の半値幅は０．１４４°であった。また、水分量は１２ｐｐｍ、硫酸イオン量は３８ｐｐｍであった。Comparative Example 6
Comparative Example 4 was carried out in the same manner as Comparative Example 4 except that the zinc sulfide composite was heated and fired at 1100 ° C. The obtained zinc sulfide composite was a powder having a particle size D50 of 38 μm. It was 0.08 m < 2 > / g when the specific surface area of the obtained zinc sulfide composite powder was measured. The half width at 2θ = 33 ° was 0.144 °. The water content was 12 ppm, and the sulfate ion content was 38 ppm.

３０ｍｍφのモールドに、得られた硫化亜鉛複合体１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Ｐａまで減圧し、１０分間保持、アルゴンにて常圧に解放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。12 g of the obtained zinc sulfide composite was put into a 30 mmφ mold and filled in a hot press machine. The inside of the mold was depressurized to 130 Pa, held for 10 minutes, and released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours.

モールドから成型体をはずし、３０ｍｍφ、厚さ４．３５ｍｍの円筒形ターゲット材を得た。得られたターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．８２であった。得られたターゲット材の嵩密度は３．０７ｇ／ｃｍ３であり、相対密度（嵩密度と理論密度との比）は０．７７であった。また、水分量は１５ｐｐｍ、硫酸イオン量は３３ｐｐｍであった。 The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 4.35 mm. A part of the obtained target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.82. The obtained target material had a bulk density of 3.07 g / cm 3 and a relative density (ratio of bulk density to theoretical density) of 0.77. The water content was 15 ppm and the sulfate ion content was 33 ppm.

実施例８
２Lセパラブルフラスコに、硝酸亜鉛六水和物３６０．０ｇ、硫酸マグネシウム７．２ｇ、０．１Ｍ硝酸銀水溶液５７．０ｍＬ、硝酸ガリウム八水和物３．６６ｇを取り、イオン交換水１２００ｇを加えて溶解した。そこに硝酸１．５ｇを添加して、系中のｐHを２程度に調整する。そのフラスコに、攪拌器、温度計、還流管を装着し、ｐHを調整した液を攪拌しながら、９０℃まで昇温する。所定の温度に到達したところで、チオアセトアミド１３３．６ｇを固体で添加した。添加終了後、２時間攪拌した後、反応停止のため、系内を３０℃まで冷却した。冷却中、窒素を流気し、系内の硫化水素を排出した。得られた反応液からデカンテーションで反応液を除き、更にイオン交換水にて残りの固体の洗浄を行い、洗液のｐＨが５以上になるまで洗浄を行なった。洗浄が終了した固体を、１５０℃にて１２時間熱風乾燥し、銀がドーピングされた硫化亜鉛複合体９３．５ｇを得た。得られた硫化亜鉛複合体は粒径Ｄ５０が１６μｍの粉末であった。得られた粉末をX線回折（ＸＲＤ）測定したところ、２θ＝３３°の回折ピークの半値幅は１．３６３°であった。また、水分は６１２ｐｐｍ、硫酸イオンは４４７ｐｐｍであった。Example 8
To a 2 L separable flask, take 360.0 g of zinc nitrate hexahydrate, 7.2 g of magnesium sulfate, 57.0 mL of 0.1 M silver nitrate aqueous solution, and 3.66 g of gallium nitrate octahydrate, and add 1200 g of ion-exchanged water. Dissolved. To this, 1.5 g of nitric acid is added to adjust the pH in the system to about 2. The flask is equipped with a stirrer, a thermometer, and a reflux tube, and the temperature is raised to 90 ° C. while stirring the liquid whose pH has been adjusted. When the predetermined temperature was reached, 133.6 g of thioacetamide was added as a solid. After completion of the addition, the mixture was stirred for 2 hours, and then the system was cooled to 30 ° C. to stop the reaction. During cooling, nitrogen was passed to discharge hydrogen sulfide in the system. The reaction solution was removed from the obtained reaction solution by decantation, and the remaining solid was washed with ion-exchanged water until the pH of the washing solution became 5 or higher. The solid after the washing was dried with hot air at 150 ° C. for 12 hours to obtain 93.5 g of a zinc sulfide composite doped with silver. The obtained zinc sulfide composite was a powder having a particle size D50 of 16 μm. When the obtained powder was measured by X-ray diffraction (XRD), the half width of the diffraction peak at 2θ = 33 ° was 1.363 °. The water content was 612 ppm and the sulfate ion was 447 ppm.

３０ｍｍφのモールドに、上記で得られた硫化亜鉛複合体粉末１２ｇを入れ、ホットプレス機に充填した。モールド内を１３０Paまで減圧し、１０分間保持、減圧をアルゴンにて常圧に開放した。この操作を３回実施し、モールド内の減圧をアルゴンガスで常圧に開放し、プレス圧（２００Ｋｇ／ｃｍ２）を硫化亜鉛複合体にかけながら９００℃まで１時間で昇温した。昇温後プレス圧を解除し、２時間で室温まで冷却した。モールドから成型体をはずし、３０ｍｍφ、厚さ５．４９ｍｍの円筒形ターゲット材を得た。得られたターゲット材の嵩密度は３．８９ｇ／ｃｍ３であり、相対密度は０．９７であった。得られた円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９２であった。また、水分量は２４ｐｐｍ、硫酸イオン量は４６ｐｐｍであった。12 g of the zinc sulfide composite powder obtained above was placed in a 30 mmφ mold and filled in a hot press machine. The inside of the mold was reduced to 130 Pa, held for 10 minutes, and the reduced pressure was released to normal pressure with argon. This operation was carried out three times, the pressure inside the mold was released to normal pressure with argon gas, and the temperature was raised to 900 ° C. over 1 hour while applying a press pressure (200 Kg / cm 2 ) to the zinc sulfide composite. After raising the temperature, the press pressure was released, and the mixture was cooled to room temperature in 2 hours. The molded body was removed from the mold to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.49 mm. The obtained target material had a bulk density of 3.89 g / cm 3 and a relative density of 0.97. A part of the obtained cylindrical target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.92. The water content was 24 ppm, and the sulfate ion content was 46 ppm.

実施例９
実施例８において、硫酸マグネシウムの使用量を２．５ｇ、硝酸の使用量を０．５ｇとし、洗浄が終了した固体の乾燥温度を２００℃にした以外は、実施例８と同様に実施し、銀がドーピングされた硫化亜鉛複合体９１．５ｇを得た。得られた硫化亜鉛複合体は粒径Ｄ５０が６７μｍの粉末であった。その硫化亜鉛複合体粉末の２θ＝３３°の回折ピークの半値幅は１．３３３°であった。また、水分は５０６ｐｐｍ、硫酸イオン量は４１７ｐｐｍであった。この粉末を実施例８と同様にしてプレスして３０ｍｍφ、厚さ５．０９ｍｍの円筒形ターゲット材を得た。得られたターゲット材の嵩密度は３．６１ｇ／ｃｍ３であり、相対密度は０．９０であった。得られた円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．９３であった。また、水分量は２６ｐｐｍ、硫酸イオン量は４８ｐｐｍであった。Example 9
In Example 8, the amount of magnesium sulfate used was 2.5 g, the amount of nitric acid used was 0.5 g, and the drying temperature of the solid after the washing was changed to 200 ° C. 91.5 g of zinc sulfide composite doped with silver was obtained. The obtained zinc sulfide composite was a powder having a particle size D50 of 67 μm. The half width of the diffraction peak at 2θ = 33 ° of the zinc sulfide composite powder was 1.333 °. The water content was 506 ppm and the sulfate ion content was 417 ppm. This powder was pressed in the same manner as in Example 8 to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 5.09 mm. The obtained target material had a bulk density of 3.61 g / cm 3 and a relative density of 0.90. A part of the obtained cylindrical target material was taken, dissolved in 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.93. The water content was 26 ppm, and the sulfate ion content was 48 ppm.

比較例７
実施例２において、硫化亜鉛複合体粉末１２ｇに塩化ナトリウム１．５ｇ及び塩化マグネシウム３ｇを添加し、１１００℃で加熱焼成した以外は、実施例２と同様に実施し、焼成後の硫化亜鉛複合体を得た。得られた硫化亜鉛複合体は粒径Ｄ５０が１０４μｍの粉末であった。その硫化亜鉛複合体粉末の２θ＝３３°の回折ピークの半値幅は０．１９８°、水分は７７ｐｐｍ、硫酸イオン量は６７ｐｐｍであった。この粉末を実施例２と同様にしてプレスして３０ｍｍφ、厚さ４．５２ｍｍの円筒形ターゲット材を得た。得られたターゲット材の嵩密度は３．２０ｇ／ｃｍ３であり、相対密度は０．８０であった。得られた円筒形ターゲット材の一部を取り、１Ｎ塩酸で溶解、ＥＤＴＡ溶液で滴定し、金属含量を定量した結果、硫黄／亜鉛＝０．８８であった。また、水分量は２１ｐｐｍ、硫酸イオン量は３３ｐｐｍであった。Comparative Example 7
In Example 2, the same procedure as in Example 2 was carried out except that 1.5 g of sodium chloride and 3 g of magnesium chloride were added to 12 g of the zinc sulfide composite powder and heated and fired at 1100 ° C. Got. The obtained zinc sulfide composite was a powder having a particle size D50 of 104 μm. The full width at half maximum of the diffraction peak at 2θ = 33 ° of the zinc sulfide composite powder was 0.198 °, the water content was 77 ppm, and the sulfate ion content was 67 ppm. This powder was pressed in the same manner as in Example 2 to obtain a cylindrical target material having a diameter of 30 mm and a thickness of 4.52 mm. The obtained target material had a bulk density of 3.20 g / cm 3 and a relative density of 0.80. A part of the obtained cylindrical target material was taken, dissolved with 1N hydrochloric acid, titrated with an EDTA solution, and the metal content was quantified. As a result, sulfur / zinc = 0.88. The water content was 21 ppm, and the sulfate ion content was 33 ppm.

Figure 2009028641
Figure 2009028641

Figure 2009028641
Figure 2009028641

本発明によれば、1に近い硫黄／亜鉛比を有する硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも1種の元素を含む硫化物とを含む高い成型性を有する複合硫化物の成型体を提供することができる。かかる成型体は発光層を形成する際のターゲット材として有用である。また、本発明の成型体の製造方法によれば、このような成型体を高い生産性で生産することができ、産業上有用である。  According to the present invention, a composite sulfide having high moldability comprising zinc sulfide or zinc sulfide having a sulfur / zinc ratio close to 1 and a sulfide containing at least one element of silver, copper, manganese and rare earths is obtained. A molded body can be provided. Such a molded body is useful as a target material for forming a light emitting layer. Moreover, according to the manufacturing method of the molded object of this invention, such a molded object can be produced with high productivity, and it is industrially useful.

Claims (7)

硫黄／亜鉛の比が０．９以上である硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物からなる成型体。A molded article comprising zinc sulfide or zinc sulfide having a sulfur / zinc ratio of 0.9 or more and a composite sulfide containing sulfide containing at least one element of silver, copper, manganese and rare earth. 該成型体の相対密度が０．９以上である請求項１記載の成型体。The molded body according to claim 1, wherein the molded body has a relative density of 0.9 or more. 該成型体に含有される水分が５０ｐｐｍ以下である請求項１または２記載の成型体。The molded article according to claim 1 or 2, wherein the moisture contained in the molded article is 50 ppm or less. 該成型体に含有される硫酸イオンが５００ｐｐｍ以下である請求項１〜３いずれかに記載の成型体。The molded article according to any one of claims 1 to 3, wherein the molded article contains 500 ppm or less of sulfate ions. 粒径が１００μｍ以下であり、比表面積測定において、０．２ｍ２／ｇ〜５０ｍ２／ｇである硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物を７００℃以上１１００℃以下の温度下に加圧成型することを特徴とする硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物からなる成型体の製造方法。Particle size is at 100μm or less, in the specific surface area measurement, a sulfide containing 0.2m 2 / g~50m 2 / g and a zinc sulfide or zinc sulfide and silver, copper, at least one element of manganese, and rare earth Zinc sulfide or zinc sulfide, and a sulfide containing at least one element of silver, copper, manganese, and rare earth, characterized in that a composite sulfide containing is pressure-molded at a temperature of 700 ° C. to 1100 ° C. The manufacturing method of the molded object which consists of a composite sulfide containing. 該硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物の、Ｘ線結晶解析における、２θ＝３３°の回折ピークの半値幅が０．２°〜１．５°である請求項５記載の成型体の製造方法。The half width of the diffraction peak at 2θ = 33 ° in the X-ray crystal analysis of the composite sulfide containing zinc sulfide or zinc sulfide and a sulfide containing at least one element of silver, copper, manganese and rare earth is 0. The method for producing a molded body according to claim 5, wherein the angle is 2 ° to 1.5 °. 硫化亜鉛または硫化亜鉛と銀、銅、マンガンおよび希土類の少なくとも１種の元素を含む硫化物とを含む複合硫化物が水溶液下で調製される請求項５または６記載の成型体の製造方法。
The method for producing a molded article according to claim 5 or 6, wherein a composite sulfide containing zinc sulfide or zinc sulfide and a sulfide containing at least one element of silver, copper, manganese and rare earth is prepared in an aqueous solution.
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