CN1176044C - Bismuth sodium titanate series film material and preparing process thereof - Google Patents
Bismuth sodium titanate series film material and preparing process thereof Download PDFInfo
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- CN1176044C CN1176044C CNB02135524XA CN02135524A CN1176044C CN 1176044 C CN1176044 C CN 1176044C CN B02135524X A CNB02135524X A CN B02135524XA CN 02135524 A CN02135524 A CN 02135524A CN 1176044 C CN1176044 C CN 1176044C
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Abstract
The present invention belongs to the technical field of a film, which is characterized in that sodium bismuth titanate series film materials are prepared from titanium, bismuth, sodium, barium, plumbum, strontium, calcium and oxygen ions, and the molecular formula of the film materials is (1-X)(Bi<0.5>Na<0.5>)TiO3+XMTiO3, wherein X is from 0 to 0.6, and M is barium, plumbum, strontium or calcium. The film materials are prepared by adopting a metallic organic solution depositing method. The film materials overcome the disadvantages of high electric conductivity of sodium bismuth titanate ceramics in a ferroelectric area, narrow sintering temperature range, easy water absorption, etc. The present invention has good storage characteristic, and high thermoelectric property, and can be widely used for the technical fields of microelectrons, photoelectrons, computers, sensors, aerospace, etc.
Description
(1) technical field
The present invention relates to a kind of bismuth sodium titanate series film material and preparation method thereof, belong to the thin-film material technical field.
(2) background technology
The molecular formula of bismuth-sodium titanate material is (Bi
1/2Na
1/2) TiO
3It is the perovskite typed ferroelectrics of nineteen sixty by people such as Smolensky invention.It has following advantage: strong (the residual polarization Pr=38 μ C/cm of ferroelectricity
2); Big (the k of piezo-electric modulus
t, k
33, about 50%); DIELECTRIC CONSTANT r is 240～340; Pyroelectric property and lead titanate are suitable with lead titanate-zirconate PZT; Good (its frequency constant N ρ=3200Hzm), thereby help making surface acoustic wave device of acoustical behavior; It also has the ferroelectric characteristic of relaxation property, and firing temperature belongs to intermediate sintering temperature.Have following weakness as the stupalith bismuth-sodium titanate: coercive electric field higher (73kv/cm) is difficult to polarization; This pottery is higher in the specific conductivity of ferroelectric phase region; This series ceramic sintering range is narrow; Na
2O easily absorbs water.
People such as the scholar K.Sakata of Tokyo college of science and T.Takenaka are devoted for years to and have successfully solved the bismuth-sodium titanate pottery in the study on the modification of bismuth-sodium titanate pottery and be difficult to the polar problem, and have obtained the non-plumbum ferroelectric piezoelectric ceramics of better performances.Specifically be divided into following four classes:
(1) (1-X) BNT+X (Sr
aPb
bCa
c) TiO
3(a+b+c=1); (2) (1-X) BXT+XBaTiO
3(3) (1-X) BNT+XMNbO
3(M is Na, K); (4) (1-X) BNT+ (1/2) * (Bi
2O
3.Sc
2O
3).
People such as scientist in Poland K.ROLEDERD in 1989 adopt flux method to prepare and are of a size of 0.5 * 0.5 * 0.2mm
3The bismuth-sodium titanate monocrystalline, determined the structure and the transformation temperature of bismuth-sodium titanate substantially.
So far, do not see the relevant report of any bismuth sodium titanate series film in the world as yet.
(3) summary of the invention
In order to reduce environmental pollution, overcome of the Lead contamination of the present Pb-based lanthanumdoped zirconate titanates series film material that is using to environment, reduce plumbous content in thin-film material to greatest extent, in order to improve the specific inductivity of this type of thin-film material, reduce dielectric loss, reduce dielectricity with variation of temperature, improve the anti-disruptive strength of this type of thin-film material.The present invention has prepared a kind of bismuth sodium titanate series film material, and has provided the preparation method.
The present invention is realized by following technical scheme:
The prepared bismuth sodium titanate series film material of the present invention is made up of titanium, bismuth, sodium, barium, lead, strontium, calcium and oxonium ion, has the thin-film material of perovskite structure.Their molecular formula is (1-X) (Bi
1/2Na
1/2) TiO
3+ XMTiO
3, wherein the X value is 0～0.6; M is any one in barium, lead, strontium or the calcium constituent.
The technological process of preparation bismuth sodium titanate series film material is as follows:
(1) configuration solution in early stage, early stage, solution can be a kind of of following situation:
1. pure bismuth-sodium titanate (Bi
1/2Na
1/2) TiO
3Solution, i.e. X=0
Stoichiometric ratio by molecular formula takes by weighing Bismuth trinitrate or bismuth acetate and SODIUMNITRATE or sodium-acetate raw material, formerly insert mill respectively or shredder grinds to form fine powder with what weigh up, the SODIUMNITRATE that grinds to form fine powder is dissolved in ethylene glycol monomethyl ether, and constantly heat and stir, temperature is controlled at 40 ℃～200 ℃, makes 1# solution; Bismuth trinitrate is dissolved in the Glacial acetic acid, and constantly heats and stir, temperature is controlled at 40 ℃～200 ℃, makes 2# solution;
2. adulterated bismuth sodium titanate series (1-X) (Bi
1/2Na
1/2) TiO
3+ XMTiO
3Solution i.e. 0＜X≤0.6
Stoichiometric ratio by molecular formula takes by weighing bismuth acetate or Bismuth trinitrate, sodium-acetate or SODIUMNITRATE and acetic acid M or nitric acid M, M is wherein any one of barium, lead, strontium or calcium, with the sodium-acetate or SODIUMNITRATE and the acetic acid M that weigh up or nitric acid M raw material inserts mill respectively or shredder grinds to form fine powder, the various raw materials that grind to form fine powder are dissolved in ethylene glycol monomethyl ether, and constantly heat and stir, temperature is controlled at 40 ℃～200 ℃, makes 1# solution; Bismuth acetate is dissolved in the Glacial acetic acid, and constantly heats and stir, temperature is controlled at 40 ℃～200 ℃, makes 2# solution;
(2) select a kind of of solution in early stage, pour 1# solution into 2# solution, and lasting heated and stirred, heating and temperature control mixes until solution at 40 ℃～200 ℃; Then mixing solutions is reduced to room temperature, added the methyl ethyl diketone of stabilization again to solution; Then
(3) accurately measure metatitanic acid four fourth fat by the stoichiometric ratio of molecular formula and join in the solution in early stage, the spent glycol methyl ether arrives needed volumetric molar concentration with solution dilution then;
(4) allow the early stage solution be the strainer of 0.2 μ m by the aperture, filter out impurities and suspended matter, obtain the precursor solution of bismuth sodium titanate series film; Then
(5) select the substrate of the silicon chip of process cleaning as film; Then
(6) with the precursor solution of sol evenning machine to the bismuth sodium titanate series film, even glue is 4～10 seconds under 200～600 rev/mins speed, even glue is 20～60 seconds under 2000～6000 rev/mins speed, the wet film of gained is heat-treated in air, rise to 300 ℃～600 ℃ with 10 ℃～20 ℃/minute temperature rise rates, and kept 10～40 minutes, reduce to room temperature then; Repeat this step, can obtain the bismuth sodium titanate series film of 20～1000 nanometer thickness;
(7) again the bismuth sodium titanate series film is carried out anneal, temperature is controlled at 400 ℃～800 ℃, and the time is 20～180 minutes, can obtain the bismuth sodium titanate series film of more stable polycrystalline of performance or orientation crystalline state.
The used silicon chip type of substrate material is P type or N type; Silicon chip is oriented to (111) or (100).
The present invention adopts the sedimentary method of metal organosol to prepare the bismuth sodium titanate series ferroelectric membranc, has a series of critical natures such as ferroelectric, pyroelectricity and photoelectricity.Adopt the bismuth sodium titanate series film can prepare film capacitor at present, it has following advantage than ordinary capacitor: (1) specific inductivity is big, and (2) dielectric loss is little, and (3) dielectricity varies with temperature little, (4) height of anti-the disruptive strength.The bismuth sodium titanate series film can also be used to preparing ferroelectric random memory (non-volatile memory FERAM and FEFET), and be characterized in: (1) coercive electric field is low, and (2) dielectric loss is little, (3) resistivity height.The bismuth sodium titanate series film has overcome also that the bismuth-sodium titanate pottery is higher in the specific conductivity of ferroelectric phase region, sintering range is narrow and easy weakness such as suction.The market outlook of estimating bismuth sodium titanate series film maximum can be aspect the ferroelectric smart card of manufacturing.Also can be widely used in numerous areas such as microelectronics, photoelectron, computer, transmitter and aeronautical and space technology as a kind of new thin-film material bismuth sodium titanate series film material.It is the most promising newcomer in the ferroelectric membranc extended familys.
(4) embodiment
Embodiment 1.
Bismuth-sodium titanate (the Bi of one liter of 0.5mol concentration of configuration
1/2Na
1/2) TiO
3Solution selects X=0 in the molecular formula, concrete preparation process is as follows:
(1) stoichiometric ratio by molecular formula accurately takes by weighing analytically pure raw material: Bismuth trinitrate 49.00 grams, and SODIUMNITRATE 8.58 grams are inserted mill or shredder respectively, grind to form fine powder; The SODIUMNITRATE that grinds to form fine powder is dissolved in the 300ml ethylene glycol monomethyl ether, and constantly heats and stir, Heating temperature is 100 ℃; Make 1# solution; Bismuth trinitrate is dissolved in the 600ml Glacial acetic acid, and constantly heats and stir, temperature is 100 ℃, makes 2# solution;
(2) pour 1# solution into 2# solution, and lasting heated and stirred, heating and temperature control mixes until solution at 100 ℃; Then mixing solutions is reduced to room temperature, added the methyl ethyl diketone 25ml of stabilization again to solution; Then
(3) accurately measure metatitanic acid four fourth fat 69ml by the stoichiometric ratio of molecular formula and join in the solution in early stage, the spent glycol methyl ether arrives 1000ml with solution dilution then;
(4) allow the early stage solution be the strainer of 0.2 μ m by the aperture, filter out impurities and suspended matter, obtain the precursor solution of bismuth sodium titanate series film; Then;
(5) the P type silicon chip of selecting process to clean, silicon chip is oriented to (111), as the substrate of film; Then
(6) with the precursor solution of sol evenning machine to the bismuth sodium titanate series film, even glue is 6 seconds under 500 rev/mins speed, even glue is 30 seconds under 4500 rev/mins speed, the wet film of gained is heat-treated in air, rise to 500 ℃ with 15 ℃/minute temperature rise rates, and kept 15 minutes, reduce to room temperature then; This step repeats 4 times, can obtain the bismuth-sodium titanate film of 220 nanometer thickness;
(7) again the bismuth sodium titanate series film is carried out anneal, temperature is controlled at 650 ℃, and the time is 150 minutes,
Can obtain the bismuth sodium titanate series film of more stable polycrystalline of performance or orientation crystalline state.
Embodiment 2.
The barium sodium bismuth titanate Ba of one liter of 0.5mol concentration of configuration
0.1(Bi
1/2Na
1/2)
0.9TiO
3Solution selects X=0.1 in the molecular formula; M=Ba, concrete preparation process is as follows:
(1) stoichiometric ratio by molecular formula accurately takes by weighing analytically pure raw material: bismuth acetate 35.10 grams, and sodium-acetate 7.46 grams, barium acetate 5.52 grams are inserted mill or shredder respectively, grind to form fine powder; The sodium-acetate and the barium acetate that grind to form fine powder are dissolved in the 300ml ethylene glycol monomethyl ether, and constantly heat and stir, Heating temperature is 100 ℃; Make 1# solution; Bismuth trinitrate is dissolved in the 600ml Glacial acetic acid, and constantly heats and stir, temperature is 100 ℃, makes 2# solution;
(2)～(7) processing step is identical with (2)～(7) processing step of embodiment 1.
Embodiment 3.
The plumbous Pb of the bismuth-sodium titanate of one liter of 0.5mol concentration of configuration
0.2(Bi
1/1Na
1/2)
0.8TiO
3Solution selects X=0.1 in the molecular formula; M=Pb, concrete preparation process is as follows:
(1) stoichiometric ratio by molecular formula accurately takes by weighing analytically pure raw material: Bismuth trinitrate 39.20 grams, and SODIUMNITRATE 6.87 grams, plumbic acetate 15.33 grams are inserted mill or shredder respectively, grind to form fine powder; The SODIUMNITRATE and the plumbic acetate that grind to form fine powder are dissolved in the 600ml ethylene glycol monomethyl ether, and constantly heat and stir, Heating temperature is 100 ℃; Make 1# solution; Bismuth trinitrate is dissolved in the 300ml Glacial acetic acid, and constantly heats and stir, temperature is 100 ℃, makes 2# solution;
(2)～(7) processing step is identical with (2)～(7) processing step of embodiment 1.
Embodiment 4.
The bismuth-sodium titanate calcium Ca of one liter of 0.5mol concentration of configuration
0.1(Bi
1/2Na
1/2)
0.9TiO
3, select X=0.1 in the molecular formula; M=Ca, concrete preparation process is as follows:
(1) stoichiometric ratio by molecular formula accurately takes by weighing analytically pure raw material: bismuth acetate 35.10 grams, and sodium-acetate 7.46 grams, calcium acetate 3.20 grams are inserted mill or shredder respectively, grind to form fine powder; The bismuth acetate and the sodium-acetate that grind to form fine powder are dissolved in the 300ml ethylene glycol monomethyl ether, and constantly heat and stir, Heating temperature is 100 ℃; Make 1# solution; Bismuth trinitrate is dissolved in the 600ml Glacial acetic acid, and constantly heats and stir, temperature is 100 ℃, makes 2# solution;
(2)～(7) processing step is identical with (2)～(7) processing step of embodiment 1.
Embodiment 5.
The bismuth-sodium titanate strontium Sr0.1 (Bi of one liter of 0.5mol concentration of configuration
1/2Na
1/2)
0.9TiO
3Solution selects X=0.1 in the molecular formula; M=Sr, concrete preparation process is as follows:
(1) stoichiometric ratio by molecular formula accurately takes by weighing analytically pure raw material: bismuth acetate 35.10 grams, and sodium-acetate 7.46 grams, strontium acetate 4.16 grams are inserted mill or shredder respectively, grind to form fine powder; The bismuth acetate and the sodium-acetate that grind to form fine powder are dissolved in the 300ml ethylene glycol monomethyl ether, and constantly heat and stir, Heating temperature is 100 ℃; Make 1# solution; Bismuth trinitrate is dissolved in the 600ml Glacial acetic acid, and constantly heats and stir, temperature is 100 ℃, makes 2# solution;
(2)～(7) processing step is identical with (2)～(7) processing step of embodiment 1.
Claims (3)
1. bismuth sodium titanate series film material is characterized in that it is made up of titanium, bismuth, sodium, barium, lead, strontium, calcium and oxonium ion, and its ingredient formula is (1-X) (Bi
1/2Na
1/2) TiO
3+ XMTiO
3, wherein the value of X is 0～0.6; M is any one in barium, lead, strontium or the calcium constituent.
2. preparation method who prepares bismuth sodium titanate series film material as claimed in claim 1 is characterized in that preparation process is as follows:
(1) configuration solution in early stage, early stage, solution can be a kind of of following situation:
1. pure bismuth-sodium titanate (Bi
1/2Na
1/2) TiO
3Solution, i.e. X=0
Stoichiometric ratio by molecular formula takes by weighing Bismuth trinitrate or bismuth acetate and SODIUMNITRATE or sodium-acetate raw material, the raw material that weighs up is inserted mill respectively or shredder grinds to form fine powder, the SODIUMNITRATE that grinds to form fine powder is dissolved in ethylene glycol monomethyl ether, and constantly heat and stir, temperature is controlled at 40 ℃～200 ℃, makes 1# solution; Bismuth trinitrate is dissolved in the Glacial acetic acid, and constantly heats and stir, temperature is controlled at 40 ℃～200 ℃, makes 2# solution;
2. adulterated bismuth sodium titanate series (1-X) (Bi
1/2Na
1/2) TiO
3+ XMTiO
3Solution i.e. 0＜X≤0.6
Stoichiometric ratio by molecular formula takes by weighing bismuth acetate or Bismuth trinitrate, sodium-acetate or SODIUMNITRATE and acetic acid M or nitric acid M, M is wherein any one of barium, lead, strontium or calcium, with the sodium-acetate or SODIUMNITRATE and the acetic acid M that weigh up or nitric acid M raw material inserts mill respectively or shredder grinds to form fine powder, the various raw materials that grind to form fine powder are dissolved in ethylene glycol monomethyl ether, and constantly heat and stir, temperature is controlled at 40 ℃～200 ℃, makes 1# solution; Bismuth acetate is dissolved in the Glacial acetic acid, and constantly heats and stir, temperature is controlled at 40 ℃～200 ℃, makes 2# solution;
(2) select a kind of of solution in early stage, pour 1# solution into 2# solution, and lasting heated and stirred, heating and temperature control mixes until solution at 40 ℃～200 ℃; Then mixing solutions is reduced to room temperature, added the methyl ethyl diketone of stabilization again to solution: then
(3) accurately measure metatitanic acid four fourth fat by the stoichiometric ratio of molecular formula and join in the solution in early stage, the spent glycol methyl ether arrives needed volumetric molar concentration with solution dilution then;
(4) allow the early stage solution be the strainer of 0.2 μ m by the aperture, filter out impurities and suspended matter, obtain the precursor solution of bismuth sodium titanate series film; Then
(5) select the substrate of the silicon chip of process cleaning as film; Then
(6) with the precursor solution of sol evenning machine to the bismuth sodium titanate series film, even glue is 4～10 seconds under 200～600 rev/mins speed, even glue is 20～60 seconds under 2000～6000 rev/mins speed, the wet film of gained is heat-treated in air, rise to 300 ℃～600 ℃ with 10 ℃～20 ℃/minute temperature rise rates, and kept 10～40 minutes, reduce to room temperature then; Repeat this step, can obtain the bismuth sodium titanate series film of 20～1000 nanometer thickness;
(7) again the bismuth sodium titanate series film is carried out anneal, temperature is controlled at 400 ℃～800 ℃, and the time is 20～180 minutes, can obtain the bismuth sodium titanate series film of more stable polycrystalline of performance or orientation crystalline state.
3. the preparation method of bismuth sodium titanate series film material according to claim 2 is characterized in that the silicon chip type is P type or N type; Silicon chip is oriented to (111) or (100).
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Families Citing this family (10)
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|---|---|---|---|---|
| CN100341590C (en) * | 2004-10-15 | 2007-10-10 | 洪克森 | Material for rehabilitation therapy capable of emitting biological photon wave spectrum |
| CN101215172B (en) * | 2008-01-09 | 2010-06-09 | 华中科技大学 | Method for preparing bismuth sodium titanate base leadless piezoelectricity thick film |
| CN103043719B (en) * | 2012-11-15 | 2014-05-07 | 华中科技大学 | Method for preparing sodium bismuth titanate oriented film and product thereof |
| CN103708739A (en) * | 2013-07-02 | 2014-04-09 | 济南大学 | Zinc-doped sodium bismuth titanate film and low temperature preparation method thereof |
| CN104072129A (en) * | 2014-04-18 | 2014-10-01 | 济南大学 | B-position equivalent zirconium doped sodium bismuth titanate film |
| CN104103755B (en) * | 2014-07-14 | 2017-05-24 | 上海交通大学 | Sodium bismuth titanate thin film system based resistance random access memory and preparation method thereof |
| CN107365152A (en) * | 2017-09-04 | 2017-11-21 | 苏州云舒新材料科技有限公司 | A kind of preparation method of the sub- ceramic membrane material of pyroelectricity |
| CN110451954B (en) * | 2019-07-23 | 2021-12-07 | 同济大学 | Sodium bismuth titanate-based low-lead piezoelectric film with high inverse piezoelectric coefficient and preparation method thereof |
| CN112341191B (en) * | 2020-10-26 | 2022-02-22 | 同济大学 | Lead-free ceramic dielectric with high energy storage density and high energy storage efficiency and preparation method thereof |
| CN115677342A (en) * | 2021-07-28 | 2023-02-03 | 中国科学院上海硅酸盐研究所 | Preparation method of perovskite structure BNT/LNO heteroepitaxial film |
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