CN102173783B - Preparation method of binary gradiently doped barium strontium titanate (BST) film - Google Patents
Preparation method of binary gradiently doped barium strontium titanate (BST) film Download PDFInfo
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Abstract
The invention provides a preparation method of a binary gradiently doped barium strontium titanate (BST) film, aiming at the technical problem that the comprehensive dielectric property of the BST film is difficult to increase owning to the ferroelectric phase or paraelectric phase single-phase structure caused by the narrow Curie temperature (Tc) range of the conventional BST film, and belonging to the technical field of functional materials. By controlling the molar ratio of Ba and Sr to Ti, the doping element, the concentration, the gradient, the direction and the film design and the preheating treatment and the film thickness (or layer number), the binary gradiently doped BST film with a wider Tc range, a ferroelectric phase and paraelectric phase composite structure and excellent comprehensive performance can be prepared, wherein the dielectric constant is less than 240, the tuning rate is more than 25%, the dielectric loss is less than 0.63% and the permittivity-temperature coefficient is less than 0.0024/K. The method is convenient, fast, cheap and efficient; and the prepared binary gradiently doped BST film can be used in microwave tuning elements.
Description
Technical field
The invention belongs to technical field of function materials, relate to the preparation method of binary grade doping bst thin film, make and widen the Tc scope, thereby the comprehensive dielectric properties of bst thin film are increased substantially.
Background technology
The bst thin film specific inductivity is with a wide range of applications in microwave regime with the nonlinearities change characteristic of external electric field, becomes to substitute ferrite and semi-conductive preferred material.Realize the application of bst thin film at the microwave neck; Require this film to have excellent comprehensive dielectric tuning performance, the dielectric tuning rate, the dielectric loss less than 1%, the specific inductivity less than 300 that promptly have simultaneously greater than 20% reach the dielectric temperature coefficient less than 0.005/K.But, conventional bst thin film Tc narrow range, specific inductivity, tuning rate and dielectric loss are all higher and paraelectric phase is all lower during ferroelectric phase, and promptly comprehensive dielectric properties are difficult to improve, thereby become the bottleneck of restriction bst thin film microwave application.People have carried out a large amount of research during the nearly last ten years, but the DeGrain that comprehensive dielectric properties improve, and improve a certain performance often to sacrifice another or several performances are cost.For example, doping can make dielectric loss be reduced to less than 1%, but tuning rate often is reduced to below 10% significantly, and specific inductivity also significantly reduces.For another example, film is oriented growth on monocrystal chip, and the dielectric tuning rate can increase to more than 50%, but dielectric loss is often greater than 3%, and the dielectric temperature coefficient is far above 0.005/K.Up to the present, the report that seldom has comprehensive dielectric properties obviously to improve.We were devoted to improve the comprehensive Dielectric Properties of bst thin film in recent years, had obtained certain effect, had applied for several national inventing patents.Mix (seeing that application number is 200810044613.X " indium-and-yttrium-codoped strontium titanate material an and preparation method thereof " patent), crystallization processing (seeing that application number is 200910216407.7 " a kind of preparation method of nano-crystalline BST film " patent) and binary alternatively-doped (seeing that number of patent application is 200910216406.2 " a kind of preparation method of binary alternatively-doped BST membrane " patent) in advance altogether through bst thin film being carried out binary; The comprehensive dielectric properties of bst thin film have bigger improvement, can realize the application of bst thin film microwave Low Medium Frequency.X-ray diffraction shows that the improvement of these comprehensive dielectric properties directly causes the compound mutually relevant of ferroelectric phase and paraelectric phase with the widening of Tc scope of bst thin film.Therefore, widen the Tc scope and obtain to be fit to composite phase-structured be the key that increases substantially the comprehensive dielectric properties of bst thin film.
Research shows, Ba
xSr
1-xTi
1+yO
3+zEvery dielectric properties of (BST, 0＜x＜1,0≤y≤0.25) film all are function of functions of a plurality of parameters.The first, (Ba+Sr)/the Ti mol ratio is a significant parameter of decision BST specific inductivity.When (Ba+Sr)/Ti mol ratio less than 1 the time, specific inductivity reduces and significantly reduces with this mol ratio, when this mol ratio was reduced to 0.8, specific inductivity can be reduced to below 100.Therefore, a moderate specific inductivity be obtained, (Ba+Sr)/Ti mol ratio must be controlled well.The second, doping is an important factor that influences the bst thin film current carrier.Doping can reduce the carrier density of bst thin film, and the binary doped effect that reduces is more obvious, and different doped layers can serve as the heterojunction blocking layer that stops carrier transport, and dielectric loss is further reduced.Grade doping also can significantly improve Jie's temperature stability of bst thin film.But mixing also makes specific inductivity obviously reduce, and then controlling binary doped especially grade doping is to guarantee that BST has the key of moderate specific inductivity, the dielectric loss that significantly reduces and the high temperature stability that is situated between.The 3rd, bst thin film capacity plate antenna or specific inductivity and thickness are inversely proportional to, and the thickness or the number of plies of control film can obtain suitable specific inductivity; Simultaneously, the increase of thickness also can significantly increase the transmission road of current carrier and closely serve as the blocking layer, significantly reduces dielectric loss, then must control bst thin film thickness.The 4th, bst thin film technology also is a key parameter of decision dielectric properties.
Summary of the invention
To the technical problem that conventional bst thin film has the limitation of single ferroelectric phase or paraelectric phase and the comprehensive dielectric properties of bst thin film that cause are difficult to improve, the invention provides a kind of preparation method of binary grade doping bst thin film.The present invention widens bst thin film Tc scope through the binary grade doping and obtains the composite phase-structured of ferroelectric phase and paraelectric phase, and the comprehensive dielectric properties of bst thin film are increased substantially, and can satisfy the application of bst thin film in microwave-tuned device.
Technical scheme of the present invention is following:
A kind of preparation method of binary grade doping bst thin film, as shown in Figure 1, may further comprise the steps:
Step 1: preparation BST colloidal sol.
Ba: Sr: Ti=x: (1-x) in molar ratio: (1+y), wherein the precursor of Ba, Sr and Ti is prepared in 0＜x＜1,0≤y≤0.25; The precursor of Ba and Sr is dissolved in forms barium strontium precursor liquid in the hot Glacial acetic acid min. 99.5, the precursor of Ti is dissolved in methyl ethyl diketone forms titanium precursor liquid; Barium strontium precursor liquid and titanium precursor liquid are mixed and add Vinylpyrrolidone polymer (PVP) make the strontium-barium titanate precursor liquid; Regulate with Glacial acetic acid min. 99.5 between pH value to 3～4 of strontium-barium titanate precursor liquid, last spent glycol methyl ether constant volume obtains the BST colloidal sol of 0.2～0.4 mol.
Step 2: prepare Y, Mn or Ce precursor liquid respectively.
Y, Mn or Ce presoma are dissolved in respectively in the hot Glacial acetic acid min. 99.5; The Hydrocerol A that adding is equivalent to Y, Mn or Ce precursor 10～30% molar weights is as stablizer; Add methyl ethyl diketone, EGME and terepthaloyl moietie hydrotropy again; Regulate between pH value to 3～4 with Glacial acetic acid min. 99.5, the spent glycol constant volume obtains Y, Mn or the Ce precursor liquid of 0.04～0.1 mol.
Step 3: the serial BST colloidal sol of preparation binary grade doping.
Two kinds in the BST colloidal sol of getting series of steps 1 preparation and Y, Mn or the Ce precursor liquid that series of steps 2 prepares are mixed, and control the mole doping content and the gradient of binary doped element, obtain the serial BST colloidal sol of binary grade doping.Wherein the mole doping content of binary doped element is respectively m% and n%, 0＜m＜6,0＜n＜6; The gradient of the mole doping content of binary doped element is Δ 1 and Δ 2,0＜Δ 1≤0.1,0＜Δ 2≤0.1.
Step 4: preparation binary grade doping bst thin film.
Adopt spin-coating method to be spun on the high or minimum binary doped BST colloidal sol of doping content in the serial BST colloidal sol of the serial binary grade doping of step 3 preparation on the substrate base surface; Form wet film, then successively through 5～10 minutes, 250～350 ℃ pyrolysis of 100～120 ℃ of dryings 10～15 minutes, through 400～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to room temperature and get the 1st layer of binary doped bst thin film; Preparation process according to the binary doped bst thin film of the first layer; The mode of successively decreasing according to doping content on the binary doped bst thin film of the first layer surface or increasing progressively prepares the 2nd layer, the 3rd layer successively; Until the binary doped bst thin film of n layer, obtain the binary doped or last binary doped decrystallized film of BST of gradient of gradient under the N layer; At last with the decrystallized film of BST 650～800 ℃ of following crystallization obtained in 60～120 minutes under the N layer gradient binary doped or on the binary doped bst thin film of gradient.
Need to prove:
1, Ba that adopts in the step 1 and the precursor of Sr are acetate or the nitrate salt of Ba and Sr, and the presoma of Ti is a butyl(tetra)titanate; The add-on of Vinylpyrrolidone polymer is 0.25～1.25 (1+y) %.
2, the presoma of the Y that adopts in the step 2, Mn, Ce is acetate or Y, the Mn of Y, Mn, Ce, the nitrate salt of Ce.
3, the preparation of relevant precursor liquid or colloidal sol is all carried out under 70～80 ℃ temperature condition in step 1～step 3.
4, m in the step 3 and n, Δ 1 and Δ 1 can be identical or different.
5, " 400～600 ℃ thermal pretreatment 10～15 minutes " in the step 4 can carry out the first layer film, odd-level film or random layer film.
6, prepared binary grade doping bst thin film has yttrium manganese grade doping bst thin film, cerium manganese grade doping bst thin film or cerium yttrium grade doping bst thin film in the step 4.If preparation cerium yttrium grade doping bst thin film, the thermal pretreatment temperature in the step 4 are 600～700 ℃ of 400～550 ℃, crystallization temperature; If preparation yttrium manganese grade doping bst thin film or cerium manganese grade doping bst thin film, thermal pretreatment temperature are 700～850 ℃ of 500～600 ℃, crystallization temperature.
7, the preparation method of binary grade doping bst thin film provided by the invention; Also be fit to the non-grade doping bst thin film of preparation monobasic, monobasic grade doping bst thin film and the non-grade doping bst thin film of binary; The dielectric properties of the binary grade doping bst thin film of preparation are all improved significantly; And through (Ba+Sr)/Ti mol ratio, the control of alloying element, concentration, gradient and direction and film design, thermal pretreatment and thickness (or number of plies), the amplitude of improvement further increases.Specific as follows:
(1) the unoptimizable parameter is to the influence of comprehensive dielectric properties
First; When (Ba+Sr)/Ti mol ratio be 1 with film when being 6 layers, the specific inductivity 126～315 of Y doped BST membrane, Mn doped BST membrane, Y and the binary doped bst thin film of Mn, Y grade doping bst thin film, Mn grade doping bst thin film, tuning rate 17.8～43.7%; Dielectric loss 1.2～3.5%; The warm coefficient 0.0031～0.0054/K that is situated between, and Y and Mn binary grade doping bst thin film be followed successively by 171～406, tuning rate 29.8～45.6%; Dielectric loss 1.7～2.6%, warm coefficient 0.0028～0.0035/K is situated between.
Second; When (Ba+Sr)/Ti mol ratio be 0.8 with film when being 6 layers, the specific inductivity 101～244 of Y doped BST membrane, Mn doped BST membrane, Y and the binary doped bst thin film of Mn, Y grade doping bst thin film, Mn grade doping bst thin film, tuning rate 10～15.8%; Dielectric loss 0.6～1.4%; The warm coefficient 0.0022～0.0034/K that is situated between, and Y and Mn binary grade doping bst thin film be followed successively by 198～238, tuning rate 11.2～13%; Dielectric loss 0.9～1.6%, warm coefficient 0.0023～0.0026/K is situated between.
The 3rd; When (Ba+Sr)/Ti mol ratio be 1 with film when being 12 layers, the specific inductivity 65～242 of Y doped BST membrane, Mn doped BST membrane, Y and the binary doped bst thin film of Mn, Y grade doping bst thin film, Mn grade doping bst thin film, tuning rate 18.4～41.4%; Dielectric loss 0.3～1.8%; The warm coefficient 0.0022～0.0029/K that is situated between, and Y and Mn binary grade doping bst thin film be followed successively by specific inductivity 121～313, tuning rate 37.4～44.5%; Dielectric loss 0.5～1.2%, warm coefficient 0.0021～0.0023/K is situated between.
The 4th; When (Ba+Sr)/Ti mol ratio be 0.8 with film when being 12 layers, the specific inductivity 65～131 of Y doped BST membrane, Mn doped BST membrane, Y and the binary doped bst thin film of Mn, Y grade doping bst thin film, Mn grade doping bst thin film, tuning rate 4.2～11.1%; Dielectric loss 0.14～1.75%; The warm coefficient 0.002～0.0027/K that is situated between, and Y and Mn binary grade doping bst thin film be followed successively by 114～136, tuning rate 12.2～14.1%; Dielectric loss 0.36～0.75%, warm coefficient 0.0018～0.0019/K is situated between.
It is thus clear that binary grade doping bst thin film shows the comprehensive dielectric properties of improving, but to satisfy the application of microwave-tuned device, also need further to optimize.
(2) parameters optimization is to the influence of comprehensive dielectric properties
First; When (Ba+Sr)/Ti=0.8,3～4 layers, binary grade doping, first floor doping doping content are 0.7～0.8%, an end layer doping content is 1%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 143～226; Tuning rate 16～37%, dielectric loss 0.73～0.85%, warm coefficient 0.0023～0.0036/K is situated between.
Second; When (Ba+Sr)/Ti=0.85～0.95,4～5 layer, binary grade doping, first floor doping doping content are 0.5～0.7%, an end layer doping content is 1%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 119～202; Tuning rate 19～37%, dielectric loss 0.67～0.96%, warm coefficient 0.0025～0.0032/K is situated between.
The 3rd; When (Ba+Sr)/Ti=0.8,3～4 layers, binary grade doping, first floor doping doping content are 0.4～0.6%, an end layer doping content is 0.6～0.9%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 131～226; Tuning rate 25～42%, dielectric loss 0.84～0.98%, warm coefficient 0.0024～0.0037/K is situated between.
The 4th; When (Ba+Sr)/Ti=1,8～9 layers, binary grade doping, first floor doping doping content are 1.5～1.6%, an end layer doping content is 2.4～2.5%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 114～169; Tuning rate 26～32%, dielectric loss 0.61～0.92%, warm coefficient 0.0025～0.0031/K is situated between.
The 5th; When (Ba+Sr)/Ti=1,6 layers, binary grade doping, first floor doping doping content are 1.5%, an end layer doping content is 2%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 93～183; Tuning rate 17～23%, dielectric loss 0.57～0.98%, warm coefficient 0.0027～0.0038/K is situated between.
The 6th; When (Ba+Sr)/Ti=0.85～0.95,8～10 layer, binary grade doping, first floor doping doping content are 1.5～1.6%, an end layer doping content is 2.3～2.5%, the doping content gradient is 0.1% and when going up grade doping; Specific inductivity 83～238; Tuning rate 25～52%, dielectric loss 0.51～0.62%, warm coefficient 0.0018～0.0023/K is situated between.
Obviously, through Parameter Optimization, the comprehensive dielectric properties of binary grade doping bst thin film increase substantially, and can satisfy the application need of microwave-tuned device fully.
To sum up; The present invention is through the binary grade doping to bst thin film; Obtain suitable ferroelectric phase and paraelectric phase composite structure; The Tc scope is widened, so obtain specific inductivity less than 240, tuning rate greater than 25%, dielectric loss less than 0.63% and the warm coefficient that is situated between less than the excellent comprehensive dielectric properties of 0.0024/K, satisfy the microwave application needs.
Description of drawings
Fig. 1 is a schematic flow sheet of the present invention.
The constitutional features of grade doping bst thin film on Fig. 2 embodiment 1 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f6 representes first respectively to the layer 6 film; (b) the two-dimentional pattern of film AFM (AFM); (c) film AFM three-dimensional appearance.
The constitutional features of gradient doped BST membrane under Fig. 3 embodiment 2 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f6 representes first respectively to the layer 6 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of grade doping bst thin film on Fig. 4 embodiment 3 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f12 representes first respectively to the Floor 12 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of gradient doped BST membrane under Fig. 5 embodiment 4 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f12 representes first respectively to the Floor 12 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of grade doping bst thin film on Fig. 6 embodiment 8 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f6 representes first respectively to the layer 6 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of gradient doped BST membrane under Fig. 7 embodiment 9 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f6 representes first respectively to the layer 6 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of grade doping bst thin film on Fig. 8 embodiment 10 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f12 representes first respectively to the Floor 12 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
The constitutional features of gradient doped BST membrane under Fig. 9 embodiment 11 corresponding binary: (a) membrane structure synoptic diagram, wherein S representes matrix, f1～f12 representes first respectively to the Floor 12 film; (b) film AFM two dimension pattern; (c) film AFM three-dimensional appearance.
Embodiment
Below in conjunction with examples of implementation, the present invention is specified, but embodiment of the present invention is not limited thereto.
Embodiment 1: grade doping (Ba on yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 6 layers, (Ba+Sr)/and Ti=0.8, the doping content of first floor film yttrium and manganese is 0.5% mol ratio, and the doping content gradient is 0.1% mol ratio, and the doping content of layer 6 film yttrium and manganese is 1% mol ratio.Its structural representation is shown in Fig. 2 (a).
Its preparation process is following:
(1) by (Ba
0.6Sr
0.4)
0.8TiO
3Ba, Sr, Ti mol ratio 0.48: 0.32: 1 prepare barium acetate, strontium acetate, butyl(tetra)titanate, barium acetate and strontium acetate be dissolved in form barium strontium precursor liquid in the hot Glacial acetic acid min. 99.5, butyl(tetra)titanate is dissolved in methyl ethyl diketone formation titanium precursor liquid; With the mixed strontium-barium titanate precursor liquid that gets of the PVP of two precursor liquids and 0.75% mol ratio, regulate pH value 3～4 with Glacial acetic acid min. 99.5, spent glycol methyl ether constant volume obtains the stable BST colloidal sol of 0.2～0.4M.
(2) respectively manganese acetate and acetic acid yttrium are dissolved in the hot Glacial acetic acid min. 99.5; 0.1～0.3 the Hydrocerol A that adds manganese acetate or acetic acid yttrium mole number plays stabilization; Add methyl ethyl diketone, EGME and terepthaloyl moietie hydrotropy again; Regulate pH value 3～4 with hot Glacial acetic acid min. 99.5, the spent glycol constant volume obtains the Mn precursor liquid or the Y precursor liquid of the stable transparent of 0.05M.
(3) press Ti: Mn: the mol ratio 100 of Y: m: n (m=n=1,0.9,0.8,0.7; 0.6,0.5) respectively BST colloidal sol, Mn precursor liquid and Y precursor liquid thorough mixing are obtained Mn and the Y doping content is 1%, 0.9% respectively; The BST colloidal sol of 0.8%, 0.7%, 0.6% and 0.5% mol ratio.
(4) on substrate evenly drop Mn and Y doping content be the BST colloidal sol of 0.5% mol ratio, it is first with 3000～3500 rev/mins of even glue 5～8 seconds, again with 4500～5000 rev/mins of gluings formation in 25～30 seconds the first layer wet film to purify spreadometer with the CKF-411 type.Wet film successively through 100～120 ℃ of dryings 5～10 minutes, 250～350 ℃ pyrolysis 10～15 minutes, through 500～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to the room temperature layer film of winning.
(5) according to the first layer film step on the first layer film evenly drop Mn and the Y doping content BST colloidal sol that is 0.6% mol ratio prepare second layer film; In like manner, the form that Mn and Y doping content increase progressively with the gradient of 0.1% mol ratio respectively on second layer film prepares the 3rd layer, the 4th layer, layer 5, layer 6 film respectively.So prepared 6 layers of last decrystallized bst thin film of grade doping that Mn and Y doping content increase progressively.Obtained grade doping bst thin film on 6 layers of Mn and the Y in 60～120 minutes 700～850 ℃ of following crystallization at last.
The monobasic doped BST membrane shows, in doping content 0.5%～1% molar ratio range, Y or Mn are that gradient zero doping all makes the phase structure strength reduction with any doped in concentrations profiled, and increases with the degree of the increase phase structure strength reduction of doping content.But by all enhancings to some extent of phase structure than the bst thin film of the doping of 6 layers of monobasic zero gradient or grade doping and the non-grade doping of binary of the phase structure of grade doping bst thin film on 6 layers of binary of above-mentioned steps preparation, the Tc scope is broadening to some extent also.But, because (Ba
0.6Sr
0.4)
0.8TiO
3Phase structure strength ratio Ba
0.6Sr
0.4TiO
3Obviously weaken, then the effect of the Tc scope of broadening is difficult to give full play to.Like Fig. 2 (b) with (c), the pattern of grade doping bst thin film also makes moderate progress on the binary, and crystal grain is tiny, even, and crystal boundary is obvious, and the average crystal grain size is about 45nm, and roughness is 2.33nm.
Embodiment 2: grade doping (Ba under yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 6 layers, (Ba+Sr)/and Ti=0.8, the doping content of first floor film yttrium and manganese is 1% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of layer 6 film yttrium and manganese is 0.5% mol ratio.Its structural representation is shown in Fig. 3 (a).
Preparation process is following:
Step (1)～(3) are identical with embodiment's 1, just:
(4) on substrate evenly drop Mn and Y doping content be the BST colloidal sol of 1% mol ratio, it is first with 3000～3500 rev/mins of even glue 5～8 seconds, again with 4500～5000 rev/mins of gluings formation in 25～30 seconds the first layer wet film to purify spreadometer with the CKF-411 type.Wet film successively through 100～120 ℃ of dryings 5～10 minutes, 250～350 ℃ pyrolysis 10～15 minutes, through 500～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to the room temperature layer film of winning.
(5) according to the first layer film step on the first layer film evenly drop Mn and the Y doping content BST colloidal sol that is 0.9% mol ratio prepare second layer film; In like manner, Mn and Y doping content prepare the 3rd layer, the 4th layer, layer 5, layer 6 film respectively with the form of the gradient descending of 0.1% mol ratio respectively on second layer film.So prepared 6 layers of decrystallized bst thin film of following grade doping that Mn and Y doping content are successively decreased.Obtained gradient doped BST membrane under 6 layers of Mn and the Y in 60～120 minutes 700～850 ℃ of following crystallization at last.
By slightly poor than last grade doping of the phase structure of gradient doped BST membrane under 6 layers of binary of above step preparation and pattern.Its pattern is like Fig. 3 (b) with (c), and crystal grain is mellow and full, tiny, and its surfaceness is 2.57nm and even, and grain size is 42nm.
Embodiment 3: grade doping (Ba on yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 12 layers; (Ba+Sr)/Ti=0.8; The doping content of the first and second layer film yttriums and manganese is 0.5% mol ratio, and the third and fourth layer film doping content is 0.6% mol ratio, by that analogy; The doping gradient of adjacent two odd-levels or even level is 0.1% mol ratio, and the 11 is 1% mol ratio with the doping content of Floor 12 film.Its structural representation is shown in Fig. 4 (a).
Preparation process is following:
Step (1)～(3) are identical with embodiment's 1, just:
(4) on substrate evenly drop Mn and Y doping content be the BST colloidal sol of 0.5% mol ratio, it is first with 3000～3500 rev/mins of even glue 5～8 seconds, again with 4500～5000 rev/mins of gluings formation in 25～30 seconds the first layer wet film to purify spreadometer with the CKF-411 type.Wet film successively through 100～120 ℃ of dryings 5～10 minutes, 250～350 ℃ pyrolysis 10～15 minutes, through 500～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to the room temperature layer film of winning.In like manner, the step of repetition the first layer film prepares second layer film.
(5) according to the first layer film step on second layer film evenly drop Mn and the Y doping content BST colloidal sol that is 0.6% mol ratio prepare three-layer thin-film; In like manner, the step that repeats three-layer thin-film prepares four-level membrane.By that analogy, the form that all increases progressively with the gradient of 0.1% mol ratio of Mn and Y doping content prepares the the the the 5th and the 6th, the 7th and the 8th, the 9th and the tenth and the 11 and the Floor 12 film respectively.So prepared 12 layers of last decrystallized bst thin film of grade doping that Mn and Y doping content increase progressively.Obtained grade doping bst thin film on 12 layers of Mn and the Y in 60～120 minutes 700～850 ℃ of following crystallization at last.
Strengthen to some extent by the phase structure of grade doping bst thin film on 12 layers of binary of above step preparation than grade doping bst thin film on 6 layers of binary, pattern makes moderate progress, from Fig. 4 (b) and pattern (c) can know that crystal grain is more evenly tiny, roughness is littler.
Embodiment 4: grade doping (Ba under yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 12 layers; (Ba+Sr)/Ti=0.8; The doping content of the first and second layer film yttriums and manganese is 1% mol ratio, and the third and fourth layer film doping content is 0.9% mol ratio, by that analogy; The doping gradient of adjacent two odd-levels or even level is 0.1% mol ratio, and the 11 is 0.5% mol ratio with the doping content of Floor 12 film.Its structural representation is shown in Fig. 5 (a).
Preparation process is following:
Step (1)～(3) are identical with embodiment's 1, just:
(4) on substrate evenly drop Mn and Y doping content be the BST colloidal sol of 1% mol ratio, it is first with 3000～3500 rev/mins of even glue 5～8 seconds, again with 4500～5000 rev/mins of gluings formation in 25～30 seconds the first layer wet film to purify spreadometer with the CKF-411 type.Wet film successively through 100～120 ℃ of dryings 5～10 minutes, 250～350 ℃ pyrolysis 10～15 minutes, through 500～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to the room temperature layer film of winning.In like manner, the step of repetition the first layer film prepares second layer film.
(5) evenly drop Mn and Y doping content are the (Ba of 0.9% mol ratio on second layer film according to the first layer film step
0.6Sr
0.4)
0.8TiO
3Colloidal sol prepares three-layer thin-film; In like manner, the step that repeats three-layer thin-film prepares four-level membrane.By that analogy, Mn and Y doping content all prepare the the the the 5th and the 6th, the 7th and the 8th, the 9th and the tenth and the 11 and the Floor 12 film respectively with the form of the gradient descending of 0.1% mol ratio.So prepared 12 layers of decrystallized bst thin film of following grade doping that Mn and Y doping content are successively decreased respectively.Obtained gradient doped BST membrane under 12 layers of Mn and the Y in 60～120 minutes 700～850 ℃ of following crystallization at last.
By slightly poor than grade doping bst thin film on 12 layers of binary of the phase structure of gradient doped BST membrane under 12 layers of binary of above step preparation and pattern.Fig. 5 (b) and (c) shown in pattern making moderate progress than 6 layers of following gradient doped BST membrane.
Embodiment 5: grade doping (Ba on yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 4 layers, (Ba+Sr)/and Ti=0.8, the doping content of first floor film yttrium and manganese is 0.7% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of four-level membrane yttrium and manganese is 1% mol ratio.
Preparation process is following:
Step (1)～(2) are identical with embodiment's 1, just:
(3) press Ti: Mn: the mol ratio 100 of Y: m: n (m=n=1,0.9,0.8,0.7) is measured (Ba respectively
0.6Sr
0.4)
0.8TiO
3Colloidal sol, Mn precursor liquid and Y precursor liquid thorough mixing obtain Mn and the Y doping content is the BST colloidal sol of 1%, 0.9%, 0.8% and 0.7% mol ratio respectively.
(4) on substrate evenly drop Mn and Y doping content be the BST colloidal sol of 0.7% mol ratio, it is first with 3000～3500 rev/mins of even glue 5～8 seconds, again with 4500～5000 rev/mins of gluings formation in 25～30 seconds the first layer wet film to purify spreadometer with the CKF-411 type.Wet film successively through 100～120 ℃ of dryings 5～10 minutes, 250～350 ℃ pyrolysis 10～15 minutes, through 500～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to the room temperature layer film of winning.
(5) according to the first layer film step on the first layer film evenly drop Mn and the Y doping content BST colloidal sol that is 0.8% mol ratio prepare second layer film; In like manner, Mn and Y doping content prepare the 3rd layer and four-level membrane respectively with the form that the gradient of 0.1% mol ratio increases progressively respectively on second layer film.So prepared 4 layers of last decrystallized bst thin film of grade doping that Mn and Y doping content increase progressively respectively.Obtained grade doping bst thin film on 4 layers of Mn and the Y in 60～120 minutes 700～850 ℃ of following crystallization at last.
By grade doping bst thin film on 4 layers of binary of above step preparation, its Tc scope is broadening to some extent, the weakening slightly of grade doping bst thin film on 6 layers of binary of phase structure strength ratio, but the average crystal grain size increases.
Embodiment 6: grade doping (Ba on yttrium and the manganese
0.6Sr
0.4)
0.9TiO
3Film preparation.Condition: 4 layers, (Ba+Sr)/and Ti=0.9, the doping content of first floor film yttrium and manganese is 0.7% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of four-level membrane yttrium and manganese is 1% mol ratio.
Preparation process is following:
Identical about step and embodiment 5, just:
Press Ba, Sr, the preparation in 0.54: 0.36: 1 of Ti mol ratio barium acetate, strontium acetate and butyl(tetra)titanate in the step (1).
By grade doping bst thin film on 4 layers of binary of above step preparation, the obvious enhancing of grade doping bst thin film on the binary of its phase structure strength ratio embodiment 5, and also increase to some extent of average grain size, but surfaceness slightly increases.
Embodiment 7: grade doping (Ba on yttrium and the manganese
0.6Sr
0.4)
0.8TiO
3Film preparation.Condition: 4 layers, (Ba+Sr)/and Ti=0.8, the doping content of first floor film yttrium and manganese is 0.4% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of four-level membrane yttrium and manganese is 0.7% mol ratio.
Preparation process is following:
Its preparation process is identical with embodiment's 5, just:
Press Ti: Mn: the mol ratio 100 of Y: m: n (m=n=0.7,0.6,0.5,0.4) is measured (Ba respectively
0.6Sr
0.4)
0.8TiO
3Colloidal sol, Mn precursor liquid and Y precursor liquid thorough mixing obtain Mn and the Y doping content is the BST colloidal sol of 0.7%, 0.6%, 0.5% and 0.4% mol ratio respectively.From the first floor to the binary doped concentration of four-level membrane is 0.4%, 0.5%, 0.6% and 0.7% mol ratio respectively.
By grade doping bst thin film on 4 layers of binary of above-mentioned steps preparation, compare with embodiment 5, because the doping content of every layer film reduces, the phase structure intensity enhancing, average grain size increases to some extent.
Embodiment 8: grade doping Ba on yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 6 layers, (Ba+Sr)/and Ti=1, the doping content of first floor film yttrium and manganese is 0.5% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of layer 6 film yttrium and manganese is 1% mol ratio.Its structural representation is shown in Fig. 6 (a).
Preparation process is following:
Preparation process is identical with embodiment 1, just " Ba, Sr, Ti mol ratio 0.48: 0.32: 1 " in the step (1) is replaced with " 0.6: 0.4: 1 ".
By grade doping bst thin film on 6 layers of binary of above step preparation, compare with embodiment 1 because (Ba+Sr)/Ti increases, its phase structure intensity obviously strengthens, Fig. 6 (b) with (c) shown in the also obviously enhancing of crystallization effect.
Embodiment 9: grade doping Ba under yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 6 layers, (Ba+Sr)/and Ti=1, the doping content of first floor film yttrium and manganese is 1% mol ratio, and doping gradient is 0.1% mol ratio, and the doping content of layer 6 film yttrium and manganese is 0.5% mol ratio.Its structural representation is shown in Fig. 7 (a).
Preparation process is following:
Preparation process is identical with embodiment 8, and just the doping content of the first layer film is 1%, and the doping content of the second layer to layer 6 film is decremented to 0.5% with 0.1% mol ratio.
By gradient doped BST membrane under 6 layers of binary of above step preparation, a little less than the summary of its phase structure strength ratio embodiment 8, Fig. 7 (b) and (c) shown in pattern approaching, the crystallization effect is slightly poor.
Embodiment 10: grade doping Ba on yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 12 layers; (Ba+Sr)/and Ti=1, the doping content of the first and second layer film yttriums and manganese is 0.5% mol ratio, and the third and fourth layer film doping content is 0.6% mol ratio; By that analogy; Doping gradient is 0.1% mol ratio, and promptly doping content of other next-door neighbour double-layer films yttrium and manganese all increases progressively with 0.1% mol ratio, the 11 and the doping content of Floor 12 film be 1% mol ratio.Its structural representation is shown in Fig. 8 (a).
Preparation process is following:
Identical about step and embodiment 3 is just with (Ba
0.6Sr
0.4)
0.8TiO
3Replace with Ba
0.6Sr
0.4TiO
3Get final product.
By grade doping bst thin film on 12 layers of binary of above-mentioned steps preparation, the remarkable enhancing of its phase structure strength ratio embodiment 8, its pattern is like Fig. 8 (b) with (c), and the film local growth is fine and close, but inhomogeneous, the crystal boundary fuzzy.
Embodiment 11: grade doping Ba under yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 12 layers; (Ba+Sr)/and Ti=1, the doping content of the first and second layer film yttriums and manganese is 1% mol ratio, and the third and fourth layer film doping content is 0.9% mol ratio; By that analogy; Doping gradient is 0.1% mol ratio, and promptly doping content of other next-door neighbour double-layer films yttrium and manganese is all successively decreased with 0.1% mol ratio, the 11 and the doping content of Floor 12 film be 0.5% mol ratio.Its structural representation is shown in Fig. 9 (a).
Preparation process is following:
Identical about step and embodiment 10, just to be that 1%, the three layer of doping content to the 12 film is whenever two-layer be decremented to 0.5% with 0.1% mol ratio to the doping content of the first layer and second layer film.
By gradient doped BST membrane under 12 layers of binary of above-mentioned steps preparation, its phase structure intensity and embodiment's 10 is approaching, but its pattern slightly improves, homogeneous grain size, densification, and crystal boundary is clearly demarcated, like Fig. 9 (b) with (c).
Embodiment 12: grade doping Ba on yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 8 layers; (Ba+Sr)/Ti=1; The doping content of the first and second layer film yttriums and manganese is 0.7% mol ratio; The third and fourth layer film doping content is 0.8% mol ratio, the 5th with layer 6 film two doping contents be 0.9% mol ratio, the 7th and the 8th layer film two doping contents are 1% mol ratio.
Preparation process is following:
Preceding 8 layer films of step and embodiment 10 identical, just the doping content with corresponding rete all increases by 0.2% mol ratio.
By grade doping bst thin film on 8 layers of binary of above-mentioned steps preparation, because the minimizing of the film number of plies weakens phase structure intensity to some extent, then its phase structure is more to some extent than the weakening of embodiment 10, but its appearance makes moderate progress, and crystallization strengthens to some extent.
Embodiment 13: grade doping Ba on yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 8 layers, (Ba+Sr)/and Ti=1, the doping content of the first layer film yttrium and manganese is 1% mol ratio, and doping gradient is 0.1% mol ratio, and the 8th layer film two doping contents are 1.7% mol ratio.
Preparation process is following:
Step is identical with embodiment's 12, and just the binary doped concentration from the first floor to the eight layer films increases to 1.7% mol ratio from 1% mol ratio by 0.1% mol ratio.
By grade doping bst thin film on 8 layers of binary of above-mentioned steps preparation, because the increase of doping content weakens phase structure intensity to some extent, weakening to some extent of its phase structure strength ratio embodiment 12 then, and morphology change is not obvious.
Embodiment 14: grade doping Ba on yttrium and the manganese
0.6Sr
0.4TiO
3Film preparation.Condition: 8 layers, the doping content of the first layer film yttrium and manganese is 1% mol ratio, and doping gradient is 0.2% mol ratio, and the 8th layer film two doping contents are 2.4% mol ratio.
Preparation process is following:
Step is identical with embodiment's 12, and just the binary doped concentration from the first floor to the eight layer films increases to 2.4% mol ratio from 1% mol ratio by 0.2% mol ratio.
By grade doping bst thin film on 8 layers of binary of above-mentioned steps preparation, its phase structure intensity because of the further increase of doping content than further the weakening to some extent of embodiment 13, but morphology change is not obvious.
Other examples of implementation are not enumerated one by one.
Control through above correlation parameter; The binary grade doping bst thin film Tc scope that obtains is widened; Have ferroelectric phase and paraelectric phase composite structure; Pattern comprises crystallization and surfaceness improvement; Overcome the limitation of conventional bst thin film Tc narrow range and ferroelectric phase or the single phase structure of paraelectric phase, obtain specific inductivity less than 240, tuning rate greater than 25%, dielectric loss less than 0.63% and the warm coefficient that is situated between less than the comprehensive dielectric properties of 0.0024/K, can satisfy microwave-tuned device needs.
Claims (4)
1. the preparation method of a binary grade doping bst thin film may further comprise the steps:
Step 1: preparation BST colloidal sol;
Ba: Sr: Ti=x: (1-x) in molar ratio: (1+y) prepare the presoma of Ba, Sr and Ti, wherein 0 < x < 1,0≤y≤0.25; The presoma of Ba and Sr is dissolved in forms barium strontium precursor liquid in the hot Glacial acetic acid min. 99.5, the presoma of Ti is dissolved in methyl ethyl diketone forms titanium precursor liquid; Barium strontium precursor liquid and titanium precursor liquid are mixed and add Vinylpyrrolidone polymer make the strontium-barium titanate precursor liquid, regulate with Glacial acetic acid min. 99.5 between pH value to 3～4 of strontium-barium titanate precursor liquid, spent glycol methyl ether constant volume obtains the BST colloidal sol of 0.2～0.4 mol at last;
Step 2: prepare Y, Mn or Ce precursor liquid respectively;
Y, Mn or Ce presoma are dissolved in respectively in the hot Glacial acetic acid min. 99.5; The Hydrocerol A that adding is equivalent to Y, Mn or Ce presoma 10～30% molar weights is as stablizer; Add methyl ethyl diketone, EGME and terepthaloyl moietie hydrotropy again; Regulate between pH value to 3～4 with Glacial acetic acid min. 99.5, the spent glycol constant volume obtains Y, Mn or the Ce precursor liquid of 0.04～0.1 mol;
Step 3: the serial BST colloidal sol of preparation binary grade doping;
Two kinds in the BST colloidal sol of getting series of steps 1 preparation and Y, Mn or the Ce precursor liquid that series of steps 2 prepares are mixed, and control the mole doping content and the gradient of binary doped element, obtain the serial BST colloidal sol of binary grade doping; Wherein the mole doping content of binary doped element is respectively m% and n%, and 0 < m < 6,0 < n < 6; The gradient of the mole doping content of binary doped element is Δ 1 and Δ 2,0 < Δ 1=Δ 2≤0.1;
Step 4: preparation binary grade doping bst thin film;
Adopt spin-coating method to be spun on the high or minimum binary doped BST colloidal sol of doping content in the serial BST colloidal sol of the serial binary grade doping of step 3 preparation on the substrate base surface; Form wet film, then successively through 5～10 minutes, 250～350 ℃ pyrolysis of 100～120 ℃ of dryings 10～15 minutes, through 400～600 ℃ of thermal pretreatment 10～15 minutes and naturally cool to room temperature and get the 1st layer of binary doped bst thin film; Preparation process according to the binary doped bst thin film of the first layer; The mode of successively decreasing according to doping content on the binary doped bst thin film of the first layer surface or increasing progressively prepares the 2nd layer, the 3rd layer successively; Until the binary doped bst thin film of n layer, obtain the binary doped or last binary doped decrystallized film of BST of gradient of gradient under the N layer; At last with the decrystallized film of BST 650～800 ℃ of following crystallization obtained in 60～120 minutes under the N layer gradient binary doped or on the binary doped bst thin film of gradient.
2. the preparation method of binary grade doping bst thin film according to claim 1 is characterized in that, Ba that adopts in the step 1 and the presoma of Sr are acetate or the nitrate salt of Ba and Sr, and the presoma of Ti is a butyl(tetra)titanate; The add-on of Vinylpyrrolidone polymer is 0.25～1.25 (1+y) %.
3. the preparation method of binary grade doping bst thin film according to claim 1 is characterized in that, the presoma of the Y that adopts in the step 2, Mn, Ce is acetate or Y, the Mn of Y, Mn, Ce, the nitrate salt of Ce.
4. the preparation method of binary grade doping bst thin film according to claim 1 is characterized in that, the preparation of relevant precursor liquid or colloidal sol is all carried out under 70～80 ℃ temperature condition in step 1～step 3.
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