CN1693281A - Process for preparing quantum para electric EuTiO3 film by sol-gel - Google Patents
Process for preparing quantum para electric EuTiO3 film by sol-gel Download PDFInfo
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- CN1693281A CN1693281A CN 200510025072 CN200510025072A CN1693281A CN 1693281 A CN1693281 A CN 1693281A CN 200510025072 CN200510025072 CN 200510025072 CN 200510025072 A CN200510025072 A CN 200510025072A CN 1693281 A CN1693281 A CN 1693281A
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Abstract
A process for preparing the quantum paraelectric EuTiO3 film by sol-gel method includes such steps as chemically preparing organic colloid solution of EuTiO3 from europium nitrate, tetrabutyl titanate and ethanediol mether, spinning-coating on the SrTiO3 substrate, gelatinizing, low-temp roasting, high-temp calcining and annealing in H3.
Description
Technical field
The present invention relates to a kind of sol-gel (Sol-Gel) preparation quantum paraelectrics EuTiO
3(ETO) method of thin-film material, be a kind of colloidal sol by sol evenning machine spin coating one deck europium (Eu) and titanium (Ti) on substrate of strontium titanate, and, prepare EuTiO through anneal under high-temperature calcination and the nitrogen atmosphere at last by control colloidal sol volumetric molar concentration, spin coating time and rotating speed control film thickness
3The novel method of film.
Background technology
With common RTiO
3R in (R is a rare earth element) material
3+Difference, EuTiO
3Eu is generally+divalent in the material, and neutron-diffraction study shows EuTiO
3A kind of G-type anti-ferromagnetic structure is arranged, X ray ABSORPTION EDGE structure, dielectric test shows EuTiO
3Be a kind of elementary ferroelectric material, cause people's attention thus.Recently, people [Katsufuji T. such as Japanese T.Katsufuji; Tokura, Y.Phys.Rev.B 1999,60, and 15021 and Katsufuji, T.; Mori, S.; Masaki, M.; Moritomo, Y.; Yamamoto, N.; Takagi, H.Phys.Rev.B2001,64,104419 and Katsufuji T.; Takagi, H.Phys.Rev.B 2001,64, and 054415] under the argon atmospher condition, prepared EuTiO by float-zone method
3And adulterated EuTiO such as La, Gd
3Crystal, and find that its specific inductivity enlarges markedly about 5.5K, this shows and occurs a kind of magnetic interaction with this understanding.In addition, they have also studied the influence of the interpolation (La, Dy etc.) of impurity element, and for example La mixes and can make it change antiferromagnetic phase mutually into by ferromagnetic.The people such as H.H Wang of U.S. Cornell university have also carried out research [Wang, the H.H. of this respect recently; Fleet, A.; Dale, D.; Suzuki, Y.; Brock, J.D.J.Appl.Phys.2004,96,5324.], and adopt pulsed laser deposition (pulsed laser deposition is called for short PLD) at strontium titanate (SrTiO
3, or STO) on deposited the EuTiO of one deck 20 nanometer thickness
3Film, its target is high temperature solid state reaction synthetic EuTiO repeatedly
3The pottery compressing tablet.No matter be preparation EuTiO below
3Bulk still is that the method for film all relates to one and is higher than 1500 ℃ of high temperature building-up processes, owing to need to feed nitrogen atmosphere, has increased difficulty and danger to experiment simultaneously, and from H.H Wang report, it adopts the EuTiO of PLD method preparation
3Film unijunction crystallinity and orientation are all bad, and quality has much room for improvement.
Summary of the invention
The object of the present invention is to provide a kind of sol-gel to prepare quantum paraelectrics EuTiO
3The novel method of film need not expensive experimental equipment and complicated processing step, can be implemented on the single crystal substrate such as strontium titanate can reach tens EuTiO to the hundreds of micron according to specific oriented epitaxial growth one layer thickness
3Film.
In order to realize such purpose, the present invention adopts europium (Eu) and titanium (Ti) colloidal sol to make presoma, to reduce the temperature of reaction of system, make substrate material by the strontium titanate monocrystal body substrate that (100) planar orientation is precise polished, with simple sol evenning machine spin coating one deck EuTiO
3Colloidal sol, and, prepare EuTiO through anneal under high-temperature calcination and the nitrogen atmosphere at last by control colloidal sol volumetric molar concentration, spin coating time and rotating speed control film thickness
3Film.The present invention prepares certain density EuTiO by chemical process
3Organosol liquid utilizes this sol solutions at certain thickness colloidal sol in the spin coating equably on the strontium titanate substrate base then, makes it change gel-unformed shape-Eu into by colloidal sol by heating again
2Ti
2O
7Phase obtains EuTiO by anneal under the hydrogen condition at last
3The phase film.
The present invention adopts sol-gel processing to prepare quantum paraelectrics EuTiO
3The concrete operations of film are as follows: 1. and be main raw material with europium nitrate and tetrabutyl titanate, preparation EuTiO
3Colloidal sol: at first measure ethylene glycol monomethyl ether and pour beaker into, again according to Eu: Ti=1: 1 mol ratio adds europium nitrate and tetrabutyl titanate, making Eu and Ti volumetric molar concentration is 0.5～1mol/L, and adding acetic acid, regulate its pH value and be about 4～5, drip the methyl ethyl diketone used as stabilizers of 1～2% volume ratio, added the water of 5～10% volume ratios and heating in water bath then 2～4 hours, filter at last and can be prepared into EuTiO
3Colloidal sol leaves standstill several days spin coating usefulness fully.
With sol evenning machine with the above-mentioned EuTiO for preparing
3Colloidal sol is spin-coated on the strontium titanate monocrystal body substrate base: the spin coating time is 30～60 seconds, and speed of rotation is 1500～4000 rev/mins (rpm).
3. the substrate of the good colloidal sol of spin coating is put on the hot platform, slowly being warming up to 80～100 ℃ of gelations of carrying out 10～30 minutes handles, again the gel film that obtains is put into High Temperature Furnaces Heating Apparatus, slowly be warming up to 450 ℃ of organic composition calcination process 30～60 minutes of volatilizing, only contained the intermediate product film of Eu, Ti and oxygen.
4. at last the intermediate product film after the roasting is passed through two step process:, obtain Eu 1000 ℃ of calcinings 4～8 hours
2Ti
2O
7The phase film, again with its under 1050 ℃ of conditions in the hydrogen deoxidation treatment just obtained final EuTiO in 2 hours
3/ SrTiO
3Film; Perhaps by a step process: directly with the intermediate product film after the roasting under 1050～1100 ℃ of conditions in the hydrogen deoxidation treatment just obtained the EuTiO of single phase in 4～8 hours
3/ SrTiO
3Film.
The present invention adopts substrate of strontium titanate to make substrate colloidal sol-preparing gel EuTiO
3Mould material mainly contains following three advantages: equipment is simple, and cost is low, especially can reduce EuTiO greatly by sol gel process
3Material sinter the phase temperature into, the relatively good control of its technology is that sol-gel method is at EuTiO
3Thin-film material prepares the first Application of aspect, can obtain the EuTiO of big area, composition and rerum natura homogeneous fast by this method
3Mould material, and by single crystalline substrate may command EuTiO
3The oriented growth of film is optimized its performance.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is further described.
Embodiment 1:
1, EuTiO
3The preparation of colloidal sol: at first measure ethylene glycol monomethyl ether 15ml, accurately pipette tetrabutyl titanate 4.90ml again, weighing contains anhydrous Eu (NO
3)
35.04g, and add acetic acid 1.5ml successively, and methyl ethyl diketone 0.3ml, water 1ml, heating in water bath is 2 hours then, filters at last and obtains EuTiO
3Colloidal sol, and leave standstill several days standby;
2, with sol evenning machine with the above-mentioned EuTiO for preparing
3Colloidal sol is spin-coated on SrTiO
3On the mono-crystalline substrate substrate: the spin coating time is 60 seconds, and speed of rotation is 4000 rev/mins (rpm);
3, the substrate of the good colloidal sol of spin coating is put on the hot platform, be warming up to 100 ℃ of gelations of carrying out 10min in 30 minutes and handle, and the gel film/substrate that obtains is put into High Temperature Furnaces Heating Apparatus, be warming up to 450 ℃ of organic composition calcination process 60 minutes of volatilizing in 60 minutes;
4, at last with the intermediate product film after the roasting by two step process: be warming up to 1000 ℃ in 120 minutes, insulation calcining 4 hours obtains Eu
2Ti
2O
7The phase film; Again it is being placed hydrogen, be warming up to 1050 ℃ of deoxidation treatment and just obtained final EuTiO in 2 hours in 4 hours
3/ SrTiO
3Film.
Embodiment 2:
1, EuTiO
3The preparation of colloidal sol: at first measure ethylene glycol monomethyl ether 25ml, accurately pipette tetrabutyl titanate 4.90ml again, weighing contains anhydrous Eu (NO
3)
35.04g, and add acetic acid 2ml successively, and methyl ethyl diketone 0.3ml, water 1ml, heating in water bath is 2 hours then, filters at last and obtains EuTiO
3Colloidal sol, and leave standstill several days standby;
2, with sol evenning machine with the above-mentioned EuTiO for preparing
3Colloidal sol is spin-coated on SrTiO
3On the mono-crystalline substrate substrate: the spin coating time is 30 seconds, and speed of rotation is 1500 rev/mins (rpm);
3, the substrate of the good colloidal sol of spin coating is put on the hot platform, be warming up to 80 ℃ of gelations of carrying out 30min in 120 minutes and handle, and the gel film that obtains is put into High Temperature Furnaces Heating Apparatus, be warming up to 450 ℃ of organic composition calcination process 30 minutes of volatilizing in 120 minutes;
4, at last by a step process: directly the intermediate product film after the roasting was warming up to 1050 ℃ in 4 hours, direct deoxidation treatment just obtained the EuTiO of single phase in 4 hours in hydrogen
3/ SrTiO
3Film.
Claims (1)
1, a kind of sol-gel prepares quantum paraelectrics EuTiO
3The method of film is characterized in that comprising the steps:
1) measures ethylene glycol monomethyl ether and pour beaker into, again according to Eu: Ti=1: 1 mol ratio adds europium nitrate and tetrabutyl titanate, making Eu and Ti volumetric molar concentration is 0.5～1mol/L, and adding acetic acid, regulating its pH value is 4～5, drip the methyl ethyl diketone used as stabilizers of 1～2% volume ratio, added the water of 5～10% volume ratios and heating in water bath then 2～4 hours, after the filtration EuTiO
3Colloidal sol, leave standstill several days standby;
2) with sol evenning machine with the above-mentioned EuTiO for preparing
3Colloidal sol is spin-coated on SrTiO
3On the mono-crystalline substrate substrate, the spin coating time is 30～60 seconds, and speed of rotation is 1500～4000 rev/mins;
3) substrate of the good colloidal sol of spin coating is put on the hot platform, slowly being warming up to 80～100 ℃ of gelations of carrying out 10～30 minutes handles, again the gel film that obtains is put into High Temperature Furnaces Heating Apparatus, slowly be warming up to 450 ℃ of organic composition calcination process 30～60 minutes of volatilizing, only contained the intermediate product film of Eu, Ti and oxygen;
4) at last the intermediate product film after the roasting is passed through two step process:, obtain Eu 1000 ℃ of calcinings 4～8 hours
2Ti
2O
7The phase film, again with its under 1050 ℃ of conditions in the hydrogen deoxidation treatment just obtained final EuTiO in 2 hours
3/ SrTiO
3Film; Perhaps by a step process: directly with the intermediate product film after the roasting under 1050～1100 ℃ of conditions in the hydrogen deoxidation treatment just obtained the EuTiO of single phase in 4～8 hours
3/ SrTiO
3Film.
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385263C (en) * | 2006-05-26 | 2008-04-30 | 中国科学院上海技术物理研究所 | Strontium barium titanate Bragg mirror and its preparing method |
| CN100527482C (en) * | 2006-12-27 | 2009-08-12 | 中国科学院上海微系统与信息技术研究所 | Making method for LiFePO4-carbon composite cathode material of lithium ion battery |
| CN109643032A (en) * | 2016-09-02 | 2019-04-16 | 马克斯·普朗克科学促进学会 | Magneto-optic formula optical modulator |
-
2005
- 2005-04-14 CN CN 200510025072 patent/CN1285541C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100385263C (en) * | 2006-05-26 | 2008-04-30 | 中国科学院上海技术物理研究所 | Strontium barium titanate Bragg mirror and its preparing method |
| CN100527482C (en) * | 2006-12-27 | 2009-08-12 | 中国科学院上海微系统与信息技术研究所 | Making method for LiFePO4-carbon composite cathode material of lithium ion battery |
| CN109643032A (en) * | 2016-09-02 | 2019-04-16 | 马克斯·普朗克科学促进学会 | Magneto-optic formula optical modulator |
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|---|---|
| CN1285541C (en) | 2006-11-22 |
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