CN102153352B - Composite adhesive and application thereof in preparation of sintering target - Google Patents
Composite adhesive and application thereof in preparation of sintering target Download PDFInfo
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- CN102153352B CN102153352B CN201010593657.5A CN201010593657A CN102153352B CN 102153352 B CN102153352 B CN 102153352B CN 201010593657 A CN201010593657 A CN 201010593657A CN 102153352 B CN102153352 B CN 102153352B
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- polyvinyl alcohol
- sintering
- target
- binding agent
- thermal debinding
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Abstract
The invention relates to composite adhesive, which mainly consists of the following three components: pure water or deionized water, polyvinyl alcohol and polyethylene glycol, wherein the selected molecular weight of the polyethylene glycol is 800 to 2,000, and the selected molecular weight of the polyvinyl alcohol is 800 to 10,000; and in the formula of the adhesive, the volume ratio of the polyethylene glycol to the polyvinyl alcohol is 1:9, and the weight content of the polyvinyl alcohol in the water is 1 to 5 percent. An application method of the adhesive is characterized in that: the adhesive is added into AZO powder, grease is mixed to form a formed block, and the grease mixed polyvinyl alcohol and polyethylene glycol account for 1 to 10 percent of the whole mass. The defects of micro cracks, micro pores and high carbon residue during single thermal degreasing can be well overcome. By a subsequent sintering process, the sintering density of the target can be improved, and the density of each part of the target is the same.
Description
Technical field
The invention belongs to field of photovoltaic materials, relate to a kind of compound binding agent and the application on preparation sintering target thereof.
Background technology
Along with the fast development of electronics and information industry, photovoltaic industry and building energy saving industry, membrane science application is increasingly extensive.
Magnetron sputtering method is one of major technique preparing thin-film material, the starting material of sputter-deposited thin films are exactly target, the film density plated out on magnetron sputter by target is high, tack good, and target has been one of mainstay industry of microelectronic industry, photovoltaic industry, building energy conservation coated glass industry etc.
Target shape has rectangle, square, circular, right cylinder and irregularly shaped, and the performance of target has influence on the performance that it makes film to a great extent.High performance target will lean on good sintering process to ensure.The sintering method of target has a variety of, comprises normal pressure-sintered (or minute-pressure sintering), hot pressed sintering, HIP sintering, discharge plasma sintering etc.HIP sintering and discharge plasma sintering process complexity, required equipment cost is high, and sintering target size is little; Hot pressed sintering, equipment is more expensive, and technique is simple, but sintering target size is little, and graphite jacket can pollute target.Normal pressure-sintered (or minute-pressure sintering) technique is comparatively simple, and cost is low, and can sinter large size target, is the common method sintering now target.
The performance requriements of target is very strict, general chemical purity must reach 99.9% and more than, electroconductibility will be got well, and sintered density wants high, and crystal grain is tiny.General provision relative density more than 94% is high density target, and relative density more than 98% is super-high density target.The difficult point of target sintering preparation improves sintered density exactly.When sintered density is not high, target inner aperture is more, and this micropore is very large on sputter coating impact, target material surface " poisoning " when it can cause sputtering, i.e. dross, and surface-discharge when causing sputtering, the film uniformity simultaneously plated out just declines greatly.Not increasing crystal grain again while improving sintered density, is one of direction of each target producer tackling key problem now.
The general production technique of present sintering target is: powder adds a kind of binding agent, coldmoulding, or carries out the density of isostatic cool pressing secondary again, then sinters in sintering oven after thermal debinding.The shortcoming of existing technique is: single binding agent, for keeping shaping rear intensity, needs to add more binding agent; When after coldmoulding, (or after the density of secondary isostatic cool pressing) carries out thermal debinding, owing to being heated inside and outside the binding agent in forming blocks simultaneously, the binding agent decomposes of outside can comparatively fast be deviate from, and the binding agent of inside is not opened completely because decomposes deviates from external hole, thus occur that the inner partial pressure of forming blocks is large, generate tiny crack and micropore, simultaneously inner after thermal debinding have a large amount of carbon to remain.Occur that both of these case all can cause follow-up sintering defect, tiny crack is not easy healing, causes target density low, block density skewness; Carbon remains when can cause sintering and oxide target material reaction, generates CO
2with CO gas, gas is difficult to all discharge block, causes the not high and density unevenness of sintered density.
Chinese patent CN101440470A, adopt chemical coprecipitation to prepare zinc oxide aluminium powder, then adopt the method for vacuum hotpressing to be incubated 2-5 hour at 1200 DEG C-1400 DEG C, sintering prepares the AZO target that relative density is not less than 95%.Chinese patent CN101285164A discloses a kind of transparent conductive film and prepares AZO target used, the preparation method of electrically conducting transparent membrane preparation method and transparency conductive electrode, only propose composition and the film coating method of AZO target, the preparation method of AZO target is not provided.
Summary of the invention
The defect that the object of the invention is to overcome prior art provides a kind of compound binding agent, and prepares the method for sintering target with this binding agent.
The present invention realizes according to following proposal:
A kind of compound binding agent, is formed primarily of three kinds of compositions: pure water or deionized water, polyvinyl alcohol and polyoxyethylene glycol; Wherein molecular weight chosen by polyoxyethylene glycol is 800-2000, and molecular weight chosen by polyvinyl alcohol is 800-10000, and caking agent formula is: polyoxyethylene glycol volume and polyvinyl alcohol volume ratio are 1-9, and the weight content of polyvinyl alcohol in water is 1%-5%;
The application method of described binding agent is added by caking agent in AZO powder to carry out mixing fat, and form forming blocks, after mixing fat, polyvinyl alcohol and polyoxyethylene glycol account for the per-cent of total quality is 1%-10%;
The forming blocks of having added binding agent carries out solution-off fat, temperature 0-60 DEG C, time 4-48 hour, and solution-off agent adopts methylene dichloride, the mixture of methylene dichloride and raw spirit, ethyl acetate, any one in tetracol phenixin;
Described solution-off fat carries out thermal debinding, and thermal debinding can be Vacuum Heat degreasing, also can be the thermal debinding of flowing atmosphere, top temperature 600 DEG C, thermal debinding time 4-48 hour;
The biscuit that described thermal debinding is complete, sinters in sintering oven, and sintering atmosphere can be air, also can be oxygen, sintering temperature 1300 DEG C-1500 DEG C, sintering time 4-48 hour, and room temperature is come out of the stove;
The method is also applicable to ITO, IGZO, SnO
2, TiO
2, TiO, SiO
2, SiO sinters the preparation of target.
The shortcoming that the present invention is directed to existing technique proposes effective solution, specifically invent a kind of compound binding agent, degreasing adopts to dissolve after degreasing carries out thermal debinding again, can generate tiny crack, micropore, carbon remains high shortcoming when can well solve single thermal debinding like this.Through follow-up sintering technique, target sintered density can be improved, and make the density of target each several part identical.
Feature of the present invention:
1. the polyoxyethylene glycol of compound binding agent and polyvinyl alcohol all water-soluble, binding agent can be realized when powder adds binding agent and be uniformly distributed.
2. degreasing to adopt after solvent degreasing thermal debinding again, is different from conventional single thermal debinding.By polyoxyethylene glycol stripping, open pores can be formed, is conducive to thermal debinding gas purging below during solvent degreasing.Polyvinyl alcohol is insoluble to organic solvent, in base substrate, play cohesive action.
3. the target density that the preparation of target materials method adopting the present invention to sinter target density ratio routine obtains is high.
Embodiment
Embodiment 1
Take a certain amount of polyvinyl alcohol, be dissolved in hot water, be made into the polyvinyl alcohol water solution that concentration is 4%.Take the polyvinyl alcohol water solution of 18.834g, the polyoxyethylene glycol taking 3.0134g joins in the polyvinyl alcohol water solution taken and dissolves.The AZO powder taking 71.569g joins in the binder solution prepared, and stirs.After drying at 50 DEG C in an oven, grinding is sieved.
Take the AZO powder that 15g has mixed binding agent, be pressed into the right cylinder of Φ 18 × 10mm on a hydraulic press, then in the density of isostatic cool pressing secondary.AZO biscuit is put into methylene dichloride, temperature 40 DEG C, 16 hours time.The complete biscuit of solution-off fat is put into thermal debinding furnace and is carried out segmentation thermal debinding, top temperature 600 DEG C, 48 hours cycle time.Room temperature is come out of the stove.
Biscuit after thermal debinding is put into sintering oven, and sintering atmosphere is air, average heating speed 100 DEG C/h, and sinter at top temperature 1500 DEG C, average cooling rate 100 DEG C/h, obtaining sintered density is 5.58 g/cm
3, relative density is 99.5%.
Embodiment 2
Take a certain amount of polyvinyl alcohol, be dissolved in hot water, be made into the polyvinyl alcohol water solution that concentration is 4%.Take the polyvinyl alcohol water solution of 28.251g, the polyoxyethylene glycol taking 2.6368g joins in the polyvinyl alcohol water solution taken and dissolves.The AZO powder taking 71.569g joins in the binder solution prepared, and stirs.After drying at 50 DEG C in an oven, grinding is sieved.
Shaping, degreasing and sintering adopt the method for embodiment 1, and the density obtaining sintered compact is 5.57g/cm
3, relative density is 99.2%.
Embodiment 3
Take a certain amount of polyvinyl alcohol, be dissolved in hot water, be made into the polyvinyl alcohol water solution that concentration is 4%.Take the polyvinyl alcohol water solution of 47.085g, the polyoxyethylene glycol taking 1.8834g joins in the polyvinyl alcohol water solution taken and dissolves.The AZO powder taking 71.569g joins in the binder solution prepared, and stirs.After drying at 50 DEG C in an oven, grinding is sieved.
Degreasing and sintering adopt the method for embodiment 1, and the density obtaining sintered compact is 5.56g/cm
3, relative density is 99.1%.
Comparative example
Take a certain amount of polyvinyl alcohol, be dissolved in hot water, be made into the polyvinyl alcohol water solution that concentration is 4%.Take the polyvinyl alcohol water solution of 47.085g, the AZO powder taking 71.569g joins in the binder solution prepared, and stirs.After drying at 50 DEG C in an oven, grinding is sieved.
Take the AZO powder that 15g has mixed binding agent, be pressed into the right cylinder of Φ 18 × 10mm on a hydraulic press, then in the density of isostatic cool pressing secondary.
Biscuit is put into thermal debinding furnace and is carried out segmentation thermal debinding, top temperature 600 DEG C, 48 hours cycle time.Room temperature is come out of the stove.Biscuit after thermal debinding is put into sintering oven, and sintering atmosphere is air, average heating speed 100 DEG C/h, and sinter at top temperature 1500 DEG C, average cooling rate 100 DEG C/h, obtaining sintered density is 5.50g/cm
3. relative density is 98.0%.
Claims (2)
1. an application method for compound binding agent, binding agent is formed primarily of three kinds of compositions: pure water or deionized water, polyvinyl alcohol and polyoxyethylene glycol; Wherein molecular weight chosen by polyoxyethylene glycol is 800-2000, and molecular weight chosen by polyvinyl alcohol is 800-10000, and caking agent formula is: polyoxyethylene glycol volume and polyvinyl alcohol volume ratio are 1-9, and the weight content of polyvinyl alcohol in water is 1%-5%;
Added by caking agent in AZO powder and carry out mixing fat, form forming blocks, after mixing fat, polyvinyl alcohol and polyoxyethylene glycol account for the per-cent of total quality is 1%-10%;
The forming blocks of having added binding agent carries out solution-off fat, and solvent adopts methylene dichloride, the mixture of methylene dichloride and raw spirit, ethyl acetate, any one in tetracol phenixin, temperature 0-60 DEG C, time 4-48 hour;
Carry out thermal debinding after described molten skimming processes completes, thermal debinding is Vacuum Heat degreasing, or the thermal debinding of flowing atmosphere, top temperature 600 DEG C, thermal debinding time 4-48 hour;
The biscuit that described thermal debinding is complete, sinters in sintering oven, and sintering atmosphere is air, or oxygen, and sintering temperature 1300 DEG C-1500 DEG C, sintering time 4-48 hour, room temperature is come out of the stove.
2. binding agent application method as claimed in claim 1, is characterized in that the method is also applicable to ITO, IGZO, SnO
2, TiO
2, TiO, SiO
2, SiO sinters the preparation of target.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010593657.5A CN102153352B (en) | 2010-12-17 | 2010-12-17 | Composite adhesive and application thereof in preparation of sintering target |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010593657.5A CN102153352B (en) | 2010-12-17 | 2010-12-17 | Composite adhesive and application thereof in preparation of sintering target |
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| Publication Number | Publication Date |
|---|---|
| CN102153352A CN102153352A (en) | 2011-08-17 |
| CN102153352B true CN102153352B (en) | 2015-05-20 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5741325B2 (en) * | 2011-08-29 | 2015-07-01 | 三菱マテリアル株式会社 | Sputtering target, manufacturing method thereof, thin film using the target, thin film sheet including the thin film, and laminated sheet |
| CN104057091A (en) * | 2013-03-20 | 2014-09-24 | 江苏天一超细金属粉末有限公司 | Metal, ceramic powder and polymer mixture used for manufacturing metal and ceramic products and method for hydrolyzing and removing polymer from moldings |
| CN104416160B (en) * | 2013-09-11 | 2017-04-19 | 安泰科技股份有限公司 | High-density zinc oxide based target and preparation method thereof |
| CN109665834B (en) * | 2019-03-01 | 2021-08-03 | 郑州大学 | Phase-composition-controllable indium gallium zinc oxide target and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100595318C (en) * | 2007-04-11 | 2010-03-24 | 北京京东方光电科技有限公司 | Method for preparing transparent conductive film and electrode |
| CN101440470B (en) * | 2008-12-17 | 2010-08-11 | 石家庄同人伟业科技有限公司 | Preparation of AZO target material for thin-film solar cell |
| CN101580384B (en) * | 2009-06-10 | 2012-09-26 | 东莞南玻陶瓷科技有限公司 | Yttrium-doped AZO target and preparation method thereof |
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Address after: No. 119, Dawukou metallurgy Road, Dawukou, Shizuishan, Ningxia Co-patentee after: National Special Metal Materials Engineering Research Center of Tantalum and Niobium Patentee after: Northwest rare metal materials research institute Ningxia Co., Ltd. Address before: 753000 No. 119 metallurgical Road, Dawukou District, Shizuishan, the Ningxia Hui Autonomous Region Co-patentee before: National Special Metal Materials Engineering Research Center of Tantalum and Niobium Patentee before: Xibei Inst. of Rare Metal Material |
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Effective date of registration: 20180726 Address after: No. 119, Dawukou metallurgy Road, Dawukou, Shizuishan, Ningxia Patentee after: Ningxia medium color new materials Co., Ltd. Address before: No. 119, Dawukou metallurgy Road, Dawukou, Shizuishan, Ningxia Co-patentee before: National Special Metal Materials Engineering Research Center of Tantalum and Niobium Patentee before: Northwest rare metal materials research institute Ningxia Co., Ltd. |
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