TW200925308A - ITO sinter and ITO sputtering target - Google Patents

Abstract

This invention provides an ITO sinter through which an ITO film with excellent physicals can be filmed with further improved yield an ITO sputtering target, an ITO sputtering target material and an ITO sputtering target, especially an ITO sprttering taget material by which a film with an excellent low resistance and an amorphous stability can be obtained by using the ITO sinter with a low bulk resistance value, an ITO sputtering target, and a method for manufacturing the ITO sinter suitable for the ITO sprttering taget material and the ITO sputtering target are pravided. The ITO sinter of the present invention is the one wherein a fine particle of In4Sn3O12 exsists in an parent phase of In2O3 as a main crystal grain, and is characterized by that the fine particle has a three-dimensional stellar shape formed with a needle-like projection in radiation from an imaginary center of the particle.

Description

200925308 IX. Description of the Invention: [Technical Field] The present invention relates to an ITOdndium TinOxide, indium oxide (ITO), and ιτο sputtering target. More specifically, it is a 1T sintered body in which fine particles composed of ImSmO! 2 having a specific shape exist in a parent phase belonging to the main crystal grain, and a sputtering target material using the sintered body of the above-mentioned 0 IT0 [Prior Art] The ❹ 膜 0 film system is used as a transparent electrode of a flat panel display because of its high penetrability and electrical conductivity. The formation of this ΙΤ0 film is performed by sputtering a ΙΤ0 sputtering target. Regarding the IT0 sintered body used as the sputtering target material, it has been conventionally used to reduce or prevent the occurrence of arcing or the generation of fine particles in order to make the film formation yield better. Review. For example, it has been attempted to prevent the occurrence of arcing by reducing the surface roughness of the 丨τ〇 sputtering target within a specific range (see Patent Documents 1 and 2). When the bulk resistance of the sintered body itself is lowered, the arc generated during sputtering at the time of film formation can be reduced and the film formation speed can be increased. Therefore, various reviews have been made (see Patent Document 3). On the other hand, the step of etching the IT film is required at the time of forming the transparent electrode. As long as the (10) obtained by performing the cesium-sintering of the tantalum sintered body is factory-made, the electrical resistivity of the film itself can be lowered, and I will be crystallized. , and the remaining moments without causing residual residue must use strong acid. If 320513 5 200925308 is used to process such a strong acid, there is a problem that the wiring material is broken, etc., and many problems are apt to occur. It is desirable to have an amorphous etch which can be easily etched without using a strong acid. membrane. However, if the ΙΤ0 sintered body is cut in parallel in the thickness direction thereof, and the obtained cut surface is etched to observe the fine structure, the I n2 〇 3 mother belonging to the - main, and β Ba grains In addition to the grain boundaries, it is seen that there are compound phases existing in the state of the intellectual grain boundary and fine particles existing in the parent phase of In2〇3. However, as far as the inventors have known, there has been no review as to whether or not the composition and shape of the fine particles present in the sintered body of the present invention and the physical resistance value of the sintered body of the I τ are related to the physical properties of the film formed. [Patent Document 1] Japanese Patent No. 2,502, 083 [Patent Document 2] Japanese Patent No. 3152108 [Patent Document 3] Japanese Patent Laid-Open No. 2007-31786 [Draft of the Invention] [Problems to be Solved by the Invention] OBJECTIVE: The present invention provides an IT0 sintered body, an IT0 (four) material, and an ITO paste, which can form a film having an excellent physical property by further improving the yield, and in particular, provides a ΙΤ0 sintering by using a low bulk resistance value. Body, and a method of obtaining a low-power ancestor and an amorphous stability yili (10) riding a pure material and a sputum (four) recording, money mosquitoes in the U-made sintered body. To H&IT0 [Solution to Problem] The inventors of the present invention have focused on the fine teachings composed of ί n4Sn3Qi2 in the main crystal grain Π2〇3 parent phase belonging to the ΙΤ0 sintered body: fine 320513 6 200925308 particles have The specific shape and the causal relationship between the film formation yield and the film properties of the film formation were positively reviewed and found to be based on the control of the fine particles composed of IruSmO!2 present in the In2〇3 parent phase. Shape ho • Sintered body, which can provide a 溅0 splashing light material and Τ〇 Τ〇 Τ〇 欢 成 成 藉 藉 藉 藉 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 That is, the sintered body of the present invention is a fine particle composed of IruSmOi2 in the In2〇3 parent phase belonging to the main crystal grain, and the fine particle hand has a radiation shape formed from the virtual center of the particle. The three-dimensional star of the protrusion. The singularity of the singularity of the singularity of the singularity of the present invention is preferably 1.35 χ 1 ( Γ 4 Ω. cm or less. Preferably, m or more is preferable, and the average of the circularity coefficients of the fine particles is preferably not more than 0.8. © These 1το sintering systems are applicable as sputtering target 枓, and the ιτο splash of the present invention The plating target is characterized in that it comprises a sintered body and a backing plate. The method for producing the sintered body of the present invention is a mixture of indium oxide and tin oxide. Forming, and the obtained forming heat is up to a maximum sintering temperature of 158 〇 to 17 〇〇. 〇, and the maximum burning: the holding time of the shirt is set to less than 〇 seconds, 揍 溘 溘 溘 溘 第 第 第Further, 140 〇 to 1550 C, and the holding time of the second sintering temperature is set to 3 to 18 hours, and then the temperature is lowered to room temperature, which is characterized by the package 320513 7 200925308. In the second sintering temperature Set the non-oxidizing gas at a time when the holding time is at least 1 to 4 hours. The step of the environment 'and includes: obtaining the ΙΤ0 sintered body by the method of the step of decreasing the maximum sintering temperature from the highest sintering temperature to 4 〇 (rc '). In addition, in the present specification, The ΙΤ0 generally refers to a material obtained by adding 1 to 35 wt% of tin oxide (Sn〇2) to indium telluride (ImO3). [Effect of the Invention] The IT0 sintered body of the present invention is present in In2〇3 The fine particles composed of ❹ImSmOu in the parent phase have a specific shape, so that the body resistance of the IOT sintered body itself can be suppressed to a low level. Therefore, the voltage required for sputtering when used in a sputtering target can be used. The filming step can be carried out with a low suppression, and a stable film formation step can be performed. Further, the sputtering film obtained by using such an ITO sputtering target can be easily formed because of its amorphous stability at a high temperature and excellent film properties.亍 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 实施 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The memory is made up of ImSmOu The fine particle. The figure is a view showing the image of the IT0 sintered body obtained by using a scanning electron microscope (SEM: JSM_638〇A, manufactured by JEL) to set the magnification to 3000 times, and the second figure is ς As shown in the figures, in the sintered body of the present invention, the parent phase i belonging to the main crystal grain is present, and the fine particles 2 composed of ImSmOu are dispersed in plural. And out of this

S 320513 200925308 The state within the parent phase 1 exists. As shown in Fig. 3, the fine particles 2 are particles observed in an image obtained by using SEM to set the magnification to 30,000 times. In the ίτ〇• sintered body of the present invention, the composition of the fine particles 2 can be obtained by a transmission electron microscope (FE-TEM: JEM-2100F, manufactured by JEOL Ltd.), and is analyzed by composition of ruthenium. The fine particles 2 were analyzed to obtain confirmation. <Composition analysis of fine particles> In the STEM image ({).5><()々1„2 horizon _) of the fine particle 2 obtained by EDX attached to FE-TEM, (4) Depending on the analysis results of each point, the elemental analysis of the fine particles 2 is performed, and the ridge is composed of I n, Sn, and 0. In addition, the electron diffraction image from the ferrule is used. The diffraction pattern is exited, and it is confirmed that these are diffraction patterns from the fine particles 2. Next, the reciprocal lattice unit including the above-described diffraction pattern is taken out, and the reciprocal lattice is measured. (reClprocal latticeplane) interval, and further the crystal composed of ratio, %, = is extracted from the lion card. Based on these results, by analyzing the software (electronic diffraction pattern, software, Nippon Techn〇)

Material research). The composition of the composition is determined by the above-described composition analysis, and the fine particles Iii4Sn3〇i2° are determined. In the sintered body of the present invention, the virtual center of the fine particle 2 particles is formed into a scalp protrusion by radiation. ^ In the fine particles 2 pretty A six 脒曰 π m star 屯 ° ! is a three-dimensional shape, so a fine particle 2 at least "320513 9 200925308 more than one needle shape. The anterior ends of the acicular protrusions may be sharp, and may be circularly shaped, and the large J-lines of the acicular protrusions present in one of the fine particles 2 may be uneven. The fine particles 2 having such a shape are confirmed to be at least 8 〇 to 3 在 in the 3x4/m 2 Horizon range of the 观 observation. Although the reason why the fine particles 2 have such a shape is not clear, it is presumed to be caused by a certain crystal orientation effect of ImSmOi2. Further, since the "particles 2" have such a shape, the plurality of fine particles 2 can pass through the gap formed between the acicular protrusions of the other fine particles 2, respectively, so that the acicular protrusions are present in the In2.粒子3 The particles in the parent phase are fine particles 2 having such a shape, and the plurality of particles are more effective than the particles having a spherical shape, and are more effective in utilizing a limited mother phase region and easily overlap each other. It will hinder the growth of the particles of each other and enhance the mutual adhesion. This is also presumed to be due to some influence on the physical properties of the obtained film. 曰. As described above, in the sintered body of the present invention , in the ΐη2〇3 parent phase 0 I, there is a fine granule hand 2 which is controlled by 4% 3 above this specific shape. Therefore, the body resistance of the IT 〇 sintered body can be suppressed to a lower value. Therefore, when the film is formed, the occurrence of arcing during sputtering can be suppressed, and the film formation speed can be improved. Further, the film obtained by using such a sintered body as a sputtering target is Excellent amorphous stability at high temperatures Therefore, the speed of the (4) processing can be improved, and the pattern shape can be easily made good. Further, the amount of the etching residue can be reduced. In the sintered body of the present invention, the fine particles 2 are further horizontally non-retat The average diameter is 0 25 #m or more is better, better

320513 I S 10 200925308 For 〇·27 to 0. 50/zm, especially for 〇.3〇 to 〇 45/^. The horizontal Reiter diameter is the value obtained by the particle analysis in the SEM observation described above. 2 The average value of the so-called horizontal Freit diameter refers to the range of 3x4/zm2 in the horizon of the observation, which will be randomized. The average value of the level of the Feret diameter obtained by the two fine particles 2 is averaged. / • The value of the horizontal Feret diameter is specifically determined by the following method. Using the particle analysis software (particle analysis Versi〇n (version) 3〇, manufactured by Sumitomo Metal Technology Co., Ltd.), the SEM image of the fine particle 2 is first traced and the image is recognized by the scanner, and the image is given a binary value. Chemical. At this time, the conversion value is set in such a manner that the pixel is displayed in units of /zm. Then, by selecting the level of the Feret diameter as a measurement item, the value of the Leite direct control ("m) calculated from the total number of pixels in the horizontal direction of the fine particles 2 can be obtained. Right fine particle 2: The average value of the Feret diameter of this level is not shown in the (10) mother phase! The size of the fine particles 2 is suppressed to some extent, and the fine particles 2 have a specific shape. In addition, the adhesion of the particles is further improved. Therefore, the use of the IT0 sintered body as a waste is performed. When plating, it is better to read. In addition, since the circulation of the three electrons is not allowed, the body electric power of the obtained body can be reduced. In the sintered body of the present invention, the average value of the fine particle 2 into a circularity coefficient of the second particle is less than U. , better. 76; Xue Youjia is from 0·73 to 〇·49. The circularity coefficient is the same as the above-mentioned horizontal phenotype control. It is obtained by the particle analysis in SEM observation. 320513 11 200925308 The average value of the circularity coefficient refers to the range of the cum view and the 4uni horizon. Within the range, the value of the 3x shape coefficient of 2 ^ fine particles 2 will be randomly averaged. ^The circle of the shape of the shape of the shape is specifically determined in the following manner. As with the upper=Rite diameter, using the particle analysis software, first track the micro: the (10) image of the particle 2 and identify the image with the scanner, and give the image a two-pixel display in units of pixels. By setting the conversion value of 7, by selecting the area as the measurement item, the particle area Um can be obtained by forming the total number of pixels of the fine particles 2 as shown in Fig. 5. Furthermore, by selecting the peripheral length as the measurement item, as shown in Fig. 6, the peripheral length (_. from the area and the surrounding length) can be obtained from the total number of pixels around the fine particles 2 to be obtained. The value of the circularity coefficient is shown by the following number. (X1). 圆形 The circularity coefficient = 4Π The length around the area. The value of the circularity coefficient is closer to 1〇. The average shape of the fine particles 2 to be measured is closer to a spherical shape. Therefore, the average value of the circularity coefficient of the fine particles in the sintered body of the present invention is not approximately 1Q, and this point It is also shown that the fine particles 2 are in a shape that is away from the spherical shape, and has a three-dimensional star shape that forms a needle-like protrusion from the virtual center of the particle. The ΙΤ0 sintering system of the present invention has a volume resistance value of less than 1. 30x10. -4Ω · cm lower body resistance value lower limit

320513 L 12 200925308 is not particularly limited 'but usually 9x1 (Γ5 Ω · cm or more. Since the use of the sintered body of the present invention as a sputtering target, the display of such bulk resistance can effectively suppress the emission The arc is generated, and the voltage required for the deplating can be suppressed to be low, so that a stable film forming step can be performed. Such a bulk resistance value can be achieved as described above, as in the present invention. In the sintered body, the fine particles 2 have a three-dimensional star shape in which the needle-like projections are formed in a radial shape from the virtual center of the particles. Further, as shown in Fig. 2, when the SEM observation is performed at a magnification of 3,000 times, It was observed that there is no fine particle region (free 201^) in the region of the im 〇 3 parent phase of the fine particle 2 (excluding the region of the compound phase existing along the grain boundary state). From In2〇 3 The average of the width of the grain boundary 3 of the parent phase i from the fine particle-free region 5 is 〇. 3/zm or more, preferably in the range of 0.4 to 3 y m. Here, the so-called "In2〇3 mother phase" The average of the width of the grain boundary 3 of 1 without the fine particle region 5 is The value obtained by the column method is determined by using a diamond cutter to cut the IT0 sintered body in parallel in the thickness direction thereof, and the obtained cut surface is made of emery paper #170, #320, #800, #1500, #2000, staged grinding, and finally buff grinding and finishing into a recording surface. This ιτο sintered body was engraved at 40 ° C (nitrogen (60 to 61% aqueous solution) , Kanto Chemical Co., Ltd., nitric acid 1. 38 deer 1 (Note: Kanto Chemical Guaranteed Pure Primary Product) No. 28161-03), hydrochloric acid (35.0 to 37.0% aqueous solution, Kanto Chemical Co., Ltd.) System, hydrochloric acid deer grade 1 product number 18078-01) and water by volume ratio HC1: H2〇: HN03=1 : 1: 〇. 08 320513 13 200925308 ratio mixing) impregnation for 9 minutes, and the above cut surface Etching. The surface appearing was observed by SEM at a magnification of 3000 times, and all the Iri2〇3 mother particles of the entire section were observed on the photograph using the photographed SEM photograph (at the edge of the photograph, a part of the section was not photographed) The 1 secret mother particle is excluded from the ten image) For the measurement of the 畺 对象 对象 , , , , , , , , , 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象 对象3 The width of the non-fine particle region 5 in the parent phase particles. The value of this width is obtained for all Irl2〇3 parent particles as the object of the measurement, and the number of In2〇3 parent particles as the measurement object is obtained. In addition to these sums, the value obtained in this manner is taken as the average of the widths of the aforementioned fine particle-free regions 5. When the average value of the width of the grain boundary 3 from the 1n2〇3 parent phase 1 and the particle-free particle region 5 is within the above range, the region where the fine particles 2 are not present in the In2〇3 parent phase 1 belonging to the main crystal grain will be Since it is widened, the boundary between the region where the fine particles 2 are present and the region where the fine particles 2 are not present is more clearly adhered, and the fine particles 2 are present as much as possible in a limited region. As a result, by using such an IT0 sintered body as a sputtering target, an excellent ΙΤ0 film having less physical properties can be provided. Next, a method of producing the tIT sintered body of the present invention will be described in detail. The ΙΤ0 sintering system of the present invention can be produced by a so-called powder metallurgy method. In the powder metallurgy method, generally, a binder is required to be compression-molded at the end of the raw material, and if the obtained formed body is degreased as needed, the formed body is subjected to a calcination treatment to obtain a sintered body. body. The method for producing the ΙΤ0 sintered body of the present invention must be carried out under specific conditions. 320513 14 200925308 Specifically, 'indium oxide (InAO, tin oxide (Sn〇2), etc., is mixed in a desired ratio, and If necessary, a binder is added and compression-molded to obtain a molded body, and the obtained molded body may be degreased as needed. This can be carried out by a conventionally known means and conditions. In addition, the raw material powder may be subjected to calcination or classification treatment, and the raw material powder may be mixed, for example, by a ball mill or the like, and then the mixed raw material powder is filled in a molding die and compressed and formed to form a molded body. The degreasing may be carried out in an atmosphere or in an oxygen atmosphere, or may be formed by mixing the raw material powder, ion-exchanged water, or the like as described in JP-A-286-205. The slurry formed by 4 is injected into a filter forming method composed of a water-insoluble material for refining the water from the ceramics of the ceramics to obtain a shaped body. The mold is formed by grinding and draining the water in the refining to form a molded body, and the formed body may be dried and degreased. The formed body obtained in this manner is smashed into a fire under the specific conditions described below. The ΙΤ0 sintered body of the present invention can be obtained by a treatment. The firing treatment is usually composed of a heating step, a heat retention step, and a cooling step. The furnace can be used in the firing treatment, and the mouth is not particularly limited. 'And in the force: f step', the above-mentioned shaped body is placed in the furnace, and usually heated to a maximum sintering temperature of 1580 to 1700 to be placed at 1600 to 165 rc. At this time, the plate can also be used as needed. From the viewpoint of the production efficiency of the obtained sintered body, the average heating rate in the furnace is 320513 15 200925308 at 50 to 40 (TC/hour). Preferably, from the obtained ίτ. The density of the sintered body is increased, the heating step is to introduce oxygen into the furnace to perform better. The introduction into the furnace of the child Luo Xi · rolling & For (M to 500 々 small The amount of the product lm in the above heating step reaches the highest sintering temperature, and the high sintering temperature is 3 GG seconds at 7, preferably 15 Gsec or less. The lower limit of the ❹ holding time is not particularly limited. It is the best for the moment...= The maximum sintering temperature is maintained for 3 to 2 hours, but in the present case: the second is as follows: by setting the holding time of the highest sintering temperature to a very short time, The density of the obtained IT〇 sintered body can be further improved. In the holding step, it is preferably placed in the furnace under the same conditions as the heating step. The crucible is then cooled to the second sintering temperature. 14〇〇 to 15 . _ to foot C, and keep the second money junction temperature 3 to 18 small; for 〇 ^ good for 5 to 15 hours. At this time, the furnace (4) is in a non-oxidizing gas atmosphere when the holding time of the second sintering temperature is at least 1 JL for 4 hours, preferably 2 to 3 hours. However, it is assumed that the time point of the non-oxidizing gas-clothing environment is the holding time of the second sintering temperature. For example, in the case where the holding time of the second sintering temperature is 3 hours, the time at which the non-oxidizing gas atmosphere is set is the elapsed time point in which the holding time is less than 3 hours. In the case of the Setohu Jinming non-oxidizing gas environment, the second sintering temperature is maintained at the end of the time, and the oxygen concentration in the furnace is the gas ring 320513 16 200925308, specifically, 5丨I 无士 mk Λ _ ^ - There are argon gas, nitrogen gas, etc., which are replaced by oxygen, etc., gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas, gas To be embarrassed. In the cooling step, the inside of the furnace is 'continuously or stepwisely': the formed body n which has passed through the above heating step and the holding step is not only the n2 属于 of the main crystal grain of the ITQ sintered body obtained. 3 The shape of the fine particles 2 present in the parent phase 1 'from the level of controlling the particle 特! And the average value of the circularity coefficient and the average value of the width of the fine particle-free region 5 from the grain boundary 3 of the In2〇3 parent phase 1 are also adjusted from the highest sintering temperature to the above-mentioned cooling step. The cooling rate of the temperature zone of C. The average temperature drop rate in this temperature zone is 10 to 1 〇 〇 c / hour, preferably j 〇 to 4 〇. 〇 / hour. Also, that is, the temperature range from the highest sintering temperature to the highest temperature in the holding step, and the average temperature from the highest temperature in the holding step to the temperature range in the 40th generation are as described above. When the average temperature drop rate in the temperature region is within the above range, the molded body after the heating step is gradually cooled, and the growth of the fine particles 2 in the In2〇3 parent phase is easily promoted, and the particles grow. Since the directivity is controlled to some extent, the shape of the micro-, 'field particle 2 can be controlled to a specific shape. Further, it is easy to control the average value of the horizontal Freit diameter and the circularity coefficient of the particles to a specific value. Further, since the fine particles 2 are agglomerated to some extent, the average value of the width of the grain boundary of the In2〇3 parent phase without the fine particle region 5 can be controlled to 0.3/m or more. Of the above cooling steps, it has never reached 4 〇〇. The temperature range to room temperature is 320513 17 200925308, and the cooling rate is not particularly limited. In this temperature zone, essentially

Ill2〇3 in the mother phase 1 of the micro-materials Beibei 'temperature speed is suitable for the definition of 'Asia has not grown. Specifically, the drop-: speed can be appropriate, or you can adjust the cooling rate without special adjustment. Naturally cooled to room temperature. Right cold π, this m丄 well 7 τ p step, also maintain the non-oxidizing gas environment introduced in the previous step. The inert gas introduced into the furnace is usually 0.1 to 500m3 / Within the range of hours! 〇. Steps, ^ is not clear, but if the average of the above cooling steps in the oxygen environment is I: two levels of particles of the flat diameter and the circularity coefficient = =: Outside the specific range of values, there is also the difficulty in controlling the shape of the particles. For this point, the fine particles 2 are condensed in the "mystery phase ^ = body material". It is easy to precipitate in the middle and the middle, and the IT ◦ sintered body of the present invention can be obtained. ❹ ^ 2 The ITG sintered body obtained in this manner is cut into a desired shape as needed, and may be applied as a miscellaneous material after the grinding. Further, by bonding the above-mentioned IT0 sintered body to a backlng plate belonging to a cooling plate, the ribs can be obtained. At this time, the support plate is not particularly limited as long as it is generally used as a support plate for dry plating. The bonding of the 烧结0 sintered body to the support plate can be carried out by a known method, and is not particularly limited, but it is bonded by, for example, a bonding agent such as an In-weld material from the viewpoint of cost or productivity. The method is preferred. Specifically, the IT0 sintered body is cut into a desired shape as needed, 320513 18 200925308, and if necessary, after grinding, etc., 'heating to a temperature above the melting point of the In-weld material, and maintaining the temperature' can be The molten In fresh material is applied to the surface of the ΙΤ0 sintered body bonded to the support plate, bonded to the support plate, and is naturally cooled by surface pressing and cooled to room temperature to bond. The present invention will be further specifically described below based on examples, but the present invention is not limited to the examples. [Examples] [Example 1] 5 A powder of indium oxide (In2〇3) and a powder of cerium oxide (Sn〇2) were prepared in a ratio of 9 〇.10 (weight ratio), and polyvinyl alcohol (10) was added. ...咐. alcohol, PVA) as a binder for ball mill mixing. The obtained mixed powder was compression-molded at a press pressure of 8 〇〇 kg/cm 2 to obtain a molded body which was degreased in the atmosphere. The molded body obtained in this manner is placed in a phased furnace in a state where it is placed on a fired plate, and oxygen gas having an oxygen concentration of 1% by atom is passed through the inside of the furnace. (The volume in the furnace is lmV per hour), the furnace is heated to 16 ° C, and the holding time at this temperature is set to leap seconds (instantaneous) and immediately cooled to 155 (TC. Then, After 2 hours, the furnace gas was replaced with argon gas for 6 hours. At this time, the oxygen concentration in the furnace was jlU%. After that, the gas in the furnace was kept under argon and directly cooled to The IT0 sintered body was obtained at room temperature. The average heating rate of the heating step at this time was nrc/hour, and the average cooling-speed of the cooling step in the temperature range from lion to H: was 10. /hr, from 1400. The temperature drop rate of the cooling step of 320513 19 200925308 in the temperature range of 3 〇 rc is 3 〇 / hr., The firing conditions are disclosed as follows. <Burning conditions> to temperature (Oxygen environment)-&gt; (5〇.〇/hour 4〇『c_&gt; (1〇『c/hour)—80(TCx4 hours—(4〇0°c/hour 1 600〇c (instantaneous 1550 C x2) Hour—(Change to Argon Environment)—(—1 〇.(:/hour)—1400 C — (― 30〇C / hour)—30 (TC—natural cooling—room temperature ❹I was developed according to the four-probe method using a constant current voltage measuring device (Keithley: SMU236) and a measuring stand (co-developed: k_5〇4rs) and a four-probe probe (reconciliation: K89PS150#) When the volume resistivity of the obtained ΙΤ0 sintered body is measured, it is 丨34χ1〇-4ω·cm. Then 'the ΙΤ0 sintered body is horizontally oriented from the position 5mm above the sintering direction to the thickness direction. The cut surface obtained by the diamond cutter was cut, and each of the sandpapers #170, #320, #800, #1500, and #2000 was rotated by 90 degrees, and the staged grinding was performed, and finally polishing and polishing were performed. After processing into a mirror surface, '40 ° C etching solution (nitrogen (60 to 61% 7) c solution, Kanto Chemical Co., Ltd., nitric acid 1 · 38 deer grade 1 product number 28161-03), hydrochloric acid (35 0 to 37·0% aqueous solution, Kanto Chemical Co., Ltd., hydrochloric acid deer grade 1 product number 18078-01) and water mixed in a ratio of volume ratio HC1 : H2O : HN〇3 = 1 : 1 : 0. 08 Made) immersed for 9 minutes for etching' and the apparent surface is magnified by 3,000 times and 30, SEM observation (JSM-6380A: manufactured by JE0L) was performed at a magnification of 10,000. The obtained SEM image (magnification: 3000 times) was shown in Fig. 1 and the SEM image of the fine particle group portion was further enlarged (magnification: 3 0 , 0 0 0 times) is shown in Fig. 3. 20 320513 [ 200925308 From the obtained SEM image, the above-mentioned grain boundary distance is obtained without the fine particle region 5 treasure 1 method to obtain the parent phase from the ratio 2〇3, see The average degree of 佶夕 &amp; m, Yang Im〇3 parent phase grain boundary distance without fine particles *,, '" stay 1 / zm. The average value of the twist in the area is followed by the analysis of the above fine particles.

(JEM-2100F, manufactured by JEOL Ltd.) was used to observe the fine particles 2 by using FE-TEM. The spleen w acceleration voltage was set to 200kv. First, as shown in Fig. 5, the STEM image of the fine particles 2 (〇. 5x0· 5 "f horizons contains the above-mentioned fine particles. For these points, the dry analysis is performed at 6 points. The results are shown in Dijon FE-TEM affiliated bribes [Table 1]

Unit: atomic % in, Sn, and Fig. 8 This result shows that the main element detected is that the fine particle 2 is composed of such elements. The electron beam image shown in Fig. 8 is shown in Fig. 9. 320513 ΐ S i 21 200925308 Among the electronic diffraction images not shown in Fig. 9, the diffraction pattern DF from the fine particles should be 撷. The dark vision boundary image of DF is displayed on the first map. It was confirmed that this is a diffraction pattern from the fine particles 2. Furthermore, the reciprocal lattice unit including the DF is taken out, and the reciprocal lattice spacing is measured. In addition, all the crystals formed by the ICDD card are extracted. Based on such information, the substance was identified by analyzing the software (the electron beam diffraction pattern object f identification support system, manufactured by Nippon Steel Techn Research). At this time, the error of the reciprocal lattice spacing was set to 5%, and the error of the angular mobility was set to 2%. As a result, the composition of the fine particles 2 was identified as In4Sn3〇i2 of the ICDD card. / The TEM observation of the sample was carried out, and it was confirmed that there were 83 or more fine particles 2 having a three-dimensional star shape in which a needle-like projection was formed in a radial shape from the virtual center of the particle in the range of 3x4 #m2. Further, 20 of the fine particles 2 were randomly picked out, and the horizontal Freit diameter and the circularity coefficient of each particle were measured using the above-described particle analysis software. From the measured values of the obtained enthalpy, the average value of the horizontal Feret diameter and the circularity coefficient was calculated. As a result, the average value of the horizontal Freire diameter of the fine particles 2 present in the In2〇3 parent phase was 0.37 am, and the average of the circularity coefficients was 〇.6. This ιτο sputtering target was sputtered under the following conditions to form an IT film on a glass substrate (Corning: Corning #1737, 50 mm x 50 mm x 0.8 mm) at 150 °C. <Sputter conditions> Film formation conditions: Device: DC magnetron (magnetron) clock reduction device; Exhaust system: 22 320513 200925308 Cryopump, rotary pump; reaching vacuum: 3. 0xl0— 6Pa 〇 sputtering pressure: 0. 4Pa (nitrogen conversion value, Ar pressure), oxygen partial pressure: 1. 0xl (T3Pa, the obtained film was measured by X-ray diffraction, no peak was observed, and it was confirmed as Amorphous. [Reference Example 1] ΙΤ A ΙΤ0 molded body was produced in the same manner as in Example 1, and the obtained molded body was placed in a box-type furnace while being placed in a fired plate, and was placed in a furnace. Oxygen gas with a concentration of 100% oxygen (the volume of the furnace is lm3/hour per lm3) is heated to 16 〇〇〇c while maintaining the temperature at the temperature for 8 hours. When it is replaced by the atmosphere, it flows through the atmosphere (the volume of the furnace is lm3/hour per lm3), and is cooled to room temperature to obtain an I TO sintered body. The average heating rate of the heating step at this time is 117 it/hour. , © from 160 (TC to 4 〇 (the cooling step in the temperature zone of TC) The average cooling rate is 30 ° C / hour. The firing conditions are disclosed below. <Burning conditions> Room temperature - (5 ° ° c / hour) ~ 4 〇 (rc - (loot: / hour) - 800 C x 4 hours - (400 ° c / hour) - 16 〇 (pCx8 hours - &gt; (a 30 ° C / hour 3GG ° C - cooling -> room temperature (all steps are oxygen) Then, by The volume resistivity of the obtained IT0 k junction was measured by the same method as in Example ,, 丄68χ1〇-4 (Ω·咖). 23 320513 - 200925308 [Simple diagram]. The figure shows the SEM image of the sintered body of ιτο of Example 1. The second circle is a schematic diagram of the microstructure of the ίτ〇 sintered body. The f 3 figure is a SEM image showing the sintered body of the ιτο of the example. The figure is a schematic diagram showing the principle of obtaining the horizontal Freit diameter from the total number of pixels in the horizontal direction using the binary image of the binarized fine particle ^ 。. Figure 5 shows the use of binarization. The fine particle 2 ^ 'from the full pixel number of the shape of the wire to find the light of the area of the front view 第. The figure is used to indicate the use A schematic diagram of the principle of obtaining the peripheral length from the total number of pixels around the formed particles. Fig. 7 is a STEM image with fine particles 2 inside. 箄8 is a fine particle 2 The tem image is 电子 Fig. 9 is an electron diffraction image of the TEM image of Fig. 8. Fig. 10 is a dark boundary region image of the diffraction pattern DF drawn in Fig. 9. Main component symbol description

Iri2〇3 parent phase 2 grain boundary 4 no fine particle region 10 fine particles compound phase ΙΤ0 sintered body

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Claims (1)

200925308 X. Patent application scope: 1. An ITO (Indium-Tin-Oxide) sintered body is a fine particle composed of IruSmOu in the 203203 parent crystal belonging to the main crystal grain, and is characterized in that the fine particle system A three-dimensional star having a needle-like projection formed radially from a virtual center of the particle. 2. For example, the IT 〇 sintered body of the scope of the patent application, wherein the value of the bulk resistance is 1.35 χ 104 Ω·. cid or less. 3. The sintered body of the first or second aspect of the patent application, wherein the average value of the level of the Feret diameter of the fine particles is 0.25 / z m or more. 4. The IT crucible according to any one of claims 3 to 3, wherein the average of the circularity coefficients of the fine particles is less than 0.8. 5. If you apply for a patent scope! The ιτ〇 sintered body according to any one of the items 4, wherein the ΙΤ0 sintering system is a sputtering target material. ◎ 6. A ΙΤ0 sputtering target, which is characterized in that it has a sintered body of ιτο and a backing plate according to any one of the claims. . . . 7. 7. A method for producing a sintered body of ΙΤ0, which is formed by forming a mixture of indium oxide and tin oxide, and kneading the obtained shaped body to a maximum sintering temperature of 1,580 to 1,70 (rc And setting the holding time of the highest sintering temperature to 300 seconds or less 'then cooling to the second sintering temperature of 1400 to 1550t, and setting the holding time of the second sintering temperature to 3 to 18 hours' and then cooling to the chamber The temperature step is characterized in that the package 320513 25 200925308 includes: a step of setting the non-oxidizing gas environment at a time when the holding time of the second sintering temperature is at least 1 to 4 'hours, and includes: • an average cooling rate 10 to 100 ° C / hr from the highest sintering temperature to 400 ° C. 〇〇 26 320513 200925308 VII, designated representative map: (a) the representative representative of the case is: (3) map. ' (2) The symbol of the symbol of this representative figure is simple: The representative figure has no component symbol and the meaning it represents. 八 VIII. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: . Square 4320513