TW201024435A - Sintered body containing yttrium oxide, and sputtering target - Google Patents

Abstract

Provided is a sintered body which is composed of an indium oxide and an yttrium oxide and has a lattice constant between that of InYO3 and that of In2O3. The sintered body contains the oxide of two or more kinds of metals selected from among a group composed of indium, tin and zinc and the yttrium oxide, and the atom ratio of the yttrium to the two or more kinds of metals selected from among the group composed of indium, tin and zinc exceeds 0.0 but not more than 50 atm%. The sintered body is composed of the tin oxide and the yttrium oxide and contains an Y2Sn2O7 compound.

Description

201024435 VI. Description of invention:

C FIELD OF THE INVENTION The present invention relates to a sintered body containing indium oxide, tin oxide and/or cerium oxide in an oxidation term. L· Ί Background of the Invention ❿ m In recent years, development of display devices has been remarkable, and various display devices such as liquid crystal display and display devices have been actively applied to A-machines such as personal computers or text processors. Each of these display devices has a sandwich structure in which a display member is sandwiched by a transparent conductive film. The switching elements that drive these display devices are currently occupied by the Shihsian semiconductor film. This is because, in addition to stability and processability, the material has good properties such as fast closing speed and the like. The film-based slave is made by chemical vapor deposition (CVD). _However, when the Shi Xi film is amorphous, the switching speed is slow, and it is difficult to display an image when an animation such as an idle speed is desired. In addition, in the case of a crystalline thin film, the Lai switch is relatively fast, but the crystallization j is at a high temperature of 8 m: or higher, or is heated by a laser, etc., in order to manufacture the energy and many steps of the 矸4 Φ _ sudden. In addition, the lanthanide film is also a material with excellent performance as a voltage element, and the bamboo swells, however, when the current is applied, the time-dependent change of the singularity becomes a problem. It is suitable as a material for obtaining a transparent semiconductor film which is superior in stability to a Shih-my film and has a light transmittance equivalent to that of a film. 201024435 A method for supplying a material and a method for producing the same, A transparent semiconductor film formed of zinc and magnesia is proposed (for example, Patent Document 1). However, these transparent semiconductors formed of indium oxide and gallium oxide, zinc oxide or oxidized and oxidized town have a very pure rot in a weak acid. The fast feature, that is, the use of thin metal __ liquid will also be _, in the case of a gold (four) film on a transparent semiconductor film, there will be a situation of being simultaneously brain, and = as long as it is selectively _ transparent semiconductor film Metal film

Further, in Patent Document 2, there is a description of a film mainly composed of indium oxide, tin oxide, and oxidized particles, and it is described that it is not related to a compound semiconductor. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT STATEMENT

When it is used in the field, it is stable and has a good transparency and surface smoothness, and it is a sintered body of a transparent oxide semiconductor film. . In order to achieve the above object, the inventors of the present invention conducted intensive studies, _ in the process of indium oxide, zinc oxide, and/or oxidation-injection containing oxygen, and processed into a refining, and when the oxide film is obtained, the surface can be provided. Highly excellent smoothness_Oxide semiconductor; ^^ The present invention. 3 4 201024435 In the case where cerium oxide is added to 1το, there is an advantage that the grain size of the film when the substrate temperature is adjusted to a high temperature to be entangled is reduced, and a flattened film is easily obtained. However, I: ‘On the other hand, the Oxide has a problem of abnormal discharge due to its insulating property, if it exists alone in the dry material.

Therefore, in the present invention, cerium oxide is not separately present, but is mixed with other metal oxide components, for example, it is solid-solved and dispersed in other metal oxide components to form a composite oxide with other metal oxides. In order to suppress the abnormal discharge which may become a problem when the cerium oxide is present alone. According to the present invention, the following sintered body or the like is provided. A sintered body formed of indium oxide and yttrium oxide, and having a lattice constant between ΙηΥ03 and Ιη203. 2. The sintered body according to Item 1, wherein the oxidized phase is completely dissolved in indium oxide. 3. The sintered body according to Item 1 or 2, wherein the atomic ratio Υ/(Ιη+Υ) of the indium element and the elemental element exceeds 〇·〇 less than 0.5. 4. A sintered body containing two or more kinds of metal oxides and oxidized particles selected from the group consisting of indium, tin, and zinc, and two or more selected from the group consisting of indium, tin, and composition The atom of the metal exceeds 0·0 and is 50 atom% or less. 5. The sintered body according to item 4, wherein the atomic ratio is 〇〇〇10 to 40% by atom. 6. The sintered body according to item 4, wherein the atomic ratio is from 2 〇 to 15 atom%. 7. The sintered body according to any one of the items 4 to 6, wherein when the 275 or more metals contain at least indium, the indium oxide crystal in which cerium oxide is dissolved is contained. The sintered body according to the seventh aspect, wherein the indium oxide crystal is a square iron structure. The sintered body of the seventh aspect or the eighth aspect, wherein the indium oxide crucible has a crystal grain size of less than 1 μm. The sintered body according to any one of the items 7 to 9, wherein the emulsified indium crystal has a lattice constant of between InY〇4〇 In2〇3. The sintered body according to any one of the items of the present invention, wherein the indium contains 5 Å to 99.9 atom% with respect to all the metals constituting the sintered body. The sintered body according to any one of the items 1 to 11, further comprising a metal element having a positive tetravalent or higher value. The sintered body according to Item 12, which contains 100 to 1000 ppm of the above-mentioned metal element having a positive tetravalent or higher value. 14. A sintered body formed by indium oxide, cerium oxide and tin oxide, wherein cerium oxide is dissolved in indium oxide or contained in the form of a Y2Sn2〇7 compound, or a part of the emulsified solid is dissolved in indium oxide. Medium, and the remainder is contained in the form of a compound of ΥΑι^Ο7. 15. The sintered body according to item 14 §, wherein the atomic ratio Y/(In+Y+Sn) of the indium element, the elemental element, and the tin element exceeds 〇.〇2 and is less than 〇5. 16. The sintered body is formed of indium oxide, oxidized particles and zinc oxide, wherein cerium oxide is dissolved in indium oxide or contained in the form of a ΙηΥ〇3 compound, or a part of the oxidized phase is dissolved in indium oxide. Medium, and the remainder is contained in the form of a compound of Υ2Ζη; 2〇7. The sintered body according to the item 16, wherein the sintered body further contains a hexagonal layered compound represented by In2〇3. (ZnO)m (where m is an integer of 2 to 20). 18. The sintered body according to Item 16 or 17, wherein the atomic ratio γ/(Ιη+γ+Ζη) of the indium element, the yttrium element, and the zinc element exceeds 〇 〇 and is less than 〇 5 . 19_ a sintered body formed of tin oxide, cerium oxide and zinc oxide, wherein cerium oxide is dissolved in tin oxide or contained in the form of a compound, or a part of cerium oxide is dissolved in tin oxide, and The remainder is contained in the form of a Y2Sn2〇7 compound. 20. The sintered body according to item 19, which further contains a Zn2Sn〇4 compound. The sintered body according to the 19th or 20th aspect, wherein the atomic ratio Y/(Sn+Y+Zn) of the tin element and the element B is 〇, 〇1 or more and 〇4 or less. 22. A sintered body formed of tin oxide and antimony oxide and containing a Y2S1I2O7 compound. 23. The sintered body according to Item 22, wherein the atomic ratio Y/(Sn+Y) of the tin element and the lanthanum element exceeds 〇·〇 and is 0.5 or less. The method for producing a sintered body according to any one of the items 4 to 11, wherein the oxide of the metal or the cerium oxide selected from the group consisting of indium, tin, and zinc is mixed. The powder is sintered at a temperature of 12 〇 (rc ～WOOt: 2 to 200 hours. 25. The method for producing a sintered body according to Item 12 or Item 13, 7 201024435 is a mixture of indium, tin, and composition. The powder of two or more kinds of metal oxides, oxidized particles and metals having a tetravalent or higher metal selected from the group is sintered at a temperature of 1200 ° C to 1600 ° C for 2 to 200 hours. 26. For the 24th or the The method for producing a sintered body according to the above-mentioned item 25 is produced by sintering in an oxidizing atmosphere. 27. The sputtering target is produced by using the sintered body according to any one of the items 1 to 23. A metal oxide film is a film formed by the sputtering target according to item 27. 29. A semiconductor is formed of the metal oxide film according to item 28. 30. A thin film transistor is used. The semiconductor of the 29th item. 31. The thin film transistor according to item 30, which is connected The thin film transistor according to the item 30, which is an etch-resistant type. The semiconductor device according to any one of the items 30 to 32. According to the invention, it is possible to provide a sintered body which, when processed into a sputtering target, can perform stable sputtering when an oxide film is obtained, and provides a high-performance oxide semiconductor excellent in surface smoothness. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Example 1. Fig. 2 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Example 2. 8 201024435 Fig. 3 is A schematic diagram of the X-ray diffraction result of the sintered body obtained in Example 3. Fig. 4 is a schematic diagram of the X-ray diffraction result of the sintered body obtained in Example 4. Fig. 5 is a sintered body obtained from Example 5. The X-ray diffraction result is a schematic spectrum. Fig. 6 is a schematic diagram of the X-ray diffraction result of the sintered body obtained in Example 6. Fig. 7 is a schematic diagram showing the X-ray diffraction result of the sintered body obtained in Example 7. Figure 8 is the real A schematic diagram of the X-ray diffraction result of the sintered body obtained in Example 8. Fig. 9 is a schematic diagram of the X-ray diffraction result of the sintered body obtained in Example 9. Fig. 10 is an X of the sintered body obtained in Example 10. Fig. 11 is a schematic view showing the X-ray diffraction result of the sintered body obtained in Example 11. Fig. 12 is a schematic view showing the X-ray diffraction result of the sintered body obtained in Example 12. Fig. 13 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Example 13. Fig. 14 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Comparative Example 2. 9 201024435 Section 15® by Comparative Example 3 Schematic diagram of the obtained line diffraction diffraction result of the sintered body.

C. Embodiments in which the invention is used. The sintered body of the present invention contains cerium oxide in indium oxide, oxidized and/or tin oxide. A sintered body containing an oxidized phase, when processed into a sputtering (four), can be stabilized when an oxide film is obtained, and an oxide semiconductor having excellent properties of surface slip properties can be provided. Q The bond strength between oxidation and oxygen is high. Therefore, the oxygen deficiency of the crystal obtained by using the ship It made of the sintered body of the present invention is suppressed, and the film is easily semiconductorized. Further, since the ruthenium oxide itself is resistant to acid and alkali, the acid resistance and alkali resistance of the film obtained are improved. When the sintered body of the present invention contains indium oxide, the oxidation group is strong in resistance to reduction, so that reduction of indium oxide can be suppressed. Therefore, when a sputtering target formed of the sintered body of the present invention is used, occurrence of nodule can be suppressed. Further, when cerium oxide is added, since the lattice constant of the crystalline film of indium oxide is increased, the interatomic distance of the cation becomes large. Therefore, the internal stress of the obtained ruthenium film tends to become a tensile stress, and the mobility of the transistor using the film is improved, and the s value and durability are improved. When the sintered body of the present invention contains indium oxide, it is preferred to crystallize indium oxide containing an oxidized period in which it is dissolved. The indium oxide m is a square iron ore structure. Fang Tie Meng _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The crystal grain size of the indium oxide crystal is preferably less than 10 μm. If the crystallization is too large, it may cause abnormal discharge during sputtering, and it may cause granulation on the sputtered crucible. The average value of the entire field of view when the crystal grain size was observed by a scanning electron microscope at a field of 30 μηυ < 30 μm was taken as the crystal grain size (long diameter). Further, when observed in the above-described field of view, if there is no crystal of 10 μm or more, the average particle diameter is less than 1 Ομιη. Further, the lattice constant of the indium oxide crystal is preferably between InY〇4〇In2〇3. Here, the "lattice constant" is defined as the length of the lattice axis of the unit cell, which can be determined by X-ray diffraction. Because the lattice constant of ha is 1〇 118=,

The lattice constant of InY〇3 is the claw 362A, so the value therebetween is preferable (excluding lo. mA and 10.362 persons). The lattice constant of the fired or sintered body is between the order (10) and the second, which means that the cerium oxide is sufficiently dissolved in the indium oxide, and there is no single cerium oxide in the sintered body in an amount which causes abnormal discharge. φ is preferably 50 to 99 9 Å, more preferably 6 〇 to 99 atom%, and particularly preferably 7 () to 98 atom%, relative to all the metals constituting the sintered body. With this ruthenium, the mobility of the obtained oxide semiconductor is increased, and a stable thin film transistor can be obtained. Specifically, the sintered body of the present invention is formed by indium oxide and oxidized grains forming a sintered body between lattice constants Ι Ι 2 Υ Ι Ι ( ( ( ( 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 When 〇3, as long as the amount of oxidation (Υ2〇3) is controlled, the lattice constant of the sintered body is between KInY〇4〇In2〇3, which means that oxygen 11 201024435 is fully dissolved in oxidation. Indium also means that there is no separate oxidation zone in the sintered body which causes an abnormal discharge to occur. Therefore, the sputtering target obtained from the sintered body can be stably sputtered, and can provide oxidation excellent in surface smoothness. Further, "saturated solid solution" of cerium oxide means that cerium oxide alone may be contained in an amount that does not cause abnormal discharge. The oxidized phase is preferably completely dissolved in indium oxide. It is completely dissolved in indium oxide, and in the absence of ruthenium oxide alone, the spattered dry powder obtained from the sintered body can be stably sputtered and can provide an oxide semiconductor having excellent surface smoothness. Here, "completely solid. Dissolve The cerium oxide is randomly substituted into the crystal lattice of indium oxide, meaning that the diffraction peak from the y2〇3 crystal is not observed by X-ray diffraction. The solid solution state is determined by the obtained X-ray diffraction. When the lattice constant corresponds to the composition ratio of each metal element, the solid solution ratio can be determined. The amount of oxidized particles dissolved in indium oxide is preferably larger than that of the undissolved oxidized group. γ/(Ιη+γ) is preferably more than 〇〇 less than 〇5. Here, the content ratio γ/(Ιη+γ) of yttrium oxide is a metal oxide constituting a raw material by the molar ratio of metal lanthanum The ratio of the total number of moles of metal atoms is the same as the following. Υ/(Ιη+Υ) If 〇.5 or more, except for 1 〇3, γ2〇3 is detected, due to splashing An oxide semiconductor film having excellent surface smoothness cannot be obtained by abnormal discharge or the like. γ/(Ιη+γ) is preferably 〇〇〇5 or more and OK or less, more preferably 0.01 or more and 0.35 or less, and particularly suitable for 〇〇2. Above 〇3 or less. Measured by ICP (Inductively Coupled Plasma) 'Measurement of each element 12 201024435 In this case, the content (atomic ratio) of the metal element in the sintered body can be determined. The first sintered body can further contain a metal oxide having a positive tetravalent or higher. In this case, the metal oxide having a positive tetravalent or higher is also It is preferable to use a solid solution of indium oxide to exhibit only the peak of indium oxide. The bulk resistance of the sintered body obtained by adding the positive tetravalent metal oxide is lowered, and the sputtering target of the sintered body can be used for comparison. For stable sputtering, an oxide semiconductor having a stable surface and high surface smoothness can be obtained. The metal oxide having a tetravalent or higher valence is preferably 811 〇 2 and/or (^ 〇 2 is preferred. It is preferable that the oxide is Ce 〇 2. This is because Ce 〇 2 digs more S, and also ensures supply stability, and is also non-toxic. Further, in the case of Ce〇2, it is trapped in indium oxide at a high temperature (sintering temperature), and has an effect of reducing the bulk resistance of the sintered body (target) by generating a carrier, and forming a film by sputtering. Since it is not dissolved in indium oxide and does not generate a carrier, the film is easily semiconductorized. The content ratio of the metal oxide having a positive tetravalent or higher (positive tetravalent or higher metal) / [In + Y + (positive tetravalent or higher metal)] is preferably 〇 1 or more and less than 0.005. When the metal (positive tetravalent or higher metal) / [Ιη+Υ+ (positive tetravalent or higher metal)] is less than 0.0001, the amount of the metal oxide having a positive tetravalent or higher is too small, and the effect of lowering the bulk resistance cannot be obtained. Hey. When it is 0.005 or more, the solid solution of the metal oxide having a positive tetravalent or higher added is insufficient, and when it is observed by X-ray diffraction, a peak of a compound other than indium antimonide is observed. When a sputtering target made of such a sintered body containing a compound other than indium oxide is used, in the case where the obtained 13 201024435 oxide semiconductor is crystallized and reused, a carrier is generated, resulting in unsemiconducting. The situation is not suitable. Therefore, when the oxide semiconductor is crystallized and used, it is preferable that (positive tetravalent or higher metal) / [Ιη+Υ+ (positive tetravalent or higher metal)] is more than 0.005 or more than 0.005 or more. It is preferably 0.002 or less, preferably 〇〇〇. 〇〇〇 5 or more 〇〇〇 1 or less. On the other hand, when the obtained oxide semiconductor is used as it is in an amorphous state as it is, since a carrier formed by adding a metal oxide having a positive tetravalent or higher metal is not generated, there is no special addition amount. limit. However, since many crystalline films are obtained in these composition ranges, it is preferable to make the above (positive tetravalent or higher metal) / [Ιη+Υ+ (positive tetravalent or higher metal)] fall below 0.0001 and less than 0.005. The scope. The second sintered body of the present invention contains two or more kinds of metal oxides and cerium oxide selected from the group consisting of indium and tin, and two or more selected from the group consisting of indium, tin, and zinc. The atomic ratio of the metal [γ / (total of two or more kinds of metals) Χ 1 〇〇] exceeds 〇 · 〇 and is preferably 0.001 to 40 atomic % at an atomic ratio of 5 〇 atomic % or less, and preferably 2.0 〜 15 atom %. . The first embodiment of the second sintered body of the present invention is formed of indium oxide, cerium oxide, and tin oxide, and cerium oxide or solid solution is dissolved in indium oxide, and cerium is contained in the form of a compound of Y2Sn2〇7, or cerium oxide. There is - part of the solid solution in indium oxide, and the remainder is contained in the form of the Υβιιβ7 compound as a sintered body. In the case of the sintered body of the first embodiment, cerium oxide may be dissolved in indium oxide or may be present in the form of a Y2Sn2〇7 compound, and may be present in two 妒 201024435 states. Since yttrium oxide exists in this form, the oxidized period does not exist alone, and stable sputtering can be performed. In the sintered body of the first embodiment, the atomic ratio Y/(In+Y+Sn) of the indium element, the element, and the kick element is preferably more than 0.02 and preferably 0.5 or less. When Y/(In+Y+Sn) is 0.02 or less, the amount of cerium oxide added is small, and the obtained oxide film may not be semiconductorized. If it exceeds 〇5, cerium oxide alone exists and causes abnormal discharge. Preferably, it is 0.4 or less, and more preferably 〇·〇5 or more 〇·3 or less. ❿ When the sintered body containing the oxidation-like ninth embodiment is used as (4), if the obtained oxide semiconductor is crystallized, although a carrier may be generated by tin, in this case, it may be obtained. Oxide half. The conductor is used as it is in an amorphous state. The second embodiment of the second sintered body of Shuming is formed by indium oxide, cerium oxide and oxidized, cerium oxide or solid solution in indium oxide, or in the form of a compound containing 'or oxidized particles' - partially dissolved The oxidized marriage towel's and the remainder are contained in the form of a sinter compound as a sintered body. In the case of a sintered body formed of indium oxide, oxidized particles and oxidized, the oxidized particles may be dissolved in indium oxide, or may be in the form of a (6) chelating compound, or may be present in two forms. By constituting such a state, the oxidized period does not exist alone, and a high-performance oxide semiconductor film excellent in surface smoothness can be obtained without interference of abnormal discharge or the like. The sintered body of the second embodiment may further comprise a hexagonal layered compound represented by a compound of (Zn〇)m (here, the claw is an integer of 2 to 20). By constituting such a state, the body resistance of the sister can be reduced, and the sputtering of the stability of 15 201024435 can be performed. In the sintered body of the second embodiment, the atomic ratio Y/(In+Y+Zn) of indium element, lanthanum I, and zinc element exceeds 〇.〇 and is preferably 0.5 or less. If Υ/(Ιη+Υ+Ζη) exceeds 〇·5, yttrium oxide will exist alone, which may cause abnormal discharge. It is preferably 0 01 or more and 4 or less, preferably 〇〇1 and 0.35 or less.

The third embodiment of the second sintered body of the present invention is formed by tin oxide, oxygen and oxidized, cerium oxide or solid solution in tin oxide, or is contained in the form of a cerium compound or oxygen-containing Part of the solid solution is dissolved in oxygen: and the remainder is contained in the form of a Yjr^O7 compound as a sintered body. In the case of a sintered body formed of tin oxide, oxidized particles and oxidized words, the oxidation mark may be dissolved in tin oxide, or may be contained in the shape of a lion 2 〇 7 compound, and may be present in two forms. In this way, yttrium oxide does not exist alone, and a high-performance oxide semiconductor film excellent in surface smoothness can be obtained without interference of abnormal discharge or the like. The sintered body of the third embodiment may further contain Zn2Sn〇4 compound

Things. Due to the inclusion of the Zi^SnO4 compound, the bulk resistance of the target itself is lowered, and a more stable effect of sputtering is obtained. In the sintered body of the third embodiment, the atomic ratio Y/(Sn+Y+Zn) of the tin element, the lanthanum element, and the zinc element is preferably 0·01 or more and 0.4 or less. When Y/(Sn+Y+Zn) is less than 0.01, the amount of cerium oxide added is small, and the obtained oxide film may not be semiconductorized. If it exceeds 〇4, yttrium oxide will form a separate state, which may cause abnormal discharge or the like. It is preferably 0.01 or more and 0.4 or less, more preferably 0.01 or more and 〇35 or less. 16 201024435 Further, the third sintered body of the present invention is formed of tin oxide and oxidized particles, and contains a Y2Sn2〇7 compound. Since cerium oxide is used alone, it may cause abnormal discharge when it is used as a sputtering, and may adversely affect the surface smoothness of the obtained oxide semiconductor film. In the case where the oxidized period is sufficiently solid-dissolved in the sintered body by a form such as a Υθηβ7 compound, the abnormal discharge of the sputtering bond is suppressed. It is easy to obtain an oxide semiconductor film having a smooth surface. The atomic ratio Y/(Sn + Y) of the tin element and the lanthanum element is preferably more than 〇 〇 and less than 〇 5 . When Y/(Sn+Y) exceeds 0.5, cerium oxide forms a state in which it exists alone, and it is a cause of abnormal discharge. Preferably, 〇·〇1 or more and 0.4 or less, and 0.03 or more and 0.35 or less is more preferable. In the case of the sintered body, the crystallization temperature is high, and it is preferable to use an amorphous film as the oxide semiconductor than to crystallize the obtained oxide semiconductor film. Each of the above sintered bodies of the present invention preferably contains a metal element having a positive tetravalent or higher value. The content is preferably from 1 〇〇 to 1 〇〇〇 ppm. The body resistance can be further reduced by containing a metal element having a positive tetravalent or higher value. When the (7) (9) paw is exceeded, the obtained oxide semiconductor film becomes a semiconductor characteristic which does not exhibit a normally closed state. Examples of the metal element having a positive tetravalent or higher value include Ti, Zr, Hf, Nb, Ta, W, Ge Sn or Ce. Among them, Ce is preferred. When the sintering temperature of the sintered body is above, the amount of the sintered body is reduced by a small amount (1 atomic ppm or less) because of the resistance of the body of the sintered body 17 201024435. On the other hand, in the temperature at which the film is crystallized (for example, from 25 (rc^45〇t>c or so), the amount of germanium captured in the indium oxide is reduced, and the effect of the electric resistance is lowered (the carrier is generated) In this way, since the obtained oxide semiconductor of the crystalline indium oxide film can be controlled, the sintered body obtained by the present invention is easily obtained, and has a low bulk resistance and can be suitably used as a sputtering method. By using the sputtering target of the sintered body, the sputtering operation is stable, and the crystalline indium oxide film can be stably produced. Further, a film having good semiconductor characteristics can be obtained. @ The sintered body of the present invention can be used. The powder of the raw material oxide (indium oxide, tin oxide, antimony oxide, zinc oxide) corresponding to each sintered body is mixed and sintered at a temperature of 12 ° C to 16 ° C for 2 to 2 Torr. The raw material oxide is preferably a powder having a purity of 99.99% or more. When a metal element having a value of _ or more is added, for example, a compound such as an oxide of the same metal element is added. The purity of the compound is also 99.99. %the above Preferably, if the purity of each raw material is above 99.99 ° /., the amount of impurities will be lower than that of 丨〇〇 atomic ppm, which is suitable for mixing with a general mill such as a bead mill, a ball mill, or a planetary ball mill. The mixture of the above raw materials is pulverized, and then granulated and formed. The mixture is formed into a shape suitable for use as a sputtering target or the like by molding, for example, press molding, cold isostatic pressing, uniaxial pressing, Mold forming 'washing molding, injection molding, etc. In addition, molding aids such as polyethylidene glycol methylcellulose, Poly Wax, and oleic acid may be used during the molding process. 18 201024435 Burning When the temperature is lower than 12 〇 (rc, there is a case where a high-density sintered body cannot be obtained, and it is corrected that the body is aged for 2 to 2 hours to obtain a sintered body at a temperature of 1200 ° C to 1600 ° C. c, will be the case of the indium material raw material solution. Noirc - Moot: preferably, 1300t ~ 155 (rc is better.

The sintering time is preferably 2 to 200 hours. If it is shorter than 2 hours, there is a case where sintering is not completed, and there is a case where a high-density sintered body is not obtained. In addition, if it is longer than 200 hours, the heating is too long, which is not conducive to the economic situation. It is preferably 5 to 150 hours, preferably 1 to 1 hour. Sintering is preferably carried out under an oxidizing atmosphere. The oxidizing atmosphere is preferably in the air, under a stream of oxygen or under oxygen. The obtained sintered body is formed into a desired shape by cutting, grinding, or the like. By sputtering it to the backing plate, sputtering can be obtained. The metal oxide film of the present invention is formed by using the above sputtering target to form a film. Annealing may be performed as needed after film formation. The metal oxide film is a semiconductor film, which can be used for a thin film transistor such as a channel type, a money barrier type or the like. EXAMPLES Next, the examples and comparative examples will be exemplified to further specifically describe the present invention. Examples 1 to 4 Indium oxide powder and oxidized powder were weighed to the ratio shown in Table 1, placed in a polyethylene can, and mixed in a dry ball mill for 72 hours to prepare a mixed powder. 19 201024435 This mixed powder was poured into a mold, and a molded body was produced by pressurization with a waste force of 300 kg/cm 2 . This molded body was subjected to a densification treatment by CIP at a pressure of 3 ton / cm 2 . Next, the molded body was placed in an atmosphere sintering furnace under a flow of pure oxygen, and sintering was performed under the following conditions. The results of the density of the sintered body measured by the Archimedes method are shown in Table 1. The X-ray diffraction results of the obtained sintered body are shown in Figs. 1 to 4, respectively. (Sintering conditions) Heating rate: about 25. (: /hr temperature rise, oxygen partial pressure: 50mmH2 〇 (gauge pressure), oxygen linear velocity: 2.7cm / minute flow of oxygen, while sintering at the sintering temperature and sintering time shown in Table 1. X-ray The diffraction method determines the lattice constant of the obtained sintered body, and the density is measured by the Archimedes method. The conductivity of the sintered body is measured by L〇resta manufactured by Mitsubishi Petrochemical Co., Ltd., and the result of measuring the conductivity (resistance) is shown. In Table 1. In addition, the map showing the X-ray diffraction results of the sintered body is shown in Fig. 4 to Fig. 4. The lattice constant of 1~〇3 is 10.118A, and the lattice constant of Ιηγ〇3 is 10.362Α. The lattice constants of the sintered bodies of Examples 1 to 4 are each in the range of #·, and since the lattice constant changes substantially linearly with respect to the composition, it is shown that the oxidation is completely dissolved in the oxidation. Indium. For the composition of Example 2 Υ / (Ιη + Υ) = 0. Further add Ce 〇 2 to form ce / (in + Y + Ce) = 0.00 〇 8, when performing the same operation, the lattice constant The relative density of the sintered body of ^.161 ' is 98%, and the conductivity of the sintered body is 42 mQcm. It is thus known that Ce is added by adding Ce. The electrical conductivity of the sintered body was improved. Comparative Example 1 20 201024435 The indium oxide powder and the cerium oxide powder were weighed to In : Y = 1: 丨, and the same operation as in Example 1 was carried out to obtain a sintered body. The peak of 111¥〇3 was observed in the body. The lattice constant of the sintered body of Comparative Example 1 was the lattice constant of ΙηΥ〇3. "(Y〇.5ln0.5) 203 (PDF: 25-1172) 〇 〇 Α Α Α Α Α Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι 10.123 96 30 3.8 Example 2 0.1 1550 10.159 98 --- ^ 30 7.2 Example 3 0.2 1450 10.202 95 50 9.4 Example 4 0.45 10.324 ~~~^, 50 95 15〇〇Example 5

In Example 5, in addition to indium oxide and antimony oxide, tin oxide was used as the positive tetravalent metal oxide, and each metal oxide was weighed to the ratio shown in Table 2, except that the sintering shown in Table 2 was used. The sintered body was obtained in the same manner as in Example 外 except for the conditions. Further, a map showing the diffraction result of the x-ray of the sintered body is shown in Fig. 5. The sintered body of Example 5 has a peak between the peak of κΙη2〇3 and the peak of ΙηΥ〇3 in the χ-ray diffraction pattern, and it is understood that the lattice constant is between Ιη2〇3 and ΙηΥ〇3, and, in addition, observation It was found that the bulk of the obtained sintered body was lower than that of Examples 7-14 to 4 by the peak of 111 〇3. 21 201024435 [Table 2] Y/(In+Y+Sn) Sn/(In+Y+Sn) Sintering temperature (°c) Relative density of sintered body (%) Volume resistance of sintered body (mQcm) Sintering time (hr Example 5 0.05 0.0007 1450 97 1.6 30 Examples 6 and 7 Each metal oxide was weighed to the ratio shown in Table 3, and the same operation as in Example 1 was carried out except that the sintering conditions shown in Table 3 were used. Sintered body. Further, a map showing the results of X-ray diffraction of the sintered bodies is shown in Figs. 6 and 7. In the sintered bodies of Examples 7 and 7, the peaks of Y2Sn2〇7 and Sn〇2 were observed in the X-ray diffraction pattern, and the peak of γ2〇3 was not observed. [Table 3] Y/(Y+Sn) Sintering temperature (°C) Relative density (%) of sintered body Conductivity (mQcm) of sintered body Sintering time (hr) Example 6 0.1 1450 86 720 30 Example 7 0.3 1450 82 1470 30 Examples 8 and 9 Each metal oxide was weighed to the ratio shown in Table 4, and a sintered body was obtained in the same manner as in Example 1 except that the sintering conditions shown in Table 4 were used. Further, a map showing the results of X-ray diffraction of these sintered bodies is shown in Figs. 8 and 9. In the sintered body of Example 8, a peak of 2 〇 3 was observed, and it was found that cerium oxide was dissolved in indium oxide. 22 201024435 The peak observed in the sintered body of Example 9. [Table 4] Y/(Y+In+Sn) In/(Y+In+Sn) Sn/(Y+In+Sn) ----- Sintering temperature (°c) Relative density (%) of sintered body Conductivity of sintered body (mQcm) Sintering time (hr) Example 8 0.1 0.8 0.1 1550 97 0.73 30 Example 9 0.2 0.6 0.2 1550 95 0.96 30 Examples 10 and 11 Each metal oxide was weighed to be shown in Table 5. The ratio was the same as in Example 1 except that the sintering conditions shown in Table 5 were used to obtain a sintered body. Further, a map showing the results of X-ray diffraction of these sintered bodies is shown in Fig. 1 and Fig. 11 . The peaks of Ιϋ2〇3 and ΙηΥ〇3 were observed in the sintered body of Example 10. The peaks of ΙηΥ〇3 and Ιη2〇3.(ζη〇)2 were observed in the sintered body of Example 11. ❿ [Table 5] Y/(Y+In+Sn) In/(Y+In+Sn) Zn/(Y+In+Sn) Sintering temperature (°C) Relative density of sintered body (%) Conductivity of sintered body Sex (mQcm) Sintering time (hr) Example 10 0.1 0.8 0.1 1430 98 3.7 30 Example 11 0.3 0.5 0.2 1430 95 4.9 30 23 201024435 Examples 12 and 13 Each metal oxide was weighed to the ratio shown in Table 6. The sintered body was obtained in the same manner as in Example 1 except that the sintering conditions shown in Table 6 were used. Further, a map showing the results of X-ray diffraction of these sintered bodies is shown in Fig. 12 and Fig. 13.

In the sintered body of Example 12, peaks of Y2Sn207 and ZnO were observed. In the sintered body of Example 13, the peaks of Y2Sn2〇7, ZnO, and Zn2Sn04 were observed. [Table 6] Y/(Y+Sn+Zn) Sintering temperature (°c) _ Sn/(Y+Sn+Zn) relative density of sintered body of sintered body Zn/(Y+Sn+Zn) sintering time (hr) (%) (mQcm) 0.05 1400 Example 12 0.05 82 1600 0.9 30 0.2 1430 Example 13 0.4 86 6400 0.4 30 Comparative Examples 2 and 3

Each metal oxide was weighed to the ratio shown in Table 7, and the same operation as in Example 1 was carried out except that the sintering conditions shown in Table 7 were used to obtain a sintered body. Further, a map showing the results of X-ray diffraction of these sintered bodies is shown in Figs. 14 and 15. In the sintered bodies of Comparative Examples 2 and 3, peaks of Y203 and ZnO were observed. 24 201024435 [Table 7J Y/(Y+Zn) sintering temperature rc) 1 Sintering conductivity—-—Ζη/(Υ+Ζη) Sintering time relative density (%) Comparative example 2 0.1 1350 0.9 30 78 Cannot be compared Example 3 0.3 Π 7 "" 1350 ------ ~--- ^7 Λ ---~_ U. / 30 /4 Unable to move the sintered body prepared in Example 1 , Example 14

The diameter of the force is made into an oxygen-free steel

A 4 mm thick circular plate with a thickness of 5 mm, and a back plate made of the welded material is made into a material. The dried metal material was subjected to a bond under the following sputtering conditions, and the obtained metal oxide film was evaluated. (Sputtering conditions) First, evacuate the vacuum chamber to 5 > l〇-4Pa, and adjust the argon gas pressure to 〇2pa with Ar gas flow rate: 10 SCCM ', gas flow rate: 〇·5 SCCM, DC power 1 〇〇W 'Substrate temperature: at room temperature, film thickness: film 1 forming 500A. The film was heat-treated at 300 ° C ' in air.

The resistivity results of the obtained film were shown in Table 8 by κ applied AC Hall measurement. Next, the crystallinity was evaluated by X-ray diffraction of the obtained film, and the peak was observed by X-ray diffraction as the crystal f, and the peak was not observed as non-crystallized.

Further, the sputtering was performed continuously for 8 hours, and the number of times of arcing occurred at this time was measured. # In the initial 2 hours, when the arc discharge occurred between the remaining 6 hours and 1 or less times, it was regarded as no abnormal discharge. Arc discharge is using NF 25 201024435

Arc L discharge was measured by Data L〇gger EZ584® manufactured by Corporation. Comparative Example 4 A target material was produced by the same treatment as in Example 14 except that the sintered body obtained in Comparative Example 2 was used, and sputtering was performed, and the obtained film was evaluated. The results are shown in Table 8. [Table 8] Sintered sputtering film performance used Hall measurement Crystallographic sputtering with or without abnormal discharge ratio Resistance Qcm Carrier concentration/cm3 Example 14 Example 1 2xl02 1016 Crystalline No Comparative Example 4 Comparative Example 2 ( Film formation by RF sputtering) Overload - Amorphous Example 15 was used. The target material prepared in Example 14 was used on a hard doped germanium wafer to which a thermal oxide film was attached at a flow rate of 0.5 SCCM. An amorphous oxide semiconductor film having a thickness of 4 Å was formed, and a source/germanium electrode having a shape of L: αΟμηη, W: 500 μm was formed thereon by a metal mask, and 3 〇 was performed at 300 Ο C in air. After a minute heat treatment, the characteristics were measured using a semiconductor parameter device manufactured by Keithley Instruments Inc. Mobility: 22 cm 2 /V.sec, On.Off ratio: 106, Vth = 8, and it is known that it exhibits excellent semiconductor characteristics. Industrial Applicability The sintered body of the present invention is particularly useful as a crucible for drying a metal oxide film for forming a switching element material for driving various display devices. The sputtering target of the present invention can perform stable sputtering, and can manufacture 26 201024435 a high-performance transparent oxide semiconductor film excellent in transparency and surface smoothness. The embodiments of the present invention have been described in detail in the foregoing, and the embodiments of the present invention and the embodiments of the present invention are intended to be It is easy to add multiple changes to the embodiment. Accordingly, such various modifications are intended to be included within the scope of the present invention. The contents of the documents described in the present specification are all incorporated herein by reference. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the X-ray diffraction result of the sintered body obtained in Example 1. Fig. 2 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 2. Fig. 3 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 3. Fig. 4 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 4. Fig. 5 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 5. Fig. 6 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 6. Fig. 7 is a view showing the X-ray diffraction result of the sintered body obtained in Example 7. Fig. 8 is a view showing the X-ray diffraction result of the sintered body obtained in Example 8 27 201024435. Fig. 9 is a graph showing the X-ray diffraction result of the sintered body obtained in Example 9. Fig. 10 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Example 1. Fig. 11 is a schematic diagram showing the results of X-ray diffraction of the sintered body obtained in Example 11. Fig. 12 is a schematic view showing the results of X-ray diffraction of the sintered body obtained in Example 12. Fig. 13 is a schematic view showing the results of X-ray diffraction of the sintered body obtained in Example 13. Fig. 14 is a graph showing the X-ray diffraction result of the sintered body obtained in Comparative Example 2. Fig. 15 is a graph showing the X-ray diffraction result of the sintered body obtained in Comparative Example 3. [Main component symbol description] (none) 28

Claims (1)

201024435 VII. Patent application scope: 1. A sintered body formed by indium oxide and yttrium oxide with a lattice constant between ΙηΥ〇3 and ln2〇3. 2. The sintered body according to the invention of claim 2, wherein the cerium oxide is completely dissolved in the oxidized steel. 3. The sintered body according to item i or item 2 of the patent application, wherein the atomic ratio γ/(Ιη+γ) of the elemental element and the element exceeds 〇 〇 less than 〇 5. ❿ 4. A sintered body containing two or more kinds of metal oxides and cerium oxide selected from the group consisting of indium, tin, and heterogeneous groups, and cerium is selected from the group consisting of indium, tin, and zinc. The atomic ratio of the metal on the above is more than 〇.〇 and is less than 5 〇 atom%. 5. The sintered body according to claim 4, wherein the atomic ratio is 0.001 to 40% by atom. 6. The sintered body according to claim 4, wherein the front portion is 2.0 to 15 atoms. /D. The sintered body according to claim 4, wherein when the metal of the above two or more types contains at least indium, it contains a crystal which is oxidized and dissolved in the oxidized steel. 8. The sintered body according to claim 7, wherein the indium oxide crystal is a square iron ore structure. 9. The sintered body according to Item 7 or Item S, wherein the crystal grain size of the indium oxide crystal is less than 1 Ομηι. The sintered body according to the seventh or eighth aspect of the invention, wherein the crystal lattice constant of the indium oxide crystal is between ΙηΥ〇3 and Ιη2〇3. The sintered body according to the seventh or eighth aspect of the invention, wherein the marriage phase contains 5 G to 99 9 atom% of all the metals constituting the sintered body. The sintered body according to Item 2, 4, 7 or 8 of the patent application, further containing a metal element having a positive tetravalent or higher value. 13. If the application is made in the 12th item of the township, the towel contains 100~1 〇〇〇ppm of the above-mentioned metal element of the above-mentioned tetravalent or higher. Φ 14·: a sintered body', formed by indium oxide or oxidized tin-deficient tin, in which the strontium or solid solution is dissolved in indium oxide, or in the form of Y2Sn2〇7 compound = 3 or 'oxidation It is dissolved in copper oxide, and the remainder is contained in the form of a compound of Y2Sn2〇7. 1S. The sintered body according to claim 14, wherein the atomic ratio Y/(In+Y+Sn) of the indium element, the elemental element, and the tin element exceeds 〇〇2 and is sintered at 〇5 to ΊΓ0 6 . The body is formed by indium oxide, cerium oxide and zinc oxide, wherein the oxidized or solid solution is dissolved in indium oxide, or is in the form of Ιγγ〇3 compound, or a part of the oxidized phase is dissolved in indium oxide, and The remainder is contained in the form of a compound of Y2Zri2〇7. The sintered body according to claim 16, which further comprises a hexagonal layered compound represented by In2〇3.(ZnO)m (wherein m is an integer of 2 to 20). The sintered body according to claim 16 or 17, wherein the atomic ratio Υ/(Ιη+Υ+Ζη) of the indole's yttrium element and the zinc element exceeds 〇 〇 and is less than 0.5. 19. A sintered body formed by tin oxide, cerium oxide and zinc oxide, wherein 30 201024435 is cerium oxide or solid-soluble in tin oxide, or is contained in the form of a Y2Sn207 compound, or a part of cerium oxide is dissolved in tin oxide. Medium, and the remainder is contained in the form of the Y2Sn207 compound. 20. The sintered body according to claim 19, further comprising a Zn2Sn〇4 compound. The sintered body according to claim 19, wherein the atomic ratio Y/(Sn+Y+Zn) of the tin element, the lanthanum element, and the zinc element is 0.01 or more and 0.4 or less. 22. A sintered body formed of tin oxide and antimony oxide and containing a Y2Sn207 compound. 23. The sintered body according to claim 22, wherein the atomic ratio Y/(Sn+Y) of the tin element and the lanthanum element exceeds 0.0 and is 0.5 or less. A method for producing a sintered body according to the fourth aspect of the invention, wherein the oxide of two or more kinds of metal selected from the group consisting of indium, tin and zinc and the powder of cerium oxide are mixed. Sintering 2 to 200 hours at a temperature of 1200 ° C to 1600 ° C. 25. The method for producing a sintered body according to claim 12, which is an oxide of two or more kinds of metals selected from the group consisting of indium, tin, and rhodium, ruthenium oxide, and a metal having a tetravalent or higher value. The powder is mixed and sintered at a temperature of 1200 ° C to 1600 ° C for 2 to 200 hours. 26. The method of producing a sintered body according to claim 24 or 25, wherein the sintering is performed in an oxidizing atmosphere. 27. A sputtering target produced by using a sintered body as described in claim 1, 4, 14, 16, 19 or 22. 31 201024435 28. A metal oxide film formed by using a sputtering target as described in claim 27 of the patent application. A semiconductor comprising a metal oxide film as described in claim 28 of the patent application. 30. A thin film transistor using a semiconductor as recited in claim 29 of the patent application. 31. The thin film transistor according to claim 30, which is a channel etching type. 32. The thin film transistor according to claim 30, which is an etch barrier type. A semiconductor device comprising the thin film transistor according to claim 30 of the patent application. 32