CN1718561A - Barium strontium titanate film material and preparation method thereof - Google Patents
Barium strontium titanate film material and preparation method thereof Download PDFInfo
- Publication number
- CN1718561A CN1718561A CN 200410041323 CN200410041323A CN1718561A CN 1718561 A CN1718561 A CN 1718561A CN 200410041323 CN200410041323 CN 200410041323 CN 200410041323 A CN200410041323 A CN 200410041323A CN 1718561 A CN1718561 A CN 1718561A
- Authority
- CN
- China
- Prior art keywords
- barium
- tio
- film
- strontium
- acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 45
- 229910052454 barium strontium titanate Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000084 colloidal system Substances 0.000 claims abstract description 49
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 33
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 33
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000000197 pyrolysis Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 33
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- WOIHABYNKOEWFG-UHFFFAOYSA-N [Sr].[Ba] Chemical compound [Sr].[Ba] WOIHABYNKOEWFG-UHFFFAOYSA-N 0.000 claims description 26
- 229910002113 barium titanate Inorganic materials 0.000 claims description 26
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- 108010025899 gelatin film Proteins 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000011888 foil Substances 0.000 claims description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 64
- 239000010409 thin film Substances 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 5
- BTGZYWWSOPEHMM-UHFFFAOYSA-N [O].[Cu].[Y].[Ba] Chemical compound [O].[Cu].[Y].[Ba] BTGZYWWSOPEHMM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 abstract description 2
- 229910010252 TiO3 Inorganic materials 0.000 abstract 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 abstract 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000004528 spin coating Methods 0.000 abstract 1
- 238000009987 spinning Methods 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 50
- 150000002431 hydrogen Chemical class 0.000 description 8
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910009203 Y-Ba-Cu-O Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Images
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a barium strontium titanate film material and a preparation method thereof. The material comprises a metal substrate, in particular a metal substrate sequentially coated with Ba0.2～0.6Sr0.8～0.4TiO3Seed layer and BaXSr1－XTiO3A film; the method comprises obtaining a metal substrate, especially according to Ba, by conventional methods0.2～0.6Sr0.8～0.4TiO3The seed layer precursor colloid is obtained by mixing barium acetate, strontium acetate, trifluoroacetic acid, acetylacetone and butyl titanate in sequence, then the colloid is placed on a metal substrate, and the seed layer is obtained by film spinning, pyrolysis and annealing; according to BaXSr1－XTiO3(X is more than or equal to 0 and less than or equal to 1), and mixing barium acetate, strontium acetate, butyl titanate and methanol in sequence to obtain barium strontium titanate precursor colloid; then the precursor colloid is placed on a metal substrate covered with a seed layer, and Ba is obtained by spin coating, pyrolysis and annealingXSr1－XTiO3A film; repeating the steps to obtain the thin film until the Ba with the required thickness is obtainedXSr1－XTiO3And (3) forming the film, thereby preparing the highly oriented barium strontium titanate film material. It is suitable for the growth of subsequent yttrium barium copper oxide film and may be also used directly in dynamic random access memory.
Description
Technical field the present invention relates to a kind of thin-film material and method for making, especially barium strontium titanate film material and preparation method.
Background technology strontium-barium titanate (Ba
xSr
1-xTiO
3) thin-film material is because its superior dielectric/ferroelectric properties and barrier properties, be with a wide range of applications at aspects such as dynamic RAM of future generation, Y-Ba-Cu-O coating conductors.At present, people have adopted multiple preparation method in order to obtain it, as having disclosed a kind of " preparation method of barium strontium titanate film material " among the Chinese invention patent ublic specification of application CN1267653A that announces on September 27th, 2000.It is that barium acetate, strontium acetate, butyl (tetra) titanate, acetic acid and methyl ethyl diketone are hybridly prepared into stable precursor solution mutually with certain molar ratio, on platinum or titanium or silicon-dioxide or silicon substrate, spare glue, thermal treatment then, in heat treatment process, simultaneously film is applied auxiliary electric field, repeat said process, till ideal thickness.But, this preparation method exists weak point, at first, the orientation of the barium strontium titanate film material of preparing is bad, particularly when the content of barium increased, the mismatch degree of metal base band and strontium-barium titanate also increased thereupon, thereby causes the orientation of follow-up barium strontium titanate film material to degenerate, its performance is descended widely, can not satisfy the requirement of various application; Secondly, high-voltage electric field be need apply in the process of preparation, the complicacy of technology and the danger of production increased; Once more,, need at least more than five days, cause the cycle of production oversize for obtaining stable precursor solution.
The summary of the invention the technical problem to be solved in the present invention provides a kind of favorable orientation, can reach application requiring for overcoming weak point of the prior art, barium strontium titanate film material and preparation method that preparation is safe, easy.
Barium strontium titanate film material comprises metal substrate, is covered with Ba on the particularly said metal substrate
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer, said Ba
0.2～0.6Sr
0.8～0.4TiO
3Be covered with height-oriented Ba on the Seed Layer
XSr
1-XTiO
3Film.
As the further improvement of barium strontium titanate film material, described Ba
0.2～0.6Sr
0.8～0.4TiO
3The thickness of Seed Layer is 1～90nm, height-oriented Ba
XSr
1-XTiO
3The thickness of film is 1～5000nm; Described metal substrate is goldleaf or silver foil or Copper Foil or nickel foil or nickel alloy foil.
The preparation method of barium strontium titanate film material comprises with ordinary method and obtains metal substrate that particularly it is finished according to the following steps: (1), according to Ba
0.2～0.6Sr
0.8～0.4TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, measuring the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again joins in the above-mentioned mixing solutions and stirs, be adjusted to 0.05～0.1 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions, afterwards, this colloid is placed on the metal substrate, with sol evenning machine the colloid on the metal substrate is got rid of film and forms gel again, at last, the metal substrate that will have gel-film is earlier annealed them 30～240 minutes and the acquisition Seed Layer down in 850～1050 ℃ in reducing atmosphere in 300～450 ℃ of following pyrolysis 15～30 minutes again; (2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1), take by weighing barium acetate and strontium acetate earlier, put it into heated and stirred dissolving extremely fully in the acetic acid, measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.15～0.3 mol and obtain strontium-barium titanate forerunner colloid with the concentration of methyl alcohol then mixing solutions; (3), earlier strontium-barium titanate forerunner colloid is placed on the metal substrate that is covered with Seed Layer, with sol evenning machine the colloid on the metal substrate is got rid of film and forms gel again, afterwards, the metal substrate that will have gel-film earlier descended it annealing 30～240 minutes and obtained height-oriented Ba in 850～1050 ℃ in reducing atmosphere again in 300～450 ℃ of following pyrolysis 15～30 minutes
XSr
1-XTiO
3Film; (4), the process of repeating step (3), until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make barium strontium titanate film material.
As the preparation method's of barium strontium titanate film material further improvement, but described preparation method also after the process 2～5 times of repeating step (1), completing steps (2)～(4) and make barium strontium titanate film material successively again; Trifluoroacetic acid in described trifluoroacetic acid and the methyl ethyl diketone mixed solution is 0.3 to 3～7 than methyl ethyl diketone; Described reducing atmosphere is that 3～5% hydrogen adds nitrogen or argon gas; The step-length that described pyrolysis temperature is warming up to annealing temperature is 160～240 ℃/minute; It is described that barium acetate and strontium acetate are put into the temperature that acetic acid heats is 50～90 ℃; Described with methyl alcohol the concentration of mixing solutions is adjusted to 0.15～0.3 mol after, stirred 2～10 hours and obtain strontium-barium titanate forerunner colloid.
Beneficial effect with respect to prior art is, one, after using field emission scanning electron microscope, atomic force microscope and x-ray diffractometer to observe and test respectively to the Seed Layer that obtains and the thin-film material that makes, from stereoscan photograph, atomic power photo and the X-ray diffracting spectrum that obtains, and as calculated, analyze as can be known, thin-film material is by being covered with Ba on the metal substrate successively
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer and height-oriented Ba
XSr
1-XTiO
3Film constitutes, wherein, and Ba
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer has the characteristics of disperse uniform distribution and column crystal growth, and its thickness is 1～90nm, Ba
XSr
1-XTiO
3Film has fine and close pattern and little roughness, and the orientation of height, its face orientation interior and that face is outer is all fairly good, the thickness of film is 1～5000nm, the superior orientation of thin-film material, both be suitable for follow-up yttrium barium copper oxide growth for Thin Film, also can have directly applied in the dynamic RAM; Its two, at metal substrate and Ba
XSr
1-XTiO
3Increase transition layer between film, i.e. Ba
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer has properly solved metal substrate and Ba
XSr
1-XTiO
3The follow-up Ba that the mismatch degree of film is caused
XSr
1-XTiO
3The difficult problem of the poor orientation of film; Its three, for adjusting the Seed Layer and the lattice mismatch between the follow-up strontium-barium titanate layer be compounded on the metal substrate that constitutes by goldleaf or silver foil or Copper Foil or nickel foil or nickel alloy foil better, by increase Ba
0.2～0.6Sr
0.8～0.4TiO
3The number of plies of Seed Layer, and the barium in every layer and the content of strontium adjusted, can make its gradient transition of very successfully finishing the strontium-barium titanate Seed Layer of which floor heterogeneity, so that the mismatch degree is particularly well adapted for the barium strontium titanate of growing height orientation; Its four, equipment required in the preparation process is few, technology is simple, the cycle of production is short, cost is low, security is good, is suitable for suitability for industrialized production; Its five, in the preparation strontium-barium titanate forerunner colloidal process, after with methyl alcohol the concentration of mixing solutions being adjusted to 0.15～0.3 mol, restir 2～10 hours can make strontium-barium titanate forerunner colloid more stable.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 is to Ba
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer take the photograph after with the observation of LEO 1530 type field emission scanning electron microscopes and Autoprobe CP type atomic force microscope photo, wherein, (a) be stereoscan photograph, (b) be the atomic power photo;
Fig. 2 is at Ba
0.2～0.6Sr
0.8～0.4TiO
3The Ba of subsequent growth on the Seed Layer
XSr
1-XTiO
3Film take the photograph after with the observation of LEO 1530 type field emission scanning electron microscopes and Autoprobe CP type atomic force microscope photo, wherein, (a) be the atomic power photo, (b) be stereoscan photograph;
Fig. 3 is the X-ray diffracting spectrum (XRD) that obtains after thin-film material is tested with Phillips X ' Pert type x-ray diffractometer, and wherein, collection of illustrative plates (a) is standard θ-2 θ result, and collection of illustrative plates (b) is Ba
XSr
1-XTiO
3(200) face waves the toe-in fruit, and collection of illustrative plates (C) is Ba
XSr
1-XTiO
3(110) ψ scanning result in the face of face, collection of illustrative plates (a) and (b) and X-coordinate (C) are diffraction angle, ordinate zou is relative intensity, by finding out this Ba among the figure
XSr
1-XTiO
3(200) orientation is fine.
Embodiment at first makes or buys from market goldleaf, silver foil, Copper Foil, nickel foil and the nickel alloy foil as metal substrate with ordinary method, container, instrument and the equipment etc. with required use clean up again.Then,
1), according to Ba embodiment 1: finish preparation according to the following steps:
0.2Sr
0.8TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, wherein, the ratio between trifluoroacetic acid and methyl ethyl diketone is 0.1 to 1; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.05 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions; Afterwards, this colloid is placed on the goldleaf, with sol evenning machine the colloid on the goldleaf is got rid of film and forms gel again; At last, the goldleaf that will have gel-film earlier adds its hydrogen 3% in the nitrogen again and annealed 240 minutes and the acquisition Seed Layer down in 850 ℃ in 300 ℃ of following pyrolysis 30 minutes, and wherein, the step-length that pyrolysis temperature is warming up to annealing temperature is 160 ℃/minute.2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1) takes by weighing barium acetate and strontium acetate earlier, puts it in the acetic acid, is stirred to dissolving fully under 50 ℃; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, with methyl alcohol the concentration of mixing solutions is adjusted to 0.15 mol then after, stirred 2 hours and obtain strontium-barium titanate forerunner colloid.3), earlier strontium-barium titanate forerunner colloid is placed on the goldleaf that is covered with Seed Layer, with sol evenning machine the colloid on the goldleaf is got rid of film and forms gel again; Afterwards, the goldleaf that will have gel-film earlier is in 300 ℃ of following pyrolysis 30 minutes, its hydrogen 3% added in the nitrogen in 850 ℃ of annealing 240 minutes and obtain height-oriented Ba down again
XS
R-XTiO
3Film.4), repeating step 3) process, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make the barium strontium titanate film material that is similar to as shown in Figures 2 and 3, the Ba of this barium strontium titanate film material
0.2Sr
0.8TiO
3Seed Layer is similar to as shown in Figure 1.
1), according to Ba embodiment 2: finish preparation according to the following steps:
0.3Sr
0.7TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, wherein, the ratio between trifluoroacetic acid and methyl ethyl diketone is 0.3 to 4; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.06 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions; Afterwards, this colloid is placed on the silver foil, with sol evenning machine the colloid on the silver foil is got rid of film and forms gel again; At last, the silver foil that will have gel-film earlier adds its hydrogen 3.5% in the argon gas again and annealed 190 minutes and the acquisition Seed Layer down in 900 ℃ in 335 ℃ of following pyrolysis 27 minutes, and wherein, the step-length that pyrolysis temperature is warming up to annealing temperature is 180 ℃/minute; Repeat above-mentioned process 2 times, and the barium in every layer and the content of strontium are adjusted, after the strontium-barium titanate Seed Layer that obtains 2 layers of heterogeneity, carry out following step again.2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1) takes by weighing barium acetate and strontium acetate earlier, puts it in the acetic acid, is stirred to dissolving fully under 60 ℃; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, with methyl alcohol the concentration of mixing solutions is adjusted to 0.19 mol then after, stirred 4 hours and obtain strontium-barium titanate forerunner colloid.3), earlier strontium-barium titanate forerunner colloid is placed on the silver foil that is covered with Seed Layer, with sol evenning machine the colloid on the silver foil is got rid of film and forms gel again; Afterwards, the silver foil that will have gel-film earlier is in 335 ℃ of following pyrolysis 27 minutes, its hydrogen 3.5% added in the argon gas in 900 ℃ of annealing 190 minutes and obtain height-oriented Ba down again
XSr
1-XTiO
3Film.4), repeating step 3) process, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make as shown in Figures 2 and 3 barium strontium titanate film material, the Ba of this barium strontium titanate film material
0.3Sr
0.7TiO
3Seed Layer as shown in Figure 1.
1), according to Ba embodiment 3: finish preparation according to the following steps:
0.4Sr
0.6TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, wherein, the ratio between trifluoroacetic acid and methyl ethyl diketone is 0.3 to 5; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.08 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions; Afterwards, this colloid is placed on the Copper Foil, with sol evenning machine the colloid on the Copper Foil is got rid of film and forms gel again; At last, the Copper Foil that will have gel-film earlier adds its hydrogen 4% in the nitrogen again and annealed 140 minutes and the acquisition Seed Layer down in 950 ℃ in 370 ℃ of following pyrolysis 27 minutes, and wherein, the step-length that pyrolysis temperature is warming up to annealing temperature is 200 ℃/minute; Repeat above-mentioned process 3 times, and the barium in every layer and the content of strontium are adjusted, after the strontium-barium titanate Seed Layer that obtains 3 layers of heterogeneity, carry out following step again.2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1) takes by weighing barium acetate and strontium acetate earlier, puts it in the acetic acid, is stirred to dissolving fully under 70 ℃; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, with methyl alcohol the concentration of mixing solutions is adjusted to 0.23 mol then after, stirred 6 hours and obtain strontium-barium titanate forerunner colloid.3), earlier strontium-barium titanate forerunner colloid is placed on the Copper Foil that is covered with Seed Layer, with sol evenning machine the colloid on the Copper Foil is got rid of film and forms gel again; Afterwards, the Copper Foil that will have gel-film earlier is in 370 ℃ of following pyrolysis 23 minutes, its hydrogen 4% added in the nitrogen in 950 ℃ of annealing 140 minutes and obtain height-oriented Ba down again
XSr
1-XTiO
3Film.4), repeating step 3) process, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make the barium strontium titanate film material that is similar to as shown in Figures 2 and 3, the Ba of this barium strontium titanate film material
0.4Sr
0.6TiO
3Seed Layer is similar to as shown in Figure 1.
1), according to Ba embodiment 4: finish preparation according to the following steps:
0.5Sr
0.5TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, wherein, the ratio between trifluoroacetic acid and methyl ethyl diketone is 0.3 to 6; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.09 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions; Afterwards, this colloid is placed on the nickel foil, with sol evenning machine the colloid on the nickel foil is got rid of film and forms gel again; At last, the nickel foil that will have gel-film earlier adds its hydrogen 4.5% in the argon gas again and annealed 90 minutes and the acquisition Seed Layer down in 1000 ℃ in 410 ℃ of following pyrolysis 19 minutes, and wherein, the step-length that pyrolysis temperature is warming up to annealing temperature is 220 ℃/minute; Repeat above-mentioned process 4 times, and the barium in every layer and the content of strontium are adjusted, after the strontium-barium titanate Seed Layer that obtains 4 layers of heterogeneity, carry out following step again.2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1) takes by weighing barium acetate and strontium acetate earlier, puts it in the acetic acid, is stirred to dissolving fully under 80 ℃; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, with methyl alcohol the concentration of mixing solutions is adjusted to 0.26 mol then after, stirred 8 hours and obtain strontium-barium titanate forerunner colloid.3), earlier strontium-barium titanate forerunner colloid is placed on the nickel foil that is covered with Seed Layer, with sol evenning machine the colloid on the nickel foil is got rid of film and forms gel again; Afterwards, the nickel foil that will have gel-film earlier is in 410 ℃ of following pyrolysis 19 minutes, its hydrogen 4.5% added in the argon gas in 1000 ℃ of annealing 90 minutes and obtain height-oriented Ba down again
XSr
1-XTiO
3Film.4), repeating step 3) process, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make the barium strontium titanate film material that is similar to as shown in Figures 2 and 3, the Ba of this barium strontium titanate film material
0.5Sr
0.5TiO
3Seed Layer is similar to as shown in Figure 1.
1), according to Ba embodiment 5: finish preparation according to the following steps:
0.6Sr
0.4TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, wherein, the ratio between trifluoroacetic acid and methyl ethyl diketone is 0.3 to 7; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.1 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions; Afterwards, this colloid is placed on the nickel alloy foil, with sol evenning machine the colloid on the nickel alloy foil is got rid of film and forms gel again; At last, the nickel alloy foil that will have gel-film earlier adds its hydrogen 5% in the nitrogen again and annealed 30 minutes and the acquisition Seed Layer down in 1050 ℃ in 450 ℃ of following pyrolysis 15 minutes, and wherein, the step-length that pyrolysis temperature is warming up to annealing temperature is 240 ℃/minute; Repeat above-mentioned process 5 times, and the barium in every layer and the content of strontium are adjusted, after the strontium-barium titanate Seed Layer that obtains 5 layers of heterogeneity, carry out following step again.2), according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1) takes by weighing barium acetate and strontium acetate earlier, puts it in the acetic acid, is stirred to dissolving fully under 90 ℃; Measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, with methyl alcohol the concentration of mixing solutions is adjusted to 0.3 mol then after, stirred 10 hours and obtain strontium-barium titanate forerunner colloid.3), earlier strontium-barium titanate forerunner colloid is placed on the nickel alloy foil that is covered with Seed Layer, with sol evenning machine the colloid on the nickel alloy foil is got rid of film and forms gel again; Afterwards, the nickel alloy foil that will have gel-film earlier is in 450 ℃ of following pyrolysis 15 minutes, its hydrogen 5% added in the nitrogen in 1050 ℃ of annealing 30 minutes and obtain height-oriented Ba down again
XSr
1-XTiO
3Film.4), repeating step 3) process, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make the barium strontium titanate film material that is similar to as shown in Figures 2 and 3, the Ba of this barium strontium titanate film material
0.6Sr
0.4TiO
3Seed Layer is similar to as shown in Figure 1.
Obviously, those skilled in the art can carry out various changes and modification to barium strontium titanate film material of the present invention and preparation method and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1, a kind of barium strontium titanate film material comprises metal substrate, it is characterized in that being covered with Ba on the said metal substrate
0.2～0.6Sr
0.8～0.4TiO
3Seed Layer, said Ba
0.2～0.6Sr
0.8～0.4TiO
3Be covered with height-oriented Ba on the Seed Layer
XSr
1-XTiO
3Film.
2, barium strontium titanate film material according to claim 1 is characterized in that Ba
0.2～0.6Sr
0.8～0.4TiO
3The thickness of Seed Layer is 1～90nm, height-oriented Ba
XSr
1-XTiO
3The thickness of film is 1～5000nm.
3, barium strontium titanate film material according to claim 1 is characterized in that metal substrate is goldleaf or silver foil or Copper Foil or nickel foil or nickel alloy foil.
4, the preparation method of barium strontium titanate film material according to claim 1 comprises with ordinary method obtaining metal substrate, it is characterized in that finishing according to the following steps:
4.1, according to Ba
0.2～0.6Sr
0.8～0.4TiO
3The composition ratio, take by weighing barium acetate and strontium acetate earlier, put it into and be stirred to dissolving fully in the mixed solution of trifluoroacetic acid and methyl ethyl diketone evenly, measuring the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again joins in the above-mentioned mixing solutions and stirs, be adjusted to 0.05～0.1 mol and obtain Seed Layer forerunner colloid with the concentration of methyl ethyl diketone then mixing solutions, afterwards, this colloid is placed on the metal substrate, with sol evenning machine the colloid on the metal substrate is got rid of film and forms gel again, at last, the metal substrate that will have gel-film is earlier annealed them 30～240 minutes and the acquisition Seed Layer down in 850～1050 ℃ in reducing atmosphere in 300～450 ℃ of following pyrolysis 15～30 minutes again;
4.2, according to Ba
XSr
1-XTiO
3The composition ratio of (0≤X≤1), take by weighing barium acetate and strontium acetate earlier, put it into heated and stirred dissolving extremely fully in the acetic acid, measure the metatitanic acid fourth fat that adds the strontium acetate equimolar amount with barium acetate again and join in the above-mentioned mixing solutions and stir, be adjusted to 0.15～0.3 mol and obtain strontium-barium titanate forerunner colloid with the concentration of methyl alcohol then mixing solutions;
4.3, earlier strontium-barium titanate forerunner colloid is placed on the metal substrate that is covered with Seed Layer, with sol evenning machine the colloid on the metal substrate is got rid of film and forms gel again, afterwards, the metal substrate that will have gel-film earlier descended it annealing 30～240 minutes and obtained height-oriented Ba in 850～1050 ℃ in reducing atmosphere again in 300～450 ℃ of following pyrolysis 15～30 minutes
XSr
1-XTiO
3Film;
4.4, the process of repeating step 4.3, until the height-oriented Ba that obtains desired thickness
XSr
1-XTiO
3Film, thus make barium strontium titanate film material.
5, the preparation method of barium strontium titanate film material according to claim 4, it is characterized in that the process 2～5 times of repeating step 4.1 after, completing steps 4.2～4.4 and make barium strontium titanate film material successively again.
6,, it is characterized in that the trifluoroacetic acid in trifluoroacetic acid and the methyl ethyl diketone mixed solution is 0.3 to 3～7 than methyl ethyl diketone according to the preparation method of claim 4 or 5 described barium strontium titanate film materials.
7,, it is characterized in that reducing atmosphere is that 3～5% hydrogen adds nitrogen or argon gas according to the preparation method of claim 4 or 5 described barium strontium titanate film materials.
8,, it is characterized in that the step-length that pyrolysis temperature is warming up to annealing temperature is 160～240 ℃/minute according to the preparation method of claim 4 or 5 described barium strontium titanate film materials.
9,, it is characterized in that it is 50～90 ℃ that barium acetate and strontium acetate are put into the temperature that acetic acid heats according to the preparation method of claim 4 or 5 described barium strontium titanate film materials.
10,, after it is characterized in that the concentration of mixing solutions being adjusted to 0.15～0.3 mol, stirred 2～10 hours and obtain strontium-barium titanate forerunner colloid with methyl alcohol according to the preparation method of claim 4 or 5 described barium strontium titanate film materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100413231A CN1318351C (en) | 2004-07-06 | 2004-07-06 | Barium strontium titanate film material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100413231A CN1318351C (en) | 2004-07-06 | 2004-07-06 | Barium strontium titanate film material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1718561A true CN1718561A (en) | 2006-01-11 |
| CN1318351C CN1318351C (en) | 2007-05-30 |
Family
ID=35930522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100413231A Expired - Fee Related CN1318351C (en) | 2004-07-06 | 2004-07-06 | Barium strontium titanate film material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1318351C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333684B (en) * | 2008-06-03 | 2011-03-16 | 电子科技大学 | Indium-and-yttrium-codoped strontium titanate nanomaterial and its preparation method |
| CN101694789B (en) * | 2009-10-16 | 2011-04-20 | 北京工业大学 | Ti-doped YBCO film preparation process |
| CN102174697A (en) * | 2011-03-04 | 2011-09-07 | 电子科技大学 | Method for growing oxide ferroelectric film on metallic nickel substrate |
| CN102229265A (en) * | 2011-04-29 | 2011-11-02 | 中国科学院合肥物质科学研究院 | Barium strontium titanate multilayered film, and preparation method thereof |
| CN110265191A (en) * | 2019-06-14 | 2019-09-20 | 清华大学 | SrTiO3Polycrystalline circle substrate and preparation method thereof |
| CN112259374A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | BST-based multilayer dielectric enhanced film and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5559260A (en) * | 1991-12-13 | 1996-09-24 | Symetrix Corporation | Precursors and processes for making metal oxides |
| CN1049644C (en) * | 1997-03-21 | 2000-02-23 | 中国科学院上海硅酸盐研究所 | Process of preparing strontium-barium titanate film by using water as solvent for precursor solution |
-
2004
- 2004-07-06 CN CNB2004100413231A patent/CN1318351C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101333684B (en) * | 2008-06-03 | 2011-03-16 | 电子科技大学 | Indium-and-yttrium-codoped strontium titanate nanomaterial and its preparation method |
| CN101694789B (en) * | 2009-10-16 | 2011-04-20 | 北京工业大学 | Ti-doped YBCO film preparation process |
| CN102174697A (en) * | 2011-03-04 | 2011-09-07 | 电子科技大学 | Method for growing oxide ferroelectric film on metallic nickel substrate |
| CN102174697B (en) * | 2011-03-04 | 2013-06-12 | 电子科技大学 | Method for growing oxide ferroelectric film on metallic nickel substrate |
| CN102229265A (en) * | 2011-04-29 | 2011-11-02 | 中国科学院合肥物质科学研究院 | Barium strontium titanate multilayered film, and preparation method thereof |
| CN102229265B (en) * | 2011-04-29 | 2013-09-25 | 中国科学院合肥物质科学研究院 | Barium strontium titanate multilayered film, and preparation method thereof |
| CN110265191A (en) * | 2019-06-14 | 2019-09-20 | 清华大学 | SrTiO3Polycrystalline circle substrate and preparation method thereof |
| CN112259374A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | BST-based multilayer dielectric enhanced film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1318351C (en) | 2007-05-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117051368B (en) | Preparation method of strontium niobate-doped titanate film and strontium niobate-doped titanate film | |
| CN102731083B (en) | Method for preparing yttrium-barium-copper-oxygen high-temperature superconducting film | |
| US20120028810A1 (en) | Method for depositing oxide thin films on textured and curved metal surfaces | |
| CN1318351C (en) | Barium strontium titanate film material and preparation method thereof | |
| CN101333655A (en) | Process for preparing La2Zr2O7 cushioning layer film of high-temperature superconductivity coating conductor | |
| Shahid et al. | Effect of Sr-doping on ferroelectric and dielectric properties of sol-gel synthesized BaTiO3 thin films | |
| CN100586582C (en) | Method for preparing barium stan-titanate ferroelectric film | |
| Gao et al. | Band gap energy of SrTiO 3 thin film prepared by the liquid phase deposition method | |
| US6593149B2 (en) | Manufacturing method for ferroelectric thin film using sol-gel process | |
| CN104446435B (en) | The preparation method of Ag doping terres rares barium copper oxygen conductor of high-temperature superconductor coat material | |
| CN105924153A (en) | Multilayer film with sandwich structure and preparation method thereof | |
| CN101200127B (en) | Lanthanum zirconic acid/yttrium titanate film material and method for making same | |
| CN101333684B (en) | Indium-and-yttrium-codoped strontium titanate nanomaterial and its preparation method | |
| Kushida et al. | Observation of Li-atomic array in spinel-LiMn 2 O 4 films spin-coated on Si substrates using an atomic force microscopy | |
| JP2001026421A (en) | Formation of crystalline thin film by sol/gel method | |
| Gul et al. | The influence of thermal processing on microstructure of sol–gel-derived SrSnO 3 thin films | |
| CN1584112A (en) | Preparation of double axial structured CeO2 film from inorganic salt as raw material by liquid phase chemical process | |
| CN104538113B (en) | Superconducting coating Y2Ce2O7The preparation method of transition layer film | |
| CN101281804A (en) | Process for preparing single layer useful high-temperature superconduction coating conductor buffer layer thick film | |
| CN112877676A (en) | Preparation method of epitaxial growth lanthanum nickelate and lanthanum strontium manganese oxygen film | |
| Celik et al. | Texturing influence of process parameters in sol–gel Tb2O3 buffer layers on Ni tapes for YBCO coated conductors | |
| US6656390B2 (en) | Preparation of energy storage materials | |
| CN113279062B (en) | Nickel-doped lead titanate single crystal film and preparation and application thereof | |
| CN100457292C (en) | (Ba,Zr)TiO3 ferroelectric film with optimized performance and its preparing method | |
| CN1741253A (en) | Process for producing single-orientation ferroelectric thin film with double-axle texture MgO as buffer layer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070530 Termination date: 20110706 |