WO2015020029A1 - スパッタリングターゲット及びその製造方法 - Google Patents
スパッタリングターゲット及びその製造方法 Download PDFInfo
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- C04B35/453—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zinc, tin, or bismuth oxides or solid solutions thereof with other oxides, e.g. zincates, stannates or bismuthates
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3293—Tin oxides, stannates or oxide forming salts thereof, e.g. indium tin oxide [ITO]
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- C04B2235/652—Reduction treatment
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Definitions
- the present invention relates to a sputtering target capable of stably forming a uniform semiconductor film made of ZnSn oxide, a protective film for a metal thin film, or the like by direct current (DC) sputtering and a method for manufacturing the same.
- DC direct current
- ZnO zinc oxide
- SnO 2 tin oxide
- ZTO zinc oxide
- TFT thin film transistor
- the Zn 2 SnO 4 thin film is transparent and has a high refractive index characteristic. Therefore, the Zn 2 SnO 4 thin film is also used as a protective film for a transparent far-infrared reflective film made of a metal film such as an Au thin film, an Ag thin film, or a Cu thin film. Yes.
- a Zn 2 SnO 4 thin film is laminated as a transparent high refractive index film on an Ag thin film. A sputtering method is also employed for this lamination formation.
- the sputtering target made of Zn 2 SnO 4 does not have a conductivity enough to enable DC sputtering.
- the RF sputtering method In order to form a Zn 2 SnO 4 thin film using this sputtering target, the RF sputtering method must be employed, and the deposition rate is also slow. Therefore, in order to reduce the resistance in the sputtering target for forming the Zn 2 SnO 4 thin film, the resistance of the sputtering target is lowered by using ZnSnO 3 as a main phase or adding a dopant, It has been proposed to enable DC sputtering (see, for example, Patent Documents 2 to 4).
- the ZTO sputtering target mainly composed of ZnSnO 3 proposed in Patent Documents 2 and 3 even if the specific resistance of the target could be reduced, the ZTO sputtering target was used for sputtering film formation.
- the film has a high carrier concentration and low resistance, and is not suitable as a semiconductor film.
- the target surface portion is sufficiently reduced, but as the process proceeds into the target, a phase with an insufficient reduction effect remains. Resulting in. Therefore, the specific resistance varies in the thickness direction of the sputtering target.
- the surface portion has a low specific resistance, and DC sputtering is possible.
- the target is dug to the inside as the sputtering progresses, the portion with high specific resistance is exposed on the surface, so abnormal discharge occurs frequently, sputtering cannot be performed stably, and the film formation rate is also increased. It will change. As described above, there is a problem that DC sputtering cannot be performed stably and a uniform film cannot be formed.
- ZTO sputtering target disclosed in Patent Document 3, but in which the ZnSnO 3 as a main phase, which contain SnO 2 phase.
- SnO 2 phase is present in the sputtering target, there is a problem that in sputtering film formation using DC sputtering, abnormal discharge and particles are generated, and the target itself is easily broken.
- the present invention promotes the increase of oxygen vacancies uniformly and sufficiently over the thickness direction (erosion depth direction) of the ZnSn oxide (ZTO) sputtering target and promotes the reduction reaction during sintering.
- the target specific resistance is further reduced throughout the thickness direction, and stable DC sputtering is always possible up to the target life, and it is difficult to break during sputtering, which is suitable for film formation of semiconductor films and protective films for metal thin films.
- Another object is to provide a sputtering target made of ZnSn oxide and a method for producing the same.
- ZTO ZnSn oxide
- the specific resistance of the target is low at the target surface and high as it goes into the target, and this specific resistance can be lowered inside the target.
- a mixture of a predetermined amount of zinc oxide (ZnO) powder and tin oxide (SnO 2 ) powder is dried, granulated, and then reduced. It was found that after heat treatment in an atmosphere, pressure sintering should be performed in a non-oxidizing atmosphere. In the heat treatment, the reduction is promoted to the inside of the mixture, the reduction proceeds throughout the mixture, and an oxygen deficient state is generated.
- the target specific resistance is lowered in the entire region in the target thickness direction, and the movement of oxygen atoms during the sintering is promoted. As a result, the density of the sintered body is improved. As a result, it has been found that a ZTO sputtering target capable of always performing stable DC sputtering can be obtained.
- ZTO ZnSn oxide
- the density ratio is 90% or more.
- the present invention is a method for producing the sputtering target according to the above (1) to (4), in which a mixture of a predetermined amount of zinc oxide powder and tin oxide powder is dried to produce.
- the heat treatment step and the sintering step are continuously performed in a heating furnace.
- the oxygen deficient state remains, and the oxygen deficient state increases in the entire area inside the sintered body. .
- the specific resistance becomes low enough to enable DC sputtering in the entire region in the target thickness direction (erosion depth direction), and the variation in specific resistance in the target thickness direction is reduced.
- DC sputtering can be stably performed until the target life, and further, cracking of the target during sputtering can be suppressed, and uniform film formation can be realized.
- the production method of the present invention comprises a heat treatment step of drying a predetermined amount of a mixture of zinc oxide powder and tin oxide powder, granulating and then heating in a reducing atmosphere, and the heat treated mixture. And a sintering step of obtaining a sintered body by pressure sintering in a non-oxidizing atmosphere, the increase in the oxygen deficient state is promoted in the heat treatment step. Sintering is performed with the defects remaining. For this reason, the state is the same as when the reduction has proceeded to the inside of the sintered body, and the oxygen deficient state is uniformly increased throughout the interior of the sintered body. According to the manufacturing method of the present invention, it is possible to manufacture a ZTO sputtering target having a low specific resistance and a small variation in specific resistance over the entire region in the target thickness direction.
- the target specific resistance is low throughout the thickness direction and is uniform in the target surface, so that stable DC sputtering is always possible, which improves productivity. Contribute.
- Sputtering target of the present embodiment has the formula: consisting of ZnSn oxide having a composition of Zn x Sn y O z is composed of a sintered body.
- Zn 2 SnO 4 itself has a high specific resistance, the target specific resistance is lowered by bringing the ZnSn oxide (Zn 2 SnO 4 ) into an oxygen deficient state.
- the mixture in which the deficiency coefficient ⁇ is adjusted is hot-pressed in a non-oxidizing atmosphere, a sintered body made of ZnSn oxide having an increased oxygen deficiency state can be obtained.
- the defect coefficient ⁇ is in the range of 0.002 to 0.03.
- the defect coefficient ⁇ exceeds 0.03, a part of tin oxide (SnO 2 ) in the structure may be reduced, and metal tin (Sn) may be eluted. If this Sn is eluted, it adheres to the furnace during production, which causes damage to the furnace, and also results in a decrease in productivity due to cleaning in the furnace. This causes a problem that the composition of the sputtering target varies.
- the defect coefficient ⁇ is less than 0.002, the target specific resistance does not decrease, so that it is difficult to perform DC sputtering.
- the defect coefficient ⁇ is set in the range of 0.002 to 0.03. In addition, although it is more preferable that the defect coefficient ⁇ is 0.008 or more and 0.02 or less, it is not limited to this.
- the oxygen component ratio z is less than 2.1, the ratio of ZnO powder becomes too high, and the film formation rate may decrease.
- the oxygen component ratio z exceeds 3.8, the ratio of the SnO 2 powder becomes too high, and there is a risk that the specific resistance increases, abnormal discharge increases, cracks during sputtering, and the like are likely to occur. Therefore, in the present embodiment, the oxygen component ratio z is in the range of 2.1 to 3.8.
- the component ratio z of oxygen shall be 2.7 or more and 3.6 or less, it is not limited to this.
- the variation with respect to the average specific resistance in the thickness direction of the sintered body was set to 50% or less.
- the reason for this limitation is that when this variation exceeds 50%, stable DC sputtering cannot be performed and uniform film formation cannot be obtained.
- DC sputtering can be stabilized and uniform film formation can be achieved until the target lifetime. Furthermore, target cracking during sputtering can be suppressed.
- the variation with respect to the average specific resistance in the thickness direction of the sintered body is 30% or less.
- the density ratio is 90% or more, cracking hardly occurs during sputtering, and the film formation rate can be improved.
- the density ratio is preferably 95% or more.
- the bending strength is 100 N / mm 2 or more, cracks are hardly generated at the time of sputtering, and the film formation rate can be improved.
- the bending strength is preferably 130 N / mm 2 or more.
- the specific resistance when the specific resistance is 1 ⁇ ⁇ cm or less, DC sputtering can be performed stably, and the film formation rate can be improved.
- the specific resistance is preferably 0.1 ⁇ ⁇ cm or less.
- the manufacturing method of this embodiment can perform DC sputtering, and can obtain a target specific resistance suitable for film formation of a semiconductor film, a protective film for a metal thin film, and the like, and a ratio in the target thickness direction.
- the object is to obtain a ZTO sputtering target with reduced resistance variation.
- the manufacturing method of this embodiment includes a heat treatment step of heating a mixture of a predetermined amount of zinc oxide (ZnO) powder and tin oxide (SnO 2 ) powder in a reducing atmosphere after drying and granulating, A sintering step of obtaining a sintered body by pressure-sintering the heat-treated mixture in a non-oxidizing atmosphere, and the oxygen deficiency state of ZnO is increased in the heat treatment step.
- the deficiency coefficient ⁇ representing the oxygen deficient state varies depending on the temperature and time of the reduction treatment in the heat treatment step, and increases as the temperature increases and the time increases.
- the body is dried and granulated, it is put into a carbon crucible and subjected to heat treatment in a vacuum.
- the obtained mixture is subjected to conditions of 800 to 980 ° C., 2 to 9 hours, 9.8 to 49 MPa (100 to 500 kgf / cm 2 ), specifically, for example, 900 ° C.
- the ZnSn oxide (ZTO) sintered body is obtained by pressure sintering under conditions of 29.4 MPa (300 kgf / cm 2 ) for 3 hours.
- an oxygen deficient state remains throughout the entire thickness direction even after sintering.
- the sintered body is naturally cooled, taken out from the furnace, the sintered body is machined, and a backing plate is bonded to produce a ZTO sputtering target.
- variation in specific resistance in the target thickness direction can be reduced, and DC sputtering can be stably performed until the target lifetime.
- the heat treatment step and the sintering step are manufactured using different heating furnaces, but the heat treatment step and the sintering step are continuously performed using the same heating furnace.
- a carbon mold is filled with the granulated powder, heated to 900 ° C. in a vacuum, and then subjected to a hot press at a press pressure of 29.4 MPa (300 kgf / cm 2 ) for 3 hours.
- the increase in the oxygen deficient state is promoted by the heating before the press pressure is applied, and the sintering proceeds when the oxygen deficient state is increased.
- the oxygen deficient state remains in the entire region, and a sintered body similar to that obtained when using a separate heating furnace is obtained.
- Each of these powders was weighed so as to have the composition shown in Table 1.
- Each weighed raw material powder and three times its weight (weight ratio) zirconia balls (diameters 5 mm and 10 mm are the same weight) are put in a plastic container and wet-mixed in a ball mill device for 24 hours to obtain a mixed powder. It was.
- alcohol is used for the solvent in this case, for example.
- zirconia beads instead of the above-mentioned zirconia balls, zirconia beads (diameter 0.5 mm) may be used and mixed by a bead mill apparatus to obtain a mixed powder.
- the slurry obtained by this ball mill mixing was dried, granulated, and charged into a heating furnace.
- heating was started and the heat treatment process was started.
- the temperature is raised to 800 ° C. in a vacuum, and the increase in the oxygen deficiency state is promoted.
- the temperature of the heating furnace was further increased, and the process shifted to the sintering step.
- sintering was performed by hot pressing at a temperature of 900 ° C. and a press pressure of 29.4 MPa (300 kgf / cm 2 ) for 3 hours.
- sintering was performed by hot pressing at a temperature of 930 ° C.
- Example 9 sintering was performed by hot pressing at a temperature of 900 ° C. and a press pressure of 34.3 MPa (350 kgf / cm 2 ) for 3 hours.
- Example 10 sintering was performed by hot pressing at a temperature of 850 ° C. and a press pressure of 29.4 MPa (300 kgf / cm 2 ) for 3 hours. The sintering process was performed in a vacuum. After the sintering step, the obtained sintered body was taken out from the heating furnace, and the sintered body was machined to produce ZTO sputtering targets of Examples 1 to 10 having a diameter of 125 mm.
- Comparative Example 1 In order to compare with the ZTO sputtering target of the above example, the ZTO sputtering targets of Comparative Examples 1 to 4 shown in Table 1 were prepared. The hot pressing conditions were the same as in Example 1. In each of Comparative Examples 1 to 4, a mixed powder was obtained by mixing ZnO powder and SnO 2 powder, as in each example. In Comparative Example 1, a large amount of SnO 2 powder was blended, The component ratio z exceeded 3.8. In Comparative Example 2, a large amount of ZnO powder was blended, and the oxygen component ratio z was less than 2.1.
- Comparative Examples 3 and 4 the composition of the ZnO powder and the SnO 2 powder was the same as in Examples 3 and 6 to 10, but both of Comparative Examples 3 and 4 had a deficiency coefficient indicating an oxygen deficient state. ⁇ deviated from the scope of the present embodiment.
- the defect coefficient ⁇ of the ZnSn oxide composing the obtained ZTO sputtering target of Examples and Comparative Examples was calculated by the following procedure.
- (Procedure 1) ZnSn oxide powder obtained by pulverizing the target was dried by heating at 100 ° C. for 1 hour.
- (Procedure 2) 1 g of dried ZnSn oxide powder was weighed and placed in a crucible that had been heat-treated in advance and constant in weight.
- the weight of the ZnSn oxide powder after drying is a
- the weight of the crucible is b.
- Heating was performed at 800 ° C.
- the oxygen deficiency coefficient ⁇ was calculated according to the following formula.
- the atomic weight of oxygen is [O]
- the atomic weight of Zn is [Zn]
- the atomic weight of Sn is [Sn].
- the specific resistance was measured for the points.
- Table 2 shows the average value of the measured in-plane specific resistance.
- ⁇ Density ratio> The density ratio was calculated
- Test pieces (3 mm ⁇ 4 mm ⁇ 35 mm) corresponding to the respective compositions were prepared by the same method as the ZTO sputtering targets of the examples and comparative examples shown in Table 1, and the autograph AG-X manufactured by Shimadzu Corporation was used. The stress curve was measured at an indentation speed of 0.5 mm / min to determine the maximum point stress in the elastic region, which was taken as the bending strength.
- the film formation speed is measured by sputtering for 100 seconds under the above film formation conditions, depositing the target material on the masked glass substrate, and removing the mask using the step meter.
- the film formation rate was calculated by measurement. The measurement results are shown in Table 3.
- the defect coefficient ⁇ is in the range of 0.002 to 0.03, and the entire target thickness direction is observed. It has been found that the resistance can be reduced and there is little variation in the target thickness direction. Furthermore, even in the sputtering using the ZTO sputtering target of such an example, the occurrence of abnormal discharge can be greatly reduced, and no target crack was confirmed under the condition of DC800W. Therefore, since the target specific resistance can be lowered over the entire area in the target thickness direction, stable DC sputtering can always be performed, and a uniform film can be formed while improving the film formation speed.
- Example 10 in which the density ratio was 87% and the bending strength was 89 N / mm 2 , target cracking was not confirmed under the condition of DC 800 W, but target cracking was observed under the condition of DC 1200 W. In addition, the number of abnormal discharges is slightly increased. In contrast, the density ratio of 97%, bending strength carried was set to 141N / mm 2 Example 8 and the density ratio of 95%, in Example 9, the transverse rupture strength is a 130N / mm 2 is The target crack was not confirmed even under the condition of DC 1200 W, and it was confirmed that the number of occurrences of abnormal discharge was suppressed.
- Comparative Example 3 since the deficiency coefficient ⁇ is too small, the conductivity is small, and the target thickness The specific resistance in the vertical direction is too high outside the measurement range, so that DC sputtering cannot be performed. In Comparative Example 4, since the defect coefficient ⁇ is too high, elution of metal (Sn) occurs in the sputtering target, and sputtering is performed. Can not be implemented.
- the specific resistance is reduced in the entire region of the ZTO sputtering target in the thickness direction, and variations in specific resistance can be reduced.
- a reducing atmosphere is obtained by performing a vacuum using a carbon crucible, but a reducing gas such as CO, SO 2 , H 2 may be used.
- a reducing gas such as CO, SO 2 , H 2 may be used.
- the sintering process in an Example and a comparative example is performed in the vacuum, the same effect will be acquired if it is a non-oxidizing atmosphere.
- the sputtering target of the present invention it is possible to stably form a semiconductor film, a protective film for a metal thin film, and the like by direct current (DC) sputtering until the lifetime of the target. Further, according to the method for manufacturing a sputtering target of the present invention, a sputtering target capable of stably forming a semiconductor film, a protective film for a metal thin film, etc. by direct current (DC) sputtering until the lifetime of the target is manufactured. be able to.
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Abstract
Description
本願は、2013年8月6日に日本に出願された特願2013-163051号、及び2014年8月1日に日本に出願された特願2014-157914号に基づき優先権を主張し、その内容をここに援用する。
(1)本発明のスパッタリングターゲットは、化学式:ZnxSnyOz(ただし、x+y=2、且つ、z=x+2y-α(x+2y))の組成を有し、欠損係数α=0.002~0.03及び酸素の成分比z=2.1~3.8の条件を満たすZnSn酸化物からなる焼結体であって、前記焼結体の厚さ方向における比抵抗の平均に対するバラつきが50%以下である。
(2)前記(1)のスパッタリングターゲットにおいて、密度比が90%以上とされている。
(3)前記(1)、(2)のスパッタリングターゲットにおいて、抗折強度が100N/mm2以上とされている。
(4)前記(1)~(3)のスパッタリングターゲットにおいて、比抵抗が1Ω・cm以下とされている。
(5)本発明は、前記(1)~(4)のスパッタリングターゲットを製造する方法であって、その製造方法では、所定量の酸化亜鉛粉末及び酸化錫粉末の混合体を、乾燥して造粒後、還元性雰囲気中で加熱を行う熱処理工程と、熱処理された前記混合体を非酸化性雰囲気中で加圧焼結して焼結体を得る焼結工程と、を有し、前記熱処理工程において、酸素欠損状態が増加される。
(6)前記(5)の製造方法では、前記熱処理工程と前記焼結工程が、加熱炉内において連続して行われる。
本実施形態のスパッタリングターゲットは、化学式:ZnxSnyOzの組成を有するZnSn酸化物からなる焼結体で構成されている。亜鉛(Zn)と錫(Sn)の成分は、x+y=2を満たすことを条件として、ZnとSnの成分比が目標とするZnSn酸化物膜の範囲となるように設定される。さらに、Zn2SnO4自体は高比抵抗であるので、ZnSn酸化物(Zn2SnO4)を酸素欠損状態とすることにより、ターゲット比抵抗を低下させる。この酸素欠損状態のZnSn酸化物における酸素(O)の成分比zについて、z=2.1~3.8とすることが好ましい。
また、酸素の成分比zが2.1未満であると、ZnO粉末の比率が高くなりすぎて成膜速度が低下するおそれがある。一方、酸素の成分比zが3.8を超えると、SnO2粉末の比率が高くなりすぎて比抵抗の上昇、異常放電の増加、スパッタ時の割れ等が発生しやすくなるおそれがある。そこで、本実施形態では、酸素の成分比zを2.1以上3.8以下の範囲内としている。なお、酸素の成分比zを2.7以上3.6以下とすることがより好ましいが、これに限定されない。
先ず、純度4Nで平均粒径:D50=1.0μmの酸化亜鉛(ZnO)粉末、純度4Nで平均粒径:D50=15μmの酸化錫(SnO2)粉末を用意した。これらの各粉末を、表1に示される組成になるように、秤量した。この秤量した各原料粉末とその3倍量(重量比)のジルコニアボール(直径5mmと10mmを同重量)とをポリ容器に入れ、ボールミル装置にて、24時間、湿式混合し、混合粉末を得た。なお、この際の溶媒に、例えば、アルコールを用いる。なお、上述のジルコニアボールの代わりにジルコニアビーズ(直径0.5mm)を用いて、ビーズミル装置によって混合し、混合粉末を得てもよい。
焼結工程を終了して、得られた焼結体を加熱炉から取り出し、その焼結体を機械加工して、直径125mmを有する実施例1~10のZTOスパッタリングターゲットを作製した。
上記実施例のZTOスパッタリングターゲットと比較するため、表1に示される比較例1~4のZTOスパッタリングターゲットを用意した。ホットプレスの条件は実施例1と同様とした。比較例1~4のいずれも、各実施例の場合と同様に、ZnO粉末とSnO2粉末との混合により混合粉末を得たが、比較例1では、SnO2粉末が多く配合され、酸素の成分比zが3.8を超えた。比較例2では、ZnO粉末が多く配合され、酸素の成分比zが2.1未満であった。また、比較例3、4では、ZnO粉末とSnO2粉末との配合は、実施例3、6~10と同様であったが、比較例3、4のいずれも、酸素欠損状態を示す欠損係数αが、本実施形態の範囲を逸脱していた。
ここで、得られた実施例及び比較例のZTOスパッタリングターゲットを構成するZnSn酸化物の欠損係数αを以下の手順で算出した。
(手順1)ターゲットを粉砕して得られたZnSn酸化物粉を、100℃で1時間加熱して乾燥した。
(手順2)乾燥後のZnSn酸化物粉1g秤量し、予め熱処理し恒量されたるつぼに入れた。ここで、乾燥後のZnSn酸化物粉の重量をa、るつぼの重量をbとする。
(手順3)電気炉にて、800℃、2時間の加熱を行い、デシケータ内で30~60分間放冷した後、精秤した。これを恒量に達するまで繰り返した。熱処理後のZnSn酸化物粉とるつぼの重量をcとする。
(手順4)以下の計算式に従い、酸素欠損係数αを算出した。なお、酸素の原子量を[O]、Znの原子量を[Zn]、Snの原子量を[Sn]とする。
得られた実施例及び比較例のZTOスパッタリングターゲットについて、抵抗測定装置により、比抵抗を測定した。
ここで、直径125mm×厚さ10mmのZTOスパッタリングターゲットを前述の製造方法で作製し、エロージョン深さ方向(ターゲットの厚さ方向)に、表面(0mm)から、2mm、5mmまで削り、そこでの比抵抗を測定した。また、厚さ方向の比抵抗のバラつきを、変動係数の百分率で表した。なお、変動係数はターゲット厚さ方向における比抵抗の標準偏差をターゲット厚さ方向比抵抗の平均値で除して求めた。
この測定においては、抵抗測定装置として、三菱化学株式会社製の低抵抗率計(Loresta-GP)を用い、四探針法で、比抵抗(Ω・cm)を測定した。測定時の温度は23±5℃、湿度は50±20%であった。
得られた実施例及び比較例のZTOスパッタリングターゲットについて密度比を求めた。
焼結体を所定寸法に機械加工した後、重量を測定して嵩密度を求めた後、理論密度ρfnで割ることで、密度比を算出した。なお、理論密度ρfnは、原料の重量に基づいて以下の式によって算出した。なお、SnO2の密度をρ1、SnO2の質量%をC1、ZnOの密度をρ2、ZnOの質量%をC2とする。
表1に示した実施例及び比較例のZTOスパッタリングターゲットと同様の方法によって、それぞれの組成に対応する試験片(3mm×4mm×35mm)を作製し、島津製作所製オートグラフAG-Xを用いて、押し込み速度0.5mm/minで応力曲線を測定し、弾性領域の最大点応力を求め、これを抗折強度とした。
得られた実施例及び比較例のZTOスパッタリングターゲットについて、スパッタリング時の異常放電発生回数を以下の手順で測定した。
実施例及び比較例のZTOスパッタリングターゲットを用いて、以下の成膜条件により、成膜試験を行った。
・電源:DC800W/DC1200Wの2条件
・全圧:0.4Pa
・スパッタリングガス:Ar=28.5sccm、O2=1.5sccm
・ターゲット-基板(TS)距離:70mm
上記成膜条件において1時間のスパッタリングを行い、マイクロ・アーク異常放電の発生回数をスパッタ電源装置に付属したアーキングカウンターにて自動的に測定した。この測定結果を表3に示す。
成膜速度の測定は、上述の成膜条件において100秒間スパッタリングを行い、マスキングを施したガラス基板にターゲット材を堆積させ、マスキングを取り除いた後に出来た段差の高さを、段差計を用いて測定し、成膜速度を算出した。その測定結果を表3に示した。
上述の異常放電の発生回数を測定した後に、ターゲット表面を目視にて観察し、割れの有無を確認した。その観測結果を表3に示した。表3では、ターゲット割れが確認された場合を「有り」と、そして、ターゲット割れが確認されなかった場合を「無し」とそれぞれ表示した。
これに対して、密度比が97%、抗折強度が141N/mm2とされた実施例8、及び、密度比が95%、抗折強度が130N/mm2とされた実施例9においては、DC1200Wの条件下においてもターゲット割れが確認されず、異常放電発生回数も抑えられていることが確認された。
Claims (6)
- 化学式:ZnxSnyOz(ただし、x+y=2、且つ、z=x+2y-α(x+2y))の組成を有し、欠損係数α=0.002~0.03及び酸素の成分比z=2.1~3.8の条件を満たすZnSn酸化物からなる焼結体であって、
前記焼結体の厚さ方向における比抵抗の平均に対するバラつきが50%以下であるスパッタリングターゲット。 - 密度比が90%以上とされている請求項1に記載のスパッタリングターゲット。
- 抗折強度が100N/mm2以上とされている請求項1又は請求項2に記載のスパッタリングターゲット。
- 比抵抗が1Ω・cm以下とされている請求項1から請求項3のいずれか一項に記載のスパッタリングターゲット。
- 請求項1から請求項4のいずれか一項に記載のスパッタリングターゲットを製造する方法であって、
所定量の酸化亜鉛粉末及び酸化錫粉末の混合体を、乾燥して造粒後、還元性雰囲気中で加熱を行う熱処理工程と、
熱処理された前記混合体を非酸化性雰囲気中で加圧焼結して焼結体を得る焼結工程と、を有し、
前記熱処理工程において、酸素欠損状態が増加されるスパッタリングターゲットの製造方法。 - 前記熱処理工程と前記焼結工程は、加熱炉内において連続して行われる請求項5に記載のスパッタリングターゲットの製造方法。
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