JP5417720B2 - Method for producing ZnO vapor deposition material and method for forming vapor deposition film using vapor deposition material produced by the method - Google Patents
Method for producing ZnO vapor deposition material and method for forming vapor deposition film using vapor deposition material produced by the method Download PDFInfo
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- 238000007740 vapor deposition Methods 0.000 title claims description 64
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- 239000000843 powder Substances 0.000 claims description 46
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、ＡＣ型のプラズマディスプレイパネルに用いられる膜や、透明導電膜の成膜等に好適なＺｎＯ蒸着材の製造方法及び該方法により製造された蒸着材を用いて蒸着膜を形成する方法に関するものである。 The present invention relates to a method for producing a ZnO vapor deposition material suitable for a film used for an AC type plasma display panel, a film for forming a transparent conductive film, and the like, and a method for forming a vapor deposition film using the vapor deposition material produced by the method. It is about.
従来、液晶（Liquid Crystal Display : ＬＣＤ）をはじめとして、各種の平面ディスプレイの研究開発と実用化はめざましく、その生産も急増している。カラープラズマディスプレイパネル（ＰＤＰ）についても、その開発と実用化の動きが最近活発になっている。ＰＤＰは、電極構造の点で金属電極がガラス誘電体層で覆われるＡＣ型と、放電空間に金属電極が露出しているＤＣ型とに分類されるが、ＡＣ型が主流である。
このＡＣ型ＰＤＰでは、イオン衝撃のスパッタリングによりガラス誘電体層の表面が変質して放電開始電圧が上昇しないように、ガラス誘電体層表面に高い昇華熱を持つ保護膜をコーティングする必要がある。この保護膜は直接放電空間と接しているため、耐スパッタリング性の他に複数の重要な役割を担っている。即ち、保護膜に求められる特性は、放電時の耐スパッタリング性、高い二次電子放出能、絶縁性及び光透過率などである。これらの条件を満たす材料として、一般的にＭｇＯが挙げられ、このＭｇＯを蒸着材として電子ビーム蒸着法又はイオンプレーティング法により成膜されたＭｇＯ膜が使用されている。
Conventionally, research and development and practical application of various flat displays including liquid crystal display (LCD) have been remarkable, and their production has been rapidly increasing. The development and practical application of the color plasma display panel (PDP) has recently become active. PDPs are classified into an AC type in which a metal electrode is covered with a glass dielectric layer in terms of an electrode structure and a DC type in which the metal electrode is exposed in a discharge space, but the AC type is the mainstream.
In this AC type PDP, it is necessary to coat a protective film having high sublimation heat on the surface of the glass dielectric layer so that the surface of the glass dielectric layer is not altered by ion bombardment sputtering and the discharge start voltage is increased. Since this protective film is in direct contact with the discharge space, it plays multiple important roles in addition to sputtering resistance. That is, the characteristics required for the protective film are sputtering resistance during discharge, high secondary electron emission ability, insulation, light transmittance, and the like. As a material satisfying these conditions, MgO is generally used, and an MgO film formed by electron beam evaporation or ion plating using MgO as an evaporation material is used.
そして、このＭｇＯ膜を成膜するための蒸着材として、ＭｇＯ純度が９９．５％以上かつ相対密度が９７％以上の多結晶ＭｇＯの焼結体ペレットからなる多結晶ＭｇＯ蒸着材（例えば、特許文献１参照）が知られている。この特許文献１に記載された多結晶ＭｇＯ蒸着材では、高純度かつ高密度の多結晶ＭｇＯ蒸着材を用いてＡＣ型ＰＤＰ等のＭｇＯ膜を成膜すると、スプラッシュが極めて少なく高速で安定した成膜ができるとともに、膜厚分布を向上できるので、略均一な膜質を有するＭｇＯ膜を得られるとしている。 As a deposition material for forming this MgO film, a polycrystalline MgO deposition material comprising a sintered pellet of polycrystalline MgO having a MgO purity of 99.5% or more and a relative density of 97% or more (for example, a patent Document 1) is known. In the polycrystalline MgO vapor deposition material described in Patent Document 1, when a MgO film such as an AC-type PDP is formed using a high-purity and high-density polycrystalline MgO vapor deposition material, there is very little splash and a stable composition at high speed. Since a film can be formed and the film thickness distribution can be improved, an MgO film having a substantially uniform film quality can be obtained.
一方、太陽電池などの光電変換装置などを製造する場合には、透明導電膜が不可欠である。従来の透明導電膜としては、ＩＴＯ膜（錫をドープしたインジウム酸化物膜）が知られている。ＩＴＯ膜は、透明性に優れ、低抵抗であるという利点を有する。ここで、太陽電池や液晶表示装置等にあっては、その低コスト化が求められている。しかし、インジウムが高価なことから、ＩＴＯ膜を透明導電膜として用いると、その太陽電池等も必然的に高価なものになってしまう難点があった。
この点を解消するために、一層安価に作製することのできるＡｌ、Ｂ、Ｓｉなどの導電活性元素をドープした酸化亜鉛系膜を太陽電池等の透明導電膜として使用することが提案され、この酸化亜鉛系膜を電子ビーム蒸着法や、イオンプレーティング法などでの真空蒸着により形成するための酸化亜鉛系ターゲットが提案されている（例えば、特許文献２参照。）。この酸化亜鉛系ターゲットによると、上記導電活性元素を亜鉛に対して所定量含有させることにより極めて低抵抗な酸化亜鉛系焼結体が得られ、この焼結体は、原料粉末が微細で高分散性を有するほど焼結密度が向上し導電性が向上するとされている。
In order to eliminate this point, it has been proposed to use a zinc oxide-based film doped with a conductive active element such as Al, B, and Si, which can be produced at a lower cost, as a transparent conductive film for solar cells, etc. A zinc oxide-based target for forming a zinc oxide-based film by vacuum deposition such as an electron beam deposition method or an ion plating method has been proposed (for example, see Patent Document 2). According to this zinc oxide-based target, a zinc oxide-based sintered body having extremely low resistance can be obtained by containing a predetermined amount of the above-mentioned conductive active element with respect to zinc. It is said that the higher the property, the higher the sintered density and the higher the conductivity.
しかし、上記特許文献に示されたそれぞれの蒸着材は、多孔質であることから、ＭｇＯ膜又はＺｎＯ膜を成膜するためにその蒸着材を加熱すると多孔質内部のガスが膨張し、この膨張したガスの逃げ場がなく蒸着材に大きな応力が発生する。このため上記応力により蒸着材にクラックが生じ、このクラックを起点に蒸着材の一部が破損して破損微粒子が飛び散り、スプラッシュが発生する不具合があった。
本発明の目的は、膜の成膜時にスプラッシュの発生を防止することができる、ＺｎＯ蒸着材の製造方法及び該方法により製造された蒸着材を用いて蒸着膜を形成する方法を提供することにある。
However, since each vapor deposition material shown in the above-mentioned patent document is porous, when the vapor deposition material is heated to form an MgO film or a ZnO film, the gas inside the porous material expands, and this expansion There is no escape space for the generated gas, and a large stress is generated in the vapor deposition material. For this reason, a crack is generated in the vapor deposition material due to the stress, and a part of the vapor deposition material is broken starting from the crack, and the broken fine particles are scattered, resulting in a splash.
The objective of this invention is providing the manufacturing method of a ZnO vapor deposition material which can prevent generation | occurrence | production of a splash at the time of film-forming, and the method of forming a vapor deposition film using the vapor deposition material manufactured by this method. is there.
請求項１に係る発明は、ＺｎＯの多孔質焼結体からなり、前記焼結体が０．２以上１．５％未満の気孔率を有し、前記焼結体が丸みを帯びた気孔を有し、前記気孔の表面に更に細かい気孔が形成されているＺｎＯ蒸着材の製造方法であって、前記多孔質焼結体は、純度が９９．０％以上で平均粒径が０．１〜１０μｍのＺｎＯの粉末とバインダと有機溶媒とを減圧下において混合して濃度が４５〜７５質量％で粘度が２００〜１０００ｃｐｓのスラリーを調製する工程と、前記スラリーを減圧下において噴霧乾燥して平均粒径が５０〜３００μｍの造粒粉末を得る工程と、前記造粒粉末を減圧下において成形する工程と、前記成形体を３５０〜６２０℃の温度で脱脂処理する工程と、前記脱脂処理された成形体を１０００〜１４００℃の温度で１〜５時間常圧下において焼結する工程とによって、得られることを特徴とする。
この請求項１に記載された方法で製造されたＺｎＯ蒸着材は０．１〜３００μｍの範囲の平均気孔径を有する。気孔の平均気孔径が０．１〜３００μｍとすることによって、蒸発速度を高くすることが可能となり、成膜速度を大きくして製造コストを低減することができる。
なお、気孔径（気孔の内径）とは、例えばＳＥＭ（走査電子顕微鏡）等の観察手段によって蒸着材断面部分を観察した際に、存在する気孔においてその内部寸法のうち最大のものを意味する。この気孔の評価方法としては、置換法による気孔率の測定、顕微鏡法による気孔率の測定、ガス吸着による表面積及び細孔分布の測定、水銀圧入法による表面積及び細孔分布の測定、ガス透過法による表面積測定、又はＸ線小角散乱法による細孔分布の測定等を採用することができる。
The invention according to claim 1 is a porous sintered body of ZnO, wherein the sintered body has a porosity of 0.2 to 1.5%, and the sintered body has rounded pores. And a method for producing a ZnO vapor deposition material in which finer pores are formed on the surface of the pores , wherein the porous sintered body has a purity of 99.0% or more and an average particle size of 0.1 to 0.1%. 10 μm ZnO powder, a binder, and an organic solvent are mixed under reduced pressure to prepare a slurry having a concentration of 45 to 75 mass% and a viscosity of 200 to 1000 cps, and the slurry is spray-dried under reduced pressure to average A step of obtaining a granulated powder having a particle size of 50 to 300 μm, a step of molding the granulated powder under reduced pressure, a step of degreasing the molded body at a temperature of 350 to 620 ° C., and the degreasing treatment The temperature of the molded body is 1000-1400 ° C. By a step of sintering at 1 to 5 hours under normal pressure, it characterized by being obtained.
The ZnO vapor deposition material manufactured by the method described in claim 1 has an average pore diameter in the range of 0.1 to 300 μm. By setting the average pore diameter of the pores to 0.1 to 300 μm, the evaporation rate can be increased, and the film formation rate can be increased to reduce the manufacturing cost.
Note that the pore diameter (inner diameter of the pores) means the largest of the internal dimensions of the existing pores when the cross section of the vapor deposition material is observed by an observation means such as SEM (scanning electron microscope). The evaluation method of this pore includes the measurement of the porosity by the substitution method, the measurement of the porosity by the microscopic method, the measurement of the surface area and the pore distribution by gas adsorption, the measurement of the surface area and the pore distribution by the mercury intrusion method, the gas permeation method It is possible to employ a surface area measurement by means of, or a pore distribution measurement by an X-ray small angle scattering method.
請求項２に係る発明は、請求項１記載の方法により製造されたＺｎＯ蒸着材を用いて蒸着膜を形成する方法である。 The invention according to claim 2 is a method of forming a vapor deposition film using the ZnO vapor deposition material manufactured by the method according to claim 1 .
なお、この明細書において、金属酸化物粉末や多孔質造粒粉末の平均粒径の値は、レーザー回折法により算出又は測定される値とする。 In this specification, the value of the average particle diameter of the metal oxide powder or porous granulated powder is a value calculated or measured by a laser diffraction method.
本発明の蒸着材では、その気孔率を０．２以上１．５％未満とするので、蒸着材の内部に存在するガスを著しく減少させることができる。このため、膜を成膜するためにその蒸着材を加熱しても、多孔質内部のガスが膨張することに起因する応力は従来よりも減少する。これにより蒸着材にクラックが生じるようなことはなく、クラックに起因するスプラッシュの発生を有効に防止することができる。そして、気孔の平均気孔径を０．１〜３００μｍとすることによって、蒸発速度を高くすることが可能となり、成膜速度を大きくして製造コストを低減することができる。また焼結体が丸みを帯びた気孔を有し、この気孔の表面に更に細かい気孔が形成されることにより、蒸発速度を更に向上させることができる。 In the vapor deposition material of this invention, since the porosity is 0.2 or more and less than 1.5 %, the gas existing inside the vapor deposition material can be significantly reduced. For this reason, even if the vapor deposition material is heated to form a film, the stress caused by the expansion of the gas inside the porous body is reduced as compared with the conventional case. Thereby, a crack does not arise in a vapor deposition material, and generation | occurrence | production of the splash resulting from a crack can be prevented effectively. By setting the average pore diameter of the pores to 0.1 to 300 μm, the evaporation rate can be increased, and the film formation rate can be increased to reduce the manufacturing cost. Further, the sintered body has rounded pores, and finer pores are formed on the surfaces of the pores, whereby the evaporation rate can be further improved.
次に、本発明に係るＺｎＯ蒸着材の製造方法の実施の形態を詳しく説明する。
本実施形態の方法により製造されたＺｎＯ蒸着材は、気孔率が０．２以上１．５％未満の多結晶ＺｎＯの焼結体ペレットからなる。この焼結体ペレットからなるＺｎＯ蒸着材は、円板状又は球状に形成される。この蒸着材が球状である場合には、その直径は５〜３０ｍｍ、好ましくは５〜１５ｍｍに形成される。この直径を５〜３０ｍｍに限定したのは、直径が５ｍｍ未満では小さすぎてスプラッシュの発生原因となり、直径が３０ｍｍを越えると実際の製造工程において取り扱いが困難となるからである。この蒸着材が円板状である場合には、その直径は５〜４０ｍｍ、好ましくは５〜２０ｍｍであって、高さが１〜２０ｍｍ、好ましくは２〜１０ｍｍに形成される。この直径を５〜４０ｍｍに限定し、高さを１〜２０ｍｍに限定したのは、直径が５ｍｍ未満又は高さが１ｍｍ未満では小さすぎてスプラッシュの発生原因となり、直径が４０ｍｍを越えるか又は高さが２０ｍｍを越えると実際の製造工程において取り扱いが困難となるからである。
Next, an embodiment of a method for producing a ZnO vapor deposition material according to the present invention will be described in detail.
The ZnO vapor deposition material manufactured by the method of the present embodiment is made of a sintered pellet of polycrystalline ZnO having a porosity of 0.2 or more and less than 1.5%. The ZnO vapor deposition material made of this sintered pellet is formed in a disk shape or a spherical shape. When this vapor deposition material is spherical, the diameter is 5-30 mm, preferably 5-15 mm. The reason why this diameter is limited to 5 to 30 mm is that if the diameter is less than 5 mm, it is too small and causes splashing, and if the diameter exceeds 30 mm, handling becomes difficult in the actual manufacturing process. When this vapor deposition material is disk shape, the diameter is 5-40 mm, Preferably it is 5-20 mm, Comprising: Height is formed in 1-20 mm, Preferably it is 2-10 mm. This diameter is limited to 5 to 40 mm, and the height is limited to 1 to 20 mm. If the diameter is less than 5 mm or the height is less than 1 mm, it is too small and causes splash, and the diameter exceeds 40 mm or is high. If the thickness exceeds 20 mm, handling becomes difficult in the actual manufacturing process.
また、この焼結体ペレットの平均結晶粒径は１〜３００μｍであり、焼結体からなる多結晶ペレットの結晶粒内には平均気孔径０．１〜３００μｍ程度の丸みを帯びた気孔を有する多孔質焼結体とされる。更に、本実施形態のＺｎＯ蒸着材は、ＺｎＯ純度が９９．０％以上、更に好ましくは９９．５％以上、９９．９％以上の多結晶ＺｎＯの焼結体ペレットからなる。ここで、気孔率が０．２％未満である場合には、蒸発速度が所望の高さに維持できないため好ましくなく、また、気孔率が３．０％以上である場合には、スプラッシュの発生が多くなってしまうため好ましくない。 The average grain size of the sintered pellet is 1 to 300 μm, and the polycrystalline pellet made of the sintered body has round pores having an average pore diameter of about 0.1 to 300 μm. It is a porous sintered body. Furthermore, the ZnO vapor deposition material of the present embodiment is made of a sintered pellet of polycrystalline ZnO having a ZnO purity of 99.0% or more, more preferably 99.5% or more and 99.9% or more. Here, when the porosity is less than 0.2%, it is not preferable because the evaporation rate cannot be maintained at a desired height, and when the porosity is 3.0% or more, splash is generated. Is unfavorable because of an increase in the amount of.
本発明では、気孔の平均気孔径が０．１〜３００μｍであり、かつ上記の気孔率とされることによって、蒸発速度を高くすることが可能となる。更に、気孔の平均気孔径が０．１〜２５０μｍの範囲にあること、又は、気孔の平均気孔径が０．１〜１００μｍの範囲にあることにより、より一層蒸発速度を高めることが可能となる。ここで、気孔径が０．１μｍ未満である場合には、気孔を有するメリットがないため好ましくなく、気孔径が３００μｍを越えた場合には、焼結体の強度が低下するため、ＥＢ（電子ビーム）照射による破損、即ちスプラッシュの原因となるため好ましくない。 In the present invention, by setting the average pore diameter of the pores to 0.1 to 300 μm and the above porosity, the evaporation rate can be increased. Furthermore, when the average pore diameter of the pores is in the range of 0.1 to 250 μm, or the average pore diameter of the pores is in the range of 0.1 to 100 μm, the evaporation rate can be further increased. . Here, when the pore diameter is less than 0.1 μm, it is not preferable because there is no merit of having pores, and when the pore diameter exceeds 300 μm, the strength of the sintered body is reduced, so that EB (electron This is not preferable because it causes damage due to beam) irradiation, that is, splash.
なお、本発明に係る蒸着材は、気孔の形状が丸みを帯びていて、気孔の表面に更に細かい気孔が形成されていることが蒸発速度向上のために必要である。また、気孔の評価方法として、表面積測定において、５〜４０ｍ2／ｇ であることが、細孔分布の測定においては、１〜１００μｍの範囲に少なくとも一つの細孔分布のピークを持つことが必要である。 In the vapor deposition material according to the present invention, it is necessary for improving the evaporation rate that the pores are rounded and finer pores are formed on the surface of the pores . In addition, as a method for evaluating pores, it is necessary that the surface area measurement is 5 to 40 m 2 / g, and the pore distribution measurement is required to have at least one pore distribution peak in the range of 1 to 100 μm. It is .
また、気孔以外の部分（骨部分）はほぼ焼結している状態とされ、例えば、多孔質焼結体の骨部分の密度は９８％以上であることが好ましく、更に、前記ＺｎＯの焼結体からなる多結晶ペレットの平均結晶粒径が１〜３００μｍであって、焼結体ペレット内に０．１〜３００μｍ程度の丸みを帯びた気孔を有することができる。このＺｎＯ蒸着材では、多結晶ＺｎＯの焼結体ペレットが微細な結晶構造を有し、かつその結晶粒界に欠陥が生じるのを低減できるため、成膜されたＺｎＯ膜は、ＺｎＯの膜密度、膜厚分布、屈折率、耐スパッタ性、放電特性（放電電圧、放電応答性等）、絶縁性等の膜特性が優れたものとなる。ここで、平均結晶粒径が１μｍ未満であると成膜速度を低下させる不具合があり、その平均結晶粒径が３００μｍを越えると添加元素の蒸着率が不均一になる不具合がある。そしてこの平均結晶粒径は５〜４０μｍの範囲にあることが好ましく、１０〜３０μｍの範囲にあることが更に好ましい。 Further, the portions other than the pores (bone portions) are almost sintered. For example, the density of the bone portions of the porous sintered body is preferably 98% or more, and further, the ZnO is sintered. The average crystal grain size of the polycrystalline pellet made of a body is 1 to 300 μm, and the sintered pellet can have rounded pores of about 0.1 to 300 μm. In this ZnO vapor deposition material, the polycrystalline ZnO sintered body pellets have a fine crystal structure and can reduce the occurrence of defects at the crystal grain boundaries. Therefore, the formed ZnO film has a ZnO film density. Excellent film characteristics such as film thickness distribution, refractive index, sputter resistance, discharge characteristics (discharge voltage, discharge response, etc.) and insulation. Here, if the average crystal grain size is less than 1 μm, there is a problem that the film forming speed is reduced, and if the average crystal grain size exceeds 300 μm, the deposition rate of the additive element becomes non-uniform. The average crystal grain size is preferably in the range of 5 to 40 μm, and more preferably in the range of 10 to 30 μm.
次に、このように構成されたＺｎＯ蒸着材の製造方法を説明する。
まず、純度が９９．０％以上のＺｎＯ粉末とバインダと有機溶媒とを減圧下において混合して濃度が４５〜７５質量％のスラリーを調製する。スラリーの濃度を４５〜７５質量％に限定したのは、７５質量％を越えると上記スラリーが非水系であるため、安定した造粒が難しい問題点があり、４５質量％未満では均一な組織を有する緻密なＺｎＯ焼結体が得られないからである。即ち、スラリー濃度を上記範囲に限定すると、スラリーの粘度が２００〜１０００ｃｐｓとなり、スプレードライヤによる粉末の造粒を安定して行うことができる。そして、この混合を減圧下において行うことによりスラリーに含まれるガスを減少させることにより、後述する成形体の密度が高くなって緻密な焼結体の製造が可能になる。
Next, the manufacturing method of the ZnO vapor deposition material comprised in this way is demonstrated.
First, a ZnO powder having a purity of 99.0% or more, a binder, and an organic solvent are mixed under reduced pressure to prepare a slurry having a concentration of 45 to 75% by mass. The reason why the concentration of the slurry is limited to 45 to 75% by mass is that when the amount exceeds 75% by mass, the slurry is non-aqueous, so there is a problem that stable granulation is difficult. This is because a dense ZnO sintered body cannot be obtained. That is, when the slurry concentration is limited to the above range, the slurry has a viscosity of 200 to 1000 cps and can be stably granulated with a spray dryer. Then, by reducing the gas contained in the slurry by performing this mixing under reduced pressure, the density of the molded body described later is increased, and a dense sintered body can be produced.
ここで、ＺｎＯ粉末の平均粒径は０．１〜１０μｍの範囲内にあることが好ましい。ＺｎＯ粉末の平均粒径を０．１〜１０μｍと限定したのは、０．１μｍ未満では、粉末が細かすぎて凝集するため、粉末のハンドリングが悪くなり、４５質量％以上の高濃度スラリーを調製することが困難となるためであり、１０μｍを越えると、微細構造の制御が難しく、緻密な焼結体ペレットが得られないからである。またＺｎＯ粉末の平均粒径を上記範囲に限定すると、焼結助剤を用いなくても所望の焼結体ペレットが得られる利点もある。バインダとしてはポリエチレングリコールやポリビニールブチラール等を、有機溶媒としてはエタノールやプロパノール等を用いることが好ましい。バインダは０．２〜２．５質量％添加することが好ましい。ここで、バインダと添加剤とが共通のブチラール系である場合、バインダを別に添加する必要がなくなる。 Here, it is preferable that the average particle diameter of ZnO powder exists in the range of 0.1-10 micrometers. The reason why the average particle size of the ZnO powder is limited to 0.1 to 10 μm is that if it is less than 0.1 μm, the powder is too fine and agglomerates, so that the handling of the powder becomes worse and a high concentration slurry of 45% by mass or more is prepared. This is because when the thickness exceeds 10 μm, it is difficult to control the fine structure, and a dense sintered body pellet cannot be obtained. Further, when the average particle diameter of the ZnO powder is limited to the above range, there is an advantage that a desired sintered pellet can be obtained without using a sintering aid. It is preferable to use polyethylene glycol or polyvinyl butyral as the binder, and ethanol or propanol as the organic solvent. The binder is preferably added in an amount of 0.2 to 2.5% by mass. Here, when the binder and the additive are a common butyral system, it is not necessary to add a binder separately.
また、ＺｎＯ粉末とバインダと有機溶媒との湿式混合、特にＺｎＯ粉末と分散媒である有機溶媒との湿式混合は、減圧下において湿式ボールミル又は撹拌ミルにより行われることが好ましい。湿式ボールミルでは、ＺｒＯ2 製ボールを用いる場合には、直径５〜１０ｍｍの多数のＺｒＯ2 製ボールを用いて８〜２４時間、好ましくは２０〜２４時間湿式混合される。ＺｒＯ2 製ボールの直径を５〜１０ｍｍと限定したのは、５ｍｍ未満では混合が不十分となることからであり、１０ｍｍを越えると不純物が増大する不具合があるからである。また混合時間が最長２４時間と長いのは、長時間連続混合しても不純物の発生が少ないからである。一方、湿式ボールミルにおいて、鉄芯入りの樹脂製ボールを用いる場合には、直径１０〜１５ｍｍのボールを用いることが好ましい。 The wet mixing of the ZnO powder, the binder, and the organic solvent, particularly the wet mixing of the ZnO powder and the organic solvent that is the dispersion medium is preferably performed by a wet ball mill or a stirring mill under reduced pressure. In the wet ball mill, when ZrO 2 balls are used, wet mixing is performed for 8 to 24 hours, preferably 20 to 24 hours, using a large number of ZrO 2 balls having a diameter of 5 to 10 mm. The reason why the diameter of the ZrO 2 balls is limited to 5 to 10 mm is that the mixing is insufficient when the diameter is less than 5 mm, and the impurity increases when the diameter exceeds 10 mm. The reason why the mixing time is as long as 24 hours is that the generation of impurities is small even if the mixing is continued for a long time. On the other hand, in a wet ball mill, when using a resin ball with an iron core, it is preferable to use a ball having a diameter of 10 to 15 mm.
撹拌ミルでは、直径１〜３ｍｍのＺｒＯ2 製ボールを用いて０．５〜１時間湿式混合される。ＺｒＯ2 製ボールの直径を１〜３ｍｍと限定したのは、１ｍｍ未満では混合が不十分となることからであり、３ｍｍを越えると不純物が増える不具合があるからである。また、混合時間が最長１時間と短いのは、１時間を越えると原料の混合のみならず粉砕の仕事をするため、不純物の発生の原因となり、また１時間もあれば十分に混合できるからである。更に、粉末と添加剤の混合／造粒は、一般的な転動造粒法で行ってもよい。この場合、工程後のボール等との分離作業が必要なく、工程が簡略化される利点がある。 In the stirring mill, wet mixing is performed for 0.5 to 1 hour using a ZrO 2 ball having a diameter of 1 to 3 mm. The reason why the diameter of the ZrO 2 ball is limited to 1 to 3 mm is that if it is less than 1 mm, mixing is insufficient, and if it exceeds 3 mm, impurities increase. Also, the mixing time is as short as 1 hour at the longest, because if it exceeds 1 hour, not only the mixing of raw materials but also the work of pulverization causes the generation of impurities, and if it takes 1 hour, it can be sufficiently mixed. is there. Furthermore, mixing / granulation of the powder and the additive may be performed by a general rolling granulation method. In this case, there is an advantage that the process can be simplified because there is no need to separate the ball and the like after the process.
次に上記スラリーを減圧下において噴霧乾燥して平均粒径が５０〜３００μｍの造粒粉末を得た後、この造粒粉末を減圧下において所定の型に入れてその減圧下において所定の圧力で成形する。ここで、平均粒径を５０〜３００μｍと限定したのは、５０μｍ未満では成形性が悪い不具合があり、３００μｍを越えると成形体密度が低く強度も低い不具合があるからである。上記噴霧乾燥は減圧下におけるスプレードライヤを用いて行われることが好ましく、所定の型は減圧下に存在する一軸プレス装置又は冷間静水圧成形装置（ＣＩＰ（Cold Isostatic Press）成形装置）が用いられる。一軸プレス装置では、造粒粉末を１０〜２００ｋｇｆ／ｃｍ2 （０．９８〜１９．６ＭＰａ）、好ましくは１０〜１００ｋｇｆ／ｃｍ2 （０．９８〜９．８ＭＰａ）の圧力で一軸加圧成形し、ＣＩＰ成形装置では、造粒粉末を１０〜２００ｋｇｆ／ｃｍ2（０．９８〜１９．６ＭＰａ） 、好ましくは１０〜１００ｋｇｆ／ｃｍ2 （０．９８〜９．８ＭＰａ）の圧力でＣＩＰ成形する。圧力を上記範囲に限定したのは、成形体の密度を高めるとともに焼結後の変形を防止し、後加工を不要にするためである。 Next, the slurry is spray-dried under reduced pressure to obtain a granulated powder having an average particle size of 50 to 300 μm, and the granulated powder is placed in a predetermined mold under reduced pressure and at a predetermined pressure under reduced pressure. Mold. Here, the reason why the average particle size is limited to 50 to 300 μm is that if the average particle size is less than 50 μm, there is a problem that the moldability is poor, and if it exceeds 300 μm, there is a problem that the molded body density is low and the strength is low. The spray drying is preferably performed using a spray dryer under reduced pressure, and the predetermined mold is a uniaxial press apparatus or a cold isostatic pressing apparatus (CIP (Cold Isostatic Press) forming apparatus) existing under reduced pressure. . In uniaxial pressing apparatus, granulated powder 10~200kgf / cm 2 (0.98~19.6MPa), preferably uniaxial pressing at a pressure of 10~100kgf / cm 2 (0.98~9.8MPa) in CIP molding apparatus, granulated powder 10~200kgf / cm 2 (0.98~19.6MPa), preferably CIP molded under a pressure of 10~100kgf / cm 2 (0.98~9.8MPa). The reason why the pressure is limited to the above range is to increase the density of the molded body, prevent deformation after sintering, and eliminate the need for post-processing.
そして、上述したように、スラリーを調製する工程と、多孔質造粒粉末を得る工程と、多孔質成形体を得る工程とを減圧下において行うことにより、常圧に戻された状態で多孔質成形体の気孔率を著しく低下させることができる。ここで、スラリーを調製する工程と、多孔質造粒粉末を得る工程と、多孔質成形体を得る工程とは、５００ｈＰａ以下に調圧された減圧下において行われることが好ましい。５００ｈＰａを越える雰囲気下においてこれらを行っても比較的低い気孔率を有するＺｎＯ蒸着材を得ることが困難となるからである。特に、これらの工程は、比較的低い減圧下である１０Ｐａ以下に調圧された減圧下において行われることが更に好ましい。 Then, as described above, by performing the step of preparing the slurry, the step of obtaining the porous granulated powder, and the step of obtaining the porous molded body under reduced pressure, the porous material is returned to normal pressure. The porosity of the molded body can be significantly reduced. Here, the step of preparing the slurry, the step of obtaining the porous granulated powder, and the step of obtaining the porous molded body are preferably performed under a reduced pressure adjusted to 500 hPa or less. This is because it is difficult to obtain a ZnO vapor deposition material having a relatively low porosity even if these are performed in an atmosphere exceeding 500 hPa. In particular, these steps are more preferably performed under a reduced pressure adjusted to 10 Pa or less, which is a relatively low reduced pressure.
次に成形体を常圧下において焼結する。焼結する前に成形体を３５０〜６２０℃の温度で脱脂処理することが好ましい。この脱脂処理は成形体の焼結後の色むらを防止するために行われ、時間をかけて十分に行うことが好ましい。焼結は１０００〜１４００℃の温度で１〜５時間行うことが好ましい。そして、スラリーを調製する工程と、多孔質造粒粉末を得る工程と、多孔質成形体を得る工程とが減圧下において行われ、焼結のために常圧に戻された状態で多孔質成形体の気孔率は著しく低下する。このため、この多孔質成形体を焼結することにより得られたＺｎＯの多孔質焼結体にあっても、その気孔率は著しく低下し、従来製造することが困難であった０．２以上３．０％未満の範囲の比較的低い気孔率を有するＺｎＯ蒸着材を得ることができる。 Next, the compact is sintered under normal pressure. It is preferable to degrease the molded body at a temperature of 350 to 620 ° C. before sintering. This degreasing treatment is performed in order to prevent color unevenness after sintering of the molded body, and it is preferable that the degreasing treatment is sufficiently performed over time. Sintering is preferably performed at a temperature of 1000 to 1400 ° C. for 1 to 5 hours. Then, the step of preparing the slurry, the step of obtaining the porous granulated powder, and the step of obtaining the porous molded body are performed under reduced pressure, and the porous molding is performed in a state where the pressure is returned to normal pressure for sintering. Body porosity is significantly reduced. For this reason, even in the porous sintered body of ZnO obtained by sintering this porous molded body, the porosity is remarkably lowered, and 0.2 or more, which has been difficult to manufacture conventionally. A ZnO vapor deposition material having a relatively low porosity in the range of less than 3.0% can be obtained.
本実施形態の製造方法において得られた、気孔率が０．２以上１．５％未満で気孔径が０．１〜３００μｍの多結晶ペレットからなるＺｎＯ蒸着材では、その気孔率が０．２以上１．５％未満になるので、ＺｎＯ蒸着材の内部に存在するガスを著しく減少させることができる。このため、ＺｎＯ膜を成膜するためにその蒸着材を加熱しても、多孔質内部のガスが膨張することに起因する応力は従来よりも減少する。これにより蒸着材にクラックが生じるようなことはなく、クラックに起因するスプラッシュの発生を有効に防止することができる。また、ＺｎＯの多孔質焼結体が０．１〜３００μｍの範囲の平均気孔径を有するので、蒸発速度を高くすることが可能となり、成膜速度を大きくして製造コストを低減することができる。 In a ZnO vapor deposition material made of polycrystalline pellets having a porosity of 0.2 or more and less than 1.5 % and a pore diameter of 0.1 to 300 μm obtained in the manufacturing method of this embodiment, the porosity is 0.2. Since it becomes less than 1.5 % above, the gas which exists in the inside of a ZnO vapor deposition material can be reduced significantly. For this reason, even if the vapor deposition material is heated to form a ZnO film, the stress caused by the expansion of the gas inside the porous body is reduced as compared with the conventional case. Thereby, a crack does not arise in a vapor deposition material, and generation | occurrence | production of the splash resulting from a crack can be prevented effectively. In addition, since the porous sintered body of ZnO has an average pore diameter in the range of 0.1 to 300 μm, the evaporation rate can be increased, and the film formation rate can be increased to reduce the manufacturing cost. .
次に本発明の実施例を比較例とともに詳しく説明する。
以下に示す各実施例及び比較例において、市販のＺｎＯ粉末（純度９９％以上、平均粒径０．３μｍ）を使用した。何れの場合にもスラリーの調製には湿式ボールミル（直径５〜２０ｍｍのＺｒＯ2 製ボール使用）を用い、２４時間混合した。更に、何れの場合にも、成形装置として一軸成形プレス装置を用い、１００ｋｇｆ／ｃｍ2（９．８ＭＰａ）の圧力で、外径６．７ｍｍφ、厚さ２．０ｍｍに成形した。この成形体を電気炉に入れ、大気中１３００℃で３時間焼成し、焼結体ペレットにした。また、実施例及び比較例において、気孔率は置換法によって測定した。平均気孔径及び結晶粒径の測定はＳＥＭ（走査電子顕微鏡）により行った。また、以下に示す各実施例及び比較例において、「常圧」とは１気圧（１０１３ｈＰａ）の圧力下を意味し、「減圧」とは常圧である１０１３ｈＰａより低い１００ｋｇｆ／ｃｍ2（９．８ＭＰａ）の圧力下を意味するものとする。
Next, examples of the present invention will be described in detail together with comparative examples.
In each of the following examples and comparative examples, commercially available ZnO powder (purity 99% or more, average particle size 0.3 μm) was used. In any case, the slurry was prepared by using a wet ball mill (using ZrO 2 balls having a diameter of 5 to 20 mm) and mixing for 24 hours. Further, in any case, a uniaxial molding press was used as a molding apparatus, and the outer diameter was 6.7 mmφ and the thickness was 2.0 mm at a pressure of 100 kgf / cm 2 (9.8 MPa). This molded body was put into an electric furnace and fired at 1300 ° C. in the atmosphere for 3 hours to form sintered body pellets. In Examples and Comparative Examples, the porosity was measured by a substitution method. The average pore size and crystal grain size were measured by SEM (scanning electron microscope). In the following examples and comparative examples, “normal pressure” means a pressure of 1 atm (1013 hPa), and “reduced pressure” means 100 kgf / cm 2 (9. 8MPa) under pressure.
＜実施例１＞
ＺｎＯ粉末からなる原料粉末１００ｇに、バインダとしてポリビニルブラチールを１質量％添加し、更に分散媒としてメタノール変性アルコールを加えて、湿式ボールミルを用い常圧下において混合して濃度３０質量％のスラリーとした。次いで、このスラリーを減圧下において噴霧乾燥して平均粒径が約２００μｍの多孔質造粒粉末を得た。この造粒粉末を減圧下において加圧成形し、この成形体を焼成して多孔質焼結体ペレット（ＺｎＯ蒸着材）を製造した。この焼結体を実施例１とし、その気孔率を表１に示す。
<Example 1>
The raw material powder 100g of ZnO powder, the polyvinyl bra steel added 1 wt% as a binder and further a methylated spirit was added as a dispersion medium, a concentration of 30% by weight of the slurry was mixed under atmospheric pressure using a wet ball mill did. Next, this slurry was spray-dried under reduced pressure to obtain a porous granulated powder having an average particle size of about 200 μm. The granulated powder was pressure-molded under reduced pressure, and the molded body was fired to produce a porous sintered body pellet (ZnO vapor deposition material). This sintered body is referred to as Example 1, and the porosity is shown in Table 1.
＜比較例１＞
スラリーの調製と造粒と加圧成形のいずれも減圧せずに常圧下において行ったことを除き、実施例１と同一の条件及び手順により多孔質焼結体ペレット（ＺｎＯ蒸着材）を製造した。即ち、実施例１と同一のＺｎＯ粉末からなる原料粉末１００ｇに、バインダとしてポリビニルブラチールを１質量％添加し、更に分散媒としてメタノール変性アルコールを加えて、湿式ボールミルを用い常圧下において混合して濃度３０質量％のスラリーとした。次いで、このスラリーを常圧下において噴霧乾燥して平均粒径が約２００μｍの多孔質造粒粉末を得た。この造粒粉末を常圧下において加圧成形し、この成形体を焼成して多孔質焼結体ペレット（ＺｎＯ蒸着材）を製造した。この焼結体を比較例１とし、その気孔率を表１に示す。
<Comparative Example 1>
Both the preparation and granulation and pressing the slurry except that went out at normal pressure under without vacuum, producing a porous sintered body pellet (ZnO deposition material) by the same conditions and procedures as in Example 1 did. That is, 100% of the raw material powder made of the same ZnO powder as in Example 1 was added with 1% by mass of polyvinyl bratil as a binder, methanol-modified alcohol was added as a dispersion medium, and mixed under normal pressure using a wet ball mill. A slurry having a concentration of 30% by mass was obtained. Next, this slurry was spray-dried under normal pressure to obtain a porous granulated powder having an average particle size of about 200 μm. The granulated powder was pressure-molded under normal pressure, and the compact was fired to produce a porous sintered compact pellet (ZnO vapor deposition material). This sintered body is referred to as Comparative Example 1, and the porosity is shown in Table 1.
＜比較例２＞
ＺｎＯ粉末からなる原料粉末１００ｇに、バインダとしてポリビニルブラチールを１質量％添加し、さらに分散媒としてメタノール変性アルコールを加えて、濃度３０質量％のスラリーとした。次いで、このスラリーをボールミルに入れ、空気を吹き込んで湿式混合し、ガス含有スラリーとした。このスラリーを真空乾燥機にて８０℃で分散媒を気化させ、引き続き乾式解砕して、平均粒径２００μｍの多孔質造粒粉末を得た。この造粒粉末を常圧下において加圧成形し、この成形体を焼成して多孔質焼結体ペレット（ＺｎＯ蒸着材）を製造した。この焼結体を比較例２とし、その気孔率を表１に示す。
<Comparative example 2>
To 100 g of raw material powder made of ZnO powder, 1% by mass of polyvinyl bratil was added as a binder, and methanol-modified alcohol was added as a dispersion medium to obtain a slurry having a concentration of 30% by mass. Subsequently, this slurry was put into a ball mill, and air was blown in and wet mixed to obtain a gas-containing slurry. This slurry was vaporized with a vacuum dryer at 80 ° C., followed by dry crushing to obtain a porous granulated powder having an average particle size of 200 μm. The granulated powder pressing and pressure-molded at normal pressure under was prepared porous sintered body pellet (ZnO deposition material) by firing the molded body. This sintered body is referred to as Comparative Example 2, and the porosity is shown in Table 1.
＜比較例３＞
実施例１で用いた原料粉末であるＺｎＯ粉末を篩い分けし、平均粒径６０μｍおよび粒度分布が５５〜６５μｍの範囲内に含まれるＺｎＯ粉末を得た。このＺｎＯ粉末を含む原料粉末に、バインダとしてポリビニルブチラールを１質量％添加し、有機溶媒としてメタノール変性アルコールを３０質量％添加し、それらを混合してＺｎＯ粉末の濃度が３０質量％のスラリーを調製した。次いで、このスラリーを常圧下において噴霧乾燥して平均粒径が約２００μｍの多孔質造粒粉末を得た。この造粒粉末を常圧下において加圧成形し、この成形体を焼成して多孔質焼結体ペレット（ＺｎＯ蒸着材）を製造した。この焼結体を比較例３とし、その気孔率を表１に示す。
<Comparative Example 3>
The ZnO powder that is the raw material powder used in Example 1 was sieved to obtain a ZnO powder having an average particle size of 60 μm and a particle size distribution in the range of 55 to 65 μm. To this raw material powder containing ZnO powder, 1% by weight of polyvinyl butyral is added as a binder, 30% by weight of methanol-modified alcohol is added as an organic solvent, and they are mixed to prepare a slurry having a ZnO powder concentration of 30% by weight. did. Next, this slurry was spray-dried under normal pressure to obtain a porous granulated powder having an average particle size of about 200 μm. The granulated powder was pressure-molded under normal pressure, and the compact was fired to produce a porous sintered compact pellet (ZnO vapor deposition material). This sintered body is referred to as Comparative Example 3, and the porosity is shown in Table 1.
＜評価試験及び評価＞
実施例１のＺｎＯ蒸着材、比較例１〜３のＺｎＯ蒸着材を用い、電子ビーム蒸着法により、膜厚２００ｎｍのＺｎＯ膜を成膜した。即ち、電子ビーム蒸着装置のハース（直径５０ｍｍ、深さ２５ｍｍ）にサンプルの蒸着材を仕込み、到達真空度２．６６×１０-4Ｐａ（２．０×１０-6Ｔｏｒｒ）、Ｏ2分圧１．３３×１０-2Ｐａ（１．０×１０-4Ｔｏｒｒ）の雰囲気に調整し、加速電圧１０ｋＶ、ビームスキャンエリア約４０ｍｍφの電子ビームを照射してＺｎＯ蒸着材を加熱し、ＺｎＯ膜を形成した。
<Evaluation test and evaluation>
Using the ZnO vapor deposition material of Example 1 and the ZnO vapor deposition materials of Comparative Examples 1 to 3, a 200 nm-thick ZnO film was formed by electron beam vapor deposition. That is, a sample vapor deposition material is charged into a hearth (diameter 50 mm, depth 25 mm) of an electron beam vapor deposition apparatus, and the ultimate vacuum is 2.66 × 10 −4 Pa (2.0 × 10 −6 Torr), O 2 partial pressure. Adjust the atmosphere to 1.33 × 10 −2 Pa (1.0 × 10 −4 Torr), irradiate an electron beam with an acceleration voltage of 10 kV and a beam scan area of about 40 mmφ, and heat the ZnO vapor deposition material to form a ZnO film. Formed.
実施例１及び比較例１〜３で成膜したＺｎＯ膜について、電子ビーム蒸着装置のハースより飛び出したスプラッシュの数を測定した。このスプラッシュ数の測定は、電子ビームを照射したときに飛散する蒸着材の数をデジタルビデオで撮影して数えた。なお、スプラッシュの測定は１回当たり１０分間行い、５回ずつ実施し、数値は平均値とした。その結果、実施例１では０．８、比較例１では６．６、比較例２では８．２及び比較例３では１０．４であった。これらの結果を減圧したプロセスとともに以下の表１に示す。 About the ZnO film | membrane formed into a film in Example 1 and Comparative Examples 1-3, the number of the splashes which protruded from the hearth of the electron beam vapor deposition apparatus was measured. In the measurement of the splash number, the number of vapor-deposited materials scattered when irradiated with an electron beam was counted with a digital video. In addition, the measurement of splash was performed for 10 minutes per time, and it was performed 5 times, and the numerical value was an average value. As a result, in Example 1 0. 8, the ratio Comparative Examples 1 6.6, it was 10.4 in Comparative Example 2, 8.2 and Comparative Example 3. These results are shown in Table 1 below together with the decompressed process.
また、気孔率が０．２％以上１．５％未満である実施例１のＺｎＯ蒸着材は、スラリー調製工程、造粒工程及び成形プレス工程のいずれか１以上の工程を減圧下において行っており、いずれの工程も減圧しない比較例１の気孔率は３．０であった。このことから、スラリーを調製する工程、多孔質造粒粉末を得る工程、多孔質成形体を得る工程のいずれか１以上の工程を減圧下において行うことにより、気孔率が０．２％以上１．５未満のＺｎＯ蒸着材を得ることができ、全ての工程を減圧下においてに行うことにより、より気孔率の低い蒸着材が得られることが判る。
The ZnO vapor deposition material of Example 1 having a porosity of 0.2% or more and less than 1.5 % is obtained by performing any one or more of the slurry preparation step, the granulation step, and the molding press step under reduced pressure. And the porosity of the comparative example 1 which does not decompress | depressurize any process was 3.0. Therefore, preparing a slurry to obtain a porous granulated powder by any one or more of the steps of obtaining a porous molded body be carried out at reduced pressure, the porosity equal to or greater than 0.2% 1 It can be seen that a ZnO vapor deposition material of less than .5 can be obtained, and a vapor deposition material having a lower porosity can be obtained by performing all the steps under reduced pressure.
一方、気孔率が３．０以上である比較例１〜３のＺｎＯ蒸着材を用いた場合のスプラッシュは６．６を越える高いものとなった。これは、気孔率が高いので、膜を成膜するためにその蒸着材を加熱した際に、蒸着材の内部に存在するガスが膨張して蒸着材にクラックが生じ、このクラックに起因するスプラッシュの発生が増大したことによるものと考えられる。 On the other hand, the splash in the case of using the ZnO vapor deposition materials of Comparative Examples 1 to 3 having a porosity of 3.0 or more was high, exceeding 6.6. This is because the porosity is high, and when the vapor deposition material is heated to form a film, the gas existing inside the vapor deposition material expands to cause cracks in the vapor deposition material, and the splash caused by the cracks This is thought to be due to the increased occurrence of
以上のことから、本発明の蒸着材及びその製造方法が効果的であることが確認された。 From the above, it was confirmed that the vapor deposition material of the present invention and the manufacturing method thereof are effective.
Claims (2)
前記多孔質焼結体は、純度が９９．０％以上で平均粒径が０．１〜１０μｍのＺｎＯの粉末とバインダと有機溶媒とを減圧下において混合して濃度が４５〜７５質量％で粘度が２００〜１０００ｃｐｓのスラリーを調製する工程と、前記スラリーを減圧下において噴霧乾燥して平均粒径が５０〜３００μｍの造粒粉末を得る工程と、前記造粒粉末を減圧下において成形する工程と、前記成形体を３５０〜６２０℃の温度で脱脂処理する工程と、前記脱脂処理された成形体を１０００〜１４００℃の温度で１〜５時間常圧下において焼結する工程とによって、得られることを特徴とするＺｎＯ蒸着材の製造方法。 A porous sintered body of ZnO, wherein the sintered body has a porosity of 0.2 or more and less than 1.5%, the sintered body has rounded pores, on the surface of the pores; A method for producing a ZnO vapor deposition material in which fine pores are formed,
The porous sintered body has a concentration of 45 to 75% by mass by mixing ZnO powder having a purity of 99.0% or more and an average particle size of 0.1 to 10 μm, a binder and an organic solvent under reduced pressure. A step of preparing a slurry having a viscosity of 200 to 1000 cps, a step of spray-drying the slurry under reduced pressure to obtain a granulated powder having an average particle size of 50 to 300 μm, and a step of molding the granulated powder under reduced pressure And a step of degreasing the molded body at a temperature of 350 to 620 ° C. and a step of sintering the degreased molded body at a temperature of 1000 to 1400 ° C. for 1 to 5 hours under normal pressure. Z nO production method of vapor deposition material you wherein a.
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