CN112723863A - Manufacturing method of advanced-generation TFT-grade fine-grain ITO target - Google Patents
Manufacturing method of advanced-generation TFT-grade fine-grain ITO target Download PDFInfo
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- 238000005245 sintering Methods 0.000 claims abstract description 112
- 239000000843 powder Substances 0.000 claims abstract description 93
- 238000000227 grinding Methods 0.000 claims abstract description 38
- 239000013077 target material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000005469 granulation Methods 0.000 claims abstract description 26
- 230000003179 granulation Effects 0.000 claims abstract description 26
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 239000007921 spray Substances 0.000 claims abstract description 12
- 238000000748 compression moulding Methods 0.000 claims abstract description 11
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 57
- SHTGRZNPWBITMM-UHFFFAOYSA-N oxo(oxoindiganyloxy)indigane Chemical compound O=[In]O[In]=O SHTGRZNPWBITMM-UHFFFAOYSA-N 0.000 claims description 44
- 239000012298 atmosphere Substances 0.000 claims description 43
- 235000015895 biscuits Nutrition 0.000 claims description 38
- 238000001816 cooling Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- 239000011268 mixed slurry Substances 0.000 claims description 19
- 239000002002 slurry Substances 0.000 claims description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 14
- 238000005238 degreasing Methods 0.000 claims description 13
- 238000000462 isostatic pressing Methods 0.000 claims description 13
- 229910001887 tin oxide Inorganic materials 0.000 claims description 13
- 229910003437 indium oxide Inorganic materials 0.000 claims description 12
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 4
- 238000009694 cold isostatic pressing Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010409 thin film Substances 0.000 abstract 1
- 230000007547 defect Effects 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 19
- 239000013078 crystal Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002159 abnormal effect Effects 0.000 description 4
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000009388 chemical precipitation Methods 0.000 description 2
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- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
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- 238000004544 sputter deposition Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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Abstract
The invention discloses a manufacturing method of an advanced TFT (thin film transistor) grade fine-grain ITO (indium tin oxide) target material, which comprises a powder preparation step, a mixing and grinding step, a spray granulation step, a compression molding step and a sintering molding step. The method for manufacturing the ITO target can manufacture the ITO target with large-size and high-density grains, the target density is more than 99.9 percent, and the diameter of each grain is controlled to be 3 to 5 mu m.
Description
Technical Field
The invention relates to the technical field of ITO target manufacturing, in particular to a manufacturing method of a high-generation TFT-grade fine-grain ITO target.
Background
Indium tin oxide target material, referred to as ITO target material for short, is a mixture of two metal oxides of indium oxide and tin oxide, and is sintered at high temperature to form a material with ceramic function. The ITO target sintered by tin oxide doped indium oxide can form an ITO transparent conductive film on transparent substrates such as glass and the like after vacuum magnetron sputtering coating, and is a key material necessary for the liquid crystal display panel industry.
Currently, the sintering methods available for producing ITO targets include hot pressing, hot isostatic pressing, pressure atmosphere sintering, and normal pressure sintering. The blank is formed before sintering the target material by slip casting, compression molding or isostatic pressing. The ITO target manufactured by the hot pressing method and the hot isostatic pressing method is not suitable for manufacturing large-size targets due to the limitation of the size of equipment, and the atmosphere cannot be controlled during sintering, so that the oxygen loss rate of the ITO target is higher, and the control of a sputtering coating process is not facilitated. The oxygen atmosphere pressure sintering method is to prepare the ITO target under high-purity oxygen atmosphere and certain pressure, and is beneficial to obviously accelerating the densification speed of the ITO target due to the assistance of pressure, however, the ITO target manufactured by the method has low yield and difficult large size due to the limitation of the size of manufacturing equipment. The normal pressure sintering method is a method for manufacturing an ITO target under the action of oxygen atmosphere and normal pressure. Because the method does not carry out pressure operation, the size of the manufacturing equipment can be greatly improved, and the method is suitable for manufacturing large-size ITO target materials. The slip casting process adopts wet forming, and the ITO slurry is dried in the porous water-absorbing mold and is formed under the action of the forming agent. Since the moisture content of the blank is high, a slow drying process is required to prevent cracking, the production efficiency is low, and cracking and defects are easily generated when large-size blanks are produced. The isostatic compaction is combined with a normal-pressure atmosphere sintering method, and the method has stable and controllable quality, high production efficiency and small limitation on the production of large-size targets, and is the main direction of the research on the production technology of the ITO targets at present.
The high-generation TFT liquid crystal panel puts higher requirements on the indexes of the ITO target, wherein the high density and the small grain size are beneficial to reducing the nodulation phenomenon of the target in the sputtering process, prolonging the service life of the target and obtaining more stable coating quality. The disclosed technology for producing the ITO target is generally suitable for the application requirements of TP and low-generation TFT with lower requirements.
Chinese patent CN105294072B discloses a normal pressure sintering method of a TFT grade ITO target, wherein the grain size index of the ITO target is not controlled, the highest sintering temperature is 1550 to 1650 ℃, the temperature is kept for 4 to 12 hours, and the grain size of the target is inevitably larger due to high temperature. Compared with the indium oxide powder and the tin oxide nano powder with two different particle sizes, the invention has the problems that the indium tin proportioning components are difficult to accurately control, the particle sizes of the two powders cannot be respectively controlled, and the like.
Chinese patent CN105712719B discloses a normal pressure sintering manufacturing method of a large-size high-density fine-grain ITO target, the relative density of the prepared ITO target is more than 99.5%, the grain size is 6-10 μm, and the requirements of the relative density of more than 99.7% and the grain size below 5 μm required by the high-generation TFT grade ITO target cannot be met.
Chinese patent CN107010940A discloses a method for preparing ITO sputtering target for TFT-LCD by controlling oxygen content, which only focuses on the control of the oxygen content of ITO target material, and does not describe and control the grain size index of the target material. The alloy gasification method adopted by the method has the risks of insufficient metal oxidation and uneven components, and in addition, the sintering needs to be carried out in an oxygen pressure atmosphere, so that the method has high requirements on sintering equipment.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for manufacturing an advanced TFT grade fine grain ITO target material, which comprises the following steps,
1) powder preparation, namely respectively preparing indium oxide nano powder and tin oxide nano powder, wherein the indium oxide nano powder is set to have the D50 of less than 200nm and the BET of more than or equal to 12m2The tin oxide nano powder is set to have D50 less than 150nm and BET more than or equal to 15m2(ii)/g, the Cl ion content in both the indium oxide nanopowder and the tin oxide nanopowder is less than 5 ppm;
2) a mixing and grinding step, namely weighing indium oxide nano powder and tin oxide nano powder in a set proportion respectively, adding the indium oxide nano powder and the tin oxide nano powder into water to mix to form mixed slurry, grinding the mixed slurry, detecting the dispersed particle size of the mixed slurry, and stopping grinding when the D50 of the mixed slurry is less than or equal to 0.25 mu m to obtain ground slurry;
3) spray granulation, namely performing spray drying granulation on the grinding slurry to obtain ITO granulation powder with D50 of 8-12 mu m;
4) a step of compression molding, in which ITO granulated powder is subjected to compression molding to obtain an ITO biscuit with the relative density of more than 62%;
5) and sintering and forming, namely placing the ITO biscuit in a pure oxygen normal pressure atmosphere sintering furnace, degreasing and sintering the ITO biscuit integrally to complete sintering and forming, setting the highest sintering temperature range at 1500-1550 ℃, keeping the temperature of the ITO biscuit in the highest sintering temperature range for less than 12 hours, stopping introducing oxygen in the furnace in a cooling stage, and introducing air or inert gas atmosphere instead to obtain the fine-grain ITO target.
Further, in the sintering and forming step, the sintering of the ITO biscuit comprises a degreasing stage, a sintering stage and a cooling stage,
in the degreasing stage, the temperature rise speed in the sintering furnace is set to be 0.2-0.8 ℃/min, the temperature is raised from the normal temperature to 500 ℃, the temperature is kept for 6-12 hours, and the atmosphere in the sintering furnace is set to be air;
a firing stage, wherein the firing stage comprises a first firing stage and a second firing stage, the first firing stage is that the temperature rise speed in the sintering furnace is set to be 0.2-0.8 ℃/min, the temperature rises from 500 ℃ to 1000 ℃, the temperature is kept for 3-8 hours, the atmosphere in the sintering furnace is set to be pure oxygen, the second firing stage is that the temperature rise speed in the sintering furnace is set to be 2-3 ℃/min, the temperature rises from 1000 ℃ to 1500-;
and in the temperature reduction stage, the temperature reduction speed in the sintering furnace is set to be 1-1.5 ℃/min, the temperature is reduced from 1500-1550 ℃ to room temperature, the introduction of oxygen into the sintering furnace is stopped, and the atmosphere in the sintering furnace is set to be inert gas or air.
Further, in the firing stage, the concentration of pure oxygen in the sintering furnace is set to be 99.5%, and in the cooling stage, when the temperature in the sintering furnace is reduced to 500 ℃, the introduction of air or inert gas into the sintering furnace is stopped.
Further, in the powder preparation step, indium oxide powder and tin oxide powder with the purity of more than 99.99% are respectively selected and subjected to high-temperature calcination and rapid cooling treatment at 600-800 ℃ to obtain the indium oxide nano powder and the tin oxide nano powder.
Further, in the powder preparation step, the indium oxide nanopowder BET is set to 12 to 15m2Per g, BET setting of the tin oxide nanopowderIs 15 to 20m2/g。
Further, in the mixing and grinding step, grinding is stopped when the dispersed particle diameter D50 of the particle size of the mixed slurry is detected to be 0.15 to 0.25 μm, and the grinding slurry is obtained.
Further, in the step of press forming, when the planar target is manufactured, the ITO granulated powder is subjected to mould pressing at 40-80MPa, and then isostatic pressing is carried out under the pressure of 200-380 MPa;
when the rotary target is manufactured, ITO granulation powder is put into a flexible sheath for cold isostatic pressing under the pressure of 200-380 MPa.
Further, in the press molding step, when the flat target is manufactured, a dwell time for press molding is set to 90 to 120 seconds, a dwell time for isostatic pressing is set to 180 to 300 seconds,
the dwell time for isostatic pressing is set at 300 to 600 seconds when manufacturing the rotary target.
Further, in the mixing and grinding step, the indium oxide nano powder and the tin oxide nano powder are respectively weighed according to the weight ratio of 9:1, and the weighed indium oxide nano powder and tin oxide nano powder are added into pure water with a dispersing agent, a bonding agent and a defoaming agent to form the mixed slurry.
Furthermore, the target density of the fine-grain ITO target is more than 99.9 percent, the average grain diameter is controlled to be 3-5 mu m, and the maximum size of the single-chip fine-grain ITO target is not less than 1500mm multiplied by 210mm multiplied by 8 mm.
Compared with the prior art, the invention has the advantages that:
1. in the powder preparation step, the indium oxide nano powder and the tin oxide nano powder are respectively prepared, so that the component ratio between the indium oxide nano powder and the tin oxide nano powder is more accurate, adjustable and controllable. Meanwhile, indium oxide nano powder and tin oxide nano powder with different specific surface areas are selected for matching, so that the sintering activity of the powder is improved, the sintering temperature is effectively reduced, and the heat preservation time is shortened.
2. In the present invention, by selecting a polishing slurry having a dispersion particle diameter D50 as a value in the mixing and polishing step and an ITO granulating powder having a dispersion particle diameter D50 as a value in the spray granulation, it is possible to obtain an ITO green compact having high density, high uniformity and low molding defects in the press molding step while maintaining the sintering activity of the powder.
3. In the sintering and forming step of the invention, the ITO biscuit with high density, high uniformity and low forming defect is sintered by setting a special sintering curve to obtain the ITO target with the target density of more than 99.9 percent and the average grain of 3 to 5 mu m.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is an SEM photograph of high-generation TFT grade fine-grained ITO target grains of the present invention.
Detailed Description
The following are merely preferred embodiments of the present invention, and do not limit the scope of the present invention.
A manufacturing method of an advanced-generation TFT-grade fine-grain ITO target comprises the following steps:
1) powder preparation, namely respectively preparing indium oxide nano powder and tin oxide nano powder, wherein the indium oxide nano powder is set to have the D50 of less than 200nm and the BET of more than or equal to 12m2The tin oxide nano powder is set to have D50 less than 150nm and BET more than or equal to 15m2(ii)/g, the Cl ion content in both the indium oxide nanopowder and the tin oxide nanopowder is less than 5 ppm; the indium oxide nano powder and the tin oxide nano powder are prepared respectively, so that the indium tin component ratio between the indium oxide nano powder and the tin oxide nano powder is more accurate, the particle size matching problem between the two powders can be controlled respectively, and the preparation method is more adjustable and controllable. In the powder preparation stage, the Cl ion content in the indium oxide nano powder and the tin oxide nano powder is respectively controlled, so that the sintering density of the target material is improved, and abnormal growth of crystal grains is inhibited. Specifically, in the powder preparation step, indium oxide powder and tin oxide powder with the purity of more than 99.99% are respectively selected and subjected to chemical precipitation, high-temperature calcination at 600-800 ℃ and rapid cooling treatment to obtain the indium oxide nano powder and the tin oxide nano powder. More specifically, oxidationThe indium powder and the tin oxide powder are respectively treated by nitric acid dissolution, ammonia gas neutralization and chemical precipitation, high-temperature calcination and rapid cooling. The indium oxide powder and the tin oxide powder are subjected to high-temperature calcination and rapid cooling treatment, so that the initial crystal grain defect can be effectively eliminated, and the sintering activity of the powder is improved. Preferably, in the 1) powder preparation step, the indium oxide nanopowder BET is set to 12 to 15m2(ii)/g, the tin oxide nanopowder BET is set to 15 to 20m2(ii) in terms of/g. The specific surface area is the sum of all the surface areas of the particles which can contact air, the larger the specific surface area of the powder is, the higher the sintering activity of the powder is, and the indium oxide nano powder and the tin oxide nano powder with larger BET values are respectively selected, so that the sintering temperature and the heat preservation time in the sintering and forming step can be effectively reduced.
FIG. 1 shows: the high-generation TFT grade fine grain ITO target material has uniform grain size, no abnormal large grain exists, tin-rich secondary phase is uniformly distributed at the grain boundary, the average grain size of the target material is 3-5 mu m, and the maximum grain size is less than 8 mu m.
As shown in table 1.1, in the powder preparation step, powders with different cl ion contents are selected for testing, and size data of the largest grains in the final ITO target is obtained.
| Content of Cl ion | 1ppm | 3ppm | 5ppm | 10ppm | 20ppm |
| ITO target material crystalAbnormal growth rate of grains (%) | 1.2 | 1.5 | 4.5 | 7.3 | 9.6 |
| Sintered density of ITO target (%) | 99.93 | 99.92 | 99.83 | 99.72 | 99.68 |
| Average diameter (μm) of crystal grains of ITO target | 4.2 | 4.3 | 4.8 | 6.5 | 8.9 |
As can be seen from the data in table 1.1, since the melting point of the compound combining Cl ions and indium tin is low, it is easier to fuse crystal grains at the grain boundary to cause abnormal growth of crystal grains, and chloride is unstable when sintered at high temperature, and is easy to volatilize, and defects such as pores are formed to reduce the target density, when the Cl ion content is less than 5ppm, the abnormal growth rate of crystal grains of the ITO target is low and the sintering density of the ITO target is high.
2) A mixing and grinding step, namely weighing indium oxide nano powder and tin oxide nano powder in a set proportion respectively, adding the indium oxide nano powder and the tin oxide nano powder into water to mix to form mixed slurry, grinding the mixed slurry, detecting the dispersed particle size of the mixed slurry, and stopping grinding when the D50 of the mixed slurry is less than or equal to 0.25 mu m to obtain ground slurry; preferably, in the 2) mixing and grinding step, grinding is stopped when the dispersed particle diameter D50 of the particle size of the mixed slurry is detected to be 0.1 to 0.25 μm, so as to obtain the grinding slurry. More specifically, in the step 2) of mixing and grinding, the indium oxide nanopowder and the tin oxide nanopowder are respectively weighed according to the weight ratio of 9:1, and the weighed indium oxide nanopowder and tin oxide nanopowder are added into pure water with a dispersant, a binder and a defoaming agent to form the mixed slurry. In the step, the grinding slurry with the dispersion particle size D50 in the set numerical range is selected, so that the indium oxide nano powder and the tin oxide nano powder can be mixed and dispersed more uniformly, and meanwhile, the density of the ITO biscuit and the sintering activity of the powder can be improved in the subsequent 4) pressing and forming step.
Table 1.2, in the step of mixed grinding, grinding slurries with different D50 values were selected to obtain different values of the relative density of the ITO biscuit, the molding defect and the average diameter of the grains of the ITO target.
As can be seen from Table 1.2, the D50 of the mixed slurry during the mixing and grinding step, if too low, results in a decrease in biscuit density and an increase in molding defects. If D50 is too high, the green density will be increased, but the reduction in powder uniformity leads to increased formation defects and reduced sintering activity. Both of these conditions result in a decrease in the sintered density of the target and an increase in the average grain size. D50 of 0.15 mu m or less and 0.25 mu m or less are the best conditions for obtaining the balance of density and grain size.
3) Spray granulation, namely performing spray drying granulation on the grinding slurry to obtain ITO granulation powder with D50 of 8-12 mu m; in the step, the ITO granulated powder with the D50 of 8-12 mu m is selected, so that the ITO granulated powder has better fluidity, and the method is favorable for improving the density of an ITO biscuit, improving the sintering activity of powder, reducing defects in a formed biscuit and improving the uniformity of the biscuit in the subsequent 4) compression forming step.
Table 1.3, in the spray granulation step, ITO granulation powders with different D50 values were selected to obtain different values of the relative density of the ITO biscuit, the molding defect, and the average diameter of the grains of the ITO target.
As can be seen from table 1.3, in the spray granulation step, when D50 of the ITO granulated powder is 8-12 μm, the ITO granulated powder has high relative density when made into an ITO biscuit, which can reach 62% or more, due to good particle size uniformity and good fluidity; the forming defect rate of the ITO biscuit is low, and the average grain diameter of the ITO target material reaches 3-5 mu m.
In the spray granulation step, when the D50 of the ITO granulated powder is 2-6 μm, the bulk density of the granulated powder is reduced, so that the powder is fluffy, and the relative density of the ITO granulated powder is lower when the ITO granulated powder is prepared into an ITO biscuit; because the granularity of the granulated powder is not uniform, the forming defect rate of the ITO biscuit is higher; and the grains are not uniformly grown during sintering, so that the average diameter of the grains of the ITO target material is larger and can only reach 6 to 9 mu m.
In the spray granulation step, when the D50 of the ITO granulated powder is 20-30 μm, the ITO granulated powder has lower relative density when being made into an ITO biscuit because the granules are larger and are difficult to compress and compact; due to the reduction of roundness and poor fluidity caused by large particles, the forming defect rate of the ITO biscuit is higher; due to the problems of density reduction, defects and nonuniformity of the biscuit, the average diameter of the crystal grains of the ITO target material is larger and can only reach 7 to 10 mu m.
4) A step of compression molding, in which ITO granulated powder is subjected to compression molding to obtain an ITO biscuit with the relative density of more than 62%; specifically, when the planar target is manufactured, the ITO granulation powder is subjected to mould pressing at 40-80MPa, the pressure is set to be 200-380 MPa, isostatic pressing is carried out, the pressure holding time of the mould pressing is set to be 90-120 seconds, and the pressure holding time of the isostatic pressing is set to be 180-300 seconds;
when the rotary target is manufactured, ITO granulated powder is put into a flexible sheath for cold isostatic pressing at a pressure of 200 to 380MPa, and the pressure maintaining time of isostatic pressing is set to 300 to 600 seconds when the rotary target is manufactured.
Because the set value intervals are selected for the slurry granularity in the step 2) of mixing and grinding and the D50 of the ITO granulating powder in the step 3) of spray granulation, the ITO biscuit with high density, high uniformity and low forming defects is obtained in the step 4) of press forming, and the forming defects comprise defects such as air holes, microcracks or warping deformation.
5) And sintering and forming, namely placing the ITO biscuit in a pure oxygen normal pressure atmosphere sintering furnace, degreasing and sintering the ITO biscuit integrally to complete sintering and forming, setting the highest sintering temperature range at 1500-1550 ℃, keeping the temperature of the ITO biscuit in the highest sintering temperature range for less than 12 hours, stopping introducing oxygen in the furnace in a cooling stage, and introducing air or inert gas atmosphere instead to obtain the fine-grain ITO target. In the step of preparing the powder, the initial crystal grain defects are eliminated in the stage of preparing the powder, the sintering activity of the powder is improved, and D50 is less than 150nm and BET is more than 12m2The sintering activity of the powder in the numerical range is high, the sintering temperature in the sintering and molding step can be effectively reduced, and the heat preservation time can be shortened. The finer nanopowder also reduces the starting point of grain growth during sintering, making the sintered ITO grains smaller. The indium oxide nano powder and the tin oxide nano powder are fully and uniformly mixed by controlling the powder preparation step and the mixing and grinding step, and the particle size distribution range of the powder is centralized. In the mixing and grinding step, the dispersion particle size D50 of the grinding slurry is controlled to be less than or equal to 0.25 mu m, and in the spray granulation step, ITO granulation powder with the particle size D50 being 8-12 mu m is selected, so that the density of an ITO biscuit is respectively improved, meanwhile, the ITO granulation powder has better fluidity, and the molding defects can be effectively reduced. An ITO biscuit with high density, high uniformity and low molding defects is obtained in the step of compression molding. In the sintering and forming step, the ITO biscuit with high density, high uniformity and low forming defect is sintered to finally obtain the ITO target with the target density of more than 99.9 percent and the average grain size of 3-5 mu m, and the ITO targetThe size of the single target of the plane target reaches 1500mm 210mm 8mm at most.
Specifically, in the sintering and forming step, the sintering of the ITO biscuit comprises a degreasing stage, a sintering stage and a cooling stage.
In the degreasing stage, the temperature rise speed in the sintering furnace is set to be 0.2-0.8 ℃/min, the temperature is raised from the normal temperature to 500 ℃, the temperature is kept for 6-12 hours, and the atmosphere in the sintering furnace is set to be air;
a sintering stage, wherein the sintering stage comprises a first sintering stage and a second sintering stage, the first sintering stage is that the temperature rise speed in a sintering furnace is set to be 0.2-0.8 ℃/min, the temperature rises from 500 ℃ to 1000 ℃, the temperature is kept for 3-8 hours, the atmosphere in the sintering furnace is set to be pure oxygen, the second sintering stage is that the temperature rise speed in the sintering furnace is set to be 2-3 ℃/min, the temperature rises from 1000 ℃ to 1500-;
and in the temperature reduction stage, the temperature reduction speed in the sintering furnace is set to be 1-1.5 ℃/min, the temperature is reduced from 1500-1550 ℃ to room temperature, the introduction of oxygen in the sintering furnace is stopped, the atmosphere in the sintering furnace is set to be inert gas or air, and the introduction of air or inert gas in the sintering furnace is stopped when the temperature in the sintering furnace is reduced to 500 ℃.
Table 1.4 shows the average grain size and target density of the final ITO target by selecting different heating rates and sintering atmospheres in the sintering step.
The first scheme is as follows: is the sintering rate of the present invention.
Scheme II: sintering at a lower heating or cooling rate, except for the heating rate and atmosphere, and the other conditions are the same as in the first scheme.
The third scheme is as follows: sintering at a higher heating or cooling rate, except for the heating rate and atmosphere, and the other conditions are the same as in the first scheme.
In the first scheme, a lower heating rate of 0.2-0.8 ℃/min is adopted in the degreasing stage, the temperature is raised from the normal temperature to 500 ℃ in the atmosphere of air, and the temperature is kept for 6-12 hours, so that the forming adhesive can be fully removed in the lower heating rate, and the target material is prevented from cracking due to insufficient degreasing or severe degreasing; in the first stage of sintering, the temperature is raised from 500 deg.C to 1000 deg.C in oxygen atmosphere at a low temperature raising rate of 0.2-0.8 deg.C/min for 3-8 hr to make the crystal grain state of the target material develop uniformly in the initial growth stage and form initial crystal nucleus with uniform size. On the basis, the temperature rise rate of the firing stage is increased to 2-3 ℃/min, the temperature is increased from 1000 ℃ to 1500-1550 ℃ in the atmosphere of oxygen and is kept for 6-12 hours, so that the target material is rapidly sintered and densified, high density is rapidly obtained, excessive and uneven growth of crystal grains is prevented, the temperature is reduced from 1500-1550 ℃ to 500 ℃ in the atmosphere of inert gas or air at the temperature reduction speed of 1-1.5 ℃/min, ventilation is stopped, the temperature is reduced to room temperature at the same temperature reduction speed, and the ITO target material with the target material density of more than 99.9% and the average crystal grain of 3-5 mu m is finally obtained.
In the second scheme, the overall heating rate is slow, so that the time for growing the crystal grains is too long, the average crystal grain size is increased, and the target material is over-burnt to cause the target material density to be reduced.
In the third scheme, the whole temperature rise rate is high, so that the sintering process of the target material is insufficient, the density of the target material is obviously reduced, and meanwhile, the target material cracks due to the fact that the temperature rise is too high in the low-temperature degreasing stage.
In the process technology, the powder is respectively subjected to special treatment through the powder preparation step, the mixing grinding step and the spray granulation step to finally obtain the ITO granulated powder with more uniform and finer granularity, and simultaneously, the fluidity and the forming performance of the powder are effectively improved, so that ITO biscuit with lower defects and uniformity is obtained in the compression forming step, and then the unique firing curve in the sintering forming step is combined to finally obtain the large-size ITO target with high density, small crystal grains and high yield.
Example 1:
in the powder preparation step, indium oxide nanopowder and tin oxide nanopowder, two kinds of which are prepared separatelyThe purity of the powder is more than 99.99 percent, and the indium oxide powder and the tin oxide powder are respectively calcined at 750 ℃ and rapidly cooled to obtain indium oxide nano powder and tin oxide nano powder. Specific surface area BET of indium oxide nanopowder of 14.2m2(ii)/g, specific surface area BET of tin oxide nanopowder is 17.8m2(ii) in terms of/g. 22.5kg of indium oxide nanopowder and 2.5kg of tin oxide nanopowder are weighed and added into pure water with a dispersant, a binder and a defoaming agent, a sand mill is started for grinding, the grinding is stopped when the granularity D50 of the slurry is detected to be 0.22 mu m, spray drying and granulation are carried out, and the granularity D50 of the granulated powder is detected to be 10.4 mu m. And (3) performing compression molding on the granulated powder by using a 2000 mm-290 mm mold under the pressure of 50MPa for 90s, filling the molded blank into a flexible sheath, sealing, and then performing compression in an isostatic press under the pressure of 350MPa for 300s, wherein the density of the biscuit is measured to be 62.3%. And (3) putting the blank subjected to isostatic pressing into a normal-pressure atmosphere sintering furnace, heating to 500 ℃ at a heating rate of 0.3 ℃/min, and keeping the temperature for 8 hours, wherein the atmosphere in the furnace is air. Then the temperature is raised to 1000 ℃ at the heating rate of 0.5 ℃/min, the temperature is kept for 6 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then the temperature is raised to 1535 ℃ at the temperature rise speed of 2 ℃/min, the temperature is kept for 10 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then cooling to room temperature at a cooling rate of 1.5 ℃/min, wherein the atmosphere in the furnace is nitrogen, and stopping ventilation at the temperature below 500 ℃. And cooling to room temperature, and discharging the product. The density of the sintered ITO target material is 99.91 percent, the average crystal grain is 4.6 mu m, the machinable size of the target material is 1508 × 213 × 8mm, and the requirement of the G11TFT plane ITO target material can be met.
Example 2:
respectively preparing indium oxide nano powder and tin oxide nano powder, wherein the purity of the two powders is more than 99.99 percent, calcining the indium oxide powder and the tin oxide powder at 825 ℃, and rapidly cooling, wherein the specific surface area BET of the indium oxide nano powder is 13.5m2Specific surface area BET of tin oxide nanopowder of 16.7 m/g2(ii) in terms of/g. Weighing 22.5kg indium oxide powder and 2.5kg tin oxide powder, adding into pure water containing dispersant, binder and defoaming agent, grinding with sand mill, detecting slurry particle size D50 ═ 0.24 μm, stopping grinding, spray drying and granulating, detecting granulating powder particle size D50 ═ 10.8 μmAnd m is selected. And (3) performing compression molding on the granulated powder by using a 1310 x 288mm mold under the pressure of 50MPa for 90s, filling the molded blank into a flexible sheath for sealing, and then performing compression in an isostatic press under the pressure of 350MPa for 300s, wherein the density of the biscuit is measured to be 62.5%. And (3) putting the blank subjected to isostatic pressing into a normal-pressure atmosphere sintering furnace, heating to 500 ℃ at a heating rate of 0.4 ℃/min, and keeping the temperature for 8 hours, wherein the atmosphere in the furnace is air. Then the temperature is raised to 1000 ℃ at the heating rate of 0.5 ℃/min, the temperature is kept for 8 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then the temperature is raised to 1545 ℃ at the temperature raising speed of 2.5 ℃/min, the temperature is kept for 9 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then cooling to room temperature at a cooling rate of 1.5 ℃/min, wherein the atmosphere in the furnace is nitrogen, and stopping ventilation at the temperature below 500 ℃. And cooling to room temperature, and discharging the product. The sintered ITO target has a density of 99.92% and an average grain size of 4.5 μm, and the target can be machined to a size of 1002 × 212 × 8mm, which can meet the requirements of G8.5TFT planar ITO targets.
Example 3:
respectively preparing indium oxide nano powder and tin oxide nano powder, wherein the purity of the two powders is more than 99.99 percent, calcining the indium oxide powder and the tin oxide powder at 850 ℃, and rapidly cooling, wherein the specific surface area BET of the indium oxide nano powder is 12.5m2Specific surface area BET of 18.6 m/g of tin oxide nanopowder2(ii) in terms of/g. 27kg of indium oxide powder and 3kg of tin oxide powder were weighed, added to pure water containing a dispersant, a binder and a defoaming agent, ground by a sand mill, and spray-dried and granulated, and the particle size D50 of the granulated powder was 11.6 μm, with the detection of the particle size D50 of 0.24 μm. And (3) filling the granulated powder into a tubular silica gel flexible sheath, sealing, and pressing in an isostatic press under the pressure of 380MPa for 600s to obtain a biscuit with the density of 62.6%. And (3) putting the blank subjected to isostatic pressing into a normal-pressure atmosphere sintering furnace, heating to 500 ℃ at a heating rate of 0.2 ℃/min, and keeping the temperature for 10 hours, wherein the atmosphere in the furnace is air. Then the temperature is raised to 1000 ℃ at the heating rate of 0.4 ℃/min, the temperature is kept for 8 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then the temperature is raised to 1550 ℃ at the heating rate of 3 ℃/min, the temperature is kept for 12 hours, and the atmosphere in the furnace is 99.5 percent pure oxygen. Then cooling to room temperature at a cooling rate of 1.0 ℃/min, and heating in a furnaceThe atmosphere was argon, and the aeration was stopped at 500 ℃ or lower. And cooling to room temperature, and discharging the product. The density of the sintered ITO rotary target material is 99.92 percent, the average crystal grain is 4.8 mu m, the machining size of the target material is ID135 OD 153H 450mm, and the requirement of splicing 6 sections of the G8.5TFT rotary ITO target material can be met.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (10)
1. A manufacturing method of an advanced-generation TFT-grade fine-grain ITO target is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
1) powder preparation, namely respectively preparing indium oxide nano powder and tin oxide nano powder, wherein the indium oxide nano powder is set to have the D50 of less than 200nm and the BET of more than or equal to 12m2The tin oxide nano powder is set to have D50 less than 150nm and BET more than or equal to 15m2(ii)/g, the Cl ion content in both the indium oxide nanopowder and the tin oxide nanopowder is less than 5 ppm;
2) a mixing and grinding step, namely weighing indium oxide nano powder and tin oxide nano powder in a set proportion respectively, adding the indium oxide nano powder and the tin oxide nano powder into water to mix to form mixed slurry, grinding the mixed slurry, detecting the dispersed particle size of the mixed slurry, and stopping grinding when the D50 of the mixed slurry is less than or equal to 0.25 mu m to obtain ground slurry;
3) spray granulation, namely performing spray drying granulation on the grinding slurry to obtain ITO granulation powder with D50 of 8-12 mu m;
4) a step of compression molding, in which ITO granulated powder is subjected to compression molding to obtain an ITO biscuit with the relative density of more than 62%;
5) and sintering and forming, namely placing the ITO biscuit in a pure oxygen normal pressure atmosphere sintering furnace, degreasing and sintering the ITO biscuit integrally to complete sintering and forming, setting the highest sintering temperature range at 1500-1550 ℃, keeping the temperature of the ITO biscuit in the highest sintering temperature range for less than 12 hours, stopping introducing oxygen in the furnace in a cooling stage, and introducing air or inert gas atmosphere instead to obtain the fine-grain ITO target.
2. The method for manufacturing the advanced TFT grade fine grain ITO target material according to claim 1, wherein: in the sintering and forming step, the sintering of the ITO biscuit comprises a degreasing stage, a sintering stage and a cooling stage,
in the degreasing stage, the temperature rise speed in the sintering furnace is set to be 0.2-0.8 ℃/min, the temperature is raised from the normal temperature to 500 ℃, the temperature is kept for 6-12 hours, and the atmosphere in the sintering furnace is set to be air;
a firing stage, wherein the firing stage comprises a first firing stage and a second firing stage, the first firing stage is that the temperature rise speed in the sintering furnace is set to be 0.2-0.8 ℃/min, the temperature rises from 500 ℃ to 1000 ℃, the temperature is kept for 3-8 hours, the atmosphere in the sintering furnace is set to be pure oxygen, the second firing stage is that the temperature rise speed in the sintering furnace is set to be 2-3 ℃/min, the temperature rises from 1000 ℃ to 1500-;
and in the temperature reduction stage, the temperature reduction speed in the sintering furnace is set to be 1-1.5 ℃/min, the temperature is reduced from 1500-1550 ℃ to room temperature, the introduction of oxygen into the sintering furnace is stopped, and the atmosphere in the sintering furnace is set to be inert gas or air.
3. The method for manufacturing the advanced TFT grade fine grain ITO target material according to claim 2, wherein: in the sintering stage, the concentration of pure oxygen in the sintering furnace is set to be 99.5%, and in the cooling stage, when the temperature in the sintering furnace is reduced to 500 ℃, air or inert gas is stopped to be introduced into the sintering furnace.
4. The method for manufacturing the advanced TFT grade fine grain ITO target material of claim 3, wherein: in the powder preparation step, indium oxide powder and tin oxide powder with the purity of more than 99.99 percent are respectively selected and subjected to high-temperature calcination and rapid cooling treatment at 600-800 ℃ to obtain the indium oxide nano powder and the tin oxide nano powder.
5. A shank as set forth in claim 4The manufacturing method of the generation TFT grade fine grain ITO target material is characterized in that: in the powder preparation step, the indium oxide nanopowder BET is set to 12 to 15m2(ii)/g, the tin oxide nanopowder BET is set to 15 to 20m2/g。
6. The method for manufacturing the advanced TFT grade fine grain ITO target material of claim 5, wherein: in the mixed grinding step, grinding is stopped when the dispersed particle diameter D50 of the particle size of the mixed slurry is detected to be 0.15 to 0.25 μm, and the grinding slurry is obtained.
7. The method for manufacturing the advanced TFT grade fine grain ITO target material of claim 6, wherein: in the step of press forming, when the plane target is manufactured, the ITO granulation powder is subjected to mould pressing at 40-80MPa, and then isostatic pressing is carried out under the pressure of 200-380 MPa;
when the rotary target is manufactured, ITO granulation powder is put into a flexible sheath for cold isostatic pressing under the pressure of 200-380 MPa.
8. The method for manufacturing the advanced TFT grade fine grain ITO target material of claim 7, wherein: in the press molding step, a dwell time for press molding is set to 90 to 120 seconds, a dwell time for isostatic pressing is set to 180 to 300 seconds,
the dwell time for isostatic pressing is set at 300 to 600 seconds when manufacturing the rotary target.
9. The method for manufacturing the advanced TFT grade fine-grained ITO target according to claim 8, wherein: and in the mixing and grinding step, the indium oxide nano powder and the tin oxide nano powder are respectively weighed according to the weight ratio of 9:1, and the weighed indium oxide nano powder and tin oxide nano powder are added into pure water with a dispersing agent, an adhesive and a defoaming agent to form the mixed slurry.
10. The method for manufacturing the advanced TFT grade fine-grained ITO target according to claim 9, wherein: the target density of the fine-grain ITO target is more than 99.9 percent, the average grain diameter is controlled to be 3-5 mu m, and the maximum size of the single-chip fine-grain ITO target is not less than 1500mm multiplied by 210mm multiplied by 8 mm.
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| CN114873992A (en) * | 2022-05-10 | 2022-08-09 | 芜湖映日科技股份有限公司 | Preparation method of ITO target with high indium content |
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| CN115872734A (en) * | 2022-10-27 | 2023-03-31 | 先导薄膜材料（广东）有限公司 | ITO powder reproduced from ITO waste target, high-density target and preparation method thereof |
| CN115894009A (en) * | 2022-11-14 | 2023-04-04 | 先导薄膜材料（广东）有限公司 | Rapid sintering and degreasing method for ITO (indium tin oxide) planar target and supporting plate used by rapid sintering and degreasing method |
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