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WO2012039351A1 - Corps fritté d'oxyde, et cible de pulvérisation cathodique - Google Patents

Corps fritté d'oxyde, et cible de pulvérisation cathodique Download PDF

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Publication number
WO2012039351A1
WO2012039351A1 PCT/JP2011/071195 JP2011071195W WO2012039351A1 WO 2012039351 A1 WO2012039351 A1 WO 2012039351A1 JP 2011071195 W JP2011071195 W JP 2011071195W WO 2012039351 A1 WO2012039351 A1 WO 2012039351A1
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sintered body
metal
oxide
oxide sintered
experimental example
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Japanese (ja)
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後藤　裕史
祐紀 岩崎
中井　淳一
陽一郎 米田
得平　雅也
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Kobelco Research Institute Inc
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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
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    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3286—Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
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    • H01L21/02617—Deposition types
    • H01L21/02631—Physical deposition at reduced pressure, e.g. MBE, sputtering, evaporation

Definitions

  • the present invention relates to an oxide sintered body and a sputtering target used when an oxide semiconductor thin film of a thin film transistor (TFT) used in a display device such as a liquid crystal display or an organic EL display is formed by a sputtering method.
  • TFT thin film transistor
  • Amorphous (amorphous) oxide semiconductors used for TFTs have higher carrier mobility than general-purpose amorphous silicon (a-Si), a large optical band gap, and can be deposited at low temperatures. It is expected to be applied to next-generation displays that require high resolution and high-speed driving, and resin substrates with low heat resistance.
  • a sputtering method is preferably used in which a sputtering target made of the same material as the film is sputtered. In-plane uniformity of component composition and film thickness in the film surface direction (in the film surface) is smaller in the thin film formed by sputtering compared to thin films formed by ion plating, vacuum evaporation, and electron beam evaporation. This is because it has the advantage that a thin film having the same composition as the sputtering target can be formed.
  • the sputtering target is usually formed by mixing and sintering oxide powder and machining.
  • an In-containing amorphous oxide semiconductor (In—Ga—Zn—O, In—Zn—O, etc.) can be cited, but the rare metal In is used. Therefore, there is a concern that material costs will increase in mass production processes. Therefore, a ZTO-based oxide semiconductor that has been made amorphous by adding Sn to Zn has been proposed as an oxide semiconductor that does not contain expensive In and can reduce material costs and is suitable for mass production.
  • No. 4 discloses an oxide sintered body and a sputtering target useful for producing the ZTO-based oxide semiconductor film.
  • Patent Document 1 proposes a method of suppressing the occurrence of abnormal discharge and cracking during sputtering by performing long-time baking and controlling the structure so as not to contain a tin oxide phase.
  • Patent Document 2 also suppresses abnormal discharge during sputtering by increasing the density of the ZTO-based sintered body by performing a two-step process of a low-temperature calcined powder manufacturing process at 900 to 1300 ° C. and a main baking process.
  • a method has been proposed.
  • Patent Document 3 proposes a method of improving the conductivity and increasing the density by including a spinel-type AB 2 O 4 compound.
  • Patent Document 4 proposes a method of obtaining a dense ZTO-based sintered body by performing two steps of a low-temperature calcined powder manufacturing process at 900 to 1100 ° C. and a main baking process.
  • a sputtering target used for manufacturing an oxide semiconductor film for a display device and an oxide sintered body that is a material thereof have excellent conductivity and a high relative density.
  • a sputtering target that can be manufactured not by a high frequency (RF) sputtering method but by a direct current sputtering method that facilitates high-speed film formation.
  • Patent Document 1 described above has not been studied from the viewpoint of increasing the density, and is insufficient to stably and continuously perform DC discharge.
  • Patent Document 2 has not been studied from the viewpoint of improving the conductivity of the oxide sintered body, and is still insufficient for stable and continuous DC discharge.
  • Patent Document 3 described above has been studied from the viewpoints of higher density and higher conductivity, but contains a highly insulating Ga 2 O 3 phase in the sputtering target, and the semiconductor characteristics of the thin film. Therefore, it was insufficient to ensure homogeneity and film quality stability within the sputtering target plane.
  • Patent Document 4 is premised on an RF sputtering method that is inferior in productivity, and is difficult to apply to mass production on a large glass substrate.
  • the present invention has been made in view of the above circumstances, and an object thereof is an oxide sintered body and a sputtering target that are suitably used for manufacturing an oxide semiconductor film for a display device, and have high conductivity and relative density.
  • the object is to provide an oxide sintered body and a sputtering target having both of the above.
  • the oxide sintered body of the present invention that has solved the above problems is at least one selected from the group consisting of zinc oxide; tin oxide; Al, Hf, Ta, Ti, Nb, Mg, Ga, and rare earth elements And an oxide sintered body obtained by mixing and sintering the metal (M metal) oxide powder, and when the oxide sintered body is X-ray diffracted, a Zn 2 SnO 4 compound Is detected, but the ZnM X O y phase and M X O y phase (x and y are arbitrary integers) are not detected.
  • the content (atomic%) of the metal element contained in the oxide sintered body is [Zn], [Sn], and [M metal], respectively, [Zn] + [ The ratio of [Zn] to Sn] + [M metal] is 0.35 or more and 0.75 or less.
  • the content (atomic%) of the metal element contained in the oxide sintered body is [Zn], [Sn], and [M metal], respectively, [Zn] + [M metal] is 0.01 or more and 0.30 or less.
  • the content (atomic%) of the metal element contained in the oxide sintered body is [Zn], [Sn], and [M metal], respectively, [Zn] + [M metal] is 0.01 or more and 0.30 or less.
  • the content (atomic%) of the metal element contained in the oxide sintered body is [Zn], [Sn], and [M metal], respectively, [Zn] + [M metal] is not less than 0.01 and not more than 0.30, and the ratio of [M metal] to [Zn] + [Sn] + [M metal] is It is 0.01 or more and 0.30 or less.
  • the oxide sintered body according to any one of the above has a relative density of 90% or more and a specific resistance of 1 ⁇ cm or less.
  • the sputtering target of the present invention that has solved the above problems is a sputtering target obtained using the oxide sintered body according to any of the above, and has a relative density of 90% or more and a specific resistance of 1 ⁇ cm or less. It has a gist at some point.
  • an oxide sintered body and a sputtering target that are excellent in conductivity and have a high relative density can be obtained. Further, according to the present invention, a sputtering target having excellent direct current discharge stability, excellent in-plane uniformity and film quality stability can be obtained.
  • an oxide semiconductor film can be formed at low cost by a direct current sputtering method that facilitates high-speed film formation, so that productivity is improved.
  • FIG. 1 is a diagram showing a basic process for producing an oxide sintered body and a sputtering target of the present invention.
  • the present inventors have disclosed at least one metal (M metal) selected from the group consisting of zinc oxide (ZnO); tin oxide (SnO); Al, Hf, Ta, Ti, Nb, Mg, Ga and rare earth elements.
  • M metal selected from the group consisting of zinc oxide (ZnO); tin oxide (SnO); Al, Hf, Ta, Ti, Nb, Mg, Ga and rare earth elements.
  • Oxide oxide (M metal oxide) and an oxide sintered body obtained by mixing and sintering hereinafter sometimes abbreviated as M metal-containing ZTO oxide sintered body.
  • M metal exists as a ZnM X O y phase and M X O y phase (x and y are arbitrary integers) which are spinel type compounds.
  • M metal is contained in Zn 2 SnO 4 (in addition, when one or both of SnO 2 and ZnO are present, they are contained in Zn 2 SnO 4 or in SnO 2 and in ZnO.
  • the M metal-containing ZTO-based oxide sintered body of the present invention will be described in detail.
  • a Zn 2 SnO 4 compound is detected, but a ZnM X O y phase and a M X O y phase (x , Y is an arbitrary integer), and is characterized in that it is an oxide sintered body having such a structure that it is not detected.
  • the X-ray diffraction conditions in the present invention are as follows. Analysis device: “X-ray diffractometer RINT-1500” manufactured by Rigaku Corporation Analysis conditions Target: Cu Monochromatic: Uses a monochrome mate (K ⁇ ) Target output: 40kV-200mA (Continuous firing measurement) ⁇ / 2 ⁇ scanning Slit: Divergence 1/2 °, Scattering 1/2 °, Received light 0.15 mm Monochromator light receiving slit: 0.6mm Scanning speed: 2 ° / min Sampling width: 0.02 ° Measurement angle (2 ⁇ ): 5 to 90 °
  • the Zn 2 SnO 4 compound (phase) is formed by bonding ZnO and SnO 2 constituting the oxide sintered body of the present invention.
  • This compound is a so-called spinel-type compound, which is rich in physical properties as an electronic material and has the characteristics that the physical properties change as the crystal structure changes.
  • SnO 2 or ZnO may be included slightly.
  • the composition ratio of Zn and Sn there is a case where SnO 2 or ZnO as well Zn 2 SnO 4 compound is detected, the above SnO 2 or ZnO is a DC discharge stability of the sputtering if trace amount This is because there is no adverse effect.
  • the ZnM X O y phase and the M X O y phase are spinels that can be formed by combining M metal constituting the oxide sintered body of the present invention with oxygen (O).
  • O oxygen
  • the present invention is characterized in that these compounds are not detected when the X-ray diffraction is performed. Since these compounds (for example, Ta 2 O 5 and Al 2 O 3 ) have high insulation properties, if an oxide of M metal is contained in an oxide sintered body or sputtering target, Al that protrudes in a cluster shape.
  • oxides and Ta oxides are mixed into the film, so that the semiconductor characteristics of the thin film are deteriorated and the carrier mobility is lowered.
  • an oxide phase of M element is prevented from being formed in the oxide sintered body under the sintering conditions described later, and the M element is dissolved in the Zn 2 SnO 4 phase, etc. The characteristics can be stabilized and a decrease in carrier mobility can be prevented.
  • M metal is at least one metal selected from the group consisting of Al, Hf, Ta, Ti, Nb, Mg, Ga and rare earth elements, as will be described later.
  • M metal is Al
  • ZnAl 2 O 4 and Al 2 O 3 are not detected. “Not detected” means below the detection limit when the above-mentioned X-ray diffraction conditions are performed. It has been confirmed that all or most of the added M metal is dissolved in the Zn 2 SnO 4 compound. The remaining M metal that is not dissolved in the Zn 2 SnO 4 compound is presumed to be dissolved in SnO 2 or ZnO that can be generated by the composition of the oxide sintered body or segregated at the grain boundaries.
  • the oxide sintered body of the present invention comprises zinc oxide, tin oxide, and at least one metal (M metal) selected from the group consisting of Al, Hf, Ta, Ti, Nb, Mg, Ga, and rare earth elements. It is obtained by mixing and sintering each powder of oxide.
  • M metal metal selected from the group consisting of Al, Hf, Ta, Ti, Nb, Mg, Ga, and rare earth elements. It is obtained by mixing and sintering each powder of oxide.
  • oxides of ZnO and SnO are compounds that form a semiconductor by controlling the carrier concentration, and change the properties from insulating to semiconductor and conductive depending on the oxygen content in the oxide. Can do. This is because it is known that oxygen vacancies are intentionally generated in the oxide, and the surplus electrons become carriers, and when there are a relatively small number of carriers, it becomes a semiconductor, and when there are a large number of carriers, it degenerates and becomes a conductor. It has been.
  • M metal used in the present invention is an element useful for improving the characteristics of a film formed by sputtering, and was applied to a ZTO-based oxide in the present invention.
  • M metal is selected from the group consisting of Al, Hf, Ta, Ti, Nb, Mg, Ga and rare earth elements and may be used alone or in combination of two or more.
  • the “rare earth element” is an element group in which Sc (scandium) and Y (yttrium) are added to a lanthanoid element (a total of 15 elements from La of atomic number 57 to Lu of atomic number 71 in the periodic table).
  • one or more rare earth elements can be used.
  • the rare earth elements Gd, Nd, La, and Y are preferable from the viewpoint of semiconductor characteristics, and La and Y are more preferable.
  • Al, Nb, Ti, La, and Mg are preferable from the viewpoint of semiconductor characteristics, and Al, Nb, and La are more preferable.
  • Zn ratio when the content (atomic%) of the metal element contained in the oxide sintered body is [Zn], [Sn], and [M metal], respectively, [Zn] + [Sn] + [ [Zn] to [M metal] ratio [[Zn] / ([Zn] + [Sn] + [M metal]), hereinafter may be abbreviated as Zn ratio.
  • Zn ratio Is preferably 0.35 or more and 0.75 or less.
  • the Zn ratio is less than 0.35, fine processing (processing with high accuracy) of a thin film formed by sputtering is difficult, and etching residues are likely to occur.
  • the Zn ratio exceeds 0.75, the carrier mobility of the thin film decreases and falls below the desired level of 5 cm 2 / Vs. More preferably, it is 0.5 or more and 0.7 or less.
  • the oxide sintered body of the present invention and the sputtering target obtained using the oxide sintered body are characterized in that the relative density is 90% or more and the specific resistance is 1 ⁇ cm or less.
  • the oxide sintered body of the present invention has a very high relative density, preferably 90% or more, and more preferably 95% or more.
  • a high relative density not only can prevent the generation of cracks and nodules during sputtering, but also provides advantages such as maintaining a stable discharge continuously to the target life.
  • a ZTO-based oxide it is preferable that it is composed only of a Zn 2 SnO 4 single phase from the viewpoint of increasing the density of the sintered body, and by adding an M metal oxide powder, a ZnM X O y phase
  • a ZnM X O y phase it is known that when a plurality of phases other than Zn 2 SnO 4 are formed by forming an M x O y phase or the like, the relative density tends to decrease.
  • these ZnM X O y phases and M X O y phases are not included, the relative density is not lowered, and 90% or more of the desired level can be secured.
  • the oxide sintered body of the present invention exists as a single phase in which all or most of the M metal is dissolved in Zn 2 SnO 4 , and may contain ZnO or SnO 2 to some extent. However, such a phase structure does not hinder densification of the oxide sintered body and does not adversely affect the properties of the thin film.
  • the oxide sintered body of the present invention has a small specific resistance, preferably 1 ⁇ cm or less, more preferably 0.1 ⁇ cm or less. Accordingly, film formation by a direct current sputtering method using plasma discharge using a direct current power source is possible, and physical vapor deposition (sputtering method) using a sputtering target can be efficiently performed on the production line of the display device.
  • the oxide sintered body of the present invention comprises zinc oxide, tin oxide, and at least one metal (M metal) selected from the group consisting of Al, Hf, Ta, Ti, Nb, Mg, Ga, and rare earth elements.
  • FIG. 1 shows a basic process from a raw material powder to a sputtering target, which is an oxide sintered body obtained by mixing and sintering oxide powders.
  • oxide powder is mixed and pulverized, dried and granulated, molded, subjected to atmospheric pressure sintering, heat-treated, and then the oxide sintered body is processed and bonded to obtain a sputtering target.
  • the basic process is shown.
  • the present invention is characterized in that the sintering conditions and the subsequent heat treatment conditions are appropriately controlled as described in detail below, and the other steps are not particularly limited, and the normally used steps are appropriately selected. You can choose.
  • this invention is not the meaning limited to this.
  • zinc oxide powder, tin oxide powder, and M metal oxide powder are mixed in a predetermined ratio, mixed and pulverized.
  • the purity of each raw material powder used is preferably about 99.99% or more. This is because the presence of a trace amount of impurity elements may impair the semiconductor characteristics of the oxide semiconductor film.
  • the blending ratio of each raw material powder is preferably controlled so that the ratio of Zn and M metal falls within the above-described range.
  • Mixing and pulverization are preferably performed by using a pot mill and adding the raw material powder together with water.
  • the balls and beads used in these steps are preferably made of materials such as nylon, alumina, zirconia, and the like.
  • the mixed powder obtained in the above step is dried and granulated, and then molded.
  • the powder after drying and granulation is filled in a metal mold of a predetermined size, pre-molded by a mold press, and then molded by CIP (cold isostatic pressing) or the like.
  • CIP cold isostatic pressing
  • the molded body thus obtained is fired at normal pressure.
  • the firing temperature is about 1450 ° C. to 1600 ° C.
  • the holding time is about 8 hours or more.
  • the firing atmosphere is preferably a non-reducing atmosphere. For example, it is preferable to adjust the atmosphere by introducing oxygen gas into the furnace.
  • heat treatment is performed on the sintered body to obtain the oxide sintered body of the present invention.
  • the heat treatment temperature about 1000 ° C. or more and the holding time: about 8 hours or more in order to enable plasma discharge with a DC power source.
  • the specific resistance of the sintered body is generally improved from 100 ⁇ cm to 0.1 ⁇ cm.
  • the firing temperature is about 1100 ° C. or more, and the holding time is about 10 hours or more.
  • the firing temperature exceeds 1300 ° C., Zn evaporates and component fluctuations occur, so it is preferable to set it to 1300 ° C. or lower.
  • the holding time is preferably controlled to be approximately 30 hours or less in consideration of cost reduction and the like.
  • the heat treatment atmosphere is preferably a reducing atmosphere.
  • the sputtering target of the present invention can be obtained by processing and bonding according to a conventional method.
  • the relative density and specific resistance of the sputtering target thus obtained are also very good, like the oxide sintered body, and the preferable relative density is approximately 90% or more, and the preferable specific resistance is approximately 1 ⁇ cm or less. It is.
  • Zinc oxide powder JIS 1 type, purity 99.99%
  • granulating a mixed powder obtained in the above step was preformed molding pressure 0.5tonf / cm 2 at a die press, were present molding at a molding pressure of 3tonf / cm 2 at CIP .
  • the molded body thus obtained was sintered by holding at 1500 ° C. for 7 hours at normal pressure.
  • Oxygen gas was introduced into the sintering furnace and sintered in an oxygen atmosphere.
  • it was introduced into a heat treatment furnace and heat treated at 1200 ° C. for 10 hours.
  • Nitrogen gas was introduced into the heat treatment furnace and heat treatment was performed in a reducing atmosphere.
  • FIG. 2 and Table 1 show the results of analyzing the oxide sintered body (Ta—ZTO sintered body) thus obtained by X-ray diffraction analysis under the conditions described above. As shown in FIG. 2, although the oxide sintered body contains Zn 2 SnO 4 , no Ta oxide (Ta 2 O 5 or the like) was detected.
  • the sintered body was processed into a shape of 4 inches ⁇ and 5 mmt and bonded to a backing plate to obtain a sputtering target.
  • the sputtering target thus obtained was attached to a sputtering apparatus, and DC (direct current) magnetron sputtering was performed.
  • the sputtering conditions were a DC sputtering power of 150 W, an Ar / 0.1 volume% O 2 atmosphere, and a pressure of 0.8 mTorr. As a result, no abnormal discharge (arcing) was observed, and it was confirmed that the discharge was stable.
  • the relative density of the sputtering target thus obtained was measured by Archimedes method and found to be 90% or more. Moreover, when the specific resistance of the said sputtering target was measured by the four probe method, it was 1 ohm-cm or less, and all obtained the favorable result.
  • the oxide sintered body contained Zn 2 SnO 4, but no Al oxide (Al 2 O 3 or the like) was detected.
  • the oxide sintered body contains Zn 2 SnO 4, but no Ga oxide (Ga 2 O 3 or the like) was detected.
  • the oxide sintered body contained Zn 2 SnO 4, but no oxide of Hf (such as HfO 2 ) was detected.
  • the oxide sintered body contained Zn 2 SnO 4, but no Ti oxide (TiO 2 or the like) was detected.
  • the oxide sintered body contained Zn 2 SnO 4, but no Mg oxide (such as MgO) was detected.
  • the oxide sintered body contained Zn 2 SnO 4, but no Ga oxide (Ga 2 O 3 or the like) was detected.
  • the oxide sintered body contained Zn 2 SnO 4, but no La oxide (such as La 2 O 3 ) was detected.
  • the oxide sintered body contained Zn 2 SnO 4 .
  • the columns of “M metal oxide”, “ZnM X O y ”, and “M X O y phase” in Table 1 are “-(none)”.
  • the ZTO oxide sintered body containing M metal used in the present invention as a result of X-ray diffraction, separated the Mn metal oxide ZnM X O y phase and M X O y phase. It was confirmed that it did not form. As a result, it was found that the oxide sintered body of the present invention and the sputtering target obtained using the sintered body have a high relative density and a low specific resistance, and have extremely good characteristics.

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Abstract

L'invention concerne un corps fritté d'oxyde qui est mis en œuvre de manière appropriée dans la formation d'un film d'oxyde semi-conducteur pour dispositif d'affichage, et qui combine une conductivité et une densité relative élevées. Plus précisément, ce corps fritté d'oxyde est obtenu par mélange et frittage : d'un oxyde de zinc, d'un oxyde d'étain, et d'une poudre d'oxyde d'au moins une sorte de métal (métal M) choisie parmi un groupe constitué de Al, Hf, Ta, Ti, Nb, Mg, Ga, et de terres rares. Lorsque le corps fritté d'oxyde est soumis à une diffraction de rayons X, un composé Zn2SnO4 est détecté, cependant une phase ZnMxOy et une phase MxOy (x et y représentent des nombres entiers arbitraires), constituant des composés de type spinelle, ne sont pas détectées
PCT/JP2011/071195 2010-09-24 2011-09-16 Corps fritté d'oxyde, et cible de pulvérisation cathodique Ceased WO2012039351A1 (fr)

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CN109477206A (zh) * 2016-07-11 2019-03-15 株式会社半导体能源研究所 溅射靶材及该溅射靶材的制造方法
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JP5983163B2 (ja) * 2012-08-07 2016-08-31 日立金属株式会社 酸化物半導体ターゲットおよび酸化物半導体材料、並びにそれらを用いた半導体装置の製造方法
JP6233233B2 (ja) * 2013-08-06 2017-11-22 三菱マテリアル株式会社 スパッタリングターゲット及びその製造方法
JP6677095B2 (ja) * 2015-11-20 2020-04-08 住友金属鉱山株式会社 Ｓｎ−Ｚｎ−Ｏ系酸化物焼結体とその製造方法
WO2017086016A1 (fr) * 2015-11-20 2017-05-26 住友金属鉱山株式会社 OXYDE DE Sn-Zn-O FRITTÉ ET SON PROCÉDÉ DE PRODUCTION
JP6551683B2 (ja) * 2016-03-11 2019-07-31 住友金属鉱山株式会社 Ｓｎ−Ｚｎ−Ｏ系酸化物焼結体とその製造方法
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JP7532363B2 (ja) 2019-06-27 2024-08-13 出光興産株式会社 酸化物焼結体
CN117396630A (zh) * 2021-06-04 2024-01-12 Ｊｘ金属株式会社 溅射靶及其制造方法
CN118401695A (zh) * 2022-01-05 2024-07-26 Ｊｘ金属株式会社 氧化物膜和氧化物溅射靶
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CN117986010A (zh) * 2024-01-10 2024-05-07 中山智隆新材料科技有限公司 一种氧化锡基靶材及其制备方法和应用
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