CN111668363A - Preparation method of potassium-sodium niobate homogeneous multilayer film based on double niobium sources - Google Patents
Preparation method of potassium-sodium niobate homogeneous multilayer film based on double niobium sources Download PDFInfo
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Abstract
The invention discloses a preparation method of a potassium-sodium niobate homogeneous multilayer film based on double niobium sources, which comprises the following steps: (1) dissolving niobium pentoxide in hydrofluoric acid, adding ammonium oxalate, dropwise adding ammonia water to generate white precipitate, adding citric acid to obtain a niobium-citrate solution, continuously filtering to obtain a clear solution, adding potassium salt and sodium salt, adding ethylene glycol, and standing to obtain a clear potassium-sodium niobate precursor sol; (2) dropwise adding ethylene glycol monomethyl ether into a reaction kettle, sucking niobium ethoxide and placing the niobium ethoxide into the ethylene glycol monomethyl ether, heating the mixed solution in a water bath, dropwise adding glacial acetic acid, acetylacetone and formamide, adding sodium salt and sodium salt, and stirring to obtain bright yellow potassium-sodium niobate precursor sol; (3) and (2) alternately spin-coating the potassium-sodium niobate precursor sol prepared in the step (1) and the potassium-sodium niobate precursor sol prepared in the step (2) on a silicon wafer (100) to obtain the potassium-sodium niobate homogeneous multilayer film. The KNN multilayer film obtained by the invention has high preference in (100) orientation.
Description
Technical Field
The invention relates to a preparation method of a potassium-sodium niobate homogeneous multilayer film based on double niobium sources, belonging to the field of piezoelectric materials.
Background
The potassium-sodium niobate material belongs to one of piezoelectric materials, has the advantages of environmental friendliness, low dielectric constant, good piezoelectric performance and the like, and is an ideal piezoelectric material for replacing a lead base. The research on the potassium-sodium niobate piezoelectric material is divided into the research on bulk ceramics and films, and compared with the bulk potassium-sodium niobate ceramics, the research on the potassium-sodium niobate films is late, but the film material has the advantages of low driving voltage, high response speed and easiness in processing. With the development of electronic manufacturing industry, devices are becoming smaller and integrated, and therefore, research on potassium-sodium niobate thin films is becoming a hotspot.
At present, four main methods for preparing the potassium-sodium niobate film are available: pulsed laser methods, magnetron sputtering methods, hydrothermal methods and sol-gel methods. Among these methods, the sol-gel method has superior advantages: low cost, convenient component control and large-area film preparation. The preparation of the potassium-sodium niobate thin film by the sol-gel method is divided into a metal alkoxide method and a non-alkoxide method, and because the raw materials of the metal alkoxide method are expensive and the compactness of the thin film prepared by the non-alkoxide method is poor, the potassium-sodium niobate thin film is prepared by adopting a niobium source singly, but the mode of combining the metal alkoxide method and the non-alkoxide method for alternate spin coating does not appear.
Disclosure of Invention
Aiming at the defects of the KNN film prepared by the single niobium source in the existing sol-gel method, the invention aims to provide a method for preparing a potassium-sodium niobate homogeneous multilayer film based on double niobium sources.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a potassium-sodium niobate homogeneous multilayer film based on double niobium sources comprises the following steps:
(1) dissolving niobium pentoxide in hydrofluoric acid, heating in a water bath in a reaction kettle, adding ammonium oxalate, continuing heating in the water bath, taking out the mixed solution, dropwise adding ammonia water to generate white precipitate, washing and filtering the white precipitate, adding citric acid to obtain a niobium-citrate solution, continuing filtering to obtain a clear solution, adding potassium salt and sodium salt into the obtained clear solution, stirring, adjusting the pH value of the solution to be alkaline, adding ethylene glycol, and standing to obtain a clear potassium-sodium niobate precursor sol;
(2) dropwise adding ethylene glycol monomethyl ether into a reaction kettle, then sucking niobium ethoxide into the ethylene glycol monomethyl ether under the condition of nitrogen, heating the mixed solution in a water bath, dropwise adding glacial acetic acid, acetylacetone and formamide, continuing heating in the water bath, and adding sodium salt and sodium salt into the mixed solution at room temperature and stirring to obtain bright yellow potassium-sodium niobate precursor sol;
(3) preheating the (100) silicon wafer, spin-coating the potassium-sodium niobate precursor sol prepared in the step (1) on the (100) silicon wafer, and thermally decomposing and annealing the wet film; spin-coating the potassium-sodium niobate precursor sol prepared in the step (2), and continuing pyrolysis annealing; and (3) continuously spin-coating the potassium-sodium niobate precursor sol prepared in the step (1) on the basis, pyrolyzing and annealing the wet film, and so on, and alternately spin-coating to prepare the potassium-sodium niobate homogeneous multilayer film.
Preferably, in the step (1), every 1g of niobium pentoxide is dissolved in 5mL of hydrofluoric acid, and then the solution is heated in a water bath at a temperature of 80 ℃ for 6 hours, and after adding ammonium oxalate, the water bath heating at a temperature of 80 ℃ is continued for 2 hours.
Preferably, in the step (1), after a white precipitate is generated, the white precipitate is left to stand, and then the white precipitate is put into a vacuum drying oven to be aged for 40min at 60 ℃, and then washed.
Preferably, in the step (1), citric acid and deionized water are added into the white precipitate, and the mixture is stirred to obtain the niobium-citrate solution, wherein the mass ratio of the white precipitate to the citric acid is 1: 4.
preferably, in the step (1), the ratio of the addition amount of the potassium salt and the sodium salt to the amount of the niobium material in the solution is 1.1: 1.1: 2; the ratio of the addition amount of the ethylene glycol to the amount of the citric acid is 2:1.
preferably, in the step (2), every 2g of niobium ethoxide is dissolved in 15mL of ethylene glycol monomethyl ether, the solution is heated in a water bath at the temperature of 80 ℃ for 1h, then 1-2 drops of glacial acetic acid and acetylacetone are respectively added dropwise, 3-4 drops of formamide are added dropwise, and the heating in the water bath at the temperature of 80 ℃ is continued for 1 h.
Preferably, in the step (2), the ratio of the addition amount of the potassium salt and the sodium salt to the amount of the niobium in the solution is 1.1: 1.1: 2.
preferably, in the step (3), (100) the silicon wafer is preheated at a temperature of 500 ℃ for 10 min.
Preferably, in the step (3), the spin coating is performed on a spin coater, and the conditions are as follows: the rotating speed is 4000r/min, and the time is 30 s.
Preferably, in the step (3), the pyrolysis annealing conditions are as follows: the pyrolysis temperature was maintained at 250 ℃ for 5 minutes and the annealing temperature at 650 ℃ to 800 ℃ for 9 minutes.
Has the advantages that: compared with the prior art, the invention has the advantages that: (1) preparing a high-quality potassium-sodium niobate (KNN) homogeneous multilayer film by alternately spin-coating by using a non-alkoxide method and a metal alkoxide method of different niobium sources; (2) the potassium-sodium niobate (KNN) homogeneous multilayer film prepared by using the double niobium sources has higher (100) preferred orientation and controllable performance than the potassium-sodium niobate (KNN) film prepared by using a single niobium source; (3) the potassium-sodium niobate (KNN) homogeneous multilayer film prepared by the double niobium sources has wide application prospect in silicon-based MEMS integrated devices.
Drawings
FIG. 1 is an XRD pattern of a KNN film prepared by a sol-gel process of the invention comparing a single niobium source under annealing temperature conditions of 650 ℃ for example 1 and a comparative example;
FIG. 2 is an XRD pattern of a KNN film prepared by a sol-gel method of the invention comparing a single niobium source under the condition of an annealing temperature of 700 ℃ in example 1 and a comparative example;
FIG. 3 is an XRD pattern of a KNN film prepared by a sol-gel process with a comparative single niobium source of the present invention under the annealing temperature condition of 750 ℃ for example 1 and comparative example;
fig. 4 is an XRD pattern of KNN thin films prepared by sol-gel process of the invention and a single niobium source compared to example 1 and comparative example at an annealing temperature of 800 ℃.
Detailed Description
The invention is further illustrated with reference to the following figures and specific examples.
Example 1
1) 5g of niobium pentoxide (Nb) were weighed by an electronic balance2O5) Pouring into a reaction kettle, adding 25mL of hydrofluoric acid (HF) with the concentration of 40 wt% into the reaction kettle, and stirring the reaction kettle for 6 hours in water bath heating at the temperature of 80 ℃.
2) Adding 7g of ammonium oxalate into the reaction kettle in the step 1), and continuously heating in a water bath at 80 ℃ for 2h to obtain a mixed solution.
3) Removing the mixed solution in the step 2), adjusting the pH value of the solution by using ammonia water, and reacting the solution to generate white Nb (OH)5Precipitating, aging the precipitate for 24h, standing in vacuum drying oven at 60 deg.C for 2h, filtering off white precipitate, and repeatedly washing to obtain Nb (OH)5White precipitate.
4) Reacting Nb (OH)5White precipitate and Citric Acid (CA) were mixed in a molar ratio of 1: 4 mixing and stirring for 24 hours, and standing to obtain a clear solution.
5) The solution obtained in the step 4) is processed by the molar ratio n (Nb)5+):n(K+):n(Na+) Adding potassium acetate and sodium acetate, placing the mixture on a magnetic stirrer, stirring the mixture for 2 hours, then dropwise adding ammonia water to adjust the pH value, and then adding the mixture into a reactor according to the molar ratio of n (CA) to n (EA) to 1: and 2, dropwise adding ethylene glycol (EA), and standing the obtained solution for 24 hours to obtain clear KNN precursor sol.
6) 15mL of ethylene glycol monomethyl ether was taken out and placed in a closed flask, 2g of niobium ethoxide was dissolved in ethylene glycol monomethyl ether by a pipette under an argon atmosphere, and the mixture was heated in a water bath at 80 ℃ and stirred for 1 hour. Respectively dripping 1-2 drops of glacial acetic acid and acetylacetone, and continuing heating in a water bath for 1h by 3-4 drops of formamide. Taking down the mixed solution and placing the mixed solution into a reagent bottle according to the mass ratio n (Nb)5+):n(K+):n(Na+) 2:1.1:1.1), and finally standing and aging to obtain bright yellow KNN precursor sol.
7) And then spin-coating the clear KNN precursor sol obtained in the step 5) on a Si (100) substrate at the rotating speed of 4000r/min for 30s, pyrolyzing the obtained wet film at 250 ℃, and annealing once at 650-800 ℃.
8) Dripping the bright yellow KNN precursor sol obtained in the step 6) on the basis of the step 7), rotating at the speed of 4000r/min, spin-coating for 30s to obtain a wet film, pyrolyzing at 250 ℃, and annealing once at 650-800 ℃.
9) And repeating the step 7) and the step 8) to obtain the potassium-sodium niobate homogeneous multilayer film with high preferred orientation.
Comparative example
1) 5g of niobium pentoxide (Nb) were weighed with an electronic balance2O5) Pouring into a reaction kettle, adding 25mL of hydrofluoric acid (HF) with the concentration of 40 wt% into the reaction kettle, and stirring the reaction kettle for 6 hours in water bath heating at the temperature of 80 ℃.
2) Adding 7g of ammonium oxalate into the reaction kettle in the step 1), and continuously heating in a water bath at 80 ℃ for 2h to obtain a mixed solution.
3) Removing the mixed solution in the step 2), adjusting the pH value of the solution by using ammonia water, and reacting the solution to generate white Nb (OH)5Precipitating, aging the precipitate for 24h, standing in vacuum drying oven at 60 deg.C for 2h, filtering off white precipitate, and repeatedly washing to obtain Nb (OH)5White precipitate.
4) Reacting Nb (OH)5White precipitate and Citric Acid (CA) were mixed in a molar ratio of 1: 4 mixing and stirring for 24 hours, and standing to obtain a clear solution.
5) The solution obtained in the step 4) is processed by the molar ratio n (Nb)5+):n(K+):n(Na+) Adding potassium acetate and sodium acetate, placing the mixture on a magnetic stirrer, stirring the mixture for 2 hours, then dropwise adding ammonia water to adjust the pH value, and then adding the mixture into a reactor according to the molar ratio of n (CA) to n (EA) to 1: and 2, dropwise adding ethylene glycol (EA), and standing the obtained solution for 24 hours to obtain clear KNN precursor sol.
6) 15mL of ethylene glycol monomethyl ether was taken out and placed in a closed flask, 2g of niobium ethoxide was dissolved in ethylene glycol monomethyl ether by a pipette under an argon atmosphere, and the mixture was heated in a water bath at 80 ℃ and stirred for 1 hour. Dropwise adding 1-2 drops of glacial acetic acid and acetylacetone, and continuously heating in a water bath for 1h with 3-4 drops of formamide. Taking down the mixed solution and placing the mixed solution into a reagent bottle according to the mass ratio n (Nb)5+):n(K+):n(Na+) 2:1.1:1.1), and finally standing and aging to obtain bright yellow KNN precursor sol.
7) And then spin-coating the clear KNN precursor sol obtained in the step 5) on a Si (100) substrate at the rotating speed of 4000r/min for 30s, pyrolyzing the obtained wet film at 250 ℃, and annealing once at 650-800 ℃.
8) Dripping the metal alkoxide method KNN precursor sol obtained in the step 6) on the basis of the step 7), rotating at the speed of 4000r/min, spin-coating for 30s to obtain a wet film, pyrolyzing at 250 ℃, and annealing once at 650-800 ℃.
9) And repeating the step 7) and the step 8) to obtain the potassium-sodium niobate homogeneous multilayer film with high preferred orientation.
Fig. 1 to 4 correspond to XRD patterns of example 1 and comparative example prepared by sol-gel process at annealing temperatures of 650 c, 700 c, 750 c, 800 c compared to a single niobium source, respectively. It can be seen from the figure that the KNN homogeneous multilayer thin film prepared by the alternating spin coating of the present invention has a much higher (100) orientation than the KNN thin film prepared by a single niobium source, and has better crystallinity. The potassium-sodium niobate (KNN) homogeneous multilayer film prepared by the method has higher (100) preferred orientation, and is beneficial to the regulation and control of the performance of the KNN film.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a potassium-sodium niobate homogeneous multilayer film based on double niobium sources is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving niobium pentoxide in hydrofluoric acid, heating in a water bath in a reaction kettle, adding ammonium oxalate, continuing heating in the water bath, taking out the mixed solution, dropwise adding ammonia water to generate white precipitate, washing and filtering the white precipitate, adding citric acid to obtain a niobium-citrate solution, continuing filtering to obtain a clear solution, adding potassium salt and sodium salt into the obtained clear solution, stirring, adjusting the pH value of the solution to be alkaline, adding ethylene glycol, and standing to obtain a clear potassium-sodium niobate precursor sol;
(2) dropwise adding ethylene glycol monomethyl ether into a reaction kettle, then sucking niobium ethoxide into the ethylene glycol monomethyl ether under the condition of nitrogen, heating the mixed solution in a water bath, dropwise adding glacial acetic acid, acetylacetone and formamide, continuing heating in the water bath, and adding sodium salt and sodium salt into the mixed solution at room temperature and stirring to obtain bright yellow potassium-sodium niobate precursor sol;
(3) preheating the (100) silicon wafer, spin-coating the potassium-sodium niobate precursor sol prepared in the step (1) on the (100) silicon wafer, and thermally decomposing and annealing the wet film; spin-coating the potassium-sodium niobate precursor sol prepared in the step (2), and continuing pyrolysis annealing; and (3) continuously spin-coating the potassium-sodium niobate precursor sol prepared in the step (1) on the basis, pyrolyzing and annealing the wet film, and so on, and alternately spin-coating to prepare the potassium-sodium niobate homogeneous multilayer film.
2. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (1), 1g of niobium pentoxide is dissolved in 5mL of hydrofluoric acid, and then the solution is heated in a water bath at a temperature of 80 ℃ for 6 hours, and after ammonium oxalate is added, the solution is continuously heated in the water bath at the temperature of 80 ℃ for 2 hours.
3. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (1), after white precipitate is generated, standing, then putting into a vacuum drying oven, aging at 60 ℃ for 40min, and then washing.
4. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (1), citric acid and deionized water are added into the white precipitate, and the mixture is stirred to obtain a niobium-citrate solution, wherein the mass ratio of the white precipitate to the citric acid is 1: 4.
5. the method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (1), the ratio of the addition amount of the potassium salt and the sodium salt to the amount of the niobium material in the solution is 1.1: 1.1: 2; the ratio of the addition amount of the ethylene glycol to the amount of the citric acid is 2:1.
6. the method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (2), 2g of niobium ethoxide is dissolved in 15mL of ethylene glycol monomethyl ether, the mixture is heated in water bath at the temperature of 80 ℃ for 1h, then 1-2 drops of glacial acetic acid and acetylacetone are respectively dripped, 3-4 drops of formamide are dripped, and the heating in water bath at the temperature of 80 ℃ is continued for 1 h.
7. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (2), the ratio of the addition amount of the potassium salt and the sodium salt to the amount of the niobium in the solution is 1.1: 1.1: 2.
8. the method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (3), (100) the silicon wafer is preheated at a temperature of 500 ℃ for 10 min.
9. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (3), spin coating is performed on a spin coater under the following conditions: the rotating speed is 4000r/min, and the time is 30 s.
10. The method of preparing a potassium-sodium niobate homogeneous multilayer thin film based on a double niobium source as claimed in claim 1, wherein: in the step (3), the pyrolysis annealing conditions are as follows: the pyrolysis temperature was maintained at 250 ℃ for 5 minutes and the annealing temperature at 650 ℃ to 800 ℃ for 9 minutes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102180672A (en) * | 2011-03-22 | 2011-09-14 | 南京航空航天大学 | Preparation method of potassium sodium niobate system lead-free piezoelectric ceramic film |
| CN102276257A (en) * | 2011-03-22 | 2011-12-14 | 南京航空航天大学 | Method for preparing potassium sodium niobate leadless piezoelectric ceramic powder |
| CN110204361A (en) * | 2019-07-05 | 2019-09-06 | 南京邮电大学 | The preparation method of the potassium sodium niobate film of height preferred orientation is produced based on nickel acid lanthanum transition zone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180672A (en) * | 2011-03-22 | 2011-09-14 | 南京航空航天大学 | Preparation method of potassium sodium niobate system lead-free piezoelectric ceramic film |
| CN102276257A (en) * | 2011-03-22 | 2011-12-14 | 南京航空航天大学 | Method for preparing potassium sodium niobate leadless piezoelectric ceramic powder |
| CN110204361A (en) * | 2019-07-05 | 2019-09-06 | 南京邮电大学 | The preparation method of the potassium sodium niobate film of height preferred orientation is produced based on nickel acid lanthanum transition zone |
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