CN103265282A - Preparation method of barium-calcium carbonate and potassium-sodium niobate alternative spin-coating lead-free piezoelectric thick film - Google Patents

Preparation method of barium-calcium carbonate and potassium-sodium niobate alternative spin-coating lead-free piezoelectric thick film Download PDF

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CN103265282A
CN103265282A CN2013101872084A CN201310187208A CN103265282A CN 103265282 A CN103265282 A CN 103265282A CN 2013101872084 A CN2013101872084 A CN 2013101872084A CN 201310187208 A CN201310187208 A CN 201310187208A CN 103265282 A CN103265282 A CN 103265282A
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张德庆
杨秀英
郑方圆
孟菲
冯连振
曹茂盛
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Qiqihar University
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Abstract

The invention discloses a preparation method of a barium-calcium carbonate and potassium-sodium niobate alternative spin-coating lead-free piezoelectric thick film. The preparation method comprises the following steps of: based on a sol-gel process, preparing Bi0.5Ca0.5Ti03(BCT) precursor sol with concentration of 1mol/L by adopting barium acetate (Ba(CH3COO)2), calcium nitrate terahydrate (Ca(NO3)2.4H2O) and tetrabutyl titanate (C16H36O4Ti) as the materials, adopting ethylene glycol monomethyl ether (C3H8O2) and glacial acetic acid (CH3COOH) as solvent, and adopting acetylacetone (C5H8O2) as stabilizing agent; preparing K0.5Na0.5NbO3 (KNN) precursor sol with concentration of 0.6mol/L by adopting ethylene glycol (C2H6O2) as esterifying agent, adopting nitric acid as metal coordination agent and introducing polyvinylpyrrolidone (PVP) as modifying agent; coating the KNN sol on the (Pt/TiO2/Ti/SiO2/Si) substrate, and coating the BCT sol after the thermal treatment; repeating the steps by three times, i.e., carrying out spin-coating for six layers alternatively; and obtaining the KNN-BCT film through annealing treatment. The obtained film is uniform in crystalline grain, compact in arrangement, smooth in surface and free of cracks.

Description

A kind of barium titanate calcium and potassium-sodium niobate replace the preparation method of spin coating lead-free piezoelectric thick film
Technical field
The invention belongs to technical field of chemistry, relate to the preparation method that a kind of barium titanate calcium and potassium-sodium niobate replace the spin coating lead-free piezoelectric thick film.
Background technology
Along with electronic devices and components miniaturization and new electronic component (as microelectronic mechanical devices, abbreviation MEMS) development, greatly promoted the transformation of research from the body material to mould material of material, thus from the nineties in 20th century countries in the world scientific worker be devoted to seek that a kind of piezoelectric property is superior, the preparation method simply and does not bring the lead-free ceramics film of infringement to environment.Has ABO 3The Ba of type perovskite structure 0.5Ca 0.5TiO 3(BCT) and K 0.5Na 0.5NbO 3(KNN) the based leadless piezoelectric ceramics film has characteristics such as piezo-electric modulus height, specific inductivity are little, Curie temperature height, is considered to be hopeful most to substitute the leadless piezoelectric material material system of PZT piezoceramic material.But when pure BCT leadless piezoelectric ceramics film surpassed 120 ℃ when temperature, its ferroelectricity disappeared, and has influenced its application in the high temperature field; And traditional technology is in the pure KNN leadless piezoelectric ceramics thin-film process of preparation, because alkali metal volatilizees, is difficult to obtain the film of surface compact, the saturated characteristics such as ferroelectric hysteresis loop of difficult acquisition easily in film forming and the heat treatment process, has also restricted the practicability development of KNN leadless piezoelectric film.
In recent years, begin both at home and abroad to attempt by prepared in various methods BCT and KNN leadless piezoelectric ceramics and films such as doping vario-property researchs, and obtained certain progress.People such as Zhang Y J adopt sol-gel method successfully to prepare (1-x) BaZr 0.2Ti 0.8O 3-xBa 0.7Ca 0.3TiO 3(BZT-BCT) leadless piezoelectric ceramics, the ceramic sintering temperature of this method preparation is low than conventional solid-state method, and its ferroelectric piezoelectricity can be the ceramic phase ratio with PZT also; The towering group that appoints of domestic Xi'an Communications University adopts the complex sol method, makes the KNN powder be dissolved in BaZr 0.5Ti 0.95O 3In the precursor sol, use spin-coating method to make the KNN-BZT thick film in the Si substrate, the prepared thick film of this kind method is ferroelectric and piezoelectricity is all better, for the practicability of leadless piezoelectric ceramics film is had laid a good foundation.
Summary of the invention
The objective of the invention is to overcome the defective that exists in the prior art, provide a kind of simple, manageable barium titanate calcium and potassium-sodium niobate replace the preparation method of spin coating lead-free piezoelectric thick film, prepare stable BCT and KNN colloidal sol respectively, by alternately spin coating, control sol-gel technology, heat-treat condition, pattern with the control film makes it can synthesize uniform crystal particles under specific processing condition, smooth surface, the pure perovskite phase, the KNN-BCT thick film of final thickness 1～5 μ m, this mould material may have application promise in clinical practice in leadless piezoelectric ceramics film and the preparation of 1-3 type piezo-electricity composite material.
Its concrete technical scheme is:
A kind of barium titanate calcium and potassium-sodium niobate replace the preparation method of spin coating lead-free piezoelectric thick film, may further comprise the steps:
A, preparation KNN colloidal sol:
A1) take by weighing oxalic acid and be dissolved in 80 ℃ of deionized waters, with Nb (OH) 5Be dissolved in this solution and form the Nb-oxalic acid solution, reaction 0.5h clarifies to solution becomes;
A2) in the Nb-oxalic acid solution, add excessive ammonia and form Nb (OH) 5Precipitation, until PH～9, ageing 6h in 80 ℃ of water-baths then;
A3) use hot deionized water wash suction filtration Nb (OH) repeatedly 5Precipitation is to remove the ammonium oxalate in the solution;
A4) take by weighing citric acid and be dissolved in 80 ℃ of deionized waters, with Nb (OH) 5Be dissolved in this solution and form the Nb-citric acid solution, reaction 1h clarifies to solution becomes; Add CH 3COOK and CH 3COONa treats its whole dissolvings, adds ethylene glycol in solution, behind 80 ℃ of stirring in water bath 0.5h, obtains transparent settled solution;
A5) add PVP, after waiting to dissolve solution is constantly stirred evaporation in 80 ℃ of water-baths, obtain water white transparency KNN precursor sol.
B, preparation BCT colloidal sol:
B1) take by weighing barium acetate and be dissolved in 80 ℃ of glacial acetic acids, ethylene glycol monomethyl ether is dissolved in this solution forms the Ba-acetic acid solution, reaction 10min clarifies to solution becomes, treat that it is cooled to room temperature, add ethylene glycol monomethyl ether, stirring at room mixes, and obtains the 1mol/LBa precursor monomer;
B2) tetrabutyl titanate and methyl ethyl diketone are dissolved in the ethylene glycol monomethyl ether, room temperature reaction, and stir solution is mixed, obtain 1mol/L Ca precursor monomer;
B3) add four water-calcium nitrate in the precursor aqueous solution of Ca, constantly stir, stirring velocity is 200r/min, obtains settled solution; Then 1mol/L Ba precursor monomer solution is added, obtain BCT colloidal sol.
C, alternate plating thermal treatment:
C1) at Pt/TiO 2/ Ti/SiO 2By spin-coating method plating KNN film, rotating speed is 3200r/min on the/Si substrate, and the time is 30s, and wet film is dried moisture at 200 ℃;
C2) be raised in 500 ℃ the retort furnace insulation 10min, second layer plating BCT film and then with 4 ℃/min;
C3) same heat-treat condition repeats above-mentioned steps c1)-step c2) three times, alternately spin coating is 6 layers, and 700 ℃ of anneal 10min then finally make the KNN-BCT thick film of thickness 4 μ m.
Further preferred, the raw material that adopts is barium acetate (Ba (CH 3COO) 2), four water-calcium nitrate (Ca (NO 3) 24H 2O), tetrabutyl titanate (C 16H 36O 4Ti), ethylene glycol monomethyl ether (C 3H 8O 2), methyl ethyl diketone (C 5H 8O 2), niobium hydroxide (Nb (OH) 5), potassium acetate (CH 3COOK), sodium acetate (CH 3COONa), ethylene glycol, citric acid, polyvinylpyrrolidone (PVP), oxalic acid, ammoniacal liquor, deionized water etc., wherein r (Ti 4+: Ba 2+: Ca 2+)=1: 1: 1, v (CH 3COOH: C 5H 8O 2)=4: 1, r (C 16H 36O 4Ti: C 5H 8O 2)=1: 2, r (K +: Na +: Nb 5+)=0.8: 0.8: 1, r (EG: CA)=2: 1, r (the PVP monomer: KNN)=1: 1.
Compared with prior art, beneficial effect of the present invention is:
The present invention is different from characteristics such as adopting metal alkoxide is expensive, facile hydrolysis, bad control in other sol-gel methodes, adopts (the Nb (OH) of secondary sedimentation 5) be the niobium source, improved the activity of niobium, make its easier and citric acid generation complex reaction;
Preparation method of the present invention is that solvent is prepared KNN and BCT precursor sol respectively by water and ethylene glycol monomethyl ether, has reduced reaction cost, has promoted later industrial practicability;
Technical scheme of the present invention is introduced the PVP modification when preparation KNN colloidal sol, can reduce pyrolysis temperature, suppresses the volatilization of alkalimetal ion, has reduced the porous characteristics on KNN film surface on the part degree;
The present invention adopts alternately spin coating, and one deck is BCT colloidal sol at last, can remedy the unsound defective of KNN film porous surface, has reduced leakage current, thereby has improved electrical property.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention is done explanation in further detail.
The preparation method that a kind of barium titanate calcium of the present invention and potassium-sodium niobate replace the spin coating lead-free piezoelectric thick film is based on sol-gel method, with barium acetate (Ba (CH 3COO) 2), four water-calcium nitrate (Ca (NO 3) 24H 2O), tetrabutyl titanate (C 16H 36O 4Ti) be raw material, ethylene glycol monomethyl ether (C 3H 8O 2), glacial acetic acid (CH 3COOH) be solvent, methyl ethyl diketone (C 5H 8O 2) be stablizer, preparation concentration is the Bi of 1mol/L 0.5Ca 0.5TiO 3(BCT) precursor sol; With niobium hydroxide (Nb (OH) 5), potassium acetate (CH 3COOK), sodium acetate (CH 3COONa) be raw material, with ethylene glycol (C 2H 6O 2) for esterifying agent, citric acid are the metal-complexing agent, introducing polyvinylpyrrolidone (PVP) is properties-correcting agent, compound concentration is the K of 0.6mol/L 0.5Na 0.5NbO 3(KNN) precursor sol is then earlier at (Pt/TiO 2/ Ti/SiO 2/ Si) plate KNN colloidal sol on the substrate, plate BCT colloidal sol after the thermal treatment again, it is inferior to repeat above step 3, namely replaces 6 layers of spin coatings, and anneal obtains the KNN-BCT thick film then.Resulting film uniform crystal particles, arrange closely, surface smoothing, nothing cracking.
Embodiment 1:
Be 0.6mol/L KNN colloidal sol with preparation 60ml concentration, 40ml concentration is that 1mol/L BCT colloidal sol is example, and required raw material is oxalic acid 30g, niobium hydroxide 10g, citric acid 25g, potassium acetate 2.74g, sodium acetate 3.58g, ethylene glycol 15g, PVP3.68g, deionized water is an amount of, ammoniacal liquor is an amount of; Barium acetate 10.2g, four water-calcium nitrate 9.5g, glacial acetic acid 30mL, ethylene glycol monomethyl ether 28ml, methyl ethyl diketone 8ml, tetrabutyl titanate 13.6ml.Concrete operations are as follows:
1, preparation KNN colloidal sol:
1) 30g oxalic acid is dissolved in the deionized water that adds pyromagnetic stirring under 200ml80 ℃, with 10g Nb (OH) 5Be dissolved in this solution, reaction 0.5h clarifies to solution becomes.Generate Nb (OH) with the excessive ammonia titration then 5Precipitation stops until PH～9, and ageing 6h in 80 ℃ of water-baths, repetitive scrubbing suction filtration obtain the Nb (OH) of secondary sedimentation 5Precipitation;
2) the 25g citric acid is dissolved in the deionized water that adds pyromagnetic stirring under 200ml80 ℃, with the Nb (OH) that newly makes 5Be dissolved in this solution, the clarification of reaction 1h solution obtains the Nb-citric acid solution;
3) get the molality that 11.574gNb-citric acid solution high temperature sintering is measured niobium, measuring result is 1.6*10 -4Mol/g is according to r (K +: Na +: Nb 5+)=0.8: 0.8: 1 adds in the Nb-citric acid solution of pyromagnetic stirring under respectively 2.74g potassium acetate and 3.58g sodium acetate being added 80 ℃, fully reacts 0.5h, obtains transparent clear soln;
4) with ammoniacal liquor regulator solution pH value to 3.5, stablize 15min after, dropwise dropping 15g ethylene glycol in the solution constantly stirs 2h, obtains faint yellow transparent KNN precursor sol, and is standby;
5) (the PVP monomer: KNN)=1: 1 ratio adds 3.68gPVP, after waiting to dissolve solution constantly stirred evaporation in 80 ℃ of water-baths, obtaining 60ml concentration is the water white transparency KNN precursor sol of 0.6mol/L with r.
2, preparation BCT colloidal sol:
1 is dissolved in the 10.2g barium acetate in the glacial acetic acid that adds pyromagnetic stirring under 30ml80 ℃, treats that barium acetate dissolves fully, and it is cooled to room temperature, adds the 10ml ethylene glycol monomethyl ether then, shake up 1mol/L Ba precursor monomer solution;
2 are dissolved in 13.6ml tetrabutyl titanate, 8ml methyl ethyl diketone in the ethylene glycol monomethyl ether that magnetic under the 18ml room temperature stirs, and treat that it mixes, and obtain Ti precursor monomer solution;
3 add the 9.5g four water-calcium nitrate in the precursor monomer solution of Ti, treat that it dissolves safely after, Ba precursor monomer solution is added, stir solution mixed, can obtain BCT colloidal sol.
3, alternate plating thermal treatment:
At (Pt/TiO 2/ Ti/SiO 2/ Si) plate the KNN film by spin-coating method on the substrate, rotating speed is 3200r/min, and the time is 30s, and wet film is dried moisture at 200 ℃, then in be raised to 500 ℃ retort furnace with 4 ℃/min, insulation 10min, second layer plating BCT film, same heat-treat condition, repeat above-mentioned steps three times, namely replace 6 layers of spin coatings, then at 700 ℃ of anneal 10min, finally make the KNN-BCT thick film of thickness～4 μ m.
Embodiment 2:
Be 0.6mol/LKNN colloidal sol with preparation 30ml concentration, 40ml concentration is that 1mol/L BCT colloidal sol is example, and required raw material is oxalic acid 15g, niobium hydroxide 5g, citric acid 12.5g, potassium acetate 1.32g, sodium acetate 1.65g, ethylene glycol 7.5g, PVP1.34g, deionized water is an amount of, ammoniacal liquor is an amount of; Barium acetate 10.5g, glacial acetic acid 29mL, four water-calcium nitrate 9.3g, ethylene glycol monomethyl ether 28.9ml, methyl ethyl diketone 8.2ml, tetrabutyl titanate 14ml.Concrete operations are as follows:
1, preparation KNN colloidal sol:
1) 15g oxalic acid is dissolved in the deionized water that adds pyromagnetic stirring under 100ml80 ℃, with 5g Nb (OH) 5Be dissolved in this solution, reaction 0.5h clarifies to solution becomes.Generate Nb (OH) with the excessive ammonia titration then 5Precipitation stops until PH～9, and ageing 6h in 80 ℃ of water-baths, repetitive scrubbing suction filtration obtain the Nb (OH) of secondary sedimentation 5Precipitation;
2) the 12.5g citric acid is dissolved in the deionized water that adds pyromagnetic stirring under 100ml80 ℃, with the Nb (OH) that newly makes 5Be dissolved in this solution, the clarification of reaction 1h solution obtains the Nb-citric acid solution;
3) get the molality that 13.28gNb-citric acid solution high temperature sintering is measured niobium, measuring result is 1.53*10 -4Mol/g is according to r (K +: Na +: Nb 5+)=0.8: 0.8: 1 adds in the Nb-citric acid solution of pyromagnetic stirring under respectively 1.32g potassium acetate and 1.65g sodium acetate being added 80 ℃, fully reacts 0.5h, obtains transparent clear soln;
4) with ammoniacal liquor regulator solution pH value to 3.5, stablize 15min after, dropwise dropping 7.5g ethylene glycol in the solution constantly stirs 2h, obtains faint yellow transparent KNN precursor sol, and is standby;
5) (the PVP monomer: KNN)=1: 1 ratio adds 1.34gPVP, after waiting to dissolve solution constantly stirred evaporation in 80 ℃ of water-baths, obtaining 30ml concentration is the water white transparency KNN precursor sol of 0.6mol/L with r.
2, preparation BCT colloidal sol:
1) the 10.5g barium acetate is dissolved in the glacial acetic acid that adds pyromagnetic stirring under 29ml80 ℃, treats that barium acetate dissolves fully, it is cooled to room temperature, add the 11ml ethylene glycol monomethyl ether then, shake up 1mol/L Ba precursor monomer solution;
2) 14ml tetrabutyl titanate, 8.2ml methyl ethyl diketone are dissolved in the ethylene glycol monomethyl ether that magnetic stirs under the 17.9ml room temperature, treat that it mixes, obtain Ti precursor monomer solution;
3) the 9.3g four water-calcium nitrate is added in the precursor monomer solution of Ti, treat that it dissolves safely after, Ba precursor monomer solution is added, stir solution mixed, can obtain BCT colloidal sol.
3, alternate plating thermal treatment:
At (Pt/TiO 2/ Ti/SiO 2/ Si) plate the KNN film by spin-coating method on the substrate, rotating speed is 3200r/min, and the time is 30s, and wet film is dried moisture at 200 ℃, then in be raised to 500 ℃ retort furnace with 4 ℃/min, insulation 10min, second layer plating BCT film, same heat-treat condition, repeat twice of above-mentioned steps, namely replace 4 layers of spin coatings, then at 700 ℃ of anneal 10min, finally make the KNN-BCT thick film of thickness～3.6 μ m.
Embodiment 3:
Be 0.6mol/lKNN colloidal sol with preparation 120ml concentration, 20ml concentration is that 1mol/l BCT colloidal sol is example, and required raw material is oxalic acid 60 grams, niobium hydroxide 20 grams, citric acid 50g, potassium acetate 5.81g, sodium acetate 9.36g, ethylene glycol 30g, PVP7.56g, deionized water is an amount of, ammoniacal liquor is an amount of; Barium acetate 5.1 grams, four water-calcium nitrate 4.7 grams, ethylene glycol monomethyl ether 13ml, methyl ethyl diketone 4g, tetrabutyl titanate 6.9g, glacial acetic acid 16ml.Concrete operations are as follows:
1, preparation KNN colloidal sol:
1) 60g oxalic acid is dissolved in the deionized water that adds pyromagnetic stirring under 400ml80 ℃, with 20g Nb (OH) 5Be dissolved in this solution, reaction 0.5h clarifies to solution becomes.Generate Nb (OH) with the excessive ammonia titration then 5Precipitation stops until PH～9, and ageing 6h in 80 ℃ of water-baths, repetitive scrubbing suction filtration obtain the Nb (OH) of secondary sedimentation 5Precipitation;
2) the 50g citric acid is dissolved in the deionized water that adds pyromagnetic stirring under 100ml80 ℃, with the Nb (OH) that newly makes 5Be dissolved in this solution, the clarification of reaction 1h solution obtains the Nb-citric acid solution;
3) get the molality that 15.04gNb-citric acid solution high temperature sintering is measured niobium, measuring result is 1.7*10 -4Mol/g is according to r (K +: Na +: Nb 5+)=0.8: 0.g: 1 adds in the Nb-citric acid solution of pyromagnetic stirring under respectively 5.81g potassium acetate and 9.36g sodium acetate being added 80 ℃, fully reacts 0.5h, obtains transparent clear soln;
4) with ammoniacal liquor regulator solution pH value to 3.5, stablize 15min after, dropwise dropping 30g ethylene glycol in the solution constantly stirs 2h, obtains faint yellow transparent KNN precursor sol, and is standby.
5) (the PVP monomer: KNN)=1: 1 ratio adds 7.56gPVP, after waiting to dissolve solution constantly stirred evaporation in 80 ℃ of water-baths, obtaining 30ml concentration is the water white transparency KNN precursor sol of 0.6mol/L with r.
2, preparation BCT colloidal sol:
1) the 5.1g barium acetate is dissolved in the glacial acetic acid that adds pyromagnetic stirring under 16ml80 ℃, treats that barium acetate dissolves fully, it is cooled to room temperature, add the 4ml ethylene glycol monomethyl ether then, shake up 1mol/L Ba precursor monomer solution;
2) 6.9ml tetrabutyl titanate, 4ml methyl ethyl diketone are dissolved in the ethylene glycol monomethyl ether that magnetic stirs under the 9ml room temperature, treat that it mixes, obtain Ti precursor monomer solution;
3) the 4.7g four water-calcium nitrate is added in the precursor monomer solution of Ti, treat that it dissolves safely after, Ba precursor monomer solution is added, stir solution mixed, can obtain BCT colloidal sol.
3, alternate plating thermal treatment:
At (Pt/TiO 2/ Ti/SiO 2/ Si) plate the KNN film by spin-coating method on the substrate, rotating speed is 3200r/min, and the time is 30s, and wet film is dried moisture at 200 ℃, then in be raised to 500 ℃ retort furnace with 4 ℃/min, insulation 10min, second layer plating BCT film, same heat-treat condition, repeat above-mentioned steps four times, namely replace 8 layers of spin coatings, then at 700 ℃ of anneal 10min, finally make the KNN-BCT thick film of thickness～5.1 μ m.
The above; only be the preferable embodiment of the present invention; protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses, the simple change of the technical scheme that can obtain apparently or equivalence are replaced and are all fallen within the scope of protection of the present invention.

Claims (2)

1. a barium titanate calcium and potassium-sodium niobate replace the preparation method of spin coating lead-free piezoelectric thick film, it is characterized in that, may further comprise the steps:
A, preparation KNN colloidal sol:
A1) take by weighing oxalic acid and be dissolved in 80 ℃ of deionized waters, with Nb (OH) 5Be dissolved in this solution and form the Nb-oxalic acid solution, reaction 0.5h clarifies to solution becomes;
A2) in the Nb-oxalic acid solution, add excessive ammonia and form Nb (OH) 5Precipitation, until PH～9, ageing 6h in 80 ℃ of water-baths then;
A3) use hot deionized water wash suction filtration Nb (OH) repeatedly 5Precipitation is to remove the ammonium oxalate in the solution;
A4) take by weighing citric acid and be dissolved in 80 ℃ of deionized waters, with Nb (OH) 5Be dissolved in this solution and form the Nb-citric acid solution, reaction 1h clarifies to solution becomes; Add CH 3COOK and CH 3COONa treats its whole dissolvings, adds ethylene glycol in solution, behind 80 ℃ of stirring in water bath 0.5h, obtains transparent settled solution;
A5) add PVP, after waiting to dissolve solution is constantly stirred evaporation in 80 ℃ of water-baths, obtain water white transparency KNN precursor sol.
B, preparation BCT colloidal sol:
B1) take by weighing barium acetate and be dissolved in 80 ℃ of glacial acetic acids, ethylene glycol monomethyl ether is dissolved in this solution forms the Ba-acetic acid solution, reaction 10min clarifies to solution becomes, treat that it is cooled to room temperature, add ethylene glycol monomethyl ether, stirring at room mixes, and obtains the 1mol/LBa precursor monomer;
B2) tetrabutyl titanate and methyl ethyl diketone are dissolved in the ethylene glycol monomethyl ether, room temperature reaction, and stir solution is mixed, obtain 1mol/L Ca precursor monomer;
B3) add four water-calcium nitrate in the precursor aqueous solution of Ca, constantly stir, stirring velocity is 200r/min, obtains settled solution; Then 1mol/L Ba precursor monomer solution is added, obtain BCT colloidal sol.
C, alternate plating thermal treatment:
C1) at Pt/TiO 2/ Ti/SiO 2By spin-coating method plating KNN film, rotating speed is 3200r/min on the/Si substrate, and the time is 30s, and wet film is dried moisture at 200 ℃;
C2) be raised in 500 ℃ the retort furnace insulation 10min, second layer plating BCT film and then with 4 ℃/min;
C3) same heat-treat condition repeats above-mentioned steps c1)-step c2) three times, alternately spin coating is 6 layers, and 700 ℃ of anneal 10min then finally make the KNN-BCT thick film of thickness 4 μ m.
2. barium titanate calcium according to claim 1 and potassium-sodium niobate replace the preparation method of spin coating lead-free piezoelectric thick film, it is characterized in that, wherein r (Ti 4+: Ba 2+: Ca 2+)=1: 1: 1, v (CH 3COOH: C 5H 8O 2)=4: 1, r (C 16H 36O 4Ti: C 5H 8O 2)=1: 2, r (K +: Na +: Nb 5+)=0.8: 0.8: 1, r (EG: CA)=2: 1, r (the PVP monomer: KNN)=1: 1.
CN2013101872084A 2013-05-14 2013-05-14 Preparation method of barium-calcium carbonate and potassium-sodium niobate alternative spin-coating lead-free piezoelectric thick film Pending CN103265282A (en)

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CN103572370A (en) * 2013-10-29 2014-02-12 西安交通大学 Bismuth ytterbnate single crystal epitaxial film and preparation method thereof
CN103572370B (en) * 2013-10-29 2016-02-24 西安交通大学 A kind of ytterbium acid bismuth single crystal epitaxial film and preparation method thereof
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CN104045340B (en) * 2014-06-04 2016-03-30 同济大学 Bismuth sodium titanate based and barium phthalate base MULTILAYER COMPOSITE piezoelectric membrane and preparation method thereof
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CN112374885B (en) * 2015-12-01 2023-01-20 意法半导体股份有限公司 Precursor solution and method for preparing lead-free piezoelectric material
CN110540427A (en) * 2019-08-13 2019-12-06 兰州大学 Preparation method for improving high-performance thermal stability of lead-free electronic ceramic
CN110540427B (en) * 2019-08-13 2022-02-15 兰州大学 Preparation method for improving high-performance thermal stability of lead-free electronic ceramic
CN112062552A (en) * 2020-09-17 2020-12-11 广西大学 Preparation method of lead-free film material by utilizing phase change induction

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