JP5292130B2 - Sputtering target - Google Patents
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- JP5292130B2 JP5292130B2 JP2009047035A JP2009047035A JP5292130B2 JP 5292130 B2 JP5292130 B2 JP 5292130B2 JP 2009047035 A JP2009047035 A JP 2009047035A JP 2009047035 A JP2009047035 A JP 2009047035A JP 5292130 B2 JP5292130 B2 JP 5292130B2
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本発明は、太陽電池、タッチパネル等の透明電極に用いられる透明導電膜をスパッタリング法で形成するためのスパッタリングターゲットに関するものである。 The present invention relates to a sputtering target for forming a transparent conductive film used for transparent electrodes such as solar cells and touch panels by a sputtering method.
近年、低コストで高い透明性、導電性および化学的安定性を有する酸化亜鉛透明導電膜が注目されている。酸化亜鉛系の透明導電膜の形成方法としては、緻密で膜質の良い膜が得られやすい、スパッタリング法が最も適しており、スパッタリングターゲット材料に用いられる酸化亜鉛焼結体が種々検討されている。 In recent years, a zinc oxide transparent conductive film having high transparency, conductivity and chemical stability at low cost has attracted attention. As a method for forming a zinc oxide-based transparent conductive film, a sputtering method is most suitable, in which a dense and good film quality can be easily obtained, and various zinc oxide sintered bodies used for sputtering target materials have been studied.
例えば、特許文献１ではＧａが添加されたターゲットであってＧａの添加量がＺｎＯ
中のＺｎに対して５原子％以下であるターゲットが記載されている。そして、Ｇａの添加量については、０．０２原子％以上２原子％以下、さらに好ましくは０．７原子％ 以上１．７原子％以下とされている。
For example, in Patent Document 1, it is a target to which Ga is added, and the added amount of Ga is ZnO.
The target which is 5 atomic% or less with respect to Zn in the inside is described. And about the addition amount of Ga, it is 0.02 atomic% or more and 2 atomic% or less, More preferably, it is 0.7 atomic% or more and 1.7 atomic% or less.
しかしながら、Ｇａの添加量を調整した酸化亜鉛焼結体をスパッタリングターゲットとして用いた場合、成膜が均一にできないことがあった。また、酸化亜鉛焼結体中に大きな気孔が生じて局所的な異常放電が頻発する場合があった。 However, when a zinc oxide sintered body with an added amount of Ga adjusted is used as a sputtering target, film formation may not be uniform. In addition, large pores are generated in the zinc oxide sintered body, and local abnormal discharge often occurs.
本発明は、これらの問題に鑑みてなされたものであり、均一に成膜でき、異常放電が生じ難いスパッタリングターゲット及びその製造方法を提供するものである。 The present invention has been made in view of these problems, and provides a sputtering target that can form a uniform film and hardly cause abnormal discharge, and a method for manufacturing the sputtering target.
本発明は、これらの問題を解決するため、酸化亜鉛焼結体からなり、酸素を除く原子について算出される原子％を単位として、Ｇａを０．０３〜０．７５原子％含み、複合酸化物がＸ線回折で検出されず、酸素を除く原子について算出される原子ｐｐｍを単位として、ＺｒおよびＳｉのうち１以上を合計で３〜１００原子ｐｐｍの範囲で含み、かつ、酸化亜鉛焼結体表面の色差ΔＥ＊ａｂが０．７以下であることを特徴とするスパッタリングターゲットを提供する。 In order to solve these problems, the present invention is composed of a zinc oxide sintered body, containing 0.03 to 0.75 atomic% of Ga in terms of atomic% calculated for atoms excluding oxygen, and a composite oxide Is not detected by X-ray diffraction , and includes one or more of Zr and Si in the range of 3 to 100 atomic ppm in total, in units of atomic ppm calculated for atoms excluding oxygen, and a zinc oxide sintered body Provided is a sputtering target having a surface color difference ΔE * ab of 0.7 or less .
均一に成膜でき、異常放電が生じ難いスパッタリングターゲットを提供することができる。 It is possible to provide a sputtering target that can form a film uniformly and hardly cause abnormal discharge.
本発明のスパッタリングターゲットは、酸化亜鉛焼結体からなり、Ｇａを０．０３〜０．７５原子％含む。通常、Ｇａを添加して酸化亜鉛焼結体を作製すると、亜鉛とＧａの複合酸化物が生成する。しかしながら、複合酸化物が生成すると、気孔が生じ異常放電も起き易くなる。また、色ムラも生じ易いので好ましくない。Ｇａの添加量を上記範囲とすることによって、複合酸化物の生成及び色ムラを抑制できるので、異常放電を防ぎ、成膜の均一性を高めることができる。さらにＧａの適切量が酸化亜鉛に固溶するのでスパッタリングターゲットの体積抵抗率の制御も容易になる。なお、Ｇａの含有量を示す原子％は、酸素を除く原子について算出したものである。 The sputtering target of this invention consists of a zinc oxide sintered compact, and contains 0.03-0.75 atomic% of Ga. Usually, when a zinc oxide sintered body is produced by adding Ga, a composite oxide of zinc and Ga is generated. However, when the composite oxide is generated, pores are generated and abnormal discharge is likely to occur. Also, color unevenness is likely to occur, which is not preferable. By setting the amount of Ga to be in the above range, generation of complex oxide and color unevenness can be suppressed, so that abnormal discharge can be prevented and film formation uniformity can be improved. Furthermore, since an appropriate amount of Ga is dissolved in zinc oxide, the volume resistivity of the sputtering target can be easily controlled. The atomic% indicating the Ga content is calculated for atoms excluding oxygen.
上述のように、本発明では、亜鉛とＧａの複合酸化物の生成を抑えているので、Ｘ線回折で複合酸化物が検出されない。複合酸化物の生成は、反応により局所的な収縮を生じ、焼結体中に気孔を形成する。そして気孔は異常放電を招く。また、気孔が形成されると、その部分の結晶粒子が脱落しやすくなるため好ましくない。 As described above, in the present invention, since the formation of a complex oxide of zinc and Ga is suppressed, the complex oxide is not detected by X-ray diffraction. The formation of the composite oxide causes local shrinkage due to the reaction and forms pores in the sintered body. The pores cause abnormal discharge. In addition, formation of pores is not preferable because the crystal grains in the portion are easily dropped.
また、スパッタリングターゲットを構成する酸化亜鉛焼結体は、Ｚｒ、Ｓｉ及びＡｌのうち１以上を含む。これにより、色ムラが抑制される。これらの含有量は、１００原子ｐｐｍ以下とすることが好ましく、３〜１００原子ｐｐｍとすることがより好ましい。この範囲に調整することで特性に影響を与えることなく色ムラを抑えることができる。なお、Ｚｒ、Ｓｉ及びＡｌの含有量を示す原子ｐｐｍは、酸素を除く原子について算出したものである。 Moreover, the zinc oxide sintered compact which comprises a sputtering target contains 1 or more among Zr, Si, and Al. Thereby, color unevenness is suppressed. The content thereof is preferably 100 atomic ppm or less, and more preferably 3 to 100 atomic ppm. By adjusting to this range, color unevenness can be suppressed without affecting the characteristics. In addition, atom ppm which shows content of Zr, Si, and Al is computed about the atom except oxygen.
これらを含むことにより結晶粒子径のバラつきが抑えられ、焼結を均一化する効果がある。また、複合酸化物の生成も抑制されていると考えられる。均一に焼結できれば、異常粒子成長に伴う気孔の形成が抑えられるので異常放電を防ぐことができる。 By including these, variation in crystal particle diameter is suppressed, and there is an effect of uniform sintering. Moreover, it is thought that the production | generation of complex oxide is also suppressed. If the sintering can be performed uniformly, the formation of pores accompanying abnormal particle growth can be suppressed, so that abnormal discharge can be prevented.
上述のように、酸化亜鉛焼結体表面の色ムラは極めて小さく抑えられている。具体的には、本発明のセラミックス部材は、Ｌ＊ａ＊ｂ＊表色系（ＪＩＳＺ８７２９）における色差ΔＥ＊ａｂを０．７以下にすることができる。色差は、以下の式で表すことができる。ΔＥ＊ａｂ＝（（ΔＬ＊）２＋（Δａ＊）２＋（Δｂ＊）２）１／２。ここで、ΔＬ＊、Δａ＊、Δｂ＊は、それぞれ酸化亜鉛焼結体表面の明度Ｌ＊、色度ａ＊、色度ｂ＊の差の最大を示す。所定数の測定箇所について明度Ｌ＊、色度ａ＊、色度ｂ＊を測定し、その差の最大を求めてΔＥ＊ａｂを算出する。本発明の酸化亜鉛焼結体では、上記のようにして求めたΔＥ＊ａｂは、全て０．７以下となる。 As described above, the color unevenness on the surface of the zinc oxide sintered body is extremely small. Specifically, the ceramic member of the present invention can make the color difference ΔE * ab in the L * a * b * color system (JISZ8729) 0.7 or less. The color difference can be expressed by the following formula. ΔE * ab = ((ΔL *) 2 + (Δa *) 2 + (Δb *) 2 ) 1/2 . Here, ΔL *, Δa *, and Δb * indicate the maximum difference in brightness L *, chromaticity a *, and chromaticity b * on the surface of the zinc oxide sintered body, respectively. The lightness L *, chromaticity a *, and chromaticity b * are measured for a predetermined number of measurement points, and the maximum difference is calculated to calculate ΔE * ab. In the zinc oxide sintered body of the present invention, ΔE * ab obtained as described above is all 0.7 or less.
スパッタリングターゲットに色ムラがあると、スパッタの発熱時にターゲット表面からの熱放射が不均一になるため温度差が生じ易い。ターゲット表面に温度差があると、高温部と低温部でスパッタリングレートが異なるため、均一な成膜は困難になる。また、色ムラがあると、ターゲット内で体積抵抗率に差が生じる恐れがある。本発明のスパッタリングターゲットであれば、色差ΔＥ＊ａｂが０．７以下と極めて色ムラが小さいので、ターゲット表面の温度差が生じ難く、成膜の均一性を高めることができ、ターゲットの体積抵抗率も均一化できる。 If the sputtering target is uneven in color, a temperature difference is likely to occur because heat radiation from the target surface becomes non-uniform when heat is generated during sputtering. If there is a temperature difference on the target surface, the sputtering rate is different between the high temperature part and the low temperature part, so that uniform film formation becomes difficult. Further, when there is color unevenness, there is a risk that a difference in volume resistivity occurs in the target. With the sputtering target of the present invention, since the color difference ΔE * ab is very small as 0.7 or less, the temperature difference of the target surface hardly occurs, the uniformity of film formation can be improved, and the volume resistance of the target The rate can also be made uniform.
酸化亜鉛焼結体の平均結晶粒径は、４０μｍ以下とすることが好ましい。４０μｍよりも粒成長が進むと気孔が生じやすくなるため好ましくない。また、これよりも大きいと曲げ強度が低下する。 The average crystal grain size of the zinc oxide sintered body is preferably 40 μm or less. If the grain growth proceeds beyond 40 μm, pores tend to be generated, which is not preferable. On the other hand, if it is larger than this, the bending strength decreases.
スパッタリングターゲットを構成する酸化亜鉛焼結体の体積抵抗率は、１×１０−２Ωｃｍ以下が好ましい。このような体積抵抗率のスパッタリングターゲットを用いるとスパッタ効率がよく、成膜される膜の耐久性が向上する。 The volume resistivity of the zinc oxide sintered body constituting the sputtering target is preferably 1 × 10 −2 Ωcm or less. When a sputtering target having such a volume resistivity is used, sputtering efficiency is good and durability of a film to be formed is improved.
次に本発明のスパッタリングターゲットの製造方法について説明する。 Next, the manufacturing method of the sputtering target of this invention is demonstrated.
酸化亜鉛粉末は、高純度のものを用いることが好ましい。その純度は、好ましくは９９％以上、より好ましくは９９．８％以上の原料粉末を用いることが望ましい。酸化亜鉛粉末の平均粒径は、１．０μｍ以下のものを用いることが好ましい。さらに好ましい範囲は、０．１〜１．０μｍである。また、Ｚｒ、Ｓｉ及びＡｌのうち１以上の含有量が１００ｐｐｍ以下、より好ましくは３〜１００ｐｐｍの酸化亜鉛粉末を用いることが好ましい。 It is preferable to use a high-purity zinc oxide powder. It is desirable to use a raw material powder having a purity of preferably 99% or more, more preferably 99.8% or more. The average particle diameter of the zinc oxide powder is preferably 1.0 μm or less. A more preferable range is 0.1 to 1.0 μm. Further, it is preferable to use zinc oxide powder having a content of one or more of Zr, Si and Al of 100 ppm or less, more preferably 3 to 100 ppm.
Ｇａは酸化物（Ｇａ２Ｏ３）の粉末で添加されることが好ましいが、これに限定されず、大気中での焼結後に酸化物を生成する炭化物、窒化物等の種々の形態であっても良い。純度は、好ましくは９９％以上、より好ましくは９９．９％以上の原料粉末を用いることが望ましい。Ｇａ２Ｏ３粉末の平均粒径は２．０μｍ以下のものを用いることが好ましい。さらに好ましい範囲は、０．０１〜２．０μｍである。 Ga is preferably added as an oxide (Ga 2 O 3 ) powder, but is not limited thereto, and may be in various forms such as carbides and nitrides that form oxides after sintering in the atmosphere. May be. It is desirable to use a raw material powder having a purity of preferably 99% or more, more preferably 99.9% or more. It is preferable to use a Ga 2 O 3 powder having an average particle size of 2.0 μm or less. A more preferable range is 0.01 to 2.0 μm.
原料粉末の混合方法は特に限定されず、ボールミル、振動ミル等を用いて湿式及び乾式のどちらでも行なうことができる。均一な結晶粒子を得る上で、混合方法は湿式ボールミル混合が最も好ましい。例えば、湿式ボールミル混合の場合には、混合時間を１０〜２０時間とすることができる。混合時間が短いと均一混合し難く、均一な結晶粒子が得難い。長時間混合しすぎると不純物が混入し易くなる。 The mixing method of the raw material powder is not particularly limited, and it can be performed by either a wet method or a dry method using a ball mill, a vibration mill or the like. In order to obtain uniform crystal particles, the mixing method is most preferably wet ball mill mixing. For example, in the case of wet ball mill mixing, the mixing time can be 10 to 20 hours. If the mixing time is short, uniform mixing is difficult and uniform crystal particles are difficult to obtain. If mixed for a long time, impurities are likely to be mixed.
成形方法は一軸プレス成形、ＣＩＰ成形、湿式成形等種々の成形方法を用いることができる。なかでもＣＩＰ成形が好ましく、その成形圧力は１．２ｔ／ｃｍ２以上とすることが好ましい。ＣＩＰ成形は、大型焼結体を得る場合に有効である。 As the molding method, various molding methods such as uniaxial press molding, CIP molding, and wet molding can be used. Of these, CIP molding is preferable, and the molding pressure is preferably 1.2 t / cm 2 or more. CIP molding is effective when obtaining a large sintered body.
次に得られた成型体を焼結するが、焼結温度は１２５０〜１６００℃、特に１３５０〜１５５０℃が焼結中の酸化物蒸発による重量変化がなく容易に高密度化するため好ましい。焼結温度が１６００℃をこえると、焼結中に酸化物の蒸発による重量減少が生じることがあり、また、焼結温度が１２５０℃未満の場合、高密度な焼結体が得られ難い。焼結時間は数時間〜数十時間が好ましい。 Next, the obtained molded body is sintered. A sintering temperature of 1250 to 1600 ° C., particularly 1350 to 1550 ° C., is preferable because it does not change in weight due to oxide evaporation during sintering and can easily be densified. When the sintering temperature exceeds 1600 ° C., weight loss may occur during the sintering due to evaporation of oxides. When the sintering temperature is less than 1250 ° C., it is difficult to obtain a high-density sintered body. The sintering time is preferably several hours to several tens of hours.
さらに焼結については、１１００℃未満の温度域では、５０℃／時間以上、好ましくは１００℃／時間以上で昇温することが好ましい。この理由は、次のように考えられる。ＺｎＯの焼結開始温度である１１００℃よりも低い温度では、ＺｎＯとＧａ２Ｏ３が反応して複合酸化物（例えば、ＺｎＧａ２Ｏ４）が生じやすいが、１１００℃に達し、ＺｎＯの焼結が始まると上記反応は起き難くなる。しがたって、１１００℃が一つの注意温度となり、それ未満では、昇温速度を速くして複合酸化物の生成を抑える方が良いのである。昇温速度の上限は特に限定されないが、焼結体の厚みや大きさを考慮して焼結が均一に進む範囲で定める必要がある。なお、焼結の前に、成形体の脱脂が行われる。脱脂温度は５００〜６００℃とすることができ、脱脂温度近辺では脱脂割れが起きないように昇温速度を下げることが好ましい。上述のように５０℃／時間の昇温速度とするのは、脱脂温度を過ぎてからが望ましい。 Furthermore, regarding the sintering, it is preferable to raise the temperature at 50 ° C./hour or more, preferably at 100 ° C./hour or more in a temperature range of less than 1100 ° C. The reason is considered as follows. At a temperature lower than 1100 ° C. which is the sintering start temperature of ZnO, ZnO and Ga 2 O 3 are likely to react to form a composite oxide (for example, ZnGa 2 O 4 ). The reaction is less likely to occur once the ligation begins. Therefore, 1100 ° C. is one caution temperature, and below that, it is better to increase the rate of temperature rise to suppress the formation of complex oxides. The upper limit of the rate of temperature increase is not particularly limited, but it is necessary to determine it within a range where the sintering proceeds uniformly in consideration of the thickness and size of the sintered body. In addition, degreasing | defatting of a molded object is performed before sintering. The degreasing temperature can be 500 to 600 ° C., and it is preferable to lower the temperature raising rate so that degreasing cracks do not occur near the degreasing temperature. As described above, it is desirable that the temperature increase rate is 50 ° C./hour after the degreasing temperature.
また、１１００℃未満の温度域の昇温速度を速くするので、１１００〜１２００℃で保持時間を入れることが好ましい。保持時間では、例えば１１００℃で所定時間キープしても良いし、１１００℃から１２００℃までの昇温を所定時間かけて行っても良い。この保持時間は製品の焼結体厚みに応じて適宜調整することができる。製品厚みをｈｍｍ、保持時間をｔ時間とすると、経験上ｈ／ｔ≦１０であることが好ましい。保持時間を経た後、１１００℃以上の温度域では、２５℃／ｈｒ以上の温度で昇温して焼結させることができる。この場合も焼結体の厚みや大きさを考慮して焼結が均一に進む範囲で定めることができる。 Moreover, since the rate of temperature increase in the temperature range below 1100 ° C. is increased, it is preferable to set the holding time at 1100 to 1200 ° C. In the holding time, for example, the temperature may be kept at 1100 ° C. for a predetermined time, or the temperature may be raised from 1100 ° C. to 1200 ° C. over a predetermined time. This holding time can be appropriately adjusted according to the thickness of the sintered product. From the experience, it is preferable that h / t ≦ 10, where hmm is the product thickness and t time is the holding time. After passing the holding time, in the temperature range of 1100 ° C. or higher, the temperature can be raised at a temperature of 25 ° C./hr or higher to be sintered. In this case as well, the thickness and size of the sintered body can be taken into consideration and determined within a range where the sintering proceeds uniformly.
１１００℃から焼結温度での保持が終了するまでの高温域の加熱時間は、脱脂温度を過ぎてから１１００℃までの低温域の加熱時間の１．４倍以上とすることが好ましい。上述のように、１１００℃未満の加熱時間を短くし、１１００℃以上の加熱時間を長くすることで、複合酸化物の生成を調整しつつ、焼結させることができる。上記高温域の加熱では、Ｇａの酸化亜鉛への固溶が起こるので、体積抵抗率が低下し、ターゲットとして好適な酸化亜鉛焼結体が得られる。 The heating time in the high temperature range from 1100 ° C. to the end of the holding at the sintering temperature is preferably 1.4 times or more of the heating time in the low temperature range up to 1100 ° C. after passing the degreasing temperature. As described above, the heating time of less than 1100 ° C. is shortened, and the heating time of 1100 ° C. or more is lengthened, whereby sintering can be performed while adjusting the generation of the composite oxide. The heating in the high temperature region causes Ga to be dissolved in zinc oxide, so that the volume resistivity is lowered and a zinc oxide sintered body suitable as a target can be obtained.
焼結雰囲気は特に限定されないが、例えば大気中、酸素中、不活性ガス雰囲気中等が例示できる。特に焼結中に酸化物の蒸発による重量減少、組成ずれの低減のためには大気中等の酸化雰囲気での焼結が好ましい。なかでも、大気雰囲気または大気気流中が好ましい。また焼結雰囲気の圧力は限定されず、減圧、常圧から数気圧の加圧まで任意に適用できる。コスト面からは常圧が好ましい。 The sintering atmosphere is not particularly limited, and examples thereof include air, oxygen, and an inert gas atmosphere. In particular, sintering in an oxidizing atmosphere such as the air is preferable in order to reduce weight due to evaporation of oxides and reduce composition deviation during sintering. Of these, the atmosphere or the air stream is preferable. The pressure of the sintering atmosphere is not limited, and any pressure can be applied from reduced pressure, normal pressure to several atmospheric pressure. Normal pressure is preferable from the viewpoint of cost.
酸化亜鉛焼結体は、ターゲット材としてバッキングプレートに接合される前に、研削加工が施される。このとき、研削歪みが生じることから、歪みを除去するために、研削加工後に仮焼することが好ましい。仮焼は、６００〜８００℃で行うことができる。このような温度範囲であれば、十分に歪みが除去でき、焼結体の粒成長等も起きないので好ましい。 The zinc oxide sintered body is ground before being joined to the backing plate as a target material. At this time, since grinding distortion occurs, it is preferable to calcine after grinding in order to remove the distortion. Calcination can be performed at 600 to 800 ° C. Such a temperature range is preferable because distortion can be sufficiently removed and grain growth of the sintered body does not occur.
酸化亜鉛焼結体からなるターゲット材が接合されるバッキングプレートとしては、銅板が熱伝導に優れるので好ましい。銅板の他には、アルミニウム合金や銅等をマトリックス金属とし、セラミックスを強化材とした金属―セラミックス複合材料も好適である。 As a backing plate to which a target material made of a zinc oxide sintered body is bonded, a copper plate is preferable because it is excellent in heat conduction. In addition to the copper plate, a metal-ceramic composite material using aluminum alloy or copper as a matrix metal and ceramic as a reinforcing material is also suitable.
バッキングプレートと酸化亜鉛焼結体からなるターゲット材との接合はインジウム接合が好適である。ただし、インジウムによって形成される接合層は、前記バッキングプレート及びターゲット材の接合面に対して少なくとも９０％の接触面積を有することが望ましい。本発明のターゲット材と銅板とをインジウムにより接合し、接触面積を９０％以上とすれば、製造時または使用中の熱応力による割れを無くすことができる。 Indium bonding is suitable for the bonding between the backing plate and the target material made of the zinc oxide sintered body. However, the bonding layer formed of indium preferably has a contact area of at least 90% with respect to the bonding surface of the backing plate and the target material. If the target material of the present invention and a copper plate are joined with indium and the contact area is 90% or more, cracks due to thermal stress during production or use can be eliminated.
以下、本発明の実施例を比較例とともに具体的に挙げ、本発明をより詳細に説明する。 EXAMPLES Hereinafter, the Example of this invention is specifically given with a comparative example, and this invention is demonstrated in detail.
Ｚｒ、Ｓｉ及びＡｌの含有量の異なる酸化亜鉛粉末（純度９９．８％、平均粒径０．５μｍ）とＧａ２Ｏ３粉末（純度９９．９％、平均粒径０．５μｍ）とを９７〜９９．９７：３〜０．０３の割合で調整し、バインダーを添加して樹脂製ポットを用い、混合媒体としてΦ１５、Φ２５の樹脂ボールを用いて、２０時間湿式混合した。混合後のスラリーを取り出し、スプレードライにより混合粉末の顆粒を作製した。得られた混合粉末を一軸プレス成形した後、ＣＩＰ成形で１.２t／ｃｍ２の圧力をかけて成形し、直径５０ｍｍ、厚さ６ｍｍの円盤状の成形体を得た。この成形体を電気炉内に空気を導入しながら大気気流中、１００℃／ｈｒで焼結温度である１３５０〜１４５０℃まで昇温し、１０時間保持して焼結した。焼結後、加熱を制御せずに炉冷とした。 Zinc oxide powders (purity 99.8%, average particle size 0.5 μm) and Ga 2 O 3 powders (purity 99.9%, average particle size 0.5 μm) having different Zr, Si and Al contents are 97 It adjusted in the ratio of -99.97: 3-0.03, the binder was added, the resin-made pot was used, and it mixed for 20 hours using the resin ball of (PHI) 15 and (PHI) 25 as a mixing medium. The mixed slurry was taken out, and granulated powder was produced by spray drying. The obtained mixed powder was uniaxial press-molded and then molded by CIP molding under a pressure of 1.2 t / cm 2 to obtain a disk-shaped molded body having a diameter of 50 mm and a thickness of 6 mm. The molded body was heated to 1350 to 1450 ° C., which is a sintering temperature, at 100 ° C./hr in air flow while introducing air into an electric furnace, and held for 10 hours for sintering. After sintering, the furnace was cooled without controlling the heating.
得られた酸化亜鉛焼結体の気孔率は、アルキメデス法により測定した。焼結体の平均結晶粒径は焼結体表面を鏡面研磨後、研磨面を熱腐食したあとにＳＥＭ観察し、線インターセプト法によって求めた。また焼結体のＺｒ、Ｓｉ及びＡｌの含有量は、ＩＣＰ発光分析によって測定した。また、体積抵抗率は上記試料の中心を直方体形状に切り出し、四端子法により測定した。また、Ｘ線回折により亜鉛とＧａの複合酸化物（Ｚｎ９Ｇａ２Ｏ１２：ＪＣＰＤＳ ５０−４４８）の有無を調べた。Ｘ線回折は、リガク社製Ｘ線回折装置ＭｕｌｔｉＦｌｅｘを使用し、ＣｕＫα線源、加速電圧４０ｋＶ、４０ｍＡで測定した。結果を表１に示す。なお、認められた亜鉛とＧａの複合酸化物はＺｎ９Ｇａ２Ｏ１２のみであり、その他の複合酸化物、例えばＺｎＡｌ２Ｏ４等は全ての試料において認められなかった。 The porosity of the obtained zinc oxide sintered body was measured by Archimedes method. The average crystal grain size of the sintered body was determined by a line intercept method after mirror-polishing the surface of the sintered body and then subjecting the polished surface to thermal corrosion, followed by SEM observation. The Zr, Si and Al contents of the sintered body were measured by ICP emission analysis. The volume resistivity was measured by a four-terminal method by cutting the center of the sample into a rectangular parallelepiped shape. In addition, the presence or absence of a complex oxide of zinc and Ga (Zn 9 Ga 2 O 12 : JCPDS 50-448) was examined by X-ray diffraction. X-ray diffraction was measured using a Rigaku X-ray diffractometer MultiFlex with a CuKα radiation source, an acceleration voltage of 40 kV, and 40 mA. The results are shown in Table 1. The recognized zinc-Ga composite oxide was only Zn 9 Ga 2 O 12 , and other composite oxides such as ZnAl 2 O 4 were not observed in all samples.
Ｇａの含有量を０．０１〜０．７５原子％とした試験Ｎｏ．１〜５、７及び８では、複合酸化物が認められなかった。これらの酸化亜鉛焼結体の気孔率は、０．０２〜０．０５％と極めて小さく、緻密化しており、平均結晶粒径は４０μｍ以下であった。ただし、Ｇａが０．０１原子％の試験Ｎｏ．５では、体積抵抗率が２．０×１０−２Ωｃｍと大きくなり、また色差ΔＥ＊ａｂも大きくなった。また、Ｚｒ、Ｓｉ及びＡｌを含有していない試験Ｎｏ．７及び含有量の多い試験Ｎｏ．８では、色差ΔＥ＊ａｂがそれぞれ、１．２３、５．２６と大きくなった。 Test No. 1 with a Ga content of 0.01 to 0.75 atomic%. In 1 to 5, 7 and 8, no complex oxide was observed. The porosity of these zinc oxide sintered bodies was as extremely small as 0.02 to 0.05%, being dense, and the average crystal grain size was 40 μm or less. However, Test No. with Ga of 0.01 atomic%. In No. 5, the volume resistivity increased to 2.0 × 10 −2 Ωcm, and the color difference ΔE * ab also increased. Moreover, test No. which does not contain Zr, Si and Al. 7 and test No. with a large content. 8, the color difference ΔE * ab increased to 1.23 and 5.26, respectively.
Ｇａの含有量を１．０、３．０原子％とした試験Ｎｏ．６、９では、複合酸化物が認められ、気孔率が大きくなった。また、色差ΔＥ＊ａｂも大きくなった。 Test No. 1 with a Ga content of 1.0 and 3.0 atomic% was used. In 6 and 9, complex oxide was observed, and the porosity increased. In addition, the color difference ΔE * ab also increased.
このように、Ｇａを０．０３〜０．７５原子％含み、複合酸化物がＸ線回折で検出されない酸化亜鉛焼結体は、気孔率が高く緻密であり、体積抵抗率が低く、色差Δ＊ａｂも小さいことからスパッタリングターゲットに適していることがわかる。また、Ｚｒ、Ｓｉ及びＡｌのうち１以上を合計で１００原子ｐｐｍ以下含ませることにより色差ΔＥ＊ａｂが小さくなり、成膜の均一性を高められることが期待できる。 Thus, the zinc oxide sintered body containing 0.03 to 0.75 atomic% of Ga and in which the composite oxide is not detected by X-ray diffraction has a high porosity, a dense volume, a low volume resistivity, and a color difference Δ Since * ab is also small, it is understood that it is suitable for a sputtering target. In addition, it can be expected that the color difference ΔE * ab is reduced by including one or more of Zr, Si, and Al in a total of 100 atomic ppm or less, and the uniformity of film formation can be improved.
Claims (1)
酸素を除く原子について算出される原子％を単位として、Ｇａを０．０３〜０．７５原子％含み、
複合酸化物がＸ線回折で検出されず、
酸素を除く原子について算出される原子ｐｐｍを単位として、ＺｒおよびＳｉのうち１以上を合計で３〜１００原子ｐｐｍの範囲で含み、かつ、酸化亜鉛焼結体表面の色差ΔＥ＊ａｂが０．７以下であることを特徴とするスパッタリングターゲット。 It consists of a zinc oxide sintered body,
Inclusive of atomic percent calculated for atoms excluding oxygen, containing 0.03 to 0.75 atomic percent of Ga,
Complex oxide is not detected by X-ray diffraction ,
With the atomic ppm calculated for atoms excluding oxygen as a unit, one or more of Zr and Si are included within a total range of 3 to 100 atomic ppm, and the color difference ΔE * ab on the surface of the zinc oxide sintered body is 0. Sputtering target characterized by being 7 or less .
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