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WO2012096267A1 - Compact fritté à base d'oxydes et cible de pulvérisation cathodique correspondante - Google Patents

Compact fritté à base d'oxydes et cible de pulvérisation cathodique correspondante Download PDF

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WO2012096267A1
WO2012096267A1 PCT/JP2012/050296 JP2012050296W WO2012096267A1 WO 2012096267 A1 WO2012096267 A1 WO 2012096267A1 JP 2012050296 W JP2012050296 W JP 2012050296W WO 2012096267 A1 WO2012096267 A1 WO 2012096267A1
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sintered body
oxide
oxide sintered
metal
relative density
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後藤　裕史
祐紀 岩崎
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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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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
  • An amorphous (amorphous) oxide semiconductor used for a TFT has a higher carrier mobility than a general-purpose amorphous silicon (a-Si), has a large optical band gap, and can be formed at a low temperature. Therefore, it is expected to be applied to next-generation displays that require large size, 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.
  • the most developed composition of an oxide semiconductor used for a display device is an In-containing In—Ga—Zn—O (IGZO) amorphous oxide semiconductor.
  • IGZO In-containing In—Ga—Zn—O
  • Patent Documents 1 to 3 high-quality IGZO-based oxide semiconductors have been proposed (for example, Patent Documents 1 to 3).
  • 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.
  • RF high frequency
  • DC direct current
  • 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 can solve the above-mentioned problems is at least one metal (M metal) selected from the group consisting of indium oxide, gallium oxide, zinc oxide, Si, Ni, and Hf.
  • M metal selected from the group consisting of indium oxide, gallium oxide, zinc oxide, Si, Ni, and Hf.
  • the content (atomic%) of the metal element contained in the oxide sintered body is set to [In], [Ga], [Zn], [M metal] ([M metal], respectively). Is the total amount of M metal contained in the oxide sintered body), the ratio of [M metal] to [In] + [Ga] + [Zn] + [M metal] is 0. 01 or more and less than 0.05.
  • the contents (atomic%) of the metal elements contained in the oxide sintered body are [In], [Ga], and [Zn], respectively, and [In] + [Ga] + [In] ratio: [Ga] ratio: [Zn] where the ratio of [In], [Ga], and [Zn] to [Zn] is [In] ratio, [Ga] ratio, and [Zn] ratio, respectively.
  • the ratio is controlled in the range of 0.32 to 0.34: 0.32 to 0.34: 0.32 to 0.34.
  • the oxide sintered body has a relative density of 90% or more and a specific resistance of 0.1 ⁇ cm or less.
  • the sputtering target of the present invention that has solved the above-mentioned problems is a sputtering target obtained using the above oxide sintered body, and has a relative density of 90% or more and a specific resistance of 0.1 ⁇ cm or less. It is what has.
  • an oxide sintered body and a sputtering target that are excellent in conductivity and have a high relative density can be obtained.
  • the sputtering target of the present invention is used, an oxide semiconductor film can be stably formed at low cost by a direct current sputtering method that facilitates high-speed film formation, and thus 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 an oxide for a sputtering target that has high conductivity and high relative density and can be applied to a direct current sputtering method for an oxide (IGZO) semiconductor containing In, Ga, and Zn. In order to provide a sintered body, investigation has been repeated.
  • IGZO oxide
  • (A) Specifically, when the oxide sintered body is subjected to X-ray diffraction, (1) InGaZnO 4 is used as a main phase, and at least M metal A part is dissolved in the InGaZnO 4 , and (2) the ZnM x O y phase and the M x O y phase (x and y are arbitrary integers) that are spinel compounds are not detected.
  • the ratio of the total amount of M metal in all metal elements is set within a predetermined range.
  • the controlled mixed powder may be subjected to predetermined sintering conditions (preferably calcined at a temperature of 1250 to 1600 ° C. for 5 hours or more in a non-reducing atmosphere) to complete the present invention. .
  • the M metal containing IGZO sintered body of the present invention when the oxide sintered body is X-ray diffracted, (1) InGaZnO 4 as a main phase, at least a part of the M metal is dissolved in the InGaZnO 4 , and (2) It is characterized in that it is an oxide sintered body having a structure in which the ZnM x O y phase and M x O y phase (x and y are arbitrary integers), which are spinel compounds, are 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 °
  • InGaZnO 4 for InGaZnO 4 compound (phase) is an oxide In, Ga, and Zn is formed by bonding of 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.
  • the above compound greatly contributes to the improvement of the relative density of the oxide sintered body.
  • the InGaZnO 4 compound is included as a main phase.
  • the “main phase” means a compound having the highest ratio among all the compounds detected by the X-ray diffraction.
  • At least a part of the M metal added in the present invention is dissolved in the InGaZnO 4 compound.
  • Preferred embodiments are those in which all of the M metal is dissolved in the InGaZnO 4 compound, oxide sintered body only the InGaZnO 4 compound is present in a single phase, relative density higher resistance Is also very useful.
  • the part of the M metal (In A Ga B Zn C M D) O 2 (A, B, C, D May be any integer).
  • M metal oxide (M oxide) is a non-conductive phase, it should be as small as possible.
  • the effects of the present invention are not hindered (In A Ga B Zn C M D Anything containing a small amount of O 2 is included within the scope of the present invention.
  • ZnM x O y phase and M x O y phase (x and y are arbitrary integers) ZnM x O y phase and M x O y phase (x and y are arbitrary integers)
  • This is a spinel compound 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.
  • the oxides formed by oxidation of M metal (for example, ZnM x O y phase or M x O y phase such as SiO 2 ) have high insulation and high resistance, so that the oxide of M metal is an oxide.
  • the resistance becomes high, or the resistance becomes locally high, which causes arcing during plasma discharge.
  • the oxide protruding in a cluster shape is mixed into the film, so that the semiconductor characteristics of the thin film are deteriorated and the carrier mobility is lowered.
  • the oxide phase of the M metal element is prevented from being formed in the oxide sintered body by controlling the sintering conditions described later, and most of the M element is converted to In A Ga B.
  • the M metal is at least one metal selected from the group consisting of Si, Ni, and Hf, as will be described later.
  • M metal when M metal is Si, it means that compounds such as ZnSiO 2 and SiO 2 are not detected. “Not detected” means below the detection limit when the above-mentioned X-ray diffraction conditions are performed. All or most of of added M metal is confirmed that the solid solution in the In A Ga B Zn C compound. Incidentally, the remaining M metal that is not dissolved in the In A Ga B Zn C compound is presumed to be segregated in the solid solution or the grain boundaries such as ZnO which may be produced by the composition of the oxide sintered body .
  • the oxide sintered body of the present invention includes indium oxide, gallium oxide, zinc oxide, and powders of at least one metal (M metal) oxide selected from the group consisting of Si, Ni, and Hf. Are obtained by mixing and sintering.
  • M metal metal
  • the oxides of In, Ga, and Zn are compounds that form a semiconductor by controlling the carrier concentration, and the properties change from insulating to semiconductor and conductive depending on the oxygen content in the oxide. Can be changed. 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 an IGZO-based oxide.
  • the M metal is selected from the group consisting of Si, Ni, and Hf, and may be used alone or in combination of two or more.
  • [In], [Ga], [Zn], [M metal] is the oxide content of the metal element contained in the oxide sintered body (atomic%), respectively.
  • the ratio of [M metal] to [In] + [Ga] + [Zn] + [M metal] (hereinafter abbreviated as M metal ratio). In some cases) is preferably 0.01 or more and less than 0.05. When the M metal ratio is less than 0.01, the effect of adding the M metal cannot be obtained, and the reliability of the TFT when a thin film is formed is lowered.
  • M metal ratio 0.05 or more
  • the density of the sintered body cannot be increased to 90% or more, and the specific resistance also increases, so the DC plasma discharge is not stable and abnormal discharge occurs. It becomes easy to do.
  • a more preferable M metal ratio is 0.035 or less.
  • M metal Si
  • the Si ratio may be abbreviated.
  • the content (atomic%) of the metal element contained in the oxide sintered body is [In], [Ga], and [Zn], respectively, with respect to [In] + [Ga] + [Zn].
  • [In], [Ga], and [Zn] ratios are [In] ratio, [Ga] ratio, and [Zn] ratio
  • [In] ratio: [Ga] ratio: [Zn] ratio 0.
  • the carrier mobility when a thin film is formed becomes high, and a high mobility of, for example, 8 cm 2 / Vs or more can be obtained.
  • 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 0.1 ⁇ 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.
  • the IGZO-based oxide preferably from the viewpoint of high density of it is a sintered body that consists of only InGaZnO 4 single phase as mentioned above, ZnM x O by the addition of M metal oxide powder It is known that when a plurality of phases other than InGaZnO 4 are formed by forming a y phase, a M x O y phase, or the like, a relative density is likely to be lowered. On the other hand, in the present invention, since 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 contains most of M metal as a solid solution in an InGaZnO 4 compound, and includes oxides such as (In A Ga B Zn C M D ) O 2 to some extent. Although obtained, such a phase structure does not inhibit the 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 very small specific resistance, preferably 0.1 ⁇ cm or less, more preferably 0.05 ⁇ 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 includes indium oxide, gallium oxide, zinc oxide, and powders of at least one metal (M metal) oxide selected from the group consisting of Si, Ni, and Hf.
  • FIG. 1 shows a basic process from raw material powder to a sputtering target.
  • Fig. 1 shows the basic steps from mixing and crushing oxide powder to drying and granulation ⁇ forming ⁇ atmospheric pressure sintering, and then processing ⁇ bonding to obtain a sputtering target. Is shown.
  • the present invention is characterized in that the sintering conditions are appropriately controlled as will be described in detail below, and the other steps are not particularly limited, and usually used steps can be appropriately selected. .
  • this invention is not the meaning limited to this.
  • indium oxide powder, gallium oxide powder, zinc 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.
  • sintering is performed at a firing temperature of about 1250 ° C. to 1600 ° C. and a holding time of about 5 hours or more in order to obtain a desired compound phase structure (phase mainly composed of InGaZnO 4 ) and increase the relative density.
  • the firing temperature is about 1300 ° C. to 1550 ° C.
  • the holding time is about 8 hours or more.
  • the holding time is preferably controlled to approximately 24 hours or less in consideration of cost reduction and the like.
  • the firing atmosphere is preferably a non-reducing atmosphere, for example, an air atmosphere. Further, the atmosphere may be adjusted by introducing oxygen gas into the furnace.
  • 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 as in the case of the oxide sintered body, the preferable relative density is generally 90% or more, and the preferable specific resistance is generally about 0. 0. 0. 1 ⁇ cm or less.
  • the mixed powder obtained in the above process is dried and granulated, pre-molded with a mold press at a molding pressure of 0.5 tonf / cm 2 , and then molded with CIP at a molding pressure of 3 tonf / cm 2. Went.
  • the molded body thus obtained was sintered at 1450 ° C. for 5 hours at normal pressure.
  • the firing atmosphere was an air atmosphere.
  • FIG. 2 shows the result of analyzing the oxide sintered body (Si-IGZO sintered body) thus obtained by X-ray diffraction under the conditions described above.
  • the oxide sintered body contains InGaZnO 4 as a main phase and contains a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase, but ZnSi x O y and SiO 2. was not detected.
  • it was 91.6% when the relative density of the oxide sintered compact obtained in this way was measured by the Archimedes method.
  • the specific resistance of the oxide sintered body was measured by a four-terminal method, it was 2.7 ⁇ 10 ⁇ 2 ⁇ cm, and both the relative density and the specific resistance had good characteristics.
  • Table 1 summarizes the results of relative density and specific resistance of the oxide sintered body containing Si as the M metal.
  • Table 2 summarizes the X-ray diffraction results of the oxide sintered bodies.
  • 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 and specific resistance of the sputtering target thus obtained are the same as the values of the oxide sintered body, and the conditions specified in the present invention (relative density of 90% or more, specific resistance of 0.1 ⁇ cm) The following was satisfied.
  • Example 2 In Example 1 described above, an oxide sintered body was obtained by performing an experiment in the same manner as in Example 1 except that sintering was performed at 1400 ° C. for 8 hours. Analysis by diffraction revealed that InGaZnO 4 was contained as the main phase and a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase was contained, but ZnSi x O y and SiO 2 were not detected ( (See Table 2).
  • Example 3 In Example 1 described above, except that sintering was performed at 1500 ° C. for 5 hours, an experiment was performed in the same manner as in Example 1 above to obtain an oxide sintered body. Analysis by diffraction revealed that InGaZnO 4 was contained as the main phase and a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase was contained, but ZnSi x O y and SiO 2 were not detected ( (See Table 2).
  • Example 5 In Example 4 described above, an oxide sintered body was obtained by performing an experiment in the same manner as in Example 4 except that sintering was performed at 1450 ° C. for 5 hours. When analysis by diffraction was performed, InGaZnO 4 was contained as a main phase and a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase was contained, but ZnSi x O y and SiO 2 were not detected. (See Table 2).
  • Example 6 In Example 4 described above, an oxide sintered body was obtained by performing an experiment in the same manner as in Example 1 except that sintering was performed at 1550 ° C. for 5 hours. When analysis by diffraction was performed, InGaZnO 4 was contained as a main phase and a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase was contained, but ZnSi x O y and SiO 2 were not detected. (See Table 2).
  • Example 7 In Example 7 described above, an oxide sintered body was obtained by performing an experiment in the same manner as in Example 7 except that sintering was performed at 1350 ° C. for 8 hours. As a result of analysis by diffraction, as in Experimental Example 7, the oxide sintered body contains InGaZnO 4 as a main phase, a small amount of (In 0.5 Ga 0.2 Zn 0.2 Si 0.1 ) O 2 phase, and a small amount of ZnSi. 2 O 4 was also included (see Table 2).
  • Example 7 In Example 7 described above, an oxide sintered body was obtained by performing an experiment in the same manner as in Example 7 except that sintering was performed at 1450 ° C. for 5 hours. Analysis by diffraction revealed that the oxide sintered body contained InGaZnO 4 as a main phase and also contained a small amount of ZnSi 2 O 4 (see Table 2).
  • Example 4 oxidized Hf powder having a purity of 99.99% was used as the M metal and sintering was performed at 1500 ° C. for 5 hours. Then, an oxide sintered body was obtained and analyzed by X-ray diffraction under the above-mentioned conditions. As a result, it contained InGaZnO 4 as a main phase and contained a small amount of (In 0.5 Ga 0.2 Zn 0.2 Hf 0.1 ) O. Although two phases were contained, ZnHf x O y and Hf x O y were not detected.
  • the IGZO 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 was not formed and contained InGaZnO 4 as a main phase. 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

Le compact fritté à base d'oxydes de la présente invention est un compact fritté à base d'oxydes obtenu par mélange et frittage de poudres de chacun parmi l'oxyde d'indium, l'oxyde de gallium, l'oxyde de zinc et un oxyde d'au moins un métal (métal (M)) choisi dans le groupe consistant en Si, Ni et Hf. Lorsque le compact fritté à base d'oxydes est soumis à une diffraction des rayons X, (1) InGaZnO4 est la phase primaire et au moins une partie du métal (M) est une solution solide dans le InGaZnO4, et (2) une phase de ZnMxOy et une phase de MxOy (où x et y sont des entiers arbitraires) ne sont pas détectées. Selon la présente invention, il est possible de fournir un compact fritté à base d'oxydes qui est idéal pour la fabrication d'un film semi-conducteur à base d'oxydes utilisé dans un dispositif d'affichage et qui est capable de former un film semi-conducteur à base d'oxydes ayant à la fois une conductivité élevée et une densité relative élevée.
PCT/JP2012/050296 2011-01-14 2012-01-11 Compact fritté à base d'oxydes et cible de pulvérisation cathodique correspondante Ceased WO2012096267A1 (fr)

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WO2013140838A1 (fr) * 2012-03-22 2013-09-26 住友金属鉱山株式会社 PASTILLE FRITTÉE À BASE D'OXYDE DE TYPE In-Ga-Zn-O ET SON PROCÉDÉ DE PRODUCTION, CIBLE DE PULVÉRISATION ET FILM SEMI-CONDUCTEUR À BASE D'OXYDE
WO2015029272A1 (fr) * 2013-08-26 2015-03-05 Jx日鉱日石金属株式会社 Corps fritté et film amorphe
JP2018021254A (ja) * 2016-07-11 2018-02-08 株式会社半導体エネルギー研究所 スパッタリングターゲット、およびスパッタリングターゲットの作製方法

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JP6278229B2 (ja) * 2012-08-10 2018-02-14 三菱マテリアル株式会社 透明酸化物膜形成用スパッタリングターゲット及びその製造方法
CN115340360B (zh) 2013-12-27 2023-06-27 出光兴产株式会社 氧化物烧结体、该烧结体的制造方法及溅射靶
JP6231924B2 (ja) * 2014-03-28 2017-11-15 出光興産株式会社 酸化物焼結体及びスパッタリングターゲット
US10000842B2 (en) * 2014-06-26 2018-06-19 Sumitomo Metal Mining Co., Ltd. Oxide sintered body, sputtering target, and oxide semiconductor thin film obtained using sputtering target
CN107924822B (zh) 2015-07-30 2022-10-28 出光兴产株式会社 晶体氧化物半导体薄膜、晶体氧化物半导体薄膜的制造方法以及薄膜晶体管
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WO2013140838A1 (fr) * 2012-03-22 2013-09-26 住友金属鉱山株式会社 PASTILLE FRITTÉE À BASE D'OXYDE DE TYPE In-Ga-Zn-O ET SON PROCÉDÉ DE PRODUCTION, CIBLE DE PULVÉRISATION ET FILM SEMI-CONDUCTEUR À BASE D'OXYDE
WO2015029272A1 (fr) * 2013-08-26 2015-03-05 Jx日鉱日石金属株式会社 Corps fritté et film amorphe
JP5690982B1 (ja) * 2013-08-26 2015-03-25 Jx日鉱日石金属株式会社 焼結体及びアモルファス膜
JP2018021254A (ja) * 2016-07-11 2018-02-08 株式会社半導体エネルギー研究所 スパッタリングターゲット、およびスパッタリングターゲットの作製方法
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JP7512346B2 (ja) 2016-07-11 2024-07-08 株式会社半導体エネルギー研究所 金属酸化物膜の作製方法

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