WO2012153507A1 - In2O3-SnO2-ZnO系スパッタリングターゲット - Google Patents
In2O3-SnO2-ZnO系スパッタリングターゲット Download PDFInfo
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- WO2012153507A1 WO2012153507A1 PCT/JP2012/002985 JP2012002985W WO2012153507A1 WO 2012153507 A1 WO2012153507 A1 WO 2012153507A1 JP 2012002985 W JP2012002985 W JP 2012002985W WO 2012153507 A1 WO2012153507 A1 WO 2012153507A1
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- sputtering target
- oxide
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Definitions
- the present invention relates to a sputtering target for forming an oxide thin film such as an oxide semiconductor or a transparent conductive film, and more particularly to a sputtering target suitable for forming an oxide thin film for a thin film transistor.
- Field effect transistors are widely used as unit electronic elements, high-frequency signal amplifying elements, liquid crystal driving elements, etc. for semiconductor memory integrated circuits, and are the most widely used electronic devices at present.
- LCD liquid crystal display devices
- EL electroluminescence display devices
- FED field emission displays
- TFTs Thin film transistors
- silicon-based semiconductor thin films are most widely used for TFT drive elements.
- a transparent semiconductor thin film made of a metal oxide has attracted attention because it is more stable than a silicon-based semiconductor thin film.
- semiconductor films using a metal oxide there is an oxide semiconductor film containing a crystalline material containing zinc oxide as a main component, and many studies have been made.
- an oxide semiconductor film containing a crystalline material mainly composed of zinc oxide is likely to have oxygen defects, and a large number of carrier electrons are generated.
- oxygen defects There was a problem that it was difficult to reduce the electrical conductivity.
- an oxide semiconductor film containing a crystalline material containing zinc oxide as a main component has a field-effect mobility (hereinafter, sometimes simply referred to as “mobility”) as low as about 1 cm 2 / V ⁇ sec,
- mobility a field-effect mobility
- the on-off ratio is small and leakage current is likely to occur. Therefore, when an oxide semiconductor film containing zinc oxide as a main component and containing a crystalline material is used as an active layer (channel layer) of a TFT, even when no gate voltage is applied, between the source terminal and the drain terminal Therefore, there is a problem that a normally-off operation of the TFT cannot be realized. It was also difficult to increase the on / off ratio of the transistor.
- a TFT obtained using an oxide semiconductor film containing zinc oxide has low mobility, low on-off ratio, large leakage current, unclear pinch-off, and is likely to be normally on. For example, the performance of the TFT may be lowered.
- the chemical resistance is inferior, there are limitations on the manufacturing process and use environment such as difficulty in wet etching.
- an oxide semiconductor film containing a crystalline material containing zinc oxide as a main component needs to be formed at a high pressure in order to improve performance such as mobility. Therefore, the film formation rate was slow. Moreover, since the high temperature process of 700 degreeC or more is required, there also existed a problem also in industrialization. In the case of a TFT using a crystalline oxide semiconductor film containing zinc oxide as a main component, TFT performance such as mobility in a bottom gate configuration is low. In order to improve performance, it is necessary to increase the film thickness to 100 nm or more with a top gate configuration. Therefore, there is a limit to the element configuration of the TFT.
- a method of driving an amorphous oxide semiconductor film made of indium oxide, gallium oxide and zinc oxide as a thin film transistor has been studied.
- studies have been made to form an amorphous oxide semiconductor film made of indium oxide, gallium oxide, and zinc oxide by a sputtering method that is industrially excellent in mass productivity.
- gallium is a rare metal and has a high raw material cost. If the amount of gallium added is reduced, there is a problem that a normally-off operation of the TFT cannot be realized unless the oxygen partial pressure during film formation is increased.
- Patent Document 1 a thin film transistor using an amorphous oxide semiconductor film made of indium oxide and zinc oxide without containing gallium has also been proposed (Patent Document 1, Non-Patent Document 1).
- Patent Document 2 a sputtering target for a protective layer of an optical information recording medium in which an additive element such as Ta, Y, or Si is added to an In 2 O 3 —SnO 2 —ZnO-based oxide containing tin oxide as a main component has been studied (patent) Literature 2, 3).
- An object of the present invention is to provide a sputtering target that realizes good TFT characteristics without increasing the oxygen partial pressure when an oxide thin film such as an oxide semiconductor or a transparent conductive film is formed using a sputtering method. Is.
- the following sputtering target and the like are provided. 1. It consists of an oxide containing indium element (In), tin element (Sn), and zinc element (Zn) and one or more elements X selected from the following group X, and the atomic ratio of each element is represented by the following formula (1 ) To (4).
- X group Mg, Si, Al, Sc, Ti, Y, Zr, Hf, Ta, La, Nd, Sm 0.10 ⁇ In / (In + Sn + Zn) ⁇ 0.85 (1) 0.01 ⁇ Sn / (In + Sn + Zn) ⁇ 0.40 (2) 0.10 ⁇ Zn / (In + Sn + Zn) ⁇ 0.70 (3) 0.70 ⁇ In / (In + X) ⁇ 0.99 (4) (In the formula, In, Sn, Zn, and X each indicate an atomic ratio of each element in the sputtering target.) 2.
- Step B for heat-treating the mixed powder obtained in Step A at a temperature of 700 to 1200 ° C., and the heat-treated powder obtained in Step B A method of producing a sputtering target according to any one of 1 to 7, comprising a step C of adding and mixing and grinding tin oxide powder and zinc oxide powder.
- 9. 8 An oxide thin film produced using the sputtering target according to any one of 1 to 7 above.
- 10. 10 A thin film transistor using the oxide thin film as described in 9 above.
- an oxide thin film such as an oxide semiconductor or a transparent conductive film using a sputtering method
- a sputtering target with suppressed generation is obtained.
- FIG. 2 is an X-ray chart of a sputtering target obtained in Example 1.
- the sputtering target of the present invention includes indium element (In), tin element (Sn), and zinc element (Zn), and Mg, Si, Al, Sc, Ti, Y, Zr, Hf, Ta, La, Nd, and Sm. And an oxide containing one or more elements X selected from the group (hereinafter referred to as group X).
- group X an oxide containing one or more elements X selected from the group.
- the oxygen partial pressure during sputtering can be lowered.
- the X group elements those that form a composite oxide with an In element, Sn element, or Zn element are preferable.
- an element having a large solid solution amount in the In-containing oxide is preferable. Note that solid solution in the In-containing oxide is more likely to occur as the difference in ionic radius between the indium element and the element X is smaller. Further, it is preferable that the difference in electronegativity between the element X and oxygen is larger than the difference in electronegativity between the In, Sn, and Zn elements and oxygen.
- the oxide of the element X is an oxide having very strong ionic bonding, the oxygen partial pressure during sputtering can be lowered.
- the group X has Mg, Si, Al, Sc, Ti, Y, Zr, Hf, Ta, La, Nd and Sm, and the difference in electronegativity with oxygen is In, Sn and Zn elements, and oxygen. If the difference is greater than the difference in electronegativity, the same effect can be obtained, and the present invention is not limited to these elements.
- Mg, Si, Al, Sc, Zr and Hf are preferable, and Al, Zr and Hf are particularly preferable.
- the amount [In / (In + Sn + Zn)] of In element in the total (atomic ratio) of In element, Sn element and Zn element in the target satisfies the relationship of the following formula (1). 0.10 ⁇ In / (In + Sn + Zn) ⁇ 0.85 (1)
- the amount of In element when the amount of In element is less than 0.10, the bulk resistance value of the sputtering target becomes high, and DC sputtering becomes impossible.
- the amount of In element is more than 0.85, the effect of lowering the oxygen partial pressure during sputtering due to the addition of element X cannot be obtained, and an oxide thin film having good TFT characteristics can be formed. It becomes difficult.
- the Zn content is small, the resulting film may be an amorphous film, and a stable oxide thin film may not be obtained.
- the amount of In element [In / (In + Sn + Zn)] is preferably 0.20 to 0.75, and more preferably 0.30 to 0.60.
- the amount of Sn element [Sn / (In + Sn + Zn)] in the total (atomic ratio) of In element, Sn element and Zn element in the target satisfies the relationship of the following formula (2). 0.01 ⁇ Sn / (In + Sn + Zn) ⁇ 0.40 (2)
- the amount of Sn element when the amount of Sn element is less than 0.01, the density of the sintered body is not sufficiently improved, and the bulk resistance value of the target may be increased. On the other hand, when the amount of Sn element is more than 0.40, the solubility of the obtained thin film in the wet etchant is lowered, so that wet etching becomes difficult.
- the amount of Sn element [Sn / (In + Sn + Zn)] is preferably 0.05 to 0.30, and more preferably 0.10 to 0.20.
- the amount [Zn / (In + Sn + Zn)] of Zn element in the total (atomic ratio) of In element, Sn element and Zn element in the target satisfies the relationship of the following formula (3). 0.10 ⁇ Zn / (In + Sn + Zn) ⁇ 0.70 (3)
- the amount of Zn element is less than 0.10, the resulting film may not be stable as an amorphous film. On the other hand, if the amount of Zn element is more than 0.70, the rate of dissolution of the resulting thin film in the wet etchant is too high, making wet etching difficult.
- the amount of Zn element [Zn / (In + Sn + Zn)] is preferably 0.25 to 0.60, and more preferably 0.40 to 0.50.
- the amount [In / (In + X)] of In element in the total (atomic ratio) of In element and element X in the target satisfies the relationship of the following formula (4). 0.70 ⁇ In / (In + X) ⁇ 0.99 (4)
- the amount of In element when the amount of In element is less than 0.70, the ratio of the element X in the target is increased, and as a result, aggregates of insulating substances are easily formed, and the resistance value of the target is reduced. Get higher. Also, abnormal discharge (arcing) is likely to occur during sputtering.
- the amount of In element is greater than 0.99, the amount of addition of element X is insufficient, and the effect of addition of element X cannot be obtained.
- the amount of In element [In / (In + X)] is preferably 0.80 to 0.99, and more preferably 0.85 to 0.99.
- the atomic ratio which X of Formula (4) shows means the sum total of the atomic ratio of the added element X.
- the maximum peak intensity (I ( In 2 O 3 )) in X-ray diffraction (XRD) of the bixbite structure compound represented by In 2 O 3 contained in the target, and a compound comprising element X and oxygen It is preferable that the ratio (I x / I (In 2 O 3)) of the maximum peak intensity (I x ) satisfies the following formula (5). I x / I (In 2 O 3) ⁇ 0.15 (5)
- the ratio of I x ) (I x / I (Zn 2 SnO 4) ) preferably satisfies the following formula (6). I x / I (Zn 2 SnO 4) ⁇ 0.15 (6)
- the ratio represented by the above formulas (5) and (6) relatively indicates the amount of the compound consisting of the element X and oxygen contained in the sputtering target. Since the compound composed of the element X and oxygen is an insulating material, if the ratio is larger than 0.15, the bulk resistance of the sputtering target may be increased.
- the ratio is preferably 0.1 or less, and particularly preferably 0.05 or less.
- the target includes a bixbite structure compound represented by In 2 O 3 , a spinel structure compound represented by Zn 2 SnO 4 , and a compound composed of element X and oxygen. it can.
- a bixbite structure compound represented by In 2 O 3 (or a rare earth oxide C-type crystal structure) is also referred to as a rare earth oxide C-type or Mn 2 O 3 (I) -type oxide.
- the stoichiometric ratio is M 2 X 3 (M is a cation, X is an anion, usually an oxygen ion), and one unit cell is composed of M 2 X 3 : 16 molecules, a total of 80 atoms (M is 32, X is 48) ing.
- the bixbite structure compound also includes a substitutional solid solution in which atoms and ions in the crystal structure are partially substituted with other atoms, and an interstitial solid solution in which other atoms are added to interstitial positions.
- the bixbite structure compound which is a constituent component of the target of the present invention is a compound represented by In 2 O 3 , that is, an X-ray diffraction, which is No. of JCPDS (Joint Committee on Powder Diffraction Standards) database. It shows a peak pattern of 06-0416 or a similar (shifted) pattern.
- the spinel structure represented by Zn 2 SnO 4 is usually an AB 2 X 4 type or an A 2 BX 4 type.
- a compound having a crystal structure called a spinel structure is called a spinel structure compound.
- anions usually oxygen
- cations are present in a part of the tetrahedral gap and octahedral gap.
- a substituted solid solution in which atoms or ions in the crystal structure are partially substituted with other atoms, and an interstitial solid solution in which other atoms are added to interstitial positions are also included in the spinel structure compound.
- the spinel structure compound that is a constituent component of the target of the present invention is a compound represented by Zn 2 SnO 4 . That is, in X-ray diffraction, the JCPDS (Joint Committee on Powder Diffraction Standards) database No. It shows a peak pattern of 24-1470 or a similar (shifted) pattern.
- JCPDS Joint Committee on Powder Diffraction Standards
- Examples of the compound composed of the element X and oxygen include MgO, SiO 2 , Al 2 O 3 , Sc 2 O 3 , TiO 2 , Y 2 O 3 , ZrO 2 , HfO 2 , Ta 2 O 5 , La 2 O 3. , Nd 2 O 3 , Sm 2 O 3 and the like. That is, in X-ray diffraction, each of Nos. In JCPDS (Joint Committee on Powder Diffraction Standards) database. Peak patterns of 45-0946, 89-1668, 46-1212, 42-1463, 21-1272, 41-1105, 37-1484, 06-0318, 18-1304, 05-0602, 43-1023, 43-1030 Or a similar (shifted) pattern.
- the average crystal grain size of the compound consisting of the element X and oxygen is 10 ⁇ m or less.
- the average crystal grain size of the compound consisting of the element X and oxygen is preferably 6 ⁇ m or less, more preferably 4 ⁇ m or less.
- the average crystal grain size is a value measured with an X-ray microanalyzer (EPMA). Details will be described in Examples.
- L * a * b * color difference is 3 measured in the CIE 1976 space between the target surface after removing the baked surface and the center portion ground by 2 mm from the surface with a surface grinder. 0.0 or less is preferable.
- ⁇ E * 3.0 or less, the visual color difference becomes inconspicuous, and the in-plane sintered body resistance value becomes uniform, thereby reducing abnormal discharge and improving the in-plane uniformity of the thin film resistance value. Etc. are obtained.
- L * a * b * is a color space based on the xyz color system, L * value represents lightness, a * and b * are chromaticity coordinates, and hue and saturation are combined.
- a * is the axis from red to green
- + a * is the red direction
- -a * is the green direction
- b * is the axis from yellow to blue
- + b * is the yellow direction
- -b * is the blue direction It represents the direction.
- the specific resistance value of the sputtering target of the present invention is preferably 30 m ⁇ cm or less, more preferably 10 m ⁇ cm or less, and particularly preferably 5 m ⁇ cm or less.
- the specific resistance is 30 m ⁇ cm or less, DC sputtering can be performed, and the uniformity of TFT characteristics and the reproducibility of TFT characteristics of the obtained thin film transistor can be improved.
- the specific resistance value of a sputtering target means the bulk resistance measured based on the four-point probe method (JISR1637).
- the relative density of the sputtering target of the present invention is preferably 90% or more, more preferably 95% or more, and particularly preferably 98% or more. If the relative density is less than 90%, the target may be broken during film formation or the film formation rate may be slow. The relative density is obtained by dividing the measured value of the target density by the theoretical density.
- metal elements other than In, Sn, Zn, and element X described above may be contained within a range not impairing the effects of the present invention.
- the metal element contained in the oxide sintered body may be substantially only In, Sn, Zn and the element X, or only In, Sn, Zn and the element X.
- “substantially” means that the effect as a sputtering target is caused by the above In, Sn, Zn and element X, or 95% by weight to 100% by weight (preferably 98% by weight) of the metal element of the sputtering target. % Or more and 100% by weight or less) means In, Sn, Zn, and element X.
- the metal element contained in the sputtering target of the present invention is substantially composed of In, Sn, Zn, and the element X, and contains other inevitable impurities as long as the effects of the present invention are not impaired. May be.
- the sputtering target of the present invention can be produced, for example, by mixing and pulverizing oxide raw materials, press-molding and sintering the obtained powder, and preferably forming the raw materials prepared in the following steps A to C. And can be manufactured by sintering.
- Process A Indium oxide powder and the oxide of element X are mixed and pulverized.
- Step B The mixed powder obtained in Step A is heat-treated at a temperature of 700 to 1200 ° C.
- Step C A tin oxide powder and a zinc oxide powder are added to the mixed powder obtained in the step B and mixed and pulverized.
- the indium oxide powder and the oxide of the element X are mixed and pulverized.
- the additive element X can be uniformly dispersed around In 2 O 3 , and the reaction rate between indium oxide and the additive element can be improved.
- the indium oxide powder as a raw material is not particularly limited, and commercially available products can be used, but it is preferable that the raw material has a high purity, for example, 4N (0.9999) or more.
- the element X oxide include MgO, SiO 2 , Al 2 O 3 , Sc 2 O 3 , TiO 2 , Y 2 O 3 , ZrO 2 , HfO 2 , Ta 2 O 5 , La 2 O 3 , Nd. 2 O 3 , Sm 2 O 3 and the like.
- a known device such as a ball mill, a bead mill, a planetary ball mill, a jet mill, or an ultrasonic device can be used.
- Conditions such as pulverization time may be adjusted as appropriate, but when a wet ball mill is used, it is preferably about 6 to 100 hours. This is because in the mixing time of 6 hours or less, the uniform dispersion of the indium oxide powder and the element X oxide may be insufficient. On the other hand, if the mixing time exceeds 100 hours, it takes too much production time and the cost becomes high, so that it cannot be used practically.
- the average particle size of the mixture after pulverization is usually 10 ⁇ m or less, preferably 3 ⁇ m or less, and particularly preferably 1 ⁇ m or less. If the average particle diameter of the mixed powder is too large, the reaction rate between the indium oxide powder and the oxide of the element X is lowered, and an aggregate of the insulating substance is easily formed.
- the average particle size after pulverization of the mixture is a volume average particle size measured by the method described in JIS R 1629.
- step B the mixed powder obtained in step A is heat-treated at a temperature of 700 to 1200 ° C.
- the element X can be substituted at the In site of In 2 O 3 to the solid solution limit, and aggregation of the added element can be suppressed.
- the heat treatment temperature is preferably 800 to 1100 ° C, more preferably 900 to 1000 ° C.
- a normal baking furnace etc. can be used for heat processing.
- the heat treatment time is about 1 to 100 hours, preferably 3 to 50 hours. This is because the reaction between the indium oxide powder and the oxide of element X may be insufficient under heat treatment conditions of less than 700 ° C. or less than 1 hour.
- the heat treatment atmosphere is not particularly limited as long as it is an oxidizing atmosphere.
- it may be an air atmosphere, and more preferably an oxygen gas atmosphere or an oxygen gas pressurization.
- the treated product may be classified or pulverized if necessary.
- the pulverizing means is not particularly limited, and known means such as various mills can be used.
- tin oxide powder and zinc oxide powder are added to the heat-treated powder obtained in the process B and mixed and pulverized. Thereby, aggregation of the element X at the time of sintering raw material powder can be suppressed, and color unevenness of the target can be reduced.
- the raw material tin oxide powder and zinc oxide powder are not particularly limited, and those commercially available can be used. However, high purity, for example, 4N (0.9999) or more is preferable.
- the element X is dissolved in the indium oxide powder in the step B, thereby reducing the probability that the element X oxide powders are in contact with each other. Thereby, generation
- the reason for selecting indium oxide powder instead of tin oxide powder or zinc oxide in step A is that element X is easily dissolved in an In-based compound, and zinc oxide is sublimable, so the raw material charge value This is because the atomic composition may change in the heat-treated product.
- the raw materials prepared in Step A to Step C are formed by a known method and sintered to obtain an oxide sintered body.
- the molding step for example, the mixed powder obtained in the step C is pressure-molded to obtain a molded body.
- the product is formed into a product shape (for example, a shape suitable as a target).
- the molding process include mold molding, cast molding, and injection molding.
- CIP cold isostatic pressure
- molding aids such as polyvinyl alcohol, methylcellulose, polywax, and oleic acid may be used.
- the sintering process is an essential process for firing the molded body obtained in the molding process. Sintering is usually performed at 1200 to 1550 ° C. for 30 minutes to 360 hours, preferably 8 to 180 hours, more preferably 12 to 96 hours in an oxygen gas atmosphere or under an oxygen gas pressure. If the sintering temperature is less than 1200 ° C., the density of the target may be difficult to increase or it may take too much time for sintering. On the other hand, if the temperature exceeds 1550 ° C., the composition may shift due to vaporization of the components, or the furnace may be damaged.
- the burning time is less than 30 minutes, the density of the target is difficult to increase, and if it is longer than 360 hours, it takes too much production time and the cost increases, so that it cannot be used practically.
- the relative density can be improved and the bulk resistance can be lowered.
- the heating rate during firing is usually 8 ° C./min or less, preferably 4 ° C./min or less, more preferably 3 ° C./min or less, and further preferably 2 ° C./min or less. If it is 8 ° C./min or less, cracks are unlikely to occur.
- the temperature decreasing rate during firing is usually 4 ° C./min or less, preferably 2 ° C./min or less, more preferably 1 ° C./min or less, still more preferably 0.8 ° C./min or less, particularly preferably 0.5 C / min or less. If it is 4 ° C./min or less, cracks are unlikely to occur. Note that the temperature increase or decrease may be changed step by step.
- a sputtering target is obtained by processing the oxide sintered body into a desired shape as necessary. The processing is performed to cut the oxide sintered body into a shape suitable for mounting on a sputtering apparatus and to attach a mounting jig such as a backing plate.
- the sintered body is ground by, for example, a surface grinder so that the surface roughness (Ra) is 5 ⁇ m or less. More preferably, the sputtering surface of the sputtering target may be mirror-finished so that the average surface roughness Ra is 1000 angstroms or less. The smoother the surface, the more particles generated at the initial stage of sputter deposition can be reduced.
- the grinding is preferably performed by 0.1 mm or more, more preferably by 0.3 mm or more, further preferably by 0.5 mm or more, and particularly preferably by 1 mm or more.
- the thickness of the target is usually 2 to 20 mm, preferably 3 to 12 mm, particularly preferably 4 to 10 mm. Further, a plurality of targets may be attached to one backing plate to make a substantially single target.
- the oxide thin film of the present invention can be formed by sputtering an object such as a substrate using the sputtering target of the present invention.
- the oxygen partial pressure during film formation can be suppressed, and the film formation speed and productivity can be improved.
- the oxygen partial pressure during sputtering is usually about 10 to 100%, but in the present invention, it can be about 1 to 5%.
- the oxide thin film of the present invention can be used for a transparent electrode, a semiconductor layer of a thin film transistor, an oxide thin film layer, and the like. Especially, it can be conveniently used as a semiconductor layer of a thin film transistor.
- Example 1 (1) Preparation of raw materials As raw materials, indium oxide powder (manufactured by Asian Physical Materials Co., Ltd., average particle size: 1 ⁇ m or less, purity: equivalent to 4N), and hafnium oxide powder (manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 1 ⁇ m or less) , Purity: 4N equivalent) was used. These were mixed so that the atomic ratio [In / (In + Hf)] of the In element to the sum of the In element and the Hf element was 0.88. The mixture was fed to a wet ball mill and mixed and ground for 12 hours. The obtained mixed slurry was taken out, filtered and dried. The dried powder was placed in a firing furnace and heat-treated at 1000 ° C.
- indium oxide powder manufactured by Asian Physical Materials Co., Ltd., average particle size: 1 ⁇ m or less, purity: equivalent to 4N
- hafnium oxide powder manufactured by Wako Pure Chemical Industries, Ltd., average particle size: 1 ⁇ m
- a mixed powder containing In element and Hf element was obtained.
- tin oxide powder manufactured by High Purity Chemical Co., average particle diameter: 1 ⁇ m or less, purity: equivalent to 4N
- zinc oxide powder manufactured by High Purity Chemical Co., average particle diameter: 1 ⁇ m or less, purity: equivalent to 4N
- the mixed powder was supplied to a wet ball mill and mixed and ground for 24 hours to obtain a raw material fine powder slurry. This slurry was filtered, dried and granulated.
- the upper and lower surfaces are ground with a surface grinder to produce a sputtering target having a diameter of 2 inches, a thickness of 5 mm, and a surface roughness (Ra) of 0.5 ⁇ m or less. did.
- XRD X-rays diffraction
- IICP-AES induction plasma emission analyzer
- Relative density (density measured by Archimedes method) ⁇ (theoretical density) x 100 (%) (D) X-ray diffraction measurement It measured with the following apparatus and conditions.
- An X-ray chart of the sputtering target obtained in Example 1 is shown in FIG.
- TFT n-type highly doped silicon substrate with a thermal oxide film was used as the substrate.
- the substrate was the gate electrode, and the thermal oxide film (100 nm) was the gate insulating film.
- an amorphous film having a thickness of 50 nm was formed using a sputtering target by DC sputtering and introducing Ar gas and O 2 gas.
- a mask for forming a source electrode and a drain electrode was attached, and Au was formed by RF sputtering to form a source electrode and a drain electrode.
- heat treatment was performed in the atmosphere at 300 ° C. for 60 minutes to obtain a TFT having a channel length of 200 ⁇ m and a channel width of 1000 ⁇ m.
- TFT characteristics are Vth ⁇ ⁇ 0.5 V and mobility (field effect mobility ( ⁇ )) ⁇
- the minimum oxygen partial pressure for achieving 5 cm 2 / Vs was determined as the required oxygen concentration.
- Examples 2 to 25 A sputtering target was prepared and evaluated in the same manner as in Example 1 except that in the preparation of the raw materials, the composition of the raw materials and the oxide of the element X were changed as shown in Table 1 or Table 2. The results are shown in Tables 1 to 3.
- the oxides of element X used are all manufactured by Wako Pure Chemical Industries.
- Example 26 In the preparation of the raw material, the sputtering target was prepared and evaluated in the same manner as in Example 1 except that the raw material composition and the oxide of the element X were changed as shown in Table 3 and mixed for 6 hours using a planetary ball mill. .
- Comparative Example 1-5 (1) Preparation of raw materials The composition of indium oxide, zinc oxide and tin oxide was as shown in Table 4, and these were mixed. This mixture was supplied to a wet ball mill and mixed and ground for 12 hours to obtain a raw material fine powder slurry. This slurry was filtered, dried and granulated.
- Comparative Example 6-10 A sputtering target was prepared and evaluated in the same manner as in Example 1 except that in the preparation of the raw materials, the composition of the raw materials and the oxide of the element X were changed as shown in Table 4. The results are shown in Table 4.
- Comparative Example 11 (1) Preparation of raw materials The same indium oxide, tin oxide, zinc oxide as in Example 1 and the same tantalum oxide as in Example 19 were used as raw materials.
- the atomic ratio [In / (In + Ta)] is 0.51
- the atomic ratio [In / (In + Sn + Zn)] is 0.50
- the atomic ratio [Sn / (In + Sn + Zn)] is 0.14
- the mixture was mixed so that (In + Sn + Zn)] was 0.36.
- This mixture was supplied to a wet ball mill and mixed and ground for 12 hours to obtain a raw material fine powder slurry. This slurry was filtered, dried and granulated.
- Comparative Examples 12-20 A sputtering target was prepared and evaluated in the same manner as in Comparative Example 11 except that the raw material composition was changed as shown in Table 5 in the preparation of the raw material. The results are shown in Table 5.
- the sputtering target of the present invention is suitable for producing an oxide thin film such as an oxide semiconductor or a transparent conductive film, particularly for forming an oxide thin film for a thin film transistor.
- the oxide thin film of the present invention can be used for transparent electrodes, semiconductor layers of thin film transistors, oxide thin film layers, and the like.
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Abstract
Description
金属酸化物を利用した半導体膜の1つとして、酸化亜鉛を主成分とした結晶質を含む酸化物半導体膜があり、多数の検討がなされている。しかしながら、工業的に一般に行われているスパッタリング法で成膜した場合には、酸化亜鉛を主成分とした結晶質を含む酸化物半導体膜は、酸素欠陥が入りやすく、キャリア電子が多数発生し、電気伝導度を小さくすることが難しいという問題があった。また、スパッタリング法による成膜の際に、異常放電が発生し、成膜の安定性が損なわれ、得られる膜の均一性及び再現性が低下する問題があった。
このように、酸化亜鉛を含有する酸化物半導体膜を使用して得られるTFTは、移動度が低い、on-off比が低い、漏れ電流が大きい、ピンチオフが不明瞭、ノーマリーオンになりやすい等、TFTの性能が低くなるおそれがあった。また、耐薬品性が劣るため、ウェットエッチングが難しい等製造プロセスや使用環境の制限があった。
また、酸化亜鉛を主成分とした結晶質を含む酸化物半導体膜を用いたTFTの場合、ボトムゲート構成での移動度等のTFT性能が低い。性能を上げるにはトップゲート構成で膜厚を100nm以上にする必要等がある。従って、TFTの素子構成に制限もあった。
また、酸化錫を主成分としたIn2O3-SnO2-ZnO系酸化物にTaやY、Siといった添加元素を含む光情報記録媒体の保護層用のスパッタリングターゲットが検討されている(特許文献2、3)。しかしながら、酸化物半導体用ではなく、また、絶縁性物質の凝集体が形成され易く、抵抗値が高くなってしまうことや異常放電が起こり易いという問題があった。
1.インジウム元素(In)、錫元素(Sn)及び亜鉛元素(Zn)と、下記のX群から選択される1以上の元素Xを含有する酸化物からなり、各元素の原子比が下記式(1)~(4)を満たすスパッタリングターゲット。
X群:Mg,Si,Al,Sc,Ti,Y,Zr,Hf,Ta,La,Nd,Sm
0.10≦In/(In+Sn+Zn)≦0.85 (1)
0.01≦Sn/(In+Sn+Zn)≦0.40 (2)
0.10≦Zn/(In+Sn+Zn)≦0.70 (3)
0.70≦In/(In+X)≦0.99 (4)
(式中、In,Sn,Zn及びXはそれぞれ、スパッタリングターゲットにおける各元素の原子比を示す。)
2.スパッタリングターゲットに含まれるIn2O3で表されるビックスバイト構造化合物の、X線回折(XRD)における最大ピーク強度(I(In2O3))と、前記元素Xと酸素からなる化合物の最大ピーク強度(Ix)が、下記式(5)を満たす1に記載のスパッタリングターゲット。
Ix/I(In2O3)≦0.15 (5)
3.スパッタリングターゲットに含まれるZn2SnO4で表されるスピネル構造化合物の、X線回折(XRD)における最大ピーク強度(I(Zn2SnO4))と、前記元素Xと酸素からなる化合物の最大ピーク強度(Ix)が、下記式(6)を満たす1に記載のスパッタリングターゲット。
Ix/I(Zn2SnO4)≦0.15 (6)
4.元素Xと酸素からなる化合物の平均結晶粒径が10μm以下である1~3のいずれかに記載のスパッタリングターゲット。
5.前記スパッタリングターゲットにおいて、焼き上がり面を除去した後のターゲット表面部と該表面から平面研削盤で2mm研削した部分とのCIE1976空間で測定されるL*a*b*色差(ΔE*)が3.0以下である1~4のいずれかに記載のスパッタリングターゲット。
6.比抵抗が30mΩcm以下、相対密度が90%以上である1~5のいずれかに記載のスパッタリングターゲット。
7.元素XがZrである1~6のいずれかに記載のスパッタリングターゲット。
8.酸化インジウム粉と元素Xの酸化物を混合、粉砕する工程Aと、前記工程Aで得た混合粉を700~1200℃の温度で熱処理する工程Bと、前記工程Bで得た熱処理粉に、酸化錫粉及び酸化亜鉛粉を加えて混合粉砕する工程Cと、を含む1~7のいずれかに記載のスパッタリングターゲットの製造方法。
9.上記1~7のいずれかに記載のスパッタリングターゲットを用いて作製した酸化物薄膜。
10.上記9に記載の酸化物薄膜を用いた薄膜トランジスタ。
0.10≦In/(In+Sn+Zn)≦0.85 (1)
0.01≦Sn/(In+Sn+Zn)≦0.40 (2)
0.10≦Zn/(In+Sn+Zn)≦0.70 (3)
0.70≦In/(In+X)≦0.99 (4)
(式中、In,Sn,Zn及びXはそれぞれ、スパッタリングターゲットにおける各元素の原子比を示す。)
上記X群の元素の中でも、In元素、Sn元素又はZn元素と複合酸化物を作るものが好ましい。複合酸化物を作らない元素の場合、In含有酸化物への固溶量が大きい元素が好ましい。尚、In含有酸化物への固溶は、インジウム元素と元素Xのイオン半径の差が少ないほど生じやすい。また、元素Xと酸素との電気陰性度の差が、In、Sn及びZn元素と、酸素との電気陰性度の差よりも大きい方が好ましい。この場合、元素Xの酸化物はイオン結合性が非常に強い酸化物となるため、スパッタリング時の酸素分圧を低くすることができる。
尚、X群はMg,Si,Al,Sc,Ti,Y,Zr,Hf,Ta,La,Nd及びSm以外にも酸素との電気陰性度の差がIn、Sn及びZn元素と、酸素との電気陰性度の差よりも大きければ、同様の効果が得られるため、これら元素に限定されることは無い。
X群の元素のうち、好ましくはMg,Si,Al,Sc,Zr及びHfであり、特に好ましくはAl,Zr及びHfである。
0.10≦In/(In+Sn+Zn)≦0.85 (1)
一方、In元素の量が0.85よりも多いと、元素Xの添加によるスパッタリング中の酸素分圧を低くする効果が得られなくなり、良好なTFT特性を有する酸化物薄膜を成膜することが難しくなる。また、Znが少ないため得られる膜が非晶質膜となり、安定した酸化物薄膜が得られない場合がある。
In元素の量[In/(In+Sn+Zn)]は、好ましくは0.20~0.75であり、さらに好ましくは、0.30~0.60である。
0.01≦Sn/(In+Sn+Zn)≦0.40 (2)
一方、Sn元素の量が0.40よりも多いと、得られる薄膜のウェットエッチャントへの溶解性が低下するため、ウェットエッチングが困難になる。
Sn元素の量[Sn/(In+Sn+Zn)]は、好ましくは0.05~0.30であり、さらに好ましくは、0.10~0.20である。
0.10≦Zn/(In+Sn+Zn)≦0.70 (3)
Zn元素の量[Zn/(In+Sn+Zn)]は、好ましくは0.25~0.60であり、さらに好ましくは、0.40~0.50である。
0.70≦In/(In+X)≦0.99 (4)
一方、In元素の量が0.99よりも多いと、元素Xの添加量が足りないため、元素Xの添加による効果が得られなくなる。
In元素の量[In/(In+X)]は、好ましくは0.80~0.99であり、さらに好ましくは、0.85~0.99である。
尚、スパッタリングターゲットに元素Xを2種以上添加する場合、式(4)のXが示す原子比は、添加した元素Xの原子比の合計を意味する。
Ix/I(In2O3)≦0.15 (5)
Ix/I(Zn2SnO4)≦0.15 (6)
上記比は0.1以下であることが好ましく、特に、0.05以下であることが好ましい。
In2O3で表されるビックスバイト構造化合物(あるいは希土類酸化物C型の結晶構造)とは、希土類酸化物C型あるいはMn2O3(I)型酸化物とも言われる。「透明導電膜の技術」((株)オーム社出版、日本学術振興会、透明酸化物・光電子材料第166委員会編、1999)等に開示されている通り、化学量論比がM2X3(Mは陽イオン、Xは陰イオンで通常酸素イオン)で、一つの単位胞はM2X3:16分子、合計80個の原子(Mが32個、Xが48個)により構成されている。
本発明のターゲットの構成成分であるビックスバイト構造化合物は、これらの内、In2O3で表される化合物、即ちX線回折で、JCPDS(Joint Committee on Powder Diffraction Standards)データベースのNo.06-0416のピークパターンか、あるいは類似の(シフトした)パターンを示すものである。
一般にスピネル構造では、陰イオン(通常は酸素)が立方最密充填をしており、その四面体隙間及び八面体隙間の一部に陽イオンが存在している。尚、結晶構造中の原子やイオンが一部他の原子で置換された置換型固溶体、他の原子が格子間位置に加えられた侵入型固溶体もスピネル構造化合物に含まれる。
尚、平均結晶粒径はX線マイクロアナライザー(EPMA)で測定した値である。詳細については実施例で説明する。
ΔE*が3.0以下であると、目視での色差が目立たなくなり、かつ面内の焼結体抵抗値が均一になることで、異常放電の低下、薄膜抵抗値の面内均一性の向上等の効果が得られる。
尚、L*a*b*とはxyz表色系に基づく色空間であり、L*値は明度を表し、a*とb*は色度座標になっており、色相と彩度を一緒に表している。L*値は色に関係なく明るさ(明度)だけを表し、L=0(黒)からL=100(白)までの値を取っており,値が大きいほど白く明るいことを意味する。a*は赤から緑への軸であり、+a*は赤方向を-a*は緑方向を表し、b*は黄から青への軸であり、+b*は黄方向を-b*は青方向を表している。
尚、スパッタリングターゲットの比抵抗値は、四探針法(JIS R 1637)に基づき測定したバルク抵抗を意味する。
尚、相対密度はターゲットの密度の実測値を理論密度で除して求める。
工程A:酸化インジウム粉と元素Xの酸化物を混合粉砕する。
工程B:前記工程Aで得た混合粉を700~1200℃の温度で熱処理する。
工程C:前記工程Bで得た混合粉に酸化スズ粉及び酸化亜鉛粉を加えて混合粉砕する。
原料である酸化インジウム粉は、特に限定はなく、工業的に市販されているものが使用できるが、高純度、例えば、4N(0.9999)以上であることが好ましい。
元素Xの酸化物としては、例えば、MgO,SiO2,Al2O3,Sc2O3,TiO2,Y2O3,ZrO2,HfO2,Ta2O5,La2O3,Nd2O3,Sm2O3等が挙げられる。
粉砕時間等の条件は、適宜調整すればよいが、湿式ボールミルを使用した場合は、6~100時間程度が好ましい。6時間以下での混合時間では、酸化インジウム粉と元素Xの酸化物の均一分散が不十分となる場合があるためである。一方、混合時間が、100時間を超えた場合には、製造時間がかかり過ぎコストが高くなるため、実用上採用できない。
酸化インジウム粉と元素Xの酸化物を混合して粉砕する場合、粉砕後の混合物の平均粒径は、通常10μm以下、好ましくは3μm以下、特に好ましくは1μm以下とすることが好ましい。混合粉の平均粒径が大きすぎると、酸化インジウム粉と元素Xの酸化物の反応率が低下し、絶縁性物質の凝集体が形成され易くなる。
混合物の粉砕後の平均粒径は、JIS R 1629に記載の方法によって測定した体積平均粒径である。
熱処理温度は、好ましくは800~1100℃であり、さらに好ましくは900~1000℃である。尚、熱処理には通常の焼成炉等を使用できる。
熱処理時間は、1~100時間程度であり、好ましくは、3~50時間である。
700℃未満又は1時間未満の熱処理条件では、酸化インジウム粉と元素Xの酸化物の反応が不十分となる場合があるためである。一方、熱処理条件が、1,200℃を超えた場合又は100時間を超えた場合には、粒子の粗大化が起こる場合があり、次工程の混合粉砕で十分に均一混合できないおそれがある。
熱処理雰囲気は、酸化雰囲気であれば特に限定されるものでは無い。例えば、大気雰囲気でもよく、より好ましくは酸素ガス雰囲気又は酸素ガス加圧下である。
熱処理後、必要な場合は処理物を分級又は粉砕してもよい。粉砕手段は特に制限なく、各種ミル等、公知の手段を使用できる。
原料である酸化錫粉及び酸化亜鉛粉は、特に限定はなく、工業的に市販されているものが使用できるが、高純度、例えば、4N(0.9999)以上であることが好ましい。
尚、工程Aにおいて酸化錫粉や酸化亜鉛ではなく、酸化インジウム粉を選択した理由は、元素XがIn系化合物に固溶し易く、また、酸化亜鉛は昇華性であるため、原料の仕込み値と熱処理物において原子組成が変化するおそれがあるためである。
成形工程では、例えば、上記工程Cで得た混合粉を加圧成形して成形体とする。この工程により、製品の形状(例えば、ターゲットとして好適な形状)に成形する。
成形処理としては、例えば、金型成形、鋳込み成形、射出成形等が挙げられるが、焼結密度の高い焼結体(ターゲット)を得るためには、冷間静水圧(CIP)等で成形するのが好ましい。
尚、成形処理に際しては、ポリビニルアルコールやメチルセルロース、ポリワックス、オレイン酸等の成形助剤を用いてもよい。
焼結条件としては、酸素ガス雰囲気又は酸素ガス加圧下に、通常、1200~1550℃において、通常30分~360時間、好ましくは8~180時間、より好ましくは12~96時間焼結する。焼結温度が1200℃未満であると、ターゲットの密度が上がり難くなったり、焼結に時間がかかり過ぎるおそれがある。一方、1550℃を超えると成分の気化により、組成がずれたり、炉を傷めたりするおそれがある。
燃焼時間が30分未満であると、ターゲットの密度が上がり難く、360時間より長いと、製造時間がかかり過ぎコストが高くなるため、実用上採用できない。前記範囲内であると相対密度を向上させ、バルク抵抗を下げることができる。
また、焼成時の降温速度は、通常4℃/分以下、好ましくは2℃/分以下、より好ましくは1℃/分以下、さらに好ましくは0.8℃/分以下、特に好ましくは0.5℃/分以下である。4℃/分以下であるとクラックが発生しにくい。
尚、昇温や降温は段階的に温度を変化させてもよい。
加工は、上記の酸化物焼結体をスパッタリング装置への装着に適した形状に切削加工し、また、バッキングプレート等の装着用治具を取り付けるために行う。酸化物焼結体をスパッタリングターゲットとするには、焼結体を、例えば、平面研削盤で研削して表面粗さ(Ra)を5μm以下とする。さらに好ましくは、スパッタリングターゲットのスパッタ面に鏡面加工を施して、平均表面粗さRaが1000オングストローム以下としてもよい。表面が平滑であるほどスパッタ成膜初期に発生するパーティクルを低減することができる。
研削は、0.1mm以上行うことが好ましく、0.3mm以上行うことがより好ましく、0.5mm以上がさらに好ましく、1mm以上行うことが特に好ましい。0.1mm以上研削することで、亜鉛等の成分が気化することなどで発生する表面付近の組成ずれした部位を取り除くことができる。
例えば、スパッタ時における酸素分圧は、通常10~100%程度であるが、本発明の場合、1~5%程度にすることができる。
(1)原料の調製
原料として、酸化インジウム粉(アジア物性材料社製、平均粒径:1μm以下、純度:4N相当)、及び酸化ハフニウム粉(和光純薬工業社製、平均粒径:1μm以下、純度:4N相当)を使用した。これらを、In元素とHf元素の合計に対するIn元素の原子比〔In/(In+Hf)〕が0.88となるように混合した。混合物を湿式ボールミルに供給し、12時間混合粉砕した。
得られた混合スラリーを取り出し、濾過、乾燥した。この乾燥粉を焼成炉に装入し、大気雰囲気下、1000℃で5時間熱処理した。
以上により、In元素とHf元素を含有する混合粉を得た。
この混合粉に、酸化錫粉(高純度化学社製、平均粒径:1μm以下、純度:4N相当)及び酸化亜鉛粉(高純度化学社製、平均粒径:1μm以下、純度:4N相当)を、原子比〔Sn/(In+Sn+Zn)〕が0.11、〔Zn/(In+Sn+Zn)〕が0.53となるように混合した。混合粉を湿式ボールミルに供給し、24時間混合粉砕して、原料微粉末のスラリーを得た。このスラリーを、濾過、乾燥及び造粒した。
上記(1)で得た造粒物をプレス成形し、さらに、2000kgf/cm2の圧力をかけて冷間静水圧プレスで成形した。
成形物を焼成炉に装入し、大気圧、酸素ガス流入条件で、1400℃、12時間の条件で焼成し、焼結体を得た。尚、室温から400℃までは昇温速度を0.5℃/分とし、400~1400℃までは1℃/分とした。一方、降温速度は1℃/分とした。
得られた焼結体の側辺をダイヤモンドカッターで切断後、上下面を平面研削盤で研削して、直径2インチ、厚さ5mm、表面粗さ(Ra)0.5μm以下のスパッタリングターゲットを作製した。
結果を表1に示す。
誘導プラズマ発光分析装置(ICP-AES)により測定した。
(B)スパッタリングターゲットのバルク抵抗値
抵抗率計(三菱化学(株)製、ロレスタ)を使用し四探針法(JIS R 1637)に基づき、焼結体の任意の10箇所についてバルク抵抗を測定し、その平均値を焼結体のバルク抵抗値とした。
(C)相対密度
原料粉の密度から計算した理論密度と、アルキメデス法で測定した焼結体の密度から、下記計算式にて算出した。
相対密度=(アルキメデス法で測定した密度)÷(理論密度)×100(%)
(D)X線回折測定
下記の装置・条件で測定した。
装置:(株)リガク製Ultima-III
X線:Cu-Kα線(波長1.5406Å、グラファイトモノクロメータにて単色化)
2θ-θ反射法、連続スキャン(1.0°/分)
サンプリング間隔:0.02°
スリット DS、SS:2/3°、RS:0.6mm
尚、実施例1で得たスパッタリングターゲットのX線チャートを図1に示す。
焼結体を樹脂に包埋し、その表面を粒径0.05μmのアルミナ粒子で研磨した後、X線マイクロアナライザー(EPMA)であるJXA-8621MX(日本電子社製)を用いて研磨面を1000倍に拡大し、焼結体表面の100μm×100μm四方を任意の3箇所測定し、それぞれの枠内で観察される添加元素Xと酸素からなる結晶粒子の最大径を測定した。この結晶粒子の最大径を平均結晶粒径とした。
研削後の焼結体表面部及び表面から平面研削盤で2mm研削した部分を、分光測色計NR11A(日本電色工業製)を用いて測定し、CIE1976空間で評価した。尚、任意の5箇所について色彩を測定し、基準値は測定値の平均値とした。
ΔE*=√(ΔL*2+Δa*2+Δb*2)
スパッタリングターゲットをDCマグネトロンスパッタリング装置に装着し、O2×100/(Ar+O2)=3%の条件下で、96時間連続してスパッタリングした際の異常放電の有無を観察した。
異常放電が1度も確認されなかった場合を「○」、確認された場合を「×」とした。
作製したスパッタリングターゲットをDCマグネトロンスパッタリング装置に装着し、以下の方法でトップコンタクトボトムゲート型のTFTを作製した。そして、チャネル層を形成する際の酸素分圧(O2/(Ar+O2))について評価した。
尚、表中、「-」との評価は、DC放電ができないためにチャネル層を形成することができなかったことを意味する。
基板は、熱酸化膜付n型高ドープシリコン基板を用いた。基板をゲート電極、熱酸化膜(100nm)をゲート絶縁膜とした。
シリコン基板にチャネル層形成用のマスクを装着した後、DCスパッタ法によりスパッタリングターゲットを使用し、Arガス及びO2ガスを導入し、膜厚50nmの非晶質膜を成膜した。
次に、ソース電極及びドレイン電極形成用のマスクを装着し、RFスパッタ法によりAuを成膜して、ソース電極及びドレイン電極を形成した。
その後、大気中300℃で60分間熱処理し、チャネル長が200μmで、チャネル幅が1000μmのTFTを得た。
チャネル層成膜時の酸素濃度(O2/(Ar+O2))を振り、TFT特性がVth≧-0.5Vかつ移動度(電界効果移動度(μ))≧5cm2/Vsとなるために最も少ない酸素分圧を必要酸素濃度とした。
尚、TFT特性は半導体パラメーターアナライザー(ケースレー4200)を用い、室温、遮光環境下で、窒素を噴きかけながら、ドレイン電圧Vds=5V及びゲート電圧Vgs=-20~20Vの条件で評価した。
原料の調製において、原料の配合及び元素Xの酸化物を表1又は表2に示すように変更した他は、実施例1と同様にしてスパッタリングターゲットを作製し、評価した。結果を表1~表3に示す。
尚、使用した元素Xの酸化物は、いずれも和光純薬工業社製である。
原料の調製において、原料の配合及び元素Xの酸化物を表3に示すように変更し、遊星ボールミルを用いて6時間混合した他は実施例1と同様にしてスパッタリングターゲットを作製し、評価した。
(1)原料の調製
酸化インジウム、酸化亜鉛及び酸化錫の配合を表4に示すようにし、これらを混合した。この混合物を湿式ボールミルに供給し、12時間混合粉砕して、原料微粉末のスラリーを得た。このスラリーを、濾過、乾燥及び造粒した。
実施例1と同様にして、スパッタリングターゲットを作製し、評価した。結果を表4に示す。
原料の調製において、原料の配合及び元素Xの酸化物を表4に示すように変更した他は、実施例1と同様にしてスパッタリングターゲットを作製し、評価した。結果を表4に示す。
(1)原料の調製
原料として、実施例1と同じ酸化インジウム、酸化錫、酸化亜鉛及び実施例19と同じ酸化タンタルを使用した。これらを、原子比〔In/(In+Ta)〕が0.51、原子比〔In/(In+Sn+Zn)〕が0.50、原子比〔Sn/(In+Sn+Zn)〕が0.14、原子比〔Zn/(In+Sn+Zn)〕が0.36となるように混合した。この混合物を湿式ボールミルに供給し、12時間混合粉砕して、原料微粉末のスラリーを得た。このスラリーを、濾過、乾燥及び造粒した。
実施例1と同様にして、スパッタリングターゲットを作製し、評価した。結果を表5に示す。
原料の調製において、原料の配合を表5に示すように変更した他は、比較例11と同様にしてスパッタリングターゲットを作製し、評価した。結果を表5に示す。
この明細書に記載の文献の内容を全てここに援用する。
Claims (10)
- インジウム元素(In)、錫元素(Sn)及び亜鉛元素(Zn)と、
下記のX群から選択される1以上の元素Xを含有する酸化物からなり、
各元素の原子比が下記式(1)~(4)を満たすスパッタリングターゲット。
X群:Mg,Si,Al,Sc,Ti,Y,Zr,Hf,Ta,La,Nd,Sm
0.10≦In/(In+Sn+Zn)≦0.85 (1)
0.01≦Sn/(In+Sn+Zn)≦0.40 (2)
0.10≦Zn/(In+Sn+Zn)≦0.70 (3)
0.70≦In/(In+X)≦0.99 (4)
(式中、In,Sn,Zn及びXはそれぞれ、スパッタリングターゲットにおける各元素の原子比を示す。) - スパッタリングターゲットに含まれるIn2O3で表されるビックスバイト構造化合物の、X線回折(XRD)における最大ピーク強度(I(In2O3))と、前記元素Xと酸素からなる化合物の最大ピーク強度(Ix)が、下記式(5)を満たす請求項1に記載のスパッタリングターゲット。
Ix/I(In2O3)≦0.15 (5) - スパッタリングターゲットに含まれるZn2SnO4で表されるスピネル構造化合物の、X線回折(XRD)における最大ピーク強度(I(Zn2SnO4))と、前記元素Xと酸素からなる化合物の最大ピーク強度(Ix)が、下記式(6)を満たす請求項1に記載のスパッタリングターゲット。
Ix/I(Zn2SnO4)≦0.15 (6) - 元素Xと酸素からなる化合物の平均結晶粒径が10μm以下である請求項1~3のいずれかに記載のスパッタリングターゲット。
- 前記スパッタリングターゲットにおいて、焼き上がり面を除去した後のターゲット表面部と該表面から平面研削盤で2mm研削した部分とのCIE1976空間で測定されるL*a*b*色差(ΔE*)が3.0以下である請求項1~4のいずれかに記載のスパッタリングターゲット。
- 比抵抗が30mΩcm以下、相対密度が90%以上である請求項1~5のいずれかに記載のスパッタリングターゲット。
- 元素XがZrである請求項1~6のいずれかに記載のスパッタリングターゲット。
- 酸化インジウム粉と元素Xの酸化物を混合、粉砕する工程Aと、
前記工程Aで得た混合粉を700~1200℃の温度で熱処理する工程Bと、
前記工程Bで得た熱処理粉に、酸化錫粉及び酸化亜鉛粉を加えて混合粉砕する工程Cと、
を含む請求項1~7のいずれかに記載のスパッタリングターゲットの製造方法。 - 請求項1~7のいずれかに記載のスパッタリングターゲットを用いて作製した酸化物薄膜。
- 請求項9に記載の酸化物薄膜を用いた薄膜トランジスタ。
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CN201280022388.4A CN103534382B (zh) | 2011-05-10 | 2012-05-07 | In2O3-SnO2-ZnO系溅射靶 |
KR1020197010807A KR20190044123A (ko) | 2011-05-10 | 2012-05-07 | In₂O₃-SnO₂-ZnO계 스퍼터링 타겟 |
JP2013513926A JP6006202B2 (ja) | 2011-05-10 | 2012-05-07 | In2O3−SnO2−ZnO系スパッタリングターゲット |
KR1020137029561A KR20140027238A (ko) | 2011-05-10 | 2012-05-07 | In₂O₃-SnO₂-ZnO계 스퍼터링 타겟 |
US14/116,322 US9214519B2 (en) | 2011-05-10 | 2012-05-07 | In2O3—SnO2—ZnO sputtering target |
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Also Published As
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KR20140027238A (ko) | 2014-03-06 |
JPWO2012153507A1 (ja) | 2014-07-31 |
TWI541362B (zh) | 2016-07-11 |
US9214519B2 (en) | 2015-12-15 |
CN103534382A (zh) | 2014-01-22 |
KR20190044123A (ko) | 2019-04-29 |
US20140103268A1 (en) | 2014-04-17 |
TW201300548A (zh) | 2013-01-01 |
JP6006202B2 (ja) | 2016-10-12 |
CN103534382B (zh) | 2016-01-20 |
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