WO2010140548A1 - 酸化物焼結体、その製造方法及び酸化物焼結体製造用原料粉末 - Google Patents
酸化物焼結体、その製造方法及び酸化物焼結体製造用原料粉末 Download PDFInfo
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- WO2010140548A1 WO2010140548A1 PCT/JP2010/059101 JP2010059101W WO2010140548A1 WO 2010140548 A1 WO2010140548 A1 WO 2010140548A1 JP 2010059101 W JP2010059101 W JP 2010059101W WO 2010140548 A1 WO2010140548 A1 WO 2010140548A1
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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 provides an sintered IGZO oxide used as a sputtering target when a transparent semiconductor IGZO film used for an active layer of a thin film transistor in a liquid crystal display device or an organic EL display device is produced by a sputtering method,
- the present invention relates to a manufacturing method and oxide powder used as a raw material for manufacturing the oxide sintered body.
- a thin film transistor having an active layer made of a silicon-based material for driving each pixel is used for a display element such as an active matrix liquid crystal display device, but the aperture ratio is reduced by a light blocking layer for preventing visible light absorption,
- a thin film transistor using a transparent oxide semiconductor has been developed due to the disadvantage that high temperature film formation is necessary.
- Transparent oxide semiconductors are attracting attention from the viewpoints of low-temperature film formation, high mobility, and the like.
- an In—Ga—Zn—O-based material hereinafter, “indium, gallium, zinc, oxygen”
- the mobility of the amorphous IGZO film is higher than that of amorphous silicon, and the field effect transistor using the amorphous IGZO film as an active layer has a high on / off ratio. Therefore, it is considered promising (see Non-Patent Document 1 and Patent Document 1).
- a sputtering method that is excellent in mass productivity is the most appropriate.
- the IGZO target needs to have a high density.
- Patent Document 2 describes a method for manufacturing an indium oxide sputtering target using indium oxide powder having a chlorine concentration of 50 mass ppm or less. However, only the effect of the chlorine concentration contained in the indium oxide powder is disclosed in the specification.
- Patent Document 3 has a description of indium oxide powder having a low halogen element content. However, in the examples, only indium nitrate is used as a raw material.
- the present invention has been made paying attention to such circumstances, and its purpose is to produce an IGZO target used as a sputtering target necessary for film formation by sputtering of a transparent semiconductor IGZO film at a high density. It is to provide an oxide raw material powder having a low impurity concentration, which is suitable as a production method, an IGZO sintered body obtained by the production method, and a raw material for producing the IGZO sintered body.
- the inventors of the present invention have disclosed a sputtering target for producing a transparent semiconductor film mainly containing indium, gallium, zinc, and oxygen, and sintered oxide sintered bodies in which the concentration ratio of these elements is within a predetermined range.
- problems such as rupture, swelling, and density reduction may occur in the sintered body, and as a result of intensive investigation of the cause, these problems are caused by the specific impurities contained in the oxide powder as a raw material.
- the present invention was completed by finding that there is a correlation with the concentration.
- Raw material powder for manufacturing an oxide sintered body comprising indium oxide, gallium oxide and zinc oxide powder each having a volatile impurity concentration of 20 ppm or less.
- the volatile impurity is a compound containing one or more selected from a chlorine compound, a nitric acid compound, a sulfuric acid compound, and an ammonium compound, for producing an oxide sintered body according to the above 12) Raw material powder.
- a method for producing a high-density IGZO oxide sintered body used as a sputtering target for producing a transparent semiconductor IGZO film and the sintered body can be provided.
- Active matrix-driven liquid crystal display device without spattering by using a sintered body and without causing abnormal discharge such as arcing, nodules on the surface, and no adverse effects.
- a good transparent semiconductor IGZO film that becomes an active layer portion of a thin film transistor in an organic EL display element can be produced.
- the oxide sintered body used in the present invention contains indium (In), gallium (Ga), zinc (Zn), and oxygen (O) as constituent elements.
- the above four types are higher in concentration than other elements, and are mixed in the process of producing the sintered body, or more than the impurity concentration mixed in from the raw material. It means very high concentration.
- the carrier concentration of the film obtained by sputtering film formation is too high, and the thin film transistor having the film as an active layer
- the on / off ratio which is an important indicator of characteristics, is deteriorated.
- the indium ratio is less than 0.2, the carrier concentration of the film obtained by sputtering film formation becomes too low, and the mobility of the film also decreases, which is not preferable in terms of device characteristics.
- the oxide sintered body according to the present invention is stable when the atomic ratio z / (x + y + z) of zinc to the total amount of indium, gallium, and zinc exceeds 0.5. Property, moisture resistance, etc. will deteriorate.
- this zinc ratio is less than 0.1, the amorphousness of the film obtained by sputtering film formation becomes weak, and crystallization becomes easy.
- the crystallized film has a large in-plane variation in film characteristics, resulting in a large variation in element characteristics.
- the decrease in the Zn ratio is an increase in the total ratio of In and Ga. Since these two types of metals are relatively expensive, the cost of the oxide sintered body is increased.
- a describes the case where the stoichiometric composition coincides with the stoichiometric composition.
- the oxygen content in the oxide sintered body of the present invention is slightly different from the stoichiometric composition.
- Oxygen deficiency is the normal state, and the present invention also includes an oxide sintered body having such oxygen deficiency.
- the “impurity” described in this specification is an element other than indium, gallium, zinc, and oxygen contained in indium oxide, gallium oxide, and zinc oxide used as a raw material.
- the impurity concentration is ICP ( (High frequency inductively coupled plasma) analysis method.
- ICP High frequency inductively coupled plasma
- an ICP (High Frequency Inductively Coupled Plasma) analysis method was performed using SII Nanotechnology-type SPS3000 to evaluate the impurity concentration in the raw material and oxide sintered body.
- “Impurity is volatile” described in the present specification means that when the temperature of the impurity is raised, the impurity is in a gaseous state and is released from the raw material. In general, when the temperature of a substance is raised, there are things that become a gas directly from a solid, and things that are in a gas after passing through a liquid. Although it will also have volatility, it shall mean here that the temperature which leaves
- the relative density of the oxide sintered body of the present invention can be 95% or more, can be 98% or more, and can be 99% or more.
- the advantage of the present invention is clear because there is a disadvantage that the generation of nodules increases with the passage of time, the frequency of occurrence of abnormal discharge increases, and the obtained film characteristics deteriorate.
- the measurement method of the relative density of the oxide sintered body can first determine the value of the density at which the relative density of the oxide sintered body is 100% from each constituent element and form for each composition.
- the density of the actually produced oxide sintered body can be obtained by the Archimedes method or the like, and the relative density can be obtained by dividing by the density value of 100%.
- the crystal structure of the oxide sintered body can be evaluated using an X-ray diffractometer. In the present invention, the crystal structure was evaluated using a RINT-1100 X-ray diffractometer manufactured by Rigaku Corporation.
- a representative example of the production process of the oxide sintered body according to the present invention is as follows.
- a raw material indium oxide (In 2 O 3 ), gallium oxide (Ga 2 O 3 ), and zinc oxide (ZnO) can be used.
- In 2 O 3 indium oxide
- gallium oxide Ga 2 O 3
- zinc oxide ZnO
- Each raw material powder is weighed so as to have a desired composition ratio. As described above, impurities inevitably contained in these are included.
- each component will segregate in the manufactured target and there will be a high resistivity region and a low resistivity region, and arcing due to charging etc. in the high resistivity region during sputter deposition. Therefore, sufficient mixing and pulverization are necessary.
- a super mixer After mixing each raw material with a super mixer, if necessary, they are packed in an alumina sagger and calcined at a temperature in the range of 950 to 1350 ° C. The holding time for calcination is 2 to 10 hours in an air atmosphere.
- the finely pulverized slurry is dried with a hot air dryer at 100 to 150 ° C. for 5 to 48 hours, and sieved with a 250 ⁇ m mesh sieve to collect the powder.
- the specific surface area of each powder is measured before and after pulverization.
- 20 cc of a PVA aqueous solution (PVA solid content 3%) is mixed with 1000 g of IGZO powder, and sieved with a sieve having an opening of 500 ⁇ m.
- a mold of ⁇ 210 mm is filled with 1000 g of powder and pressed at a surface pressure of 400 to 1000 kgf ⁇ cm 2 to obtain a molded body.
- This molded body is double vacuum packed with vinyl and CIPed at 1500 to 4000 kgf / cm 2 .
- sintering is performed at a predetermined temperature (retention time 5 to 24 hours, in an oxygen atmosphere) to obtain a sintered body.
- the oxide sintered body obtained as described above is processed into a target of, for example, 152.4 ⁇ ⁇ 5 tmm by performing cylindrical grinding on the outer periphery and surface grinding on the surface side.
- an indium alloy or the like is bonded to a copper backing plate as a bonding metal to obtain a sputtering target.
- Method for producing raw material oxide powder there are various methods for producing the raw material oxide powder according to the present invention, but the most common is the neutralization method.
- the neutralization method when manufacturing gallium oxide powder, first, the raw material gallium metal is dissolved in an acid.
- the acid used at this time include hydrochloric acid, nitric acid, sulfuric acid, and mixed acids thereof. Thereafter, the solution is neutralized with an alkaline solution. Examples of the alkaline solution used at this time include aqueous ammonia and sodium hydroxide.
- Gallium hydroxide (Ga (OH) 3 ) is precipitated by neutralization, and then water molecules are taken from the gallium hydroxide and changed to gallium oxyhydroxide (GaOOH).
- Gallium oxide powder can be obtained by thoroughly washing these hydroxides and then drying them. The method for obtaining the raw material powders of other raw materials such as indium oxide and zinc oxide is almost the same.
- residual impurity concentration especially volatile impurities, will be released at a relatively low temperature during sintering if used as a raw material for oxide sintered bodies. It was thought that there would be no adverse effect on the crystallization, and in fact, there were volatile impurities that desorbed at a relatively low temperature, so there was often no awareness of defining the residual impurity concentration.
- gallium chloride GaCl
- some volatile impurities such as gallium chloride (GaCl)
- gallium chloride (GaCl) leave only after exceeding 1300 ° C.
- gallium chloride (GaCl) even a single compound that vaporizes and leaves at a relatively low temperature may be released only when the temperature becomes higher when it adheres to the oxide raw material powder and remains in the pores.
- harmful gallium chloride (GaCl) remains in the raw material Ga 2 O 3 .
- the gallium chloride only needs to be volatilized during the sintering, but it is a substance that has a low vapor pressure of about 1 atm even near the sintering temperature and hardly volatilizes. Therefore, it can be said that it is desirable to reduce the total amount of gallium chloride (GaCl) contained in the raw material powder or the preparation stage of the raw material powder.
- the following method can be proposed as a specific method for lowering the chloride concentration.
- a) A method of sufficiently washing a gallium oxide precursor (gallium hydroxide). Specifically, after washing with 20 times the amount of pure water with respect to the amount of powder, it is baked at 1000 ° C. This reduces the chloride concentration to 200 wwtppm.
- b) A method of heat treatment at a roasting temperature of 1200 ° C. or higher when oxidizing from gallium hydroxide to gallium oxide. Specifically, the chloride concentration is reduced to 10 wtppm or less by baking the hydroxide washed with 20 times the amount of pure water with respect to the amount of powder at a baking temperature of 1200 ° C. As described above, in order to reduce the concentration of chloride, it is possible to achieve it by sufficiently washing with water and further performing the baking temperature at a high temperature.
- the oxide raw material powder having a high impurity concentration described in the comparative example in this example can be produced as described above.
- the raw material powder used in the examples is as shown in Table 1.
- the sintering temperature was changed to prepare targets and various tests were performed. Details thereof are shown in Examples 1 to 7 in Table 2.
- the molar mixing ratio (1: 1: 1) is a typical IGZO target.
- the mixing ratio of IGZO is not particularly problematic, but for Examples 1 to 6, In 2 O 3 : Ga 2 O 3 : ZnO
- the raw materials were prepared so as to be 1: 1: 1: 1.
- the bulk resistance value was measured by a four-probe method using a resistivity measuring instrument ( ⁇ -5 +, manufactured by NP Corporation).
- the specific surface area (BET) was measured by an automatic surface area meter beta soap (manufactured by Nikkiso Co., Ltd., MODEL-4200).
- Example 1 In Example 1, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (1) Ga 2 O 3 powder having a particle size of 5.6 ⁇ m, a specific surface area of 9.1 m 2 / g, and a chlorine concentration of 18 ppm, and as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area of 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 6.0 m 2 / g.
- the specific surface area (BET) after pulverization was 17.8 m 2 / g. This difference was 10.8 m 2 / g.
- Table 2 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was 14 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Example 1 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.20 g / cm 3
- the relative density is 95.5% (the true density of the composition of Example 1 is 6.495 g / cm 3 )
- the bulk resistance value is 3.0 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 1 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 2 In Example 2, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (1) Ga 2 O 3 powder having a particle size of 5.6 ⁇ m, a specific surface area of 9.1 m 2 / g, and a chlorine concentration of 18 ppm, and as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area of 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- Example 2 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.46 g / cm 3
- the relative density is 99.5% (the true density of the composition of Example 2 is 6.495 g / cm 3 )
- the bulk resistance value is 5.2 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 2 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules decreased, and abnormal discharge during sputtering was hardly recognized.
- Example 3 In Example 3, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (1) Ga 2 O 3 powder having a particle size of 5.6 ⁇ m, a specific surface area of 9.1 m 2 / g, and a chlorine concentration of 18 ppm, and as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area of 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- Example 3 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.22 g / cm 3
- the relative density is 95.8% (the true density of the composition of Example 3 is 6.495 g / cm 3 )
- the bulk resistance is 2.2 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 3 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 4 In Example 4, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (2) Ga 2 O 3 powder having a particle size of 4.6 ⁇ m, a specific surface area of 11.9 m 2 / g, and a chlorine concentration of 12 ppm, and as a ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- Example 4 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.26 g / cm 3
- the relative density is 96.4% (the true density of the composition of Example 4 is 6.495 g / cm 3 )
- the bulk resistance value is 6.0 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 4 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 5 In Example 5, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 0.7 ⁇ m, a specific surface area of 13.7 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (2) Ga 2 O 3 powder having a particle size of 4.6 ⁇ m, a specific surface area of 11.9 m 2 / g, and a chlorine concentration of 12 ppm, and as a ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 13.8 m 2 / g.
- the specific surface area (BET) after pulverization was 22.1 m 2 / g. This difference was 8.3 m 2 / g.
- Table 2 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was ⁇ 10 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Example 5 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.48 g / cm 3
- the relative density is 99.8% (the true density of the composition of Example 5 is 6.495 g / cm 3 )
- the bulk resistance value is 4.0 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 5 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 6 In Example 6, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 0.7 ⁇ m, a specific surface area of 13.7 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (2) Ga 2 O 3 powder having a particle size of 4.6 ⁇ m, a specific surface area of 11.9 m 2 / g, and a chlorine concentration of 12 ppm, and as a ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area 3 A ZnO powder with 0.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 13.8 m 2 / g.
- the specific surface area (BET) after pulverization was 22.1 m 2 / g. This difference was 8.3 m 2 / g.
- Table 2 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was ⁇ 10 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Example 6 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.44 g / cm 3
- the relative density is 99.2% (the true density of the composition of Example 6 is 6.495 g / cm 3 )
- the bulk resistance is 2.6 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 6 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 7 In Example 7, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (3) Ga 2 O 3 powder having a particle size of 4.2 ⁇ m, a specific surface area of 9.3 m 2 / g, and a chlorine concentration ⁇ 10 ppm, and as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area ZnO powder with 3.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 1.7 m 2 / g.
- the specific surface area (BET) after pulverization was 11.5 m 2 / g. This difference was 9.8 m 2 / g.
- Table 2 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was ⁇ 10 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Example 7 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.34 g / cm 3
- the relative density is 99.4% (the true density of the composition of Example 7 is 6.379 g / cm 3 )
- the bulk resistance value is 18.0 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 6 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Example 8 In Example 8, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. As the above (3) Ga 2 O 3 powder having a particle size of 4.2 ⁇ m, a specific surface area of 9.3 m 2 / g, and a chlorine concentration ⁇ 10 ppm, and as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m, specific surface area ZnO powder with 3.8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 1.7 m 2 / g.
- the specific surface area (BET) after pulverization was 11.5 m 2 / g. This difference was 9.8 m 2 / g.
- Table 2 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was ⁇ 10 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Example 8 the chlorine concentration of the sintered body was below the detection limit, that is, less than 10 ppm.
- the density is 6.27 g / cm 3
- the relative density is 98.3% (the true density of the composition of Example 8 is 6.379 g / cm 3 )
- the bulk resistance is 24.0 m ⁇ ⁇ cm.
- the occurrence of swelling or cracking of the IGZO sintered compact target of Example 6 was not recognized. As a result of performing DC sputtering under the above conditions, the generation of particles and the number of nodules were reduced, and abnormal discharge during sputtering was hardly recognized.
- Comparative Example 1 In Comparative Example 1, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and a Ga 2 O 3 raw material was used. (4) Using a Ga 2 O 3 powder having a particle size of 3.0 ⁇ m, a specific surface area of 9.4 m 2 / g, and a chlorine concentration of 156 ppm, as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m and a specific surface area of 3. ZnO powder with 8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the specific surface area (BET) before pulverization was 2.6 m 2 / g.
- the specific surface area (BET) after pulverization was 17.0 m 2 / g. This difference was 14.4 m 2 / g.
- Table 4 shows the details of powder mixing, pulverization, calcination, sintering, and target production conditions. As a result, the chlorine concentration of the granulated powder was 40 ppm. Here, the main conditions are described.
- Various measurements and evaluations were performed by the methods described in the above paragraphs [0025], [0028], and [0042].
- Comparative Example 2 In Comparative Example 2, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and the Ga 2 O 3 raw material was used. (4) Using a Ga 2 O 3 powder having a particle size of 3.0 ⁇ m, a specific surface area of 9.4 m 2 / g, and a chlorine concentration of 156 ppm, as the ZnO raw material, the above (1) particle size of 1.1 ⁇ m and a specific surface area of 3. ZnO powder with 8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- Comparative Example 3 In Comparative Example 3, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and the Ga 2 O 3 raw material was used. (4) Using a Ga 2 O 3 powder having a particle size of 3.2 ⁇ m, a specific surface area of 9.6 m 2 / g, and a chlorine concentration of 300 ppm, the above (1) particle size of 1.1 ⁇ m and a specific surface area of 3. ZnO powder with 8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- Comparative Example 4 In Comparative Example 4, as the In 2 O 3 raw material, the above (1) In 2 O 3 powder having a particle size of 10.7 ⁇ m, a specific surface area of 4.4 m 2 / g, and a chlorine concentration ⁇ 10 ppm was used, and the Ga 2 O 3 raw material was used. (5) Using a Ga 2 O 3 powder having a particle size of 3.2 ⁇ m, a specific surface area of 9.6 m 2 / g, and a chlorine concentration of 300 ppm, the above (1) particle size of 1.1 ⁇ m and a specific surface area of 3. ZnO powder with 8 m 2 / g and chlorine concentration ⁇ 10 ppm was used.
- the present invention comprises indium (In), gallium (Ga), zinc (Zn), and oxygen (O), and the formula InxGayZnzOa [wherein x / (x + y) is 0.2 to 0.8, z / (x + y + z).
- the present invention has an excellent effect that generation of nodules during sputtering is minimized, abnormal discharge is suppressed, and stable DC sputtering is possible. Furthermore, the target life can be lengthened, and there is little variation in quality, so that mass productivity can be improved.
- This In—Ga—Zn—O-based (IGZO) material is useful for a field effect transistor because an amorphous oxide having an electron carrier concentration of less than 10 18 / cm 3 can be obtained. Moreover, since it can be used as an IGZO target without hindrance for a wide range of applications, its industrial utility value is high.
Abstract
Description
2)揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする上記1記載の酸化物焼結体。
3)揮発性不純物が、塩素化合物であることを特徴とする上記1又は請求項2に記載の酸化物焼結体。
4)揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする上記1乃至請求項3のいずれか一項に記載の酸化物焼結体。
5)相対密度が95%以上であり、バルク抵抗値が5.0×10-2Ωcm以下であることを特徴とする上記1乃至4のいずれか一項に記載の酸化物焼結体。
6)相対密度が98%以上であることを特徴とする5)記載の酸化物焼結体。
7)相対密度が99%以上であることを特徴とする5)記載の酸化物焼結体。
9)揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする上記8)記載の酸化物焼結体の製造方法。
10)揮発性不純物が、塩素化合物であることを特徴とする上記8)又は9)記載の酸化物焼結体の製造方法。
11)揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする上記8)乃至10)のいずれか一項に記載の酸化物焼結体の製造方法。
13)揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする上記12)に記載の酸化物焼結体製造用原料粉末。
14)揮発性不純物が、塩素化合物であることを特徴とする上記12)又は13)記載の酸化物焼結体製造用原料粉末。
15)揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする上記12)乃至14)のいずれか一項に記載の酸化物焼結体製造用原料粉末。
結晶化膜は膜特性の面内ばらつきが大きく、素子特性のばらつきを大きくしてしまう。更に、Zn比の減少とは、InとGaの合計比の増加であり、これら2種類の金属は比較的高価であるため、酸化物焼結体のコストアップとなってしまう。
本発明では、SIIナノテクノロジ-社製型式SPS3000を用いて、ICP(高周波誘導結合プラズマ)分析法を行って、原料中及び酸化物焼結体中の不純物濃度を評価した。
酸化物焼結体の結晶構造は、X線回折装置を用いて評価することができる。本発明では、リガク社製RINT-1100X線回折装置を用いて結晶構造を評価した。
上記の本発明に係る酸化物焼結体の製造工程の代表例を示すと、次の通りである。
原料としては、酸化インジウム(In2O3)、酸化ガリウム(Ga2O3)、及び酸化亜鉛(ZnO)を使用することができる。不純物による電気特性への悪影響を避けるために、純度4N以上の原料を用いることが望ましい。各々の原料粉を所望の組成比となるように秤量する。なお、上記の通り、これらに不可避的に含有される不純物は含まれるものである。
スーパーミキサーにて各原料を混合した後、必要に応じて、これらをアルミナ製匣鉢に詰め、温度950~1350°Cの範囲で仮焼する。仮焼の保持時間は、2~10hr、大気雰囲気で行う。
大量の場合は、原料を1バッチ30kg単位で、LMZ(スターミル:アシザワファインテック製)にて2~5hr程度微粉砕(φ0.5mmジルコニアビーズ、投入電力3.0kW・Hr)する。
ターゲットの製作に際しては、上記によって得られた酸化物焼結体の外周の円筒研削、面側の平面研削をすることによって、例えば152.4φ×5tmmのターゲットに加工する。これをさらに、例えば銅製のバッキングプレートに、インジウム系合金などをボンディングメタルとして、貼り合わせることでスパッタリングターゲットとする。
本発明に係る原料酸化物粉末の製造方法としては、各種の方法が有り得るが、最も一般的なのは中和法である。例えば、酸化ガリウム粉を製造する場合は、まず、原料ガリウム金属を酸に溶解させる。この際に使用される酸としては、塩酸、硝酸、硫酸またはこれらの混合酸などがある。その後、溶解液をアルカリ溶液で中和する。
この際に使用されるアルカリ溶液としては、アンモニア水、水酸化ナトリウムなどがある。中和によって水酸化ガリウム(Ga(OH)3)が沈殿して、その後、水酸化ガリウムから水分子が取れて、オキシ水酸化ガリウム(GaOOH)に変化する。
これらの水酸化物を良く洗浄してから、乾燥させることで、酸化ガリウム粉末を得ることができる。他の原料である酸化インジウム、酸化亜鉛の原料粉を得る方法もほぼ同様である。
特に、酸化ガリウム製造時、酸として塩酸、アルカリ溶液としてアンモニア水を用いる場合は、塩化アンモニウムが残り易い。また、原料粉が微細であると、特に原料紛の凝集隙間や原料粉自体の細孔等に入り込んでしまい易く、単に、純水での洗浄では、不純物がなかなか取りきれず、充分に取り除こうとすると、非常に多くの時間と労力を要してしまう。
特に、有害な塩化ガリウム(GaCl)は原料Ga2O3中に残留する。この塩化ガリウムが焼結中に揮発すれば良いのであるが、焼結温度付近でも1気圧程度と蒸気圧が低く、揮発し難い物質である。したがって、原料粉又は原料粉の調合段階で、含有する塩化ガリウム(GaCl)の合計量を低減させることが望ましいと言える。
a)酸化ガリウム前駆体(水酸化ガリウム)を十分に洗浄する方法。
具体的には、粉量に対して20倍量の純水で洗浄した後、1000°Cで焙焼する。これによって、塩化物濃度を200wwtppmにまで低減化する。
b)ガリウム水酸化物から酸化ガリウムへ酸化させる際に、焙焼温度を1200°C以上の高温で熱処理する方法。
具体的には、粉量に対して20倍量の純水で洗浄した水酸化物を、焙焼温度1200°Cで焙焼することによって、塩化物濃度を10wtppm以下に低減化する。
以上に示すように、塩化物の濃度を低減させるためには、水洗を十分に行うこと、さらに焙焼温度を高温で行うことによって、達成することが可能である。
なお、上記モル配合比(1:1:1)は、IGZOターゲットの代表的なものである。本発明の目的とするターゲットのノジュール発生を防止するためには、IGZOの配合比は特に問題とはならないが、実施例1~実施例6については、In2O3:Ga2O3:ZnO=1:1:1となるよう原料を調合して実施した。
(粒径の測定)
粒径の測定は、粒度分布測定装置(日機装株式会社製、Microtrac MT3000)を用いて行った。
(塩素濃度の測定)
塩素濃度の測定は、塩素・硫黄分析装置(株式会社三菱アナリティック製、TOX-2100H)を用いて行った。
(密度の測定)
密度の測定は純水を溶媒として用いたアルキメデス法にて測定を行った。相対密度の算出に用いた理論密度は、JCPDSカードで報告されている密度を引用した(In:Ga:Zn=2:2:1についてはIn2Ga2ZnO7(カード番号:381097)、In:Ga:Zn=1:1:1についてはInGaZnO4(カード番号:381104)である)。
(バルク抵抗値の測定)
バルク抵抗値の測定は、抵抗率測定器(エヌピイエス株式会社製、Σ-5+)を用いて、四探針法で行った。
(比表面積の測定)
比表面積(BET)の測定は、自動表面積計ベータソープ(日機装株式会社製、MODEL-4200)で行なった。
作製したターゲットの試験片については、表3に示すスパッタリング条件でスパッタリングし、ノジュールの発生を目視観察した。
本実施例1では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(1)粒径5.6μm、比表面積9.1m2/g、塩素濃度18ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は6.0m2/gであった。また、粉砕後の比表面積(BET)は17.8m2/gであった。この差は、10.8m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。この結果、造粒粉の塩素濃度は14ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例2では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(1)粒径5.6μm、比表面積9.1m2/g、塩素濃度18ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合し、950°Cで仮焼した。粉砕前の比表面積(BET)は2.6m2/gであった。また、粉砕後の比表面積(BET)は17.0m2/gであった。この差は、14.4m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は13ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例3では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(1)粒径5.6μm、比表面積9.1m2/g、塩素濃度18ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合し、950°Cで仮焼した。粉砕前の比表面積(BET)は2.6m2/gであった。また、粉砕後の比表面積(BET)は17.0m2/gであった。この差は、14.4m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。この結果、造粒粉の塩素濃度は11ppmとなった。
ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例4では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(2)粒径4.6μm、比表面積11.9m2/g、塩素濃度12ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合し、950°Cで仮焼した。粉砕前の比表面積(BET)は3.1m2/gであった。また、粉砕後の比表面積(BET)は14.7m2/gであった。この差は、11.6m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は<10ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例5では、In2O3原料として、上記(1)粒径0.7μm、比表面積13.7m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(2)粒径4.6μm、比表面積11.9m2/g、塩素濃度12ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は13.8m2/gであった。また、粉砕後の比表面積(BET)は22.1m2/gであった。この差は、8.3m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は<10ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例6では、In2O3原料として、上記(1)粒径0.7μm、比表面積13.7m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(2)粒径4.6μm、比表面積11.9m2/g、塩素濃度12ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は13.8m2/gであった。また、粉砕後の比表面積(BET)は22.1m2/gであった。この差は、8.3m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は<10ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例7では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(3)粒径4.2μm、比表面積9.3m2/g、塩素濃度<10ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=1:1:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は1.7m2/gであった。また、粉砕後の比表面積(BET)は11.5m2/gであった。この差は、9.8m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は<10ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
本実施例8では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(3)粒径4.2μm、比表面積9.3m2/g、塩素濃度<10ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=1:1:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は1.7m2/gであった。また、粉砕後の比表面積(BET)は11.5m2/gであった。この差は、9.8m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表2に示す。
この結果、造粒粉の塩素濃度は<10ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングを上記条件で行った結果、パーティクルの発生やノジュール数は減少し、スパッタリング中の異常放電が殆ど認められなかった。
比較例1では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(4)粒径3.0μm、比表面積9.4m2/g、塩素濃度156ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合した(仮焼せず)。粉砕前の比表面積(BET)は2.6m2/gであった。また、粉砕後の比表面積(BET)は17.0m2/gであった。この差は、14.4m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表4に示す。
この結果、造粒粉の塩素濃度は40ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングに替え、スパッタリング効率が悪い高周波(RF)スパッタリングを行った結果、パーティクルの発生やノジュール数が多量に発生し、スパッタリング中の異常放電が見られた。以上の結果を、表4に示す。
比較例2では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(4)粒径3.0μm、比表面積9.4m2/g、塩素濃度156ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合し、これを950°Cで仮焼した。粉砕前の比表面積(BET)は3.3m2/gであった。また、粉砕後の比表面積(BET)は10.2m2/gであった。この差は、6.9m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表4に示す。
この結果、造粒粉の塩素濃度は38ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングに替え、スパッタリング効率が悪い高周波(RF)スパッタリングを行った結果、パーティクルの発生やノジュール数が多量に発生し、スパッタリング中の異常放電が見られた。以上の結果を、表4に示す。
比較例3では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(4)粒径3.2μm、比表面積9.6m2/g、塩素濃度300ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=2:2:1となるよう原料を調合した。
次に、これらの粉末を混合し、これを950°Cで仮焼した。粉砕前の比表面積(BET)は3.2m2/gであった。また、粉砕後の比表面積(BET)は11.4m2/gであった。この差は、8.2m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を表4に示す。
この結果、造粒粉の塩素濃度は55ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
DCスパッタリングに替え、スパッタリング効率が悪い高周波(RF)スパッタリングを行った結果、パーティクルの発生やノジュール数が多量に発生し、スパッタリング中の異常放電が見られた。以上の結果を、表4に示す。
比較例4では、In2O3原料として、上記(1)粒径10.7μm、比表面積4.4m2/g、塩素濃度<10ppmのIn2O3粉末を用い、Ga2O3原料として、上記(5)粒径3.2μm、比表面積9.6m2/g、塩素濃度300ppmのGa2O3粉末を用い、ZnO原料として、上記(1)粒径1.1μm、比表面積3.8m2/g、塩素濃度<10ppmのZnO粉末を用いた。これらの粉末を、メタル比で、In:Ga:Zn=1:1:1となるよう原料を調合した。
次に、これらの粉末を混合し、これを1050°Cで仮焼した。粉砕前の比表面積(BET)は1.7m2/gであった。また、粉砕後の比表面積(BET)は8.3m2/gであった。この差は、6.6m2/gであった。その他、粉末の混合、粉砕、仮焼、焼結、ターゲット製造条件の詳細を、表4に示す。
この結果、造粒粉の塩素濃度は62ppmとなった。ここでは、条件の主なものを記載する。また、各種の測定や評価は、上記段落[0025],[0028],[0042]に記載する方法により実施した。
密度は5.80g/cm3、相対密度は90.9%(本比較例4の組成の真密度は6.379g/cm3)と密度は高いが、バルク抵抗値は58mΩ・cmであり、DCスパッタリングを行うのが難しかった。また、比較例4のIGZO焼結体ターゲットでは、膨れや割れの発生が多数認められた。
強引にDCスパッタリングを行った結果、パーティクルの発生やノジュール数が多量に発生し、スパッタリング中の異常放電が見られた。以上の結果を、表4に示す。
さらに、ターゲットライフも長くすることができ、品質のばらつきが少なく量産性を向上させることができる。このIn-Ga-Zn-O系(IGZO)材料は、電子キャリア濃度が1018/cm3未満であるアモルファス酸化物が得られるので、電界効果型トランジスタに有用である。また、IGZOターゲットとして、広範囲な用途に支障なく使用できるので、産業上の利用価値は高い。
Claims (15)
- インジウム(In)、ガリウム(Ga)、亜鉛(Zn)及び酸素(O)からなり、式InxGayZnzOa[式中、x/(x+y)が0.2~0.8、z/(x+y+z)が0.1~0.5、a=(3/2)x+(3/2)y+z]で表される酸化物焼結体であって、該酸化物焼結体に含有される揮発性不純物の濃度が20ppm以下であることを特徴とする酸化物焼結体。
- 揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする請求項1記載の酸化物焼結体。
- 揮発性不純物が、塩素化合物であることを特徴とする請求項1又は請求項2に記載の酸化物焼結体。
- 揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする請求項1乃至請求項3のいずれか一項に記載の酸化物焼結体。
- 相対密度が95%以上であり、バルク抵抗値が5.0×10-2Ωcm以下であることを特徴とする請求項1乃至請求項4のいずれか一項に記載の酸化物焼結体。
- 相対密度が98%以上であることを特徴とする請求項5記載の酸化物焼結体。
- 相対密度が99%以上であることを特徴とする請求項5記載の酸化物焼結体。
- インジウム(In)、ガリウム(Ga)、亜鉛(Zn)及び酸素(O)からなり、式InxGayZnzOa[式中、x/(x+y)が0.2~0.8、z/(x+y+z)が0.1~0.5、a=(3/2)x+(3/2)y+z]で表される酸化物焼結体の製造方法であって、揮発性不純物濃度がそれぞれ20ppm以下である酸化インジウム、酸化ガリウム及び酸化亜鉛原料粉末を使用して焼結することを特徴とする酸化物焼結体の製造方法。
- 揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする請求項8記載の酸化物焼結体の製造方法。
- 揮発性不純物が、塩素化合物であることを特徴とする請求項8又は請求項9記載の酸化物焼結体の製造方法。
- 揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする請求項8乃至請求項10のいずれか一項に記載の酸化物焼結体の製造方法。
- 揮発性不純物濃度が、それぞれ20ppm以下である酸化インジム、酸化ガリウム及び酸化亜鉛粉末からなる酸化物焼結体製造用原料粉末。
- 揮発性不純物が、塩素化合物、硝酸化合物、硫酸化合物、アンモニウム化合物の中から選ばれた1以上を含有する化合物であることを特徴とする請求項12記載の酸化物焼結体製造用原料粉末。
- 揮発性不純物が、塩素化合物であることを特徴とする請求項12又は請求項13記載の酸化物焼結体製造用原料粉末。
- 揮発性不純物が、塩素とガリウムとの化合物であることを特徴とする請求項12乃至請求項14のいずれか一項に記載の酸化物焼結体製造用原料粉末。
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JP2018177621A (ja) * | 2017-04-21 | 2018-11-15 | 学校法人東京理科大学 | 酸化物半導体単結晶及びその製造方法、透明導電性材料、並びに透明導電性基板 |
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