CN102956811A - Sodium bismuth titanate lead-free piezoelectric composite thick film for high-frequency ultrasonic transducer and preparation method thereof - Google Patents
Sodium bismuth titanate lead-free piezoelectric composite thick film for high-frequency ultrasonic transducer and preparation method thereof Download PDFInfo
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- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910002115 bismuth titanate Inorganic materials 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000004528 spin coating Methods 0.000 claims abstract description 18
- 239000011268 mixed slurry Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 20
- 238000013019 agitation Methods 0.000 claims description 20
- 238000000498 ball milling Methods 0.000 claims description 17
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000001632 sodium acetate Substances 0.000 claims description 14
- 235000017281 sodium acetate Nutrition 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005516 engineering process Methods 0.000 claims description 10
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 6
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 5
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 238000013467 fragmentation Methods 0.000 claims description 2
- 238000006062 fragmentation reaction Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 230000005621 ferroelectricity Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 238000010897 surface acoustic wave method Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The invention relates to a piezoelectric composite thick film in an inorganic material and a preparation method thereof, and discloses a sodium bismuth titanate lead-free piezoelectric composite thick film for a high-frequency ultrasonic transducer and a preparation method thereof. The preparation method is characterized by comprising the following steps of: (1) preparing sodium bismuth titanate precursor sol according to the stoichiometric proportion of Bi0.5Na0.5TiO3; (2) preparing micro-nano scale Bi0.5Na0.5TiO3 powder; (3) mixing the micro-nano scale Bi0.5Na0.5TiO3 powder with the sodium bismuth titanate precursor sol to prepare mixed slurry, wherein the mass content of the ceramic powder is 20-80 percent; and (4) repeating a spin coating process-thermal treatment process to obtain the lead-free piezoelectric composite thick film.
Description
Technical field
The present invention relates to piezoelectric composite thick film in the inorganic material and preparation method thereof, particularly a kind of bismuth-sodium titanate leadless piezoelectric composite thick film for high-frequency transducer and preparation method thereof.
Background technology
In view of the harm that lead-containing materials causes for environment and human health in preparation, use and waste treatment process, unleaded research becomes the main research and development direction of Material Field gradually for material.At present, the potassium sodium niobate piezoelectric ceramics with perovskite structure has high piezoelectricity because of it and high Curie temperature receives much concern, but adopts traditional ceramic sintering process to be difficult to prepare the good pure potassium sodium niobate ceramic body of compactness.Bismuth-sodium titanate because of its at room temperature strong ferroelectricity receive publicity equally, but there is the shortcoming that coercive field is high, phase transition temperature is low in pure bismuth-sodium titanate piezoelectric ceramic, it is practical thereby affect.
Piezoelectric thick (1～100 micron) material has been taken into account the advantage of film (less than 1 micron) and block (grade), operating voltage is low, operating frequency range is wide, electrical property can be applied to high frequency sonar transducer, elasticity SAW (Surface Acoustic Wave) device, Novel ultrasonic transducer, pyroelectric infrared sensor, micro mechanical system, micro motor and mini drive etc. near block materials.
Summary of the invention
The object of the present invention is to provide a kind of bismuth-sodium titanate leadless piezoelectric composite thick film for high-frequency transducer and preparation method thereof, can effectively reduce the sintering temperature of thick film, reduce the volatilization of sodium, bismuth element, improve dielectric, ferroelectric, the piezoelectric property of thick film.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of preparation method of the bismuth-sodium titanate leadless piezoelectric composite thick film for high-frequency transducer may further comprise the steps:
(1), preparation bismuth-sodium titanate precursor colloidal sol: according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, with bismuth nitrate solution, sodium acetate solution, and after the tetra-n-butyl titanate mixed solution mixes, naturally cool to room temperature after, the bismuth-sodium titanate precursor colloidal sol that obtains clarifying, for subsequent use;
(2) preparation micro/nano level bismuth-sodium titanate powder: according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, with sodium carbonate, bismuth oxide, and after the titanium dioxide mixing and ball milling, dry, compressing tablet at 800 ~ 1100 ℃ of sintering, obtain having the bismuth-sodium titanate base substrate of perovskite structure, behind fragmentation, ball milling, obtain micro/nano level bismuth-sodium titanate powder, for subsequent use;
(3) preparation of mixed slurry: the bismuth-sodium titanate precursor colloidal sol that the nanoscale metatitanic acid bismuth sodium powder that step (2) is obtained and step (1) obtain mixes, and wherein, the mass content of ceramic powder is 20 ~ 80%, obtains stable mixed slurry after stirring;
(4) mixed slurry that adopts spin coating proceeding that step (3) is obtained is deposited on the silicon base of plating Pt, then heat-treats technique, obtains having the leadless piezoelectric composite thick film of bismuth-sodium titanate.
As the preferred embodiments of the present invention, in the step (1), the preparation method of described tetra-n-butyl titanate mixed solution is: be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, the room temperature magnetic agitation obtains the tetra-n-butyl titanate mixed solution;
As the preferred embodiments of the present invention, in the step (1), the preparation method of described sodium acetate is: excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drips simultaneously glacial acetic acid as catalyst, the room temperature magnetic agitation obtains sodium acetate solution;
As the preferred embodiments of the present invention, in the step (2), during ball milling, take absolute ethyl alcohol as medium;
As the preferred embodiments of the present invention, in the step (3), during mixing and ball milling, with polyvinylpyrrolidone as stable dispersant;
As the preferred embodiments of the present invention, in the step (4), described Technology for Heating Processing is: 150 ℃～200 ℃ are incubated 3 minutes first, and 350 ℃ again～450 ℃ are incubated 3～10 minutes, anneal 3～5 minutes for 650 ℃～750 ℃;
As the preferred embodiments of the present invention, in the step (4), the rotating speed of spin coating is 3000 rev/mins, and the spin coating time is 30～50 seconds.
The composite thick film that the present invention prepares determines to have following character through x x ray diffraction (XRD), electric impedance analyzer and ferroelectric analyzer test analysis:
(1), the composite thick film of preparation after 650～750 ℃ of annealing in process, phase structure presents perovskite structure, shows that the composite construction crystallization of the phase structure of sol in the phase structure of ceramic powder of crystallization and the mixed slurry is complete;
(2), thicknesses of layers is 1～10 μ m.
(3), the dielectric constant of thick film between 400～600, dielectric loss is less than 8%, the strong 2E of coercive field
cBe 150～250kV/cm, remanent polarization 2P
rBe 35～45 μ C/cm
2
Description of drawings
Fig. 1 is the XRD figure of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT40 of embodiment 1 preparation;
Fig. 2 is the dielectric loss spectrum of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT40 of embodiment 1 preparation;
Fig. 3 is the electric hysteresis loop of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT40 of embodiment 1 preparation;
Fig. 4 is the XRD figure of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT50 of embodiment 2 preparations;
Fig. 5 is the dielectric loss spectrum of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT50 of embodiment 2 preparations;
Fig. 6 is the electric hysteresis loop of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT50 of embodiment 2 preparations;
Fig. 7 is the XRD figure of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT70 of embodiment 4 preparations;
Fig. 8 is the dielectric loss spectrum of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT70 of embodiment 4 preparations;
Fig. 9 is the electric hysteresis loop of the bismuth-sodium titanate leadless piezoelectric composite thick film BNT70 of embodiment 4 preparations;
Wherein: the abscissa of Fig. 1, Fig. 4, Fig. 7 represents the X-ray diffraction angle, and ordinate represents diffracted intensity; Abscissa represents the test frequency scope among Fig. 2, Fig. 5, Fig. 8, the unit hertz, and left side ordinate represents relative dielectric constant, the right ordinate represents loss; Abscissa represents electric field strength among Fig. 3, Fig. 6, Fig. 9, every centimetre of unit kilovolt, and ordinate represents polarization intensity, every square centimeter of unit microcoulomb.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in further detail.
Embodiment 1
(1), at first according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, five excessive 2% mole water bismuth nitrates are dissolved in the EGME, room temperature magnetic agitation 30 minutes obtains bismuth nitrate solution; Excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drips simultaneously glacial acetic acid as catalyst, room temperature magnetic agitation 30 minutes obtains sodium acetate solution; Be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, room temperature magnetic agitation 40 minutes obtains the tetra-n-butyl titanate mixed solution; Then respectively bismuth nitrate solution and sodium acetate solution are dropped in the tetra-n-butyl titanate mixed solution, and 80 ℃ of lower temperature constant magnetic stirrings 1 hour, naturally cool to afterwards room temperature, finally obtain the bismuth-sodium titanate precursor colloidal sol clarified, and to adjust bismuth-sodium titanate concentration be 0.45mol/L;
(2), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion respectively weighing sodium carbonate, bismuth oxide and titanium dioxide, take absolute ethyl alcohol as the medium mixing and ball milling, compressing tablet after dry, then 1100 ℃ of lower sintering 2 hours, obtain having the bismuth-sodium titanate base substrate of perovskite structure, through broken, ball milling, obtain micro/nano level bismuth-sodium titanate powder again;
(3), be that the bismuth-sodium titanate precursor colloidal sol of 0.45mol/L mixes with micro/nano level bismuth-sodium titanate powder and concentration, wherein the mass content of bismuth-sodium titanate is 40%, then add with the equimolar polyvinylpyrrolidone of bismuth-sodium titanate colloidal sol as stable dispersant, general milling 4 hours, make it fully to be uniformly dispersed, obtain stable mixed slurry through magnetic agitation again;
(4), adopt spin coating proceeding the stable mixed slurry of gained to be deposited on the silicon base (Pt/TiO of plating Pt
2/ SiO
2/ Si) on, its medium speed is 3000 rev/mins, spin coating 30 seconds; Then heat-treat technique, wherein 150 ℃ of insulations of elder generation are 3 minutes, and 420 ℃ are incubated 10 minutes again, anneal 3 minutes for 650 ℃; Repeat above-mentioned spin coating proceeding-Technology for Heating Processing, obtaining thickness is 8.03 microns leadless piezoelectric composite thick films with bismuth-sodium titanate.
Such as Fig. 1, through XRD(Rigaku Rigaku D/Max-2400 type X-ray diffractometer, x-ray source is the Cu target.) carrying out structured testing, made thick film presents the pure perovskite phase structure, without the second dephasign.Such as Fig. 2, the dielectricity of composite thick film uses electric impedance analyzer Agilent 4294A test, and dielectric constant is 520 during 1kHz, and dielectric loss is 3%.Such as Fig. 3, the ferroelectric measuring system of RT66A of Radiant Technologies company is used in the ferroelectricity test, and coercive field 2Ec is 200kV/cm, and remanent polarization 2Pr is 40 μ C/cm
2Test result shows that composite thick film has well-crystallized's perovskite structure, and has good dielectric, ferroelectricity.
Embodiment 2
(1), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, five excessive 2% mole water bismuth nitrates are dissolved in the EGME, room temperature magnetic agitation 30 minutes obtains bismuth nitrate solution; Excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drips simultaneously glacial acetic acid as catalyst, room temperature magnetic agitation 30 minutes obtains sodium acetate solution; Be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, room temperature magnetic agitation 40 minutes obtains the tetra-n-butyl titanate mixed solution; Then respectively bismuth nitrate solution and sodium acetate solution are dropped in the tetra-n-butyl titanate mixed solution, and 80 ℃ of lower temperature constant magnetic stirrings 1 hour, naturally cool to afterwards room temperature, finally obtain the bismuth-sodium titanate precursor colloidal sol clarified, and to adjust bismuth-sodium titanate concentration be 0.45mol/L;
(2), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion respectively weighing sodium carbonate, bismuth oxide and titanium dioxide, take absolute ethyl alcohol as the medium mixing and ball milling, compressing tablet after dry, then 1000 ℃ of lower sintering 2 hours, obtain having the bismuth-sodium titanate base substrate of perovskite structure, through broken, ball milling, obtain micro/nano level bismuth-sodium titanate powder again;
(3), be that the bismuth-sodium titanate precursor colloidal sol of 0.45mol/L mixes with micro/nano level bismuth-sodium titanate powder and concentration, wherein the mass content of bismuth-sodium titanate powder is 50%, then add with the equimolar polyvinylpyrrolidone of bismuth-sodium titanate matrix as stable dispersant, general milling 4 hours, make it fully to be uniformly dispersed, obtain stable mixed slurry through magnetic agitation again;
(4), adopt spin coating proceeding the stable mixed slurry of gained to be deposited on the silicon base (Pt/TiO of plating Pt
2/ SiO
2/ Si) on, its medium speed is 3000 rev/mins, spin coating 30 seconds; Then heat-treat technique, wherein 150 ℃ of insulations of elder generation are 3 minutes, and 420 ℃ are incubated 10 minutes again, anneal 3 minutes for 750 ℃; Repeat above-mentioned spin coating proceeding-Technology for Heating Processing, obtaining thickness is 7.48 microns leadless piezoelectric composite thick films with bismuth-sodium titanate.
Such as Fig. 4, through XRD(Rigaku Rigaku D/Max-2400 type X-ray diffractometer, x-ray source is the Cu target.) carrying out structured testing, made thick film presents the pure perovskite phase structure, without the second dephasign.Such as Fig. 5, the dielectricity of composite thick film uses electric impedance analyzer Agilent 4294A test, and dielectric constant is 570 during 1kHz, and dielectric loss is 3%.Such as Fig. 6, the ferroelectric measuring system of RT66A of Radiant Technologies company is used in the ferroelectricity test, and coercive field 2Ec is 240kV/cm, and remanent polarization 2Pr is 45 μ C/cm
2Test result shows that composite thick film has well-crystallized's perovskite structure, and has good dielectric, ferroelectricity.
Embodiment 3:
(1), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, five excessive 2% mole water bismuth nitrates are dissolved in the EGME, room temperature magnetic agitation 30 minutes obtains bismuth nitrate solution; Excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drips simultaneously glacial acetic acid as catalyst, room temperature magnetic agitation 30 minutes obtains sodium acetate solution; Be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, room temperature magnetic agitation 40 minutes obtains the tetra-n-butyl titanate mixed solution; Then respectively bismuth nitrate solution and sodium acetate solution are dropped in the tetra-n-butyl titanate mixed solution, and 80 ℃ of lower temperature constant magnetic stirrings 1 hour, naturally cool to afterwards room temperature, finally obtain the bismuth-sodium titanate precursor colloidal sol clarified, and to adjust bismuth-sodium titanate concentration be 0.45mol/L;
(2), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion respectively weighing sodium carbonate, bismuth oxide and titanium dioxide, take absolute ethyl alcohol as the medium mixing and ball milling 4 hours, 80 ℃ of dryings compressing tablet after 2 hours, then 800 ℃ of lower sintering 2 hours, obtain having the bismuth-sodium titanate base substrate of perovskite structure, through broken, ball milling 7 hours, obtain micro/nano level bismuth-sodium titanate powder again;
(3), be that the bismuth-sodium titanate precursor colloidal sol of 0.45mol/L mixes with micro/nano level bismuth-sodium titanate powder and concentration, wherein the mass content of bismuth-sodium titanate is 70%, then add with the equimolar polyvinylpyrrolidone of colloidal sol as stable dispersant, general milling 4 hours, make it fully to be uniformly dispersed, obtain stable mixed slurry through magnetic agitation again;
(4), adopt spin coating proceeding the stable mixed slurry of gained to be deposited on the silicon base (Pt/TiO of plating Pt
2/ SiO
2/ Si) on, its medium speed is 3000 rev/mins, spin coating 30 seconds; Then heat-treat technique, wherein 150 ℃ of insulations of elder generation are 3 minutes, and 410 ℃ are incubated 10 minutes again, anneal 3 minutes for 750 ℃; Repeat above-mentioned spin coating proceeding-Technology for Heating Processing, obtaining thickness is 5.47 microns leadless piezoelectric composite thick films with bismuth-sodium titanate.
Such as Fig. 7, through XRD(Rigaku Rigaku D/Max-2400 type X-ray diffractometer, x-ray source is the Cu target.) carrying out structured testing, made thick film presents the pure perovskite phase structure, without the second dephasign.Such as Fig. 8, the dielectricity of composite thick film uses electric impedance analyzer Agilent 4294A test, and dielectric constant is 460 during 1kHz, and dielectric loss is 0.03.Such as Fig. 9, the ferroelectric measuring system of TF2000 of aixACT company is used in the ferroelectricity test, and coercive field 2Ec is 280kV/cm, and remanent polarization 2Pr is 40 μ C/cm
2Test result shows that composite thick film has well-crystallized's perovskite structure, and has good dielectric, ferroelectricity.
Claims (10)
1. a preparation method who is used for the leadless piezoelectric composite thick film of high-frequency transducer is characterized in that, may further comprise the steps:
(1) preparation bismuth-sodium titanate precursor colloidal sol: according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, with bismuth nitrate solution, sodium acetate solution, and after the tetra-n-butyl titanate mixed solution mixes, naturally cool to room temperature after, the bismuth-sodium titanate precursor colloidal sol that obtains clarifying, for subsequent use;
(2) preparation micro/nano level bismuth-sodium titanate powder: according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, with sodium carbonate, bismuth oxide, and after the titanium dioxide mixing and ball milling, dry, compressing tablet at 800 ~ 1100 ℃ of sintering, obtain having the bismuth-sodium titanate base substrate of perovskite structure, behind fragmentation, ball milling, obtain micro/nano level bismuth-sodium titanate powder, for subsequent use;
(3) preparation of mixed slurry: the bismuth-sodium titanate precursor colloidal sol that the nanoscale metatitanic acid bismuth sodium powder that step (2) is obtained and step (1) obtain mixes, and wherein, the mass content of ceramic powder is 20 ~ 80%, obtains stable mixed slurry after stirring;
(4) mixed slurry that adopts spin coating proceeding that step (3) is obtained is deposited on the silicon base of plating Pt, then heat-treats technique, obtains having the leadless piezoelectric composite thick film of bismuth-sodium titanate.
2. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1, it is characterized in that: in the step (1), the preparation method of described tetra-n-butyl titanate mixed solution is: be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, the room temperature magnetic agitation obtains the tetra-n-butyl titanate mixed solution.
3. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1, it is characterized in that: in the step (1), the preparation method of described sodium acetate is: excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drip simultaneously glacial acetic acid as catalyst, the room temperature magnetic agitation obtains sodium acetate solution.
4. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1 is characterized in that: in the step (2), during ball milling, take absolute ethyl alcohol as medium.
5. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1 is characterized in that: in the step (3), during mixing and ball milling, with polyvinylpyrrolidone as stable dispersant.
6. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1, it is characterized in that: in the step (4), described Technology for Heating Processing is: 150 ℃～200 ℃ are incubated 3 minutes first, 350 ℃ again～450 ℃ are incubated 3～10 minutes, anneal 3～5 minutes for 650 ℃～750 ℃.
7. the preparation method of a kind of leadless piezoelectric composite thick film for high-frequency transducer as claimed in claim 1, it is characterized in that: in the step (4), the rotating speed of spin coating is 3000 rev/mins, and the spin coating time is 30～50 seconds.
8. preparation method who is used for the leadless piezoelectric composite thick film of high-frequency transducer is characterized in that: may further comprise the steps:
(1), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion, five excessive 2% mole water bismuth nitrates are dissolved in the EGME, the room temperature magnetic agitation obtains bismuth nitrate solution; Excessive 10% mole anhydrous sodium acetate is dissolved in the EGME, drips simultaneously glacial acetic acid as catalyst, the room temperature magnetic agitation obtains sodium acetate solution; Be that tetra-n-butyl titanate and the acetylacetone,2,4-pentanedione of 1:2 is dissolved in the EGME with mol ratio, the room temperature magnetic agitation obtains the tetra-n-butyl titanate mixed solution; Then respectively bismuth nitrate solution and sodium acetate solution are dropped in the tetra-n-butyl titanate mixed solution, and at 80 ℃ of lower temperature constant magnetic stirrings, naturally cool to afterwards room temperature, the bismuth-sodium titanate precursor colloidal sol that obtains clarifying;
(2), according to Bi
0.5Na
0.5TiO
3Stoichiometric proportion respectively weighing sodium carbonate, bismuth oxide and titanium dioxide, take absolute ethyl alcohol as the medium mixing and ball milling, compressing tablet after dry, then 800 ℃ ~ 1100 ℃ lower sintering 2 hours, obtain having the bismuth-sodium titanate base substrate of perovskite structure, through broken, ball milling, obtain micro/nano level bismuth-sodium titanate powder again;
(3), micro/nano level bismuth-sodium titanate ceramic powder is mixed with bismuth-sodium titanate precursor colloidal sol, wherein the mass content of ceramic powder is 20%～80%, then add with the equimolar polyvinylpyrrolidone of bismuth-sodium titanate matrix as stable dispersant, ball milling makes it fully to be uniformly dispersed, and obtains stable mixed slurry through magnetic agitation again;
(4), adopt spin coating proceeding that the stable mixed slurry of gained is deposited on the silicon base, then heat-treat technique, repeat above-mentioned spin coating proceeding-Technology for Heating Processing, obtain having bismuth-sodium titanate leadless piezoelectric composite thick film.
9. the preparation method of a kind of bismuth-sodium titanate leadless piezoelectric composite thick film for high-frequency transducer according to claim 8, it is characterized in that, described Technology for Heating Processing is: 150 ℃～200 ℃ are incubated 3 minutes first, 350 ℃ again～450 ℃ are incubated 3～10 minutes, anneal 3～5 minutes for 650 ℃～750 ℃.
One kind according to claim 1 ~ 9 in the described a kind of bismuth-sodium titanate leadless piezoelectric composite thick film for high-frequency transducer of any one, it is characterized in that the thickness of described leadless piezoelectric composite thick film is the 1-10 micron.
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| CN112531110A (en) * | 2020-11-24 | 2021-03-19 | 华中科技大学鄂州工业技术研究院 | Surface treatment method of MAPbI3 thick film |
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