CN102259937B - Method for preparing strontium ruthenate target - Google Patents
Method for preparing strontium ruthenate target Download PDFInfo
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- CN102259937B CN102259937B CN201110203525.1A CN201110203525A CN102259937B CN 102259937 B CN102259937 B CN 102259937B CN 201110203525 A CN201110203525 A CN 201110203525A CN 102259937 B CN102259937 B CN 102259937B
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Abstract
The invention relates to a method for preparing a strontium ruthenate target. A high-density SRO (SrRuO3) ceramic target is prepared by a low-temperature presintering and high-temperature pressure sintering two-step method, and has the density which is 86 to 88 percent of theoretical density. The SRO ceramic target prepared by the method can be applied to processes such as sputtering, molecular beam epitaxy, pulsed laser deposition and the like to form an SRO film, and has the characteristics that: 1) a low temperature and short time are adopted in the process of pressing and presintering a raw material, so that the prepared precursor has low crystallinity, high activity and a small particle size; and 2) a preset sheet is directly heated and pressurized at the same position to be subjected to high-temperature hot pressed sintering after glue is discharged and stress is released, so that a dense and well formed target is obtained.
Description
Technical field
The present invention relates to a kind of strontium ruthenate target (SrRuO
3, be abbreviated as SRO) preparation method, the present invention relates to more precisely a kind of method that adopts low temperature presintering-high-temperature pressurizing sintering two-step approach to prepare the SRO ceramic target of high-compactness.
Background technology
SrRuO
3(SRO) being a kind of transition metal oxide with three-dimensional, quadrature distortion perovskite structure, is also unique oxide compound with magnetic order in 4d element; It has metallic conductivity, and room temperature resistivity is approximately 280 μ Ω cm, is often called on " bad metal ".
The SRO of high chemical stability and thermostability has high conductivity, has similar crystalline structure and good lattice match with ferroelectric material PZT of current broad research etc., and therefore, SRO is with a wide range of applications.As the buffer layer as high-temperature superconducting thin film, the metal level of high T-c Josephson junctions, un-cooled infrared focal plane array, the electrode materials of the devices such as MEMS device and Nonvolatile ferroelectric random access memory.In addition, as the SRO of magnetic oxide, at room temperature show paramagnetism, but when temperature is lower than 160K, show as ferromegnetism.Ferromegnetism SRO has vertical residual magnetization greatly and the large feature of magneto-optic coefficient, and (" conductive oxide SrRuO therefore can be applied in MTJ and magnetoresistive memory device
3the growth of film and ferroelectric integration research ", Ai Wanyong, University of Electronic Science and Technology, Master's thesis in 2007).Because SRO film has good electricity and magnetic performance and wide application prospect, for the preparation of SRO film, carried out research widely both at home and abroad.
The growing technology of the SRO film of having reported up to now, mainly contains sputter, molecular beam epitaxy (MBE), pulsed laser deposition (PLD) etc.This several method is all to take SRO target to prepare SRO film as raw material.Due to the problem of this body structure of SRO, commercially available SRO target density is all lower, only has the 75-85% of Theoretical Calculation density, thereby can affect the properties of the SRO film of final preparation.The SRO preparation of target materials method of bibliographical information has traditional solid-phase sintering method (Xiaohong Zhu etc., Journal of Crystal Growth 268 (2004) 192-197; P.TIWARI etc., Journal of Electronic Materials, 25 (1996) 51-55; " the d.c. sputtering growth of SRO film ", Huang pushes ahead vigorously, University of Electronic Science and Technology, Master's thesis in 2005), do not relate to high temperature hot pressing.The method of reporting can cause the moulding of SRO target not fine and close equally, simultaneously also can because of do not have pressure cause the moulding of SRO target time easy alice distortion, even break.
For this problem, present inventor intends adopting low temperature presintering-high temperature sintering two-step approach to prepare the SRO target that density is higher, can reach the 86-88% of theoretical density.Thereby be guided out object of the present invention.
Summary of the invention
The present invention relates to a kind of preparation method of strontium ruthenate target, adopt low temperature presintering-high-temperature pressurizing sintering two-step approach to prepare the SRO ceramic target of high-compactness, can reach the 86-88% of theoretical density.
Material preparation method:
The present invention adopts SrCO
3, Ru source 0.95-1.06 in molar ratio: 1 is mixed with SrRuO
3ratio is mixed, the even also compressing tablet of ground and mixed.Raw material after compressing tablet is pre-burning 2-24h at 550-950 ℃, and reaction finishes rear taking-up and is ground to powder, by SrRuO
3mass ratio is that the ratio of 1-10% adds binding agent again to grind and mixes to even.Powder after mixing is pressed into the preset square piece that preset disk that diameter is 10-100mm or the length of side are 5-100mm, and the thickness of preset is 2-40mm.The preset sheet material that compacting is obtained is put into hot pressing die sleeve, and carries out landfill with filler.Hot pressing die sleeve is transferred in hot pressing furnace, and temperature rises to 400-600 ℃ and be incubated 1-5h; Then temperature rises to 800-1050 ℃ and be incubated 1-15h; Insulation finishes rear temperature and rises to 1200-1600 ℃, in temperature-rise period, preset sheet material is forced into 100-200MPa gradually, afterwards heat-insulation pressure keeping 2-24h simultaneously.After finishing, take out SRO sheet material, after removing surface filler, obtain SRO target.In the inventive method, when the pre-burning of raw material compressing tablet, adopt lower temperature and shorter time, the precursor crystallinity that makes preparation compared with weak, activity is high, crystal grain is little; Preset sheet material direct coordination after binder removal and stress relief heats up to pressurize and carries out high temperature hot pressing sintering, stressed even when landfill pressurization makes SRO sheet material sintering in addition, is all conducive to obtain the SRO target of densification and forming.The 86-88% of the density reachable theoretical density of prepared SRO ceramic target.
Wherein, 1. described Ru source can be Ru, RuO
2any one or two kinds of mixtures; 2. described binding agent can be any or any two the mixture in methylcellulose gum (MC), polyvinyl alcohol (PVA), Vltra tears (HPMC) and polymeric amide (PA); 3. filler can be any one or two kinds of mixture in zircon sand and aluminum oxide powder, and packing material size is 5-200 order; 4. the pressurization of last 1200-1600 ℃ is every 30-50min, pressurization 5-20Mpa; 5. the hot-die cover material that used is silicon carbide, aluminum oxide or boron nitride.
SRO ceramic target prepared by the present invention can be applicable to the SRO film of preparing in the techniques such as sputter, molecular beam epitaxy, pulsed laser deposition.The feature of SRO ceramic target prepared by the present invention is: 1) when the pre-burning of raw material compressing tablet, adopt lower temperature and shorter time, the precursor crystallinity that makes preparation compared with weak, activity is high, crystal grain is little; 2) preset sheet material direct coordination after binder removal and stress relief heats up and pressurizes and carries out high temperature hot pressing sintering, is conducive to obtain the target of densification and forming.
Embodiment
Introduce embodiments of the invention below, further to increase understanding of the present invention, but the present invention is limited to absolutely not embodiment.
Embodiment 1:
By SrCO
3, RuO
2within 1: 1 in molar ratio, be mixed with SrRuO
3ratio is mixed, the even also compressing tablet of ground and mixed.Raw material pre-burning 8h at 750 ℃ after compressing tablet, reaction finishes rear taking-up and is ground to powder, by SrRuO
3mass ratio is that 4% ratio adds and again grinds after binding agent PVA and to evenly mixing.It is the preset disk that 75mm, thickness are 6mm that powder after mixing is pressed into diameter.The hot pressing die sleeve that it is 100mm that the preset sheet material that compacting is obtained is put into diameter, and carry out landfill with zircon sand.Hot pressing die sleeve is transferred in hot pressing furnace, and temperature rises to 500 ℃ and be incubated 3h; Then temperature rises to 950 ℃ and be incubated 5h; Insulation finishes rear temperature and rises to 1350 ℃, simultaneously in temperature-rise period every 40min to pressurize gradually 12MPa finally add to 120MPa, then heat-insulation pressure keeping 12h of sheet material.After finishing, take out SRO sheet material, obtain SRO ceramic target after removing surperficial zircon sand, its density reaches theoretical density 86-88%.
Embodiment 2:
By SrCO
3, RuO
2within 1.02: 1 in molar ratio, be mixed with SrRuO
3ratio is mixed, the even also compressing tablet of ground and mixed.Slice, thin piece is pre-burning 6h at 850 ℃, and reaction finishes rear taking-up and is ground to powder, by SrRuO
3mass ratio is that 3% ratio adds and again grinds after binding agent MC and to evenly mixing.It is the preset disk that 25mm, thickness are 4mm that powder after mixing is pressed into diameter.The hot pressing die sleeve that it is 50mm that the preset sheet material that compacting is obtained is put into diameter, and carry out landfill with aluminum oxide powder.Hot pressing die sleeve is transferred in hot pressing furnace, and temperature rises to 550 ℃ and be incubated 3h; Then temperature rises to 900 ℃ and be incubated 10h; Insulation finishes rear temperature and rises to 1400 ℃, simultaneously in temperature-rise period every 50min to pressurize gradually 20MPa finally add to 200MPa, then heat-insulation pressure keeping 20h of sheet material.After finishing, take out SRO sheet material, obtain SRO ceramic target after removing surperficial aluminum oxide powder.All the other are with embodiment 1.
Embodiment 3:
By SrCO
3, Ru, within 1: 1 in molar ratio, be mixed with SrRuO
3ratio is mixed, the even also compressing tablet of ground and mixed.Slice, thin piece is pre-burning 10h at 850 ℃, and reaction finishes rear taking-up and is ground to powder, by SrRuO
3mass ratio is that 4% ratio adds and again grinds after binding agent HPMC and to evenly mixing.It is the preset square piece that 100mm, thickness are 15mm that powder after mixing is pressed into the length of side.The hot pressing die sleeve that it is 150mm that the preset sheet material that compacting is obtained is put into the length of side, and carry out landfill with zircon sand.Hot pressing die sleeve is transferred in hot pressing furnace, and temperature rises to 550 ℃ and be incubated 5h; Then temperature rises to 1000 ℃ and be incubated 12h; Insulation finishes rear temperature and rises to 1550 ℃, simultaneously in temperature-rise period every 55min to pressurize gradually 10MPa finally add to 100MPa, then heat-insulation pressure keeping 24h of sheet material.After finishing, take out SRO sheet material, obtain SRO ceramic target after removing surperficial zircon sand.All the other are with embodiment 1
Claims (8)
1. a preparation method for ruthenic acid strontium ceramic target, is characterized in that adopting low temperature presintering-high-temperature pressurizing sintering two-step approach to prepare SRO ceramic target, and concrete preparation process is: (1) is by SrCO
3, Ru source in molar ratio 0.95-1.06:1 be mixed with SrRuO
3ratio is mixed, the even also compressing tablet of ground and mixed; (2) the pre-burning 2-24h at 550-950 ℃ of the raw material after compressing tablet, takes out and is ground to powder; Press SrRuO
3mass percent is again grind and mix to even after the ratio of 1-10% adds binding agent; (3) powder after mixing is pressed into preset disk or square piece; (4) preset sheet material compacting being obtained is put into hot pressing die sleeve, and carries out landfill with filler; (5) hot pressing die sleeve is transferred in hot pressing furnace, temperature rises to 400-600 ℃ and be incubated 1-5h; Then temperature rises to 800-1050 ℃ and be incubated 1-15h; After insulation finishes, again temperature is risen to 1200-1600 ℃, in temperature-rise period, gradually preset disk or square piece are forced into 100-200MPa simultaneously; Heat-insulation pressure keeping 2-24h afterwards; (6) finish rear taking-up SRO sheet material, after removing surface filler, obtain SRO target, described SRO is the english abbreviation of ruthenic acid strontium.
2. by method claimed in claim 1, it is characterized in that described Ru source can be Ru, RuO
2any one or two kinds of mixtures.
3. by method claimed in claim 1, it is characterized in that described binding agent is any or any two the mixture in methylcellulose gum, polyvinyl alcohol, Vltra tears or polymeric amide.
4. by method claimed in claim 1, it is characterized in that described filler is any one or two kinds of mixture in zircon sand and aluminum oxide powder.
5. by the method described in claim 1 or 4, it is characterized in that described packing material size is 5-200 order.
6. by method claimed in claim 1, it is characterized in that described pressure method is every 30-50min pressurization 5-20MPa.
7. by method claimed in claim 1, it is characterized in that hot-die cover material is silicon carbide, aluminum oxide or boron nitride.
8. by method claimed in claim 1, it is characterized in that the SRO ceramic target of preparation can reach theoretical density 86-88%.
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| CN104229867B (en) * | 2014-09-12 | 2015-08-19 | 中国科学院上海硅酸盐研究所 | A kind of zinc oxide/ruthenic acid strontium core-shell nano line and preparation method thereof |
| CN104480433A (en) * | 2014-12-31 | 2015-04-01 | 中国科学院上海硅酸盐研究所 | Method for regulating curie temperature of ferromagnetic ruthenic acid strontiam epitaxy film on silicon substrate |
| CN113735566B (en) * | 2021-09-08 | 2022-12-16 | 南京先锋材料科技有限公司 | Strontium ruthenate material and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6843975B1 (en) * | 2000-12-26 | 2005-01-18 | Nikko Materials Company, Limited | Oxide sintered body and manufacturing method thereof |
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| US6843975B1 (en) * | 2000-12-26 | 2005-01-18 | Nikko Materials Company, Limited | Oxide sintered body and manufacturing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李凤舞等.烧结SrRuO3多晶体的非自旋玻璃行为.《磁性材料及器件》.2004,第35卷(第3期),16. |
| 烧结SrRuO3多晶体的非自旋玻璃行为;李凤舞等;《磁性材料及器件》;20040630;第35卷(第3期);16 * |
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