CN102259937A - Method for preparing strontium ruthenate target - Google Patents

Method for preparing strontium ruthenate target Download PDF

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Publication number
CN102259937A
CN102259937A CN2011102035251A CN201110203525A CN102259937A CN 102259937 A CN102259937 A CN 102259937A CN 2011102035251 A CN2011102035251 A CN 2011102035251A CN 201110203525 A CN201110203525 A CN 201110203525A CN 102259937 A CN102259937 A CN 102259937A
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sro
temperature
target
described method
hot pressing
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CN102259937B (en
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黄富强
刘战强
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Shanghai Institute of Ceramics of CAS
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Shanghai Institute of Ceramics of CAS
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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

A kind of preparation method of ruthenic acid strontium target
Technical field
The present invention relates to a kind of ruthenic acid strontium target (SrRuO 3, be abbreviated as SRO) the preparation method, the present invention relates to a kind of low temperature presintering-high-temperature pressurizing sintering two-step approach that adopts more precisely and prepare the method for 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, also is unique oxide compound with magnetic order in the 4d element; It has metallic conductivity, and room temperature resistivity is approximately 280 μ Ω cm, often is called on " bad metal ".
The SRO of high chemical stability and thermostability has high conductivity, has similar crystalline structure and excellent lattice matching with ferroelectric material PZT of present 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 devices such as micromechanics electronic system device and Nonvolatile ferroelectric random access memory.In addition, at room temperature show paramagnetism, but be lower than 160K when temperature, then show as ferromegnetism as the SRO of magnetic oxide.Ferromegnetism SRO has the big and big characteristics of magneto-optic coefficient of vertical residual magnetization, and (" conductive oxide SrRuO therefore can be applied in MTJ and magnetoresistive memory device 3Growth for Thin Film and ferroelectric integration research ", Ai Wanyong, University of Electronic Science and Technology, Master's thesis in 2007).Because the SRO film has good electricity and magnetic performance and wide application prospect, has carried out extensive studies at the preparation of SRO film both at home and abroad.
Up to now, the SRO growth for Thin Film technology of having reported mainly contains sputter, molecular beam epitaxy (MBE), pulsed laser deposition (PLD) etc.This several method all is to be that feedstock production goes out the SRO film with the SRO target.Because the problem of this body structure of SRO, commercially available SRO target density is all lower, has only the 75-85% of Theoretical Calculation density, thereby can influence every performance of the SRO film of final preparation.The SRO target preparation 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.Institute's reported method can cause the moulding of SRO target not fine and close equally, easy alice distortion even break in the time of simultaneously also can causing the moulding of SRO target because of the existence that does not have pressure.
At this problem, the present inventor intends adopting low temperature presintering-high temperature sintering two-step approach to prepare the higher SRO target of density, can reach the 86-88% of theoretical density.Thereby be guided out purpose of the present invention.
Summary of the invention
The present invention relates to a kind of preparation method of ruthenic acid strontium 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 3Mixed, the even and compressing tablet of ground and mixed.Raw material behind the compressing tablet is at 550-950 ℃ of following pre-burning 2-24h, and reaction finishes the back taking-up and is ground to powder, presses SrRuO 3Mass ratio is that the ratio of 1-10% adds the binding agent regrinding and to uniform mixing.With the powder behind the mixing be pressed into diameter be 10-100mm preset disk or the length of side is the side's of presetting sheet of 5-100mm, the thickness that presets sheet is 2-40mm.The sheet material that presets that compacting obtains is put into to the hot pressing die sleeve, and carried out landfill with filler.The hot pressing die sleeve is transferred in the 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 the back temperature and rises to 1200-1600 ℃, is forced into 100-200MPa gradually to presetting sheet material simultaneously in temperature-rise period, afterwards heat-insulation pressure keeping 2-24h.Finish the back and take out the SRO sheet material, obtain the SRO target after the removing surface filler.When the pre-burning of raw material compressing tablet, adopt lower temperature in the inventive method and, make that the precursor crystallinity of preparation is weak, activity is high, crystal grain is little than the short time; Preset sheet material after binder removal and stress relief directly the coordination pressurization that heats up carry out the high temperature hot pressed sintering, when the landfill pressurization makes SRO sheet material sintering in addition stressed evenly, all help obtaining the SRO target of densification and forming.The density of prepared SRO ceramic target can reach the 86-88% of theoretical density.
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 the polyamide (PA); 3. filler can be any one or two kinds of mixture in zircon sand and the aluminum oxide powder; 4. last 1200-1600 ℃ pressurization is every 30-50min, pressurization 5-20Mpa; 5. employed hot-die cover material is silicon carbide, aluminum oxide or boron nitride.
The SRO ceramic target of the present invention preparation can be applicable to the SRO film for preparing in the technologies such as sputter, molecular beam epitaxy, pulsed laser deposition.The characteristics of the SRO ceramic target of the present invention's preparation are: 1) adopt lower temperature and than the short time, make that the precursor crystallinity of preparation is weak, activity is high, crystal grain is little when the pre-burning of raw material compressing tablet; 2) preset sheet material direct coordination after binder removal and stress relief and heat up and pressurize and carry out the high temperature hot pressed sintering, help obtaining the target of densification and forming.
Embodiment
Introduce embodiments of the invention below, to understanding of the present invention, but the present invention is limited to embodiment absolutely not with further increase.
Embodiment 1:
With SrCO 3, RuO 2Be mixed with SrRuO in 1: 1 in molar ratio 3Mixed, the even and compressing tablet of ground and mixed.Raw material is at 750 ℃ of following pre-burning 8h behind the compressing tablet, and reaction finishes the back taking-up and is ground to powder, presses SrRuO 3Mass ratio is that 4% ratio adds behind the binding agent PVA regrinding and to uniform mixing.It is that 75mm, thickness are the disk that presets of 6mm that powder behind the mixing is pressed into diameter.Sheet material puts into to diameter with presetting of obtaining of compacting is the hot pressing die sleeve of 100mm, and carries out landfill with zircon sand.The hot pressing die sleeve is transferred in the hot pressing furnace, and temperature rises to 500 ℃ and be incubated 3h; Then temperature rises to 950 ℃ and be incubated 5h; Insulation finishes the back temperature and rises to 1350 ℃, simultaneously in temperature-rise period every 40min to pressurize gradually 12MPa and finally add to 120MPa, heat-insulation pressure keeping 12h then of sheet material.Finish the back and take out the SRO sheet material, obtain the SRO ceramic target after removing surperficial zircon sand, its density reaches theoretical density 86-88%.
Embodiment 2:
With SrCO 3, RuO 2Be mixed with SrRuO in 1.02: 1 in molar ratio 3Mixed, the even and compressing tablet of ground and mixed.Slice, thin piece is at 850 ℃ of following pre-burning 6h, and reaction finishes the back taking-up and is ground to powder, presses SrRuO 3Mass ratio is that 3% ratio adds behind the binding agent MC regrinding and to uniform mixing.It is that 25mm, thickness are the disk that presets of 4mm that powder behind the mixing is pressed into diameter.Sheet material puts into to diameter with presetting of obtaining of compacting is the hot pressing die sleeve of 50mm, and carries out landfill with aluminum oxide powder.The hot pressing die sleeve is transferred in the hot pressing furnace, and temperature rises to 550 ℃ and be incubated 3h; Then temperature rises to 900 ℃ and be incubated 10h; Insulation finishes the back temperature and rises to 1400 ℃, simultaneously in temperature-rise period every 50min to pressurize gradually 20MPa and finally add to 200MPa, heat-insulation pressure keeping 20h then of sheet material.Finish the back and take out the SRO sheet material, obtain the SRO ceramic target behind the aluminum oxide powder on removing surface.All the other are with embodiment 1.
Embodiment 3:
With SrCO 3, Ru, be mixed with SrRuO in 1: 1 in molar ratio 3Mixed, the even and compressing tablet of ground and mixed.Slice, thin piece is at 850 ℃ of following pre-burning 10h, and reaction finishes the back taking-up and is ground to powder, presses SrRuO 3Mass ratio is that 4% ratio adds behind the binding agent HPMC regrinding and to uniform mixing.It is that 100mm, thickness are the side's of presetting sheet of 15mm that powder behind the mixing is pressed into the length of side.Sheet material puts into to the length of side with presetting of obtaining of compacting is the hot pressing die sleeve of 150mm, and carries out landfill with zircon sand.The hot pressing die sleeve is transferred in the hot pressing furnace, and temperature rises to 550 ℃ and be incubated 5h; Then temperature rises to 1000 ℃ and be incubated 12h; Insulation finishes the back temperature and rises to 1550 ℃, simultaneously in temperature-rise period every 55min to pressurize gradually 10MPa and finally add to 100MPa, heat-insulation pressure keeping 24h then of sheet material.Finish the back and take out the SRO sheet material, obtain the SRO ceramic target behind the zircon sand on removing surface.All the other are with embodiment 1.

Claims (8)

1. the preparation method of a ruthenic acid strontium ceramic target is characterized in that adopting low temperature presintering-high-temperature pressurizing sintering two-step approach to prepare the SRO ceramic target, and concrete preparation process is:
(1) with SrCO 3, Ru source 0.95-1.06 in molar ratio: 1 is mixed with SrRuO 3Mixed, the even and compressing tablet of ground and mixed;
(2) raw material behind the compressing tablet takes out and is ground to powder at 550-950 ℃ of following pre-burning 2-24h; Press SrRuO 3Mass percent is that the ratio of 1-10% adds behind the binding agent regrinding and to uniform mixing.
(3) powder behind the mixing is pressed into presets disk or square sheet;
(4) sheet material that presets that compacting is obtained is put into the hot pressing die sleeve, and carries out landfill with filler;
(5) the hot pressing die sleeve is transferred in the hot pressing furnace, temperature rises to 400-600 ℃ and be incubated 1-5h; Then temperature rises to 800-1050 ℃ and be incubated 1-15h; Temperature is risen to 1200-1600 ℃ again after insulation finishes, simultaneously in temperature-rise period gradually to presetting disk or square sheet is forced into 100-200MPa; Heat-insulation pressure keeping 2-24h afterwards;
(6) finish the back and take out the SRO sheet material, obtain the SRO target after the removing surface filler, described SRO is the english abbreviation of ruthenic acid strontium.
2. by the described method of claim 1, it is characterized in that described Ru source can be Ru, RuO 2Any one or two kinds of mixtures.
3. by the described method of 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 the polymeric amide.
4. by the described method of claim 1, it is characterized in that described filler is any one or two kinds of mixture in zircon sand and the aluminum oxide powder.
5. by claim 1 or 4 described methods, it is characterized in that described packing material size is the 5-200 order.
6. by the described method of claim 1, it is characterized in that described pressure method is every 30-50min pressurization 5-20MPa.
7. by the described method of claim 1, it is characterized in that the hot-die cover material is silicon carbide, aluminum oxide or boron nitride.
8. by the described method of claim 1, it is characterized in that the SRO ceramic target for preparing can reach theoretical density 86-88%.
CN201110203525.1A 2011-07-11 2011-07-11 Method for preparing strontium ruthenate target Active CN102259937B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104229867A (en) * 2014-09-12 2014-12-24 中国科学院上海硅酸盐研究所 Zinc oxide/strontium ruthenate core-shell nanowire 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
CN113735566A (en) * 2021-09-08 2021-12-03 成都先锋材料有限公司 Strontium ruthenate material and preparation method and application thereof

Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2002051769A1 (en) * 2000-12-26 2002-07-04 Nikko Materials Company, Limited Oxide sinter and process for producing the same
CN101407904A (en) * 2008-12-02 2009-04-15 株洲冶炼集团股份有限公司 Method for producing ITO target material by hot isostatic pressing

Patent Citations (3)

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WO2002051769A1 (en) * 2000-12-26 2002-07-04 Nikko Materials Company, Limited Oxide sinter and process for producing the same
US6843975B1 (en) * 2000-12-26 2005-01-18 Nikko Materials Company, Limited Oxide sintered body and manufacturing method thereof
CN101407904A (en) * 2008-12-02 2009-04-15 株洲冶炼集团股份有限公司 Method for producing ITO target material by hot isostatic pressing

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104229867A (en) * 2014-09-12 2014-12-24 中国科学院上海硅酸盐研究所 Zinc oxide/strontium ruthenate core-shell nanowire and preparation method thereof
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
CN113735566A (en) * 2021-09-08 2021-12-03 成都先锋材料有限公司 Strontium ruthenate material and preparation method and application thereof

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