CN101716838B - Method for preparing binary alternatively-doped BST membrane - Google Patents
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Abstract
The invention discloses a method for preparing a binary alternatively-doped BST membrane, belongs to the technical field of functional materials, and relates to a method for preparing a nanocrystalline BST membrane. The method adopts binary doping of Mn and Y, namely, carries out Mn or Y doping on an odd layer membrane and carries out Y or Mn doping on an even layer membrane; and the method adds a pre-crystallization processing step between cooling and crystallization steps. The membrane prepared by the method is smooth and compact with no crack or shrinkage cavity, and can greatly enhance the comprehensive dielectric tuning performance of the nanocrystalline BST membrane; and the obtained nanocrystalline BST membrane has a dielectric tuning rate of over 30.0 percent, a dielectric loss of less than 2.0 percent, a K factor of greater than 15.5, a high dielectric strength and a stable frequency characteristic and a temperature characteristic. The nanocrystalline BST membrane prepared by the method can be used for preparing a microwave tuning device (such as a phase shifter) instead of a ferrite and a semiconductor so as to remarkably reduce the manufacturing cost of the microwave tuning device; and furthermore, the nanocrystalline BST membrane prepared by the method is applicable for magnetic recording, pyroelectric focal plane arrays and the like.
Description
Technical field
The invention belongs to technical field of function materials, relate to the preparation method of nanometer crystal strontium titanate barium (BST) film.
Background technology
Bst thin film is nonlinear change because of dielectric constant with extra electric field, has high dielectric tuning rate, is with a wide range of applications in the microwave device field.For example, the bst thin film phase shifter is considered to substitute the optimal candidate of ferrite phase shifter and semiconductor diode phase shifter.But, realize the application of bst thin film, except high dielectric tuning rate, also need low dielectric loss, high stability in microwave regime, the particularly high dielectric tuning rate and the ratio of dielectric loss are the K factor, because an important symbol of the K factor comprehensive dielectric tuning performance that is BST.BST is typical A BO
3Type perovskite structure, the K factor are difficult to improve, to such an extent as to people have carried out big quantity research closely during the last ten years, indivedual performance indications have obvious breakthrough, but the K factor is not seen obvious breakthrough yet, for example, dielectric tuning rate 20%～50%, dielectric loss 0.03～0.1, the K factor 2～15.
On the other hand, realize of the real replacement of bst thin film phase shifter, also must overcome the limitation of conventional method for manufacturing thin film ferrite phase shifter and semiconductor diode phase shifter.Conventional method for manufacturing thin film has rf magnetron sputtering, pulsed laser deposition, metal organic chemical vapor deposition and sol-gel process etc.Wherein, former three equipment is all relatively more expensive, and the sedimentation rate of rf magnetron sputtering is slow, the composition of film and target differs greatly, the pld (pulsed laser deposition) lack of homogeneity, and metal organic chemical vapor deposition metal organic source difficulty is looked for and is expensive.Sol-gel process is cheap convenient, but film severe crack, the compactness of preparation are poor, shrinkage cavity is many etc.At these limitation, the report of many local improvement is arranged, but the bibliographical information difficulty that can increase substantially the comprehensive dielectric tuning performance of bst thin film is looked for.
Summary of the invention
The invention provides a kind of preparation method of binary alternatively-doped BST membrane, carry out Mn, Y binary doped in, " even glue, drying, pyrolysis, cooling, the crystallization " step that conventional sol-gel process is prepared bst thin film is improved, and adds " pre-crystallization " step between " cooling " and " crystallization " step; The smooth densification of prepared bst thin film, the bst thin film that has effectively overcome conventional sol-gel process preparation produces the limitation of shrinkage cavity, stress and crackle because of decomposition and a large amount of organic matter that volatilizees in crystallization process make film, significantly improve the interface matching relationship between bst thin film and the matrix, realized the class epitaxial growth of bst thin film in atmospheric environment.Therefore, the present invention can significantly improve the comprehensive dielectric tuning performance (the K factor) of bst thin film, for realizing that the bst thin film phase shifter really replaces ferrite phase shifter and the semiconductor diode phase shifter provides possibility.
Technical solution of the present invention is as follows:
A kind of preparation method of binary alternatively-doped BST membrane as shown in Figure 1, may further comprise the steps:
Step 1: preparation is mixed the BST colloidal sol of Mn (manganese) and is mixed the BST colloidal sol of Y (yttrium), specifically may further comprise the steps:
Step 1-1: with mol ratio is Ba: Sr=x: (1-x) inorganic barium salt that dissolves in glacial acetic acid and inorganic strontium salt are dissolved in the glacial acetic acid, stir down in 60～80 ℃ of temperature conditions and form barium strontium precursor liquid, wherein 0＜x＜1 in 60～120 minutes.
Step 1-2: be 1: 2 butyl titanate and acetylacetone,2,4-pentanedione Hybrid Heating with mol ratio and stir and formed titanium precursor liquid in 60～120 minutes.
Step 1-3: the inorganic manganese salt that will dissolve in glacial acetic acid is dissolved in the glacial acetic acid, stirs down in 60～80 ℃ of temperature conditions and forms the manganese precursor liquid in 60～120 minutes.
Step 1-4: the inorganic yttrium salts that will dissolve in glacial acetic acid is dissolved in the glacial acetic acid, stirs down in 60～80 ℃ of temperature conditions and forms the yttrium precursor liquid in 60～120 minutes.
Step 1-5: the titanium precursor liquid of the barium strontium precursor liquid of step 1-1 gained, step 1-2 gained and the manganese precursor liquid of step 1-3 gained are mixed, wherein in the barium strontium precursor liquid in the mole sum of Ba and Sr, the titanium precursor liquid in Ti mole and the manganese precursor liquid mol ratio between the Mn mole three be 1: (1～1.2): (0.005～0.05); In mixing precursor liquid, drip the polyvinylpyrrolidone (PVP) that is equivalent to Ti mole 0.5%～1% then, regulate and mix the precursor liquid pH value between 3～4; Under 60～80 ℃ of temperature conditions, stirred 60～120 minutes again; Last spent glycol methyl ether constant volume obtains the stable BST colloidal sol of mixing Mn of 0.2～0.4 mol.
Step 1-6: the titanium precursor liquid of the barium strontium precursor liquid of step 1-1 gained, step 1-2 gained and the yttrium precursor liquid of step 1-4 gained are mixed, wherein in the barium strontium precursor liquid in the mole sum of Ba and Sr, the titanium precursor liquid in Ti mole and the yttrium precursor liquid mol ratio between the Y mole three be 1: (1～1.2): (0.005～0.05); In mixing precursor liquid, drip the polyvinylpyrrolidone (PVP) that is equivalent to Ti mole 0.5%～1% then, regulate and mix the precursor liquid pH value between 3～4; Under 60～80 ℃ of temperature conditions, stirred 60～120 minutes again; Last spent glycol methyl ether constant volume obtains the stable BST colloidal sol of mixing Y of 0.2～0.4 mol.
Step 2: the preparation individual layer is mixed the bst thin film of Mn, specifically may further comprise the steps:
Step 2-1: adopt step 1-5 gained to mix BST colloidal sol and the equipment for evenly dividing glue of Mn, behind gluing, even glue, on the liner substrate, form the BST wet film that individual layer is mixed Mn.
Remove moisture and most of organic matter in the BST wet film after step 2-2:BST wet film drying, the pyrolysis.
Pre-crystallization is 10～20 minutes under the temperature conditions of step 2-3:380～550 ℃, further to remove the organic matter in the bst thin film and to form young crystal layer.
Step 2-4: cooling obtains the bst thin film that individual layer is mixed Mn naturally.
Step 2-5: crystallization obtained the bst thin film that individual layer is mixed Mn in 60～120 minutes under 600～700 ℃ temperature conditions.
Step 3: the bst thin film surface preparation individual layer of mixing Mn at individual layer is mixed the bst thin film of Mn, specifically may further comprise the steps:
Step 3-1: adopt step 1-6 gained to mix BST colloidal sol and the equipment for evenly dividing glue of Y, behind gluing, even glue, form the BST wet film that individual layer is mixed Y on the bst thin film surface that individual layer is mixed Mn.
Remove moisture and most of organic matter in the BST wet film after step 3-2:BST wet film drying, the pyrolysis.
Pre-crystallization is 10～20 minutes under the temperature conditions of step 3-3:380～550 ℃, further to remove the organic matter in the bst thin film and to form young crystal layer.
Step 3-4: cooling obtains the bst thin film that individual layer is mixed Y naturally.
Step 3-5: crystallization obtained the bst thin film that individual layer is mixed Y in 60～120 minutes under 600～700 ℃ temperature conditions.
Step 4: the bst thin film of mixing Y with the individual layer of step 3-5 gained is a substrate base, and repeating step 2 and step 3 many times obtain the binary alternatively-doped bst thin film of multilayer Mn, Y.
Need to prove, in technique scheme:
1, among the step 1-1, the described inorganic barium salt that dissolves in glacial acetic acid specifically can adopt barium acetate, barium nitrate or brium carbonate; The described inorganic strontium salt that dissolves in glacial acetic acid specifically can adopt strontium acetate, strontium nitrate or strontium carbonate.
2, among the step 1-2, the described inorganic manganese salt that dissolves in glacial acetic acid specifically can adopt manganese acetate, manganese nitrate or manganese carbonate.
3, among the step 1-3, the described inorganic yttrium salts that dissolves in glacial acetic acid specifically can adopt acetic acid yttrium, yttrium nitrate or yttrium carbonate.
4, among step 2-1 or the step 3-1, during described even glue, earlier with 3000 rev/mins of even glue 5～10 seconds, again with 6000 rev/mins of even glue 30 seconds.
5, among step 2-2 or the step 3-2, described baking temperature is 80～150 ℃, and be 5～10 minutes drying time; Described pyrolysis temperature is 200～360 ℃, and pyrolysis time is 10～15 minutes.
6, among step 2-3 or the 3-3, described pre-crystallization treatment temperature is relevant with the time: lower limit temperature carry out upper limit time, ceiling temperature carry out the lower limit time or between certain temperature certain time between carrying out, its action effect is suitable.For example, 20 minutes, 550 ℃ pre-crystallization of 380 ℃ of pre-crystallization 10 minutes or 500 ℃ of pre-crystallization 15 minutes, action effect is suitable.Drying and pyrolysis processing are also like this.
7, the thickness of the binary alternatively-doped bst thin film of prepared multilayer Mn, the Y of the present invention can change as required, and reality can adopt the number of times of repeating step 2,3 to control.
8, in the binary alternatively-doped bst thin film of prepared multilayer Mn, the Y of the present invention, the order that preparation is mixed Mn or mixed the individual layer bst thin film of Y is not particularly limited, can exchange, no matter be that preparation is earlier mixed the individual layer bst thin film of Mn or prepared the individual layer bst thin film of mixing Y earlier promptly, its effect is similar.Being embodied in the step 2 in the technical scheme and the order of step 3 can exchange.
Essence of the present invention is in the binary alternatively-doped preparation bst thin film of Mn, Y, preparing at conventional sol-gel process increases pre-crystallization treatment step between the cooling of bst thin film and the crystallization treatment step, nano-crystalline BST film with this method preparation can carry out the class epitaxial growth under atmospheric environment, the gained nano-crystalline BST film is smooth, fine and close, flawless, no shrinkage cavity, stress are little, can significantly improve surface, interface, microstructure, crystallization feature etc.With the nano-crystalline BST film of the present invention's preparation, can give full play to nanocrystalline Quantum Nonlinear effect, increase substantially comprehensive dielectric tuning performance.The dielectric tuning rate greater than 30.0%, dielectric loss less than 2.0%, the K factor greater than 15, the dielectric strength height, frequency characteristic and temperature characterisitic are stable, can satisfy the needs of microwave-tuned device.The prepared nano-crystalline BST film of employing the present invention can substitute ferrite and semiconductor is used to prepare microwave-tuned device (as phase shifter), thereby significantly reduces the manufacturing cost of microwave-tuned device; In addition, the prepared nano-crystalline BST film of the present invention also can be used for magnetic recording, pyroelectricity focal plane arrays (FPA) etc.
Description of drawings
Fig. 1 schematic flow sheet of the present invention.
The Si/SiO of Fig. 2 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 1% mole of Mn and pre-crystallization, and even level is mixed 1% mole of Y and pre-crystallization.
The Si/SiO of Fig. 3 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 1% mole of Y and pre-crystallization, and even level is mixed 1% mole of Mn and pre-crystallization.
The Si/SiO of Fig. 4 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 1.5% mole of Mn and pre-crystallization, and even level is mixed 1.5% mole of Y and pre-crystallization.
The Si/SiO of Fig. 5 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 1.5% mole of Y and pre-crystallization, and even level is mixed 1.5% mole of Mn and pre-crystallization.
The Si/SiO of Fig. 6 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 0.5% mole of Mn and pre-crystallization, and even level is mixed 0.5% mole of Y and pre-crystallization.
The Si/SiO of Fig. 7 the present invention preparation
26 layers of bst thin film of Y and Mn alternating-doping on/the Ti/Pt matrix.Odd-level is mixed 0.5% mole of Y and pre-crystallization, and even level is mixed 0.5% mole of Mn and pre-crystallization.
Among Fig. 2 to Fig. 7: (a) be membrane structure, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz, " p " is unit of capacity-pico farad among the figure, and " m " is one thousandth.
The specific embodiment
According to technical scheme of the present invention at Si/SiO
2Six layers of 1mol%Mn for preparing on/Ti/Pt the matrix and 1mol%Y alternatively-doped BST membrane, as shown in Figure 2.Wherein, the doping content of Mn or Y is meant the percentage doping content (following each embodiment is all like this) with respect to barium strontium mole in the BST colloidal sol; Odd-level is mixed Mn and pre-crystallization, and even level is mixed Y and pre-crystallization.
Prepared bst thin film as shown in Figure 2, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 2, this bst thin film smooth surface, densification, flawless, but crystal boundary shows slightly fuzzy, nanocrystal mean size 40～50nm.Under the 100kHz: electric capacity is between 17pF～28pF, and dielectric loss is between 0.01～0.0125, and the dielectric tuning rate is 39.3%, and the K factor is 31～40; Under the 1MHz: electric capacity is between 17.6pF～27.5pF, and dielectric loss is between 0.0091～0.0119, and the electric tuning rate is 36%, and the K factor is 30～40.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
According to technical scheme of the present invention at Si/SiO
2Six layers of 1mol%Y for preparing on/Ti/Pt the matrix and 1mol%Mn alternatively-doped BST membrane, as shown in Figure 3.Odd-level is mixed Y and pre-crystallization, and even level is mixed Mn and pre-crystallization.
Prepared bst thin film as shown in Figure 3, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 3, this bst thin film smooth surface, densification, flawless, but crystal boundary is more clear, and the nanocrystal mean size increases to 50～60nm.Under the 100kHz: electric capacity is between 14.3pF～21.6pF, and dielectric loss is between 0.0061～0.0097, and the dielectric tuning rate is 33.8%, and the K factor is 34～56; Under the 1MHz: electric capacity is between 14.25pF～21.5pF, and dielectric loss is between 0.0071～0.0097, and the electric tuning rate is 33.7%, and the K factor is 34～48.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
According to technical scheme of the present invention at Si/SiO
2Six layers of 1.5mol%Mn for preparing on/Ti/Pt the matrix and 1.5mol%Y alternatively-doped BST membrane, as shown in Figure 4.Odd-level is mixed Mn and pre-crystallization, and even level is mixed Y and pre-crystallization.
Prepared bst thin film as shown in Figure 4, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 4, this bst thin film smooth surface, densification, flawless, the crystal grain mean size is about 50nm.Under the 100kHz: electric capacity is between 15.5pF～23.3pF, and dielectric loss is between 0.0068～0.0088, and the dielectric tuning rate is 33.5%, and the K factor is 38～50; Under the 1MHz: electric capacity is between 15.4pF～23.2pF, and dielectric loss is between 0.0074～0.0093, and the electric tuning rate is 33.6%, and the K factor is 36～46.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
According to technical scheme of the present invention at Si/SiO
2Six layers of 1.5mol%Y for preparing on/Ti/Pt the matrix and 1.5mol%Mn alternatively-doped BST membrane, as shown in Figure 5.Odd-level is mixed Y and pre-crystallization, and even level is mixed Mn and pre-crystallization.
Prepared bst thin film as shown in Figure 5, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 5, this bst thin film smooth surface, densification, flawless, nanocrystal on average is about 50nm.Under the 100kHz: electric capacity is between 15.5pF～25.9pF, and dielectric loss is between 0.0084～0.020, and the dielectric tuning rate is 40.1%, and the K factor is 20～48; Under the 1MHz: electric capacity is between 12.2pF～18.7pF, and dielectric loss is between 0.0168～0.0228, and the electric tuning rate is 34.8%, and the K factor is 15～21.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
According to technical scheme of the present invention at Si/SiO
2Six layers of 0.5mol%Mn for preparing on/Ti/Pt the matrix and 0.5mol%Y alternatively-doped BST membrane, as shown in Figure 6.Odd-level is mixed Mn and pre-crystallization, and even level is mixed Y and pre-crystallization.
Prepared bst thin film as shown in Figure 4, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 6, this bst thin film smooth surface, densification, flawless, it is fuzzy that crystal boundary shows slightly, and the crystal grain mean size is about 50～60nm.Under the 100kHz: electric capacity is between 13.5pF～23.3pF, and dielectric loss is between 0.0123～0.0165, and the dielectric tuning rate is 42.1%, and the K factor is 25～35; Under the 1MHz: electric capacity is between 13.2pF～22.7pF, and dielectric loss is between 0.0110～0.0115, and the electric tuning rate is 41.9%, and the K factor is 36～39.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
According to technical scheme of the present invention at Si/SiO
2Six layers of 0.5mol%Y for preparing on/Ti/Pt the matrix and 0.5mol%Mn alternatively-doped BST membrane, as shown in Figure 6.Odd-level is mixed Y and pre-crystallization, and even level is mixed Mn and pre-crystallization.
Prepared bst thin film as shown in Figure 6, wherein: (a) be the membrane structure schematic diagram, (b) be the AFM pattern of film, (c) and (d) electric capacity and the dielectric loss of corresponding film under 100kHz respectively, (e) and (f) corresponding respectively electric capacity and the dielectric loss under 1MHz.
As shown in Figure 6, this bst thin film smooth surface, densification, flawless, nanocrystal on average is about 50nm.Under the 100kHz: electric capacity is between 22pF～38.6pF, and dielectric loss is between 0.0102～0.0164, and the dielectric tuning rate is 43.0%, and the K factor is 26～43; Under the 1MHz: electric capacity is between 21.5pF～38.2pF, and dielectric loss is between 0.0108～0.0157, and the electric tuning rate is 43.7%, and the K factor is 27～41.Dielectric properties under two frequencies do not have significant change, show that dielectric frequency characteristics is stable.
In sum, in the process that successively prepares bst thin film, handle, can obtain nano-crystalline BST film smooth, fine and close, flawless alternating-doping, comprehensive dielectric tuning performance is increased substantially owing to carried out the binary alternatively-doped and pre-crystallization of Mn, Y.The dielectric tuning rate greater than 30.0%, dielectric loss less than 2.0%, the K factor greater than 15, the dielectric strength height, frequency characteristic and temperature characterisitic are stable, can satisfy the needs of microwave-tuned device.The prepared nano-crystalline BST film of employing the present invention can substitute ferrite and semiconductor is used to prepare microwave-tuned device (as phase shifter), thereby significantly reduces the manufacturing cost of microwave-tuned device; In addition, the prepared nano-crystalline BST film of the present invention also can be used for magnetic recording, pyroelectricity focal plane arrays (FPA) etc.
Claims (6)
1. the preparation method of a binary alternatively-doped BST membrane may further comprise the steps:
Step 1: preparation is mixed the BST colloidal sol of Mn and is mixed the BST colloidal sol of Y, specifically may further comprise the steps:
Step 1-1: with mol ratio is Ba: Sr=x: (1-x) inorganic barium salt that dissolves in glacial acetic acid and inorganic strontium salt are dissolved in the glacial acetic acid, stir down in 60～80 ℃ of temperature conditions and form barium strontium precursor liquid, wherein 0＜x＜1 in 60～120 minutes;
Step 1-2: be 1: 2 butyl titanate and acetylacetone,2,4-pentanedione Hybrid Heating with mol ratio and stir and formed titanium precursor liquid in 60～120 minutes;
Step 1-3: the inorganic manganese salt that will dissolve in glacial acetic acid is dissolved in the glacial acetic acid, stirs down in 60～80 ℃ of temperature conditions and forms the manganese precursor liquid in 60～120 minutes;
Step 1-4: the inorganic yttrium salts that will dissolve in glacial acetic acid is dissolved in the glacial acetic acid, stirs down in 60～80 ℃ of temperature conditions and forms the yttrium precursor liquid in 60～120 minutes;
Step 1-5: the titanium precursor liquid of the barium strontium precursor liquid of step 1-1 gained, step 1-2 gained and the manganese precursor liquid of step 1-3 gained are mixed, wherein in the barium strontium precursor liquid in the mole sum of Ba and Sr, the titanium precursor liquid in Ti mole and the manganese precursor liquid mol ratio between the Mn mole three be 1: (1～1.2): (0.005～0.05); In mixing precursor liquid, drip the polyvinylpyrrolidone that is equivalent to Ti mole 0.5%～1% then, regulate and mix the precursor liquid pH value between 3～4; Under 60～80 ℃ of temperature conditions, stirred 60～120 minutes again; Last spent glycol methyl ether constant volume obtains the stable BST colloidal sol of mixing Mn of 0.2～0.4 mol;
Step 1-6: the titanium precursor liquid of the barium strontium precursor liquid of step 1-1 gained, step 1-2 gained and the yttrium precursor liquid of step 1-4 gained are mixed, wherein in the barium strontium precursor liquid in the mole sum of Ba and Sr, the titanium precursor liquid in Ti mole and the yttrium precursor liquid mol ratio between the Y mole three be 1: (1～1.2): (0.005～0.05); In mixing precursor liquid, drip the polyvinylpyrrolidone that is equivalent to Ti mole 0.5%～1% then, regulate and mix the precursor liquid pH value between 3～4; Under 60～80 ℃ of temperature conditions, stirred 60～120 minutes again; Last spent glycol methyl ether constant volume obtains the stable BST colloidal sol of mixing Y of 0.2～0.4 mol;
Step 2: the preparation individual layer is mixed the bst thin film of Mn, specifically may further comprise the steps:
Step 2-1: adopt step 1-5 gained to mix BST colloidal sol and the equipment for evenly dividing glue of Mn, behind gluing, even glue, on the liner substrate, form the BST wet film that individual layer is mixed Mn;
Remove moisture and most of organic matter in the BST wet film after step 2-2:BST wet film drying, the pyrolysis;
Pre-crystallization is 10～20 minutes under the temperature conditions of step 2-3:380～550 ℃, further to remove the organic matter in the bst thin film and to form young crystal layer;
Step 2-4: cooling obtains the pre-crystallization thin film of BST that individual layer is mixed Mn naturally;
Step 2-5: crystallization obtained the bst thin film that individual layer is mixed Mn in 60～120 minutes under 600～700 ℃ temperature conditions;
Step 3: the bst thin film surface preparation individual layer of mixing Mn at individual layer is mixed the bst thin film of Y, specifically may further comprise the steps:
Step 3-1: adopt step 1-6 gained to mix BST colloidal sol and the equipment for evenly dividing glue of Y, behind gluing, even glue, form the BST wet film that individual layer is mixed Y on the bst thin film surface that individual layer is mixed Mn;
Remove moisture and most of organic matter in the BST wet film after step 3-2:BST wet film drying, the pyrolysis;
Pre-crystallization is 10～20 minutes under the temperature conditions of step 3-3:380～550 ℃, further to remove the organic matter in the bst thin film and to form young crystal layer;
Step 3-4: cooling obtains the pre-crystallization thin film of BST that individual layer is mixed Y naturally;
Step 3-5: crystallization obtained the bst thin film that individual layer is mixed Y in 60～120 minutes under 600～700 ℃ temperature conditions;
Step 4: the bst thin film of mixing Y with the individual layer of step 3-5 gained is a substrate base, and repeating step 2 and step 3 many times obtain the binary alternatively-doped bst thin film of multilayer Mn, Y.
2. the preparation method of binary alternatively-doped BST membrane according to claim 1 is characterized in that, the inorganic barium salt that dissolves in glacial acetic acid described in the step 1-1 specifically adopts barium acetate, barium nitrate or brium carbonate; The described inorganic strontium salt that dissolves in glacial acetic acid specifically adopts strontium acetate, strontium nitrate or strontium carbonate.
3. the preparation method of binary alternatively-doped BST membrane according to claim 1 is characterized in that, the inorganic manganese salt that dissolves in glacial acetic acid described in the step 1-2 specifically adopts manganese acetate, manganese nitrate or manganese carbonate
4. the preparation method of binary alternatively-doped BST membrane according to claim 1 is characterized in that, the inorganic yttrium salts that dissolves in glacial acetic acid described in the step 1-3 specifically can adopt acetic acid yttrium, yttrium nitrate or yttrium carbonate.
5. the preparation method of binary alternatively-doped BST membrane according to claim 1 is characterized in that, during even glue described in step 2-1 or the step 3-1, earlier with 3000 rev/mins of even glue 5～10 seconds, again with 6000 rev/mins of even glue 30 seconds.
6. the preparation method of binary alternatively-doped BST membrane according to claim 1 is characterized in that, baking temperature is 80～150 ℃ described in step 2-2 or the step 3-2, and be 5～10 minutes drying time; Described pyrolysis temperature is 200～360 ℃, and pyrolysis time is 10～15 minutes.
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| CN102062770A (en) * | 2010-12-03 | 2011-05-18 | 厦门大学 | Ternary oxide air-sensitive material and synthesis method thereof |
| CN102060525A (en) * | 2010-12-09 | 2011-05-18 | 电子科技大学 | Method of preparing two-component co-doped BST (Barium Strontium Titanate) micro-nano powder |
| CN102173783B (en) * | 2011-01-23 | 2012-11-07 | 电子科技大学 | Preparation method of binary gradiently doped barium strontium titanate (BST) film |
| CN102276253A (en) * | 2011-05-26 | 2011-12-14 | 华中科技大学 | Method for preparing field pyroelectric ceramic material |
| CN105924153A (en) * | 2016-04-15 | 2016-09-07 | 电子科技大学 | Multilayer film with sandwich structure and preparation method thereof |
| CN113140354A (en) * | 2021-04-15 | 2021-07-20 | 江苏大学 | Mg2+/K+BST (barium strontium titanate) flexible electric film alternatively doped with heterogeneous ions and preparation method thereof |
-
2009
- 2009-11-27 CN CN2009102164062A patent/CN101716838B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| JP特开2006-289821A 2006.10.26 |
| 李晓光等."BST陶瓷膜制备方法及优化".《微纳电子技术》.2006,(第7期),第338～341页. |
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