阅读说明：本技术 铌酸银基无铅反铁电膜及其制备方法和应用 (Silver niobate-based lead-free antiferroelectric film and preparation method and application thereof ) 是由 李敬锋 舒亮 刘丽莎 张鑫 高静 黄宇 程月雨杉 于 2021-07-15 设计创作，主要内容包括：本发明公开了铌酸银基无铅反铁电膜及其制备方法和应用。该制备方法包括：将乙二醇独甲醚和乙二醇混合得到混合溶剂,将乙醇铌和乙二醇独甲醚混合得到乙醇铌溶液；将硝酸银、柠檬酸和一部分的混合溶剂混合,并调节混合液的pH值得到含银溶液；将乙醇铌溶液和另一部分的混合溶剂混合得到含铌溶液；将含银溶液和含铌溶液混合、陈化得到银铌溶胶；将银铌溶胶形成在衬底上并进行甩胶成膜处理形成凝胶膜；连带衬底对凝胶膜进行烘干、热解和退火处理得到铌酸银基反铁电膜。该方法不仅安全可靠、设备简单、用料省、成本低、易于实现工业化生产,而且采用的溶剂无毒无害,且溶胶合成过程中无需加热,可在衬底上沉积出纯相薄膜。(The invention discloses a silver niobate-based lead-free antiferroelectric film and a preparation method and application thereof. The preparation method comprises the following steps: mixing ethylene glycol monomethyl ether and ethylene glycol to obtain a mixed solvent, and mixing niobium ethoxide and ethylene glycol monomethyl ether to obtain a niobium ethoxide solution; mixing silver nitrate, citric acid and a part of mixed solvent, and adjusting the pH value of the mixed solution to obtain a silver-containing solution; mixing the niobium ethoxide solution and the other part of mixed solvent to obtain a niobium-containing solution; mixing the silver-containing solution and the niobium-containing solution, and aging to obtain silver-niobium sol; forming silver niobium sol on a substrate and carrying out spin coating film forming treatment to form a gel film; and drying, pyrolyzing and annealing the gel film together with the substrate to obtain the silver niobate-based antiferroelectric film. The method has the advantages of safety, reliability, simple equipment, material saving, low cost and easy realization of industrial production, and the adopted solvent is nontoxic and harmless, and the pure-phase film can be deposited on the substrate without heating in the sol synthesis process.)

1. A method for preparing a silver niobate-based lead-free antiferroelectric film, comprising:

(1) mixing ethylene glycol monomethyl ether and ethylene glycol to obtain a mixed solvent, and mixing niobium ethoxide and ethylene glycol monomethyl ether to obtain a niobium ethoxide solution;

(2) mixing silver nitrate, citric acid and a part of the mixed solvent, and adjusting the pH value of the mixed solution to obtain a silver-containing solution;

(3) mixing the niobium ethoxide solution and another part of the mixed solvent so as to obtain a niobium-containing solution;

(4) mixing and aging the silver-containing solution and the niobium-containing solution to obtain silver-niobium sol;

(5) forming the silver niobium sol on a substrate and carrying out spin coating film forming treatment so as to form a gel film;

(6) and carrying out drying, pyrolysis and annealing treatment on the gel film together with the substrate so as to obtain the silver niobate-based antiferroelectric film.

2. The method of claim 1, wherein step (1) satisfies at least one of the following conditions:

the volume fraction of the ethylene glycol in the mixed solvent is 30-60%;

the concentration of niobium ethoxide in the niobium ethoxide solution is 0.5-2 mol/L.

3. The method of claim 1, wherein step (2) satisfies at least one of the following conditions:

the molar ratio of the citric acid to the silver nitrate is (0.5-2): 1;

the molar ratio of the glycol to the citric acid in a part of the mixed solvent is not less than 5: 1;

adjusting the pH value of the mixed solution to 3-4;

adjusting the pH value of the mixed solution by adopting glacial acetic acid;

the mixing is carried out under the conditions of light isolation and air isolation;

the citric acid is citric acid monohydrate or anhydrous citric acid.

4. The method of claim 1, wherein step (3) satisfies at least one of the following conditions:

mixing acetylacetone, the niobium ethoxide solution and the mixed solvent to obtain a niobium-containing solution;

in the niobium-containing solution, the molar ratio of acetylacetone to niobium ethoxide is (0-2): 1;

in the niobium-containing solution, the molar ratio of acetylacetone to niobium ethoxide is (0.5-1): 1;

the mixing is carried out under exclusion of air.

5. The method of claim 1, wherein step (4) satisfies at least one of the following conditions:

the molar ratio of silver nitrate in the silver-containing solution to niobium ethoxide in the niobium-containing solution is 1: 1;

the aging time is 24-48 h;

the mixing is carried out under exclusion of air.

6. The method of claim 1, wherein step (5) satisfies at least one of the following conditions:

the substrate is Pt (111)/Ti/SiO₂a/Si (100) substrate;

the whirl coating treatment comprises a low-speed stage and a high-speed stage which are sequentially carried out, wherein the rotating speed of the low-speed stage is 300-800 r/min, and the time is 5-20 s; the rotating speed of the high-speed stage is 2000-8000 r/min, and the time is 20-40 s;

prior to forming the silver niobium sol on the substrate, further comprising: cleaning, annealing and drying the substrate;

prior to forming the silver niobium sol on the substrate, further comprising: and cleaning the substrate by using alcohol with the purity of not less than 99%, and annealing and drying the cleaned substrate at 350-450 ℃.

7. The method of claim 1, wherein step (6) satisfies at least one of the following conditions:

the drying temperature is 120-200 ℃, and the drying time is 10 s-2 min;

the pyrolysis temperature is 300-600 ℃, and the time is 20 s-5 min;

the annealing temperature is 680-900 ℃, and the annealing time is 1-10 min;

the temperature rising speed of drying is 20-100 ℃/s, and the temperature reduction speed after annealing is 0.5-1 ℃/s;

the pyrolysis and the annealing are carried out in a flowing oxygen atmosphere, and the flow rate of the oxygen is 1.5-3.5L/min;

the pyrolysis temperature is 400-500 ℃, and the annealing temperature is 700-850 ℃.

8. The method of any one of claims 1 to 7, further comprising:

(7) repeating the operations of steps (5) to (6) on the silver niobate-based antiferroelectric film with the substrate obtained in step (6) to obtain a silver niobate-based antiferroelectric film having a desired thickness,

optionally, the number of times steps (5) - (6) are repeated is no more than 20;

optionally, the thickness of the silver niobate-based antiferroelectric film obtained by repeating the steps (5) to (6) is increased by 20 to 40 nm.

9. A silver niobate-based lead-free antiferroelectric film characterized by being produced by the method according to any one of claims 1 to 8.

10. A capacitor comprising the silver niobate-based lead-free antiferroelectric film according to claim 9 or the silver niobate-based lead-free antiferroelectric film produced by the method according to any one of claims 1 to 8.

Technical Field

The invention belongs to the field of functional thin film materials, and particularly relates to a silver niobate-based lead-free antiferroelectric film, and a preparation method and application thereof.

Background

The dielectric capacitor has the advantages of high power density, high charging/discharging speed, long cycle life, capability of generating large pulse voltage and current in a short time and the like, and is widely applied to pulse discharging and power regulating electronic devices. With the development of pulse power devices toward miniaturization and light weight, it is particularly important to develop a dielectric material with high energy storage performance and high energy storage density and efficiency. The ceramic capacitor has higher dielectric constant and better mechanical and thermal stability, shows advantages in the field of high-temperature dielectric energy storage, but the further improvement of the energy storage density is limited by the lower compressive strength of the ceramic capacitor. Compared with ceramic body materials, the ceramic film has higher compressive strength and low working voltage, can match widely used power voltage, has good compatibility with integrated circuits, and is an energy storage material with a wide application prospect.

Among many ceramic energy storage media, antiferroelectric ceramics have received much attention due to their large energy storage density due to their unique dual hysteresis loop, but the lead-based antiferroelectric systems are still the most widely used at present. Through doping modification and process optimization, the lead-based antiferroelectric ceramic shows 10J/cm³So that the high energy storage density is obtained and the lead-based anti-ferroelectric thin film exhibits more than 50J/cm³The storage energy density of the lead is high, but a large amount of toxic lead brings great harm to human bodies and the environment in the production and waste treatment processes. Therefore, it is important to develop a new antiferroelectric energy storage material capable of replacing lead-based materials.

Disclosure of Invention

The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the invention aims to provide a silver niobate-based lead-free antiferroelectric film, a preparation method and application thereof, wherein the method is safe and reliable, simple in equipment, low in material consumption and cost, easy to realize industrial production, and the adopted solvent is non-toxic and harmless, and a pure-phase film can be deposited on a substrate without heating in the sol synthesis process.

The invention is mainly based on the following problems:

AgNbO₃(ANO) ceramic is one of a few known lead-free antiferroelectric materials, has received much attention in recent years, and is mainly focused on doping modification of silver niobate-based ceramic blocks, and the energy storage density reaches up to 7.01J/cm at present³. However, the pure phase silver niobate thin film is difficult to prepare due to the influence of the substrate and the like. Most integrated circuit processes are based on silicon materials, but at present, no precedent for successfully preparing pure phase silver niobate films on silicon substrates exists. In addition, compared with the physical method for preparing the film, the sol-gel method has the advantages of simple process, low equipment cost, low deposition temperature, easy realization of accurate component control and quantitative doping, compatibility with a semiconductor process and the like, and is widely used for the deposition of the metal oxide film. However, the sol-gel method for depositing the silver niobate thin film is rarely reported, and has three main difficulties: (1) the sol preparation is difficult: the silver source is lack of corresponding organic alkoxide, inorganic silver nitrate is decomposed by light and meets the condition that organic matters turn into grey and black to decompose silver, and niobium ethoxide is easy to hydrolyze; (2) the solvent has great harmfulness: pyridine can be used as a solvent to prepare a stable sol, but vapor and air can form an explosive mixture, the mixture is easy to burn and explode when meeting high heat, and the pyridine is listed in a category 2B carcinogen list by the world health organization and can cause great harm to human bodies (3) the pure-phase preparation is difficult: the sol has not been used for successfully preparing a pure-phase film on silicon, and a second-phase Ag which is difficult to eliminate exists₂Nb₄O₁₁。

To this end, in one aspect of the present invention, the present invention proposes a method for producing a silver niobate-based lead-free antiferroelectric film. According to an embodiment of the invention, the method comprises:

(1) mixing ethylene glycol monomethyl ether and ethylene glycol to obtain a mixed solvent, and mixing niobium ethoxide and ethylene glycol monomethyl ether to obtain a niobium ethoxide solution;

(2) mixing silver nitrate, citric acid and a part of the mixed solvent, and adjusting the pH value of the mixed solution to obtain a silver-containing solution;

(3) mixing the niobium ethoxide solution and another part of the mixed solvent so as to obtain a niobium-containing solution;

(4) mixing and aging the silver-containing solution and the niobium-containing solution to obtain silver-niobium sol;

(5) forming the silver niobium sol on a substrate and carrying out spin coating film forming treatment so as to form a gel film;

(6) and carrying out drying, pyrolysis and annealing treatment on the gel film together with the substrate so as to obtain the silver niobate-based antiferroelectric film.

Compared with the prior art, the method for preparing the silver niobate-based lead-free antiferroelectric film in the embodiment of the invention adopts a sol-gel method, and the method at least has the following advantages: 1) the solvent used for preparing the silver niobium sol is non-toxic and harmless, and heating is not needed in the sol synthesis process; 2) by pre-forming a mixed solution of ethylene glycol monomethyl ether and ethylene glycol, respectively dissolving silver nitrate and niobium ethoxide solution in a part of mixed solvent, and then mixing, the uniform and stable silver niobium sol can be formed, and the film forming property can be improved; 3) can deposit pure-phase (perovskite structure) silver niobate-based antiferroelectric film on a substrate; 4) the prepared silver niobate-based antiferroelectric film has controllable thickness, compact structure and better uniformity; 5) the preparation process is safe, high in reliability, simple in equipment, material-saving, low in cost and easy to realize industrial production.

In addition, the method for preparing a silver niobate-based lead-free antiferroelectric film according to the above embodiment of the present invention may further have the following additional technical features:

in some embodiments of the invention, step (1) satisfies at least one of the following conditions: the volume fraction of the ethylene glycol in the mixed solvent is 30-60%; in the niobium ethoxide solution, the concentration of niobium ethoxide is 0.5-2 mol/L.

In some embodiments of the invention, step (2) satisfies at least one of the following conditions: the molar ratio of the citric acid to the silver nitrate is (0.5-2): 1; adjusting the pH value of the mixed solution to 3-4; adjusting the pH value of the mixed solution by adopting glacial acetic acid; the mixing is carried out under the conditions of light isolation and air isolation; the citric acid is citric acid monohydrate or anhydrous citric acid.

In some embodiments of the invention, step (3) satisfies at least one of the following conditions: mixing acetylacetone, the niobium ethoxide solution and the mixed solvent to obtain a niobium-containing solution; in the niobium-containing solution, the molar ratio of acetylacetone to niobium ethoxide is (0-2): 1; in the niobium-containing solution, the molar ratio of acetylacetone to niobium ethoxide is (0.5-1): 1; the mixing is carried out under exclusion of air.

In some embodiments of the invention, step (4) satisfies at least one of the following conditions: the molar ratio of silver nitrate in the silver-containing solution to niobium ethoxide in the niobium-containing solution is 1: 1; the aging time is 24-48 h; the mixing is carried out under exclusion of air.

In some embodiments of the invention, step (5) satisfies at least one of the following conditions: the substrate is Pt (111)/Ti/SiO₂a/Si (100) substrate; the whirl coating treatment comprises a low-speed stage and a high-speed stage which are sequentially carried out, wherein the rotating speed of the low-speed stage is 300-800 r/min, and the time is 5-20 s; the rotating speed of the high-speed stage is 2000-8000 r/min, and the time is 20-40 s; prior to forming the silver niobium sol on the substrate, further comprising: cleaning, annealing and drying the substrate; prior to forming the silver niobium sol on the substrate, further comprising: and cleaning the substrate by using alcohol with the purity of not less than 99%, and annealing and drying the cleaned substrate at 350-450 ℃.

In some embodiments of the invention, step (6) satisfies at least one of the following conditions: the drying temperature is 120-200 ℃, and the drying time is 10 s-2 min; the pyrolysis temperature is 300-600 ℃, and the time is 20 s-5 min; the annealing temperature is 680-900 ℃, and the annealing time is 1-10 min; the temperature rising speed of drying is 20-100 ℃/s, and the temperature reduction speed after annealing is 0.5-1 ℃/s; the pyrolysis and the annealing are carried out in a flowing oxygen atmosphere, and the flow rate of the oxygen is 1.5-3.5L/min; the pyrolysis temperature is 400-500 ℃, and the annealing temperature is 700-850 ℃.

In some embodiments of the present invention, the method of preparing a silver niobate-based lead-free antiferroelectric film further comprises: (7) repeating the operations of steps (5) to (6) on the silver niobate-based antiferroelectric film with the substrate obtained in step (6) to obtain a silver niobate-based antiferroelectric film having a desired thickness.

In some embodiments of the invention, the number of repetitions of steps (5) - (6) is no greater than 20;

in some embodiments of the present invention, the thickness of the silver niobate-based antiferroelectric film obtained by repeating the steps (5) to (6) is increased by 20 to 40 nm.

According to still another aspect of the present invention, there is provided a silver niobate-based lead-free antiferroelectric film. According to an embodiment of the present invention, the silver niobate-based lead-free antiferroelectric film is obtained by the above-described method for preparing a silver niobate-based lead-free antiferroelectric film. Compared with the prior art, the silver niobate-based lead-free antiferroelectric film has low cost, is easy to obtain, has pure phase of perovskite structure, has compact film structure and better uniformity, and can be widely used in dielectric capacitors.

According to yet another aspect of the present invention, a capacitor is provided. According to an embodiment of the present invention, the capacitor has the above silver niobate-based lead-free antiferroelectric film or the silver niobate-based lead-free antiferroelectric film obtained by the above method for producing a silver niobate-based lead-free antiferroelectric film. Compared with the prior art, the energy storage material adopted by the capacitor has less harm to human bodies and environment.

Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.

Drawings

The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:

fig. 1 is a flowchart of a method for producing a silver niobate-based lead-free antiferroelectric film according to an embodiment of the present invention.

Fig. 2 is a flowchart of a method for producing a silver niobate-based lead-free antiferroelectric film according to still another embodiment of the present invention.

FIG. 3 is a graph of a product of an aged silver-containing niobium sol according to example 1 of the present invention.

FIG. 4 shows AgNbO finally obtained in example 1 of the present invention₃XRD pattern of the film.

FIG. 5 shows AgNbO finally obtained in example 1 of the present invention₃Scanning Electron Microscope (SEM) photographs of a cross section (corresponding to fig. 5(a)) and a surface (corresponding to fig. 5(a)) of a sample of the thin film, and a surface scan of an energy spectrum of three elements of Ag, Nb, and O (sequentially corresponding to fig. 5(c) - (e)).

FIG. 6 shows AgNbO finally obtained in example 1 of the present invention₃The dielectric constant of the film is plotted against temperature.

FIG. 7 shows AgNbO finally obtained in example 1 of the present invention₃The polarization intensity of the film is shown as the variation of the applied electric field.

FIG. 8 shows AgNbO finally obtained in example 1 of the present invention₃And (3) a piezoelectric response diagram of the film under an ON state of a flip piezoelectric force microscope (SS-PFM).

FIG. 9 is the AgNbO ultimately produced according to comparative examples 1, 2 and 3 of the invention₃XRD contrast pattern of thin films.

Detailed Description

Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.

In one aspect of the present invention, the present invention provides a method for preparing a silver niobate-based lead-free antiferroelectric film. According to an embodiment of the invention, as shown in fig. 1, the method comprises: (1) mixing ethylene glycol monomethyl ether and ethylene glycol to obtain a mixed solvent, and mixing niobium ethoxide and ethylene glycol monomethyl ether to obtain a niobium ethoxide solution; (2) mixing silver nitrate, citric acid and a part of mixed solvent, and adjusting the pH value of the mixed solution to obtain a silver-containing solution; (3) mixing the niobium ethoxide solution with the other part of the mixed solvent to obtain a niobium-containing solution; (4) mixing and aging the silver-containing solution and the niobium-containing solution to obtain silver-niobium sol; (5) forming silver niobium sol on a substrate and carrying out spin coating film forming treatment so as to form a gel film; (6) and carrying out drying, pyrolysis and annealing treatment on the gel film together with the substrate so as to obtain the silver niobate-based antiferroelectric film. The method has the advantages of safety, reliability, simple equipment, material saving, low cost and easy realization of industrial production, and the adopted solvent is nontoxic and harmless, and the pure-phase film can be deposited on the substrate without heating in the sol synthesis process.

The method for producing a silver niobate-based lead-free antiferroelectric film according to the above embodiment of the present invention is described in detail with reference to fig. 1 to 2.

S100: mixing ethylene glycol monomethyl ether and ethylene glycol to obtain a mixed solvent, and mixing niobium ethoxide and ethylene glycol monomethyl ether to obtain a niobium ethoxide solution

According to an embodiment of the present invention, the volume fraction of the ethylene glycol in the mixed solvent may be 30 to 60%, for example, 30%, 35%, 40%, 45%, 50%, 55%, or 60% or the like, in the present invention, a mixed solvent of ethylene glycol monomethyl ether (2-MOE) and Ethylene Glycol (EG) is used to prepare a silver niobium sol, however, the inventors found that if the volume fraction of ethylene glycol is too small, the stability of the sol formed subsequently is poor, which is not favorable for forming a uniform and stable silver-niobium sol, and as the volume fraction of ethylene glycol increases, although the stability of the silver niobium sol formed subsequently can be improved, the glycol volume solubility is too high and is not beneficial to film formation, and the mixed solvent is controlled to be the proportion, so that the stability of the silver niobium sol obtained subsequently can be improved, the film formation property of the silver niobium sol can be ensured, and the uniform and compact silver niobate-based antiferroelectric film can be obtained more favorably.

According to still another embodiment of the present invention, the niobium ethoxide solution may have a niobium ethoxide concentration of 0.5 to 2mol/L, for example, 0.5mol/L, 0.8mol/L, 1.2mol/L, 1.5mol/L, 1.8mol/L, or 2mol/L, and the inventors found that niobium ethoxide is extremely unstable and is easy to react with water in the air, and by dispersing niobium ethoxide in ethylene glycol monomethyl ether and controlling the niobium ethoxide in the solution to the above concentration range, storage of niobium ethoxide and subsequent uniform mixing with the silver-containing solution are facilitated; preferably, the mixing of niobium ethoxide and ethylene glycol monomethyl ether can be performed under air exclusion conditions to avoid reaction between niobium ethoxide and moisture in the air.

S200: mixing silver nitrate, citric acid and a part of mixed solvent, and adjusting the pH value of the mixed solution to obtain silver-containing solution

According to the embodiment of the invention, citric acid can be used as a chelating agent when preparing the silver-containing solution, but the inventor finds that if the pH value of the mixed solution is too high, the obtained silver-containing solution is unstable, and the uniform and stable silver-containing solution can be obtained more favorably by controlling the pH value of the mixed solution to be 3-4. In addition, the pH of the mixed solution may be adjusted by using an acid, wherein the type of the acid is not particularly limited, and those skilled in the art may select the acid according to actual needs as long as the conditions that the acid does not react with silver nitrate and is safe are satisfied, for example, glacial acetic acid may be preferably used to adjust the pH of the mixed solution as compared with nitric acid having a higher risk or hydrochloric acid that is liable to react with silver nitrate to generate a precipitate, wherein the acid may be mixed with the mixed solvent and citric acid and then mixed with silver nitrate, or the mixed solvent, citric acid and silver nitrate may be mixed and then added with the acid to adjust the pH. The type of citric acid used in the present invention is not particularly limited, and those skilled in the art can select the citric acid according to actual needs, and the citric acid may be, for example, citric acid monohydrate or citric acid anhydrous.

According to the embodiment of the invention, when mixing the silver nitrate, the citric acid and a part of mixed solvent, the stirring can be finished at room temperature by isolating air, so that the silver nitrate can be prevented from reacting with moisture in the air to generate silver hydroxide precipitate; more preferably, the mixing process can also be carried out under the condition of isolating air and keeping out light, thereby avoiding the silver nitrate from being decomposed by light to generate the silver simple substance. Thus, in the present invention, the chemical stability of the silver-containing solution can be further improved by carrying out the mixing process under the conditions of light and air exclusion.

According to an embodiment of the present invention, the molar ratio of citric acid to silver nitrate may be (0.5-2): 1, for example, 0.5/1, 0.8/1, 1/1, 1.2/1, 1.5/1, 1.8/1, 2/1, etc. the inventors have found that if the amount of citric acid is too small, the chelating effect is poor, and a precipitate is easily formed, and if the amount of citric acid is too large, the chelating effect can be improved, but if the amount of citric acid is too large, a problem of precipitation of citric acid crystals may occur; in addition, more importantly, if the consumption of the citric acid is too much, the citric acid is easily decomposed by heating in the subsequent treatment process to generate great heat, so that the gel film is easily subjected to pore generation to form a porous film structure, and the uniform and compact silver niobate-based antiferroelectric film is not favorably formed; meanwhile, excessive citric acid is easy to oxidize in the subsequent heat treatment process, and easily absorbs excessive oxygen to cause local oxygen deficiency, so that silver is reduced; further, the molar ratio of ethylene glycol to citric acid in the mixed solvent used for preparing the silver-containing solution is preferably not less than 5:1, and may be, for example, 6/1 or 7/1, and the inventors have found that, if the molar ratio of ethylene glycol to citric acid is too small, the silver-containing solution is also unstable and precipitation is likely to occur. According to the invention, the problem can be effectively solved by controlling the molar ratio range of the citric acid to the silver nitrate and the glycol, so that the uniform and stable silver niobate-based antiferroelectric film can be obtained more favorably.

S300: mixing the niobium ethoxide solution with the other part of the mixed solvent to obtain a niobium-containing solution

According to the embodiment of the present invention, when the niobium ethoxide solution and another part of the mixed solvent are mixed, it is also preferable to complete the mixing at room temperature without air, so that the niobium ethoxide can be prevented from reacting with water in the air to produce niobium hydroxide.

According to an embodiment of the present invention, acetylacetone, niobium ethoxide solution, and the mixed solvent may be mixed to obtain a niobium-containing solution. The inventor finds that niobium ethoxide is unstable and is easy to combine with water in the air to generate niobium hydroxide precipitate, a chelating agent can be used for remarkably improving the stability of niobium ethoxide, and acetylacetone is preferably added as the chelating agent when the niobium ethoxide solution and the mixed solvent are mixed to improve the stability of the niobium solution and the film forming property of the subsequent silver-niobium sol. Further, the molar ratio of acetylacetone to niobium ethoxide may be (0-2): 1, for example, 0.2/1, 0.5/1, 0.8/1, 1/1, 1.2/1, 1.5/1, 1.8/1, 2/1, etc., and the inventors have found that, when the amount of acetylacetone is too large, an over-chelation phenomenon (i.e., imbalance between the degree of hydrolysis and the degree of polymerization) is likely to occur, and the niobium-containing solution is gelled; meanwhile, the acetylacetone is easily decomposed by heating, and the excessive acetylacetone is also easily decomposed by heating in the subsequent treatment process to generate great heat, so that the gel film is easily subjected to pore generation to form a porous film structure, and the uniform and compact silver niobate-based antiferroelectric film is not favorably formed; in addition, too much acetylacetone is also easily oxidized in the subsequent heat treatment process, and is easy to absorb too much oxygen to cause local oxygen deficiency, and the problem of silver reduction can also occur. The problem can be effectively solved by using the acetylacetone in the dosage range, so that the uniform and stable silver niobate-based antiferroelectric film can be obtained more favorably. More preferably, the molar ratio of acetylacetone to niobium ethoxide can be (0.5-1): 1, thereby being more favorable for forming a uniform, dense and pure-phase silver niobate-based antiferroelectric thin film.

S400: mixing the silver-containing solution and the niobium-containing solution, and aging to obtain silver-niobium sol

According to the embodiment of the invention, the silver-containing solution and the niobium-containing solution can be mixed and stirred under the condition of air isolation at room temperature for 2-4 hours, and then the obtained clear and transparent solution is sealed and stored in a glass reagent bottle and is kept standing at room temperature in a dark place for aging to obtain uniform and stable mixed glue solution containing silver-niobium colloidal particles, namely silver-niobium sol. Further, AgNbO can be used₃The silver-containing solution and the niobium-containing solution are mixed according to the stoichiometric ratio, namely the molar ratio of silver nitrate in the silver-containing solution to niobium ethoxide in the niobium-containing solution is controlled to be 1:1, so that the utilization rate of raw materials can be improved, and the pure-phase silver niobate is further favorably obtainedA ferroelectric thin film.

According to a specific embodiment of the invention, the aging time can be 24-48 h, for example, 24h, 28h, 32h, 36h, 40h, 44h or 48h, and the inventors find that if the aging time is too short, the obtained silver-niobium sol is relatively thin and has insufficient viscosity, which is not favorable for forming a uniform film, the particle size of the formed colloidal particles can be increased along with the prolonging of the aging time, and the film forming uniformity in the subsequent spin coating film forming process is also better.

S500: forming silver niobium sol on a substrate, spin coating to form a gel film

According to the embodiment of the invention, the substrate can be adsorbed on the spin coater in vacuum, the mixed glue solution containing the silver-niobium colloidal particles is uniformly dripped on the substrate by using the disposable needle tube, and the glue spinning procedure is started to obtain the gel film containing the silver-niobium, which is uniformly coated.

According to an embodiment of the present invention, the substrate used in the present invention is not particularly limited, and those skilled in the art can select the substrate according to actual needs, such as Pt (111)/Ti/SiO₂The substrate being a Si (100) substrate, i.e. a SiO layer being formed beforehand on the Si substrate₂Layer of then SiO₂A Ti layer and a Pt layer are sequentially deposited on the layer. Further, in order to ensure the quality of the finally prepared silver niobate-based lead-free antiferroelectric film, before forming the silver niobium sol on the substrate, the method may further include: and cleaning and annealing and drying the substrate, thereby removing impurities on the substrate. Preferably, the substrate can be cleaned by using alcohol with the purity of not less than 99% (such as 99.7% or 99.9% purity), and the cleaned substrate is subjected to annealing and drying treatment at 350-450 ℃, so that not only can impurities such as oil stains on the surface of the substrate be sufficiently removed, but also organic matters (such as alcohol) and water remained on the surface of the substrate can be removed through annealing and drying, and the surface of the substrate can be ensured to be clean. As another example, 6mm Pt (111)/Ti/SiO may be used₂the/Si (100) substrate is cleaned by high-purity alcohol and then is homogenizedAnd (4) throwing off residual alcohol, and then placing the substrate in a rapid annealing furnace for drying for 60s at 400 ℃.

According to another embodiment of the present invention, the spin coating process may include a low speed stage and a high speed stage, which are performed sequentially, and the inventors found that the silver niobium sol can be uniformly spread on the substrate by spin coating at a low rotation speed, and then the thickness of the film can be further reduced by spin coating at a high speed, so as to obtain a gel film with a suitable thickness, wherein the low speed stage and the high speed stage can be automatically switched. Furthermore, the rotating speed of the low-speed stage can be 300-800 r/min, the time can be 5-20 s, the rotating speed of the high-speed stage can be 2000-8000 r/min, and the time can be 20-40 s, and the inventor finds that the application of the whirl coating procedure is more beneficial to obtaining the silver niobate-based lead-free antiferroelectric film with the thickness of 20-40 nm. In addition, the inventor also finds that the higher the rotating speed or the longer the continuous rotating time, the smaller the thickness of the formed gel film, and if a thin film with other thickness is needed to be obtained at a time, the specific conditions of the whirl coating procedure can be controlled by the skilled person according to the actual needs.

S600: drying, pyrolyzing and annealing the gel film together with the substrate to obtain the silver niobate-based antiferroelectric film

According to a specific embodiment of the present invention, the gel film may be dried in a glue drying table or a rapid annealing furnace, wherein the drying temperature may be 120 to 200 ℃, for example, 150 ℃ or 180 ℃, the time may be 10s to 2min, for example, 20s, 30s, 1min, 1.5min, and the temperature rise rate of the drying may be 20 to 100 ℃/s, and the drying process may volatilize the moisture and most of the solvent in the gel film to facilitate the next pyrolysis.

According to another embodiment of the present invention, the pyrolysis temperature may be 300 to 600 c, for example, the temperature can be 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃ or 600 ℃ and the like, the time can be 20 s-5 min, for example, it may be 30s, 1min, 2min, 3min, 4min or 5min, and the like, and by the pyrolysis treatment, can fully decompose residual organic matters, silver nitrate and the like in the film, remove impurity components, react silver, niobium and oxygen to obtain a precursor film, however, the inventors have found that when the pyrolysis temperature is too low, it is difficult to ensure sufficient decomposition or removal of impurities such as residual organic substances, when high-temperature annealing is carried out subsequently, organic matters which are not completely decomposed are violently decomposed, so that the crystal type is poor, and by controlling the pyrolysis conditions, the method is more favorable for fully removing impurity components such as organic matters and the like, thereby being more favorable for forming a uniform and compact pure-phase silver niobate-based lead-free antiferroelectric film.

According to another embodiment of the present invention, the annealing temperature may be 680 to 900 ℃, for example 680 ℃, 700 ℃, 720 ℃, 750 ℃, 800 ℃, 850 ℃ or 900 ℃, and the annealing time may be 1 to 10min, for example 1min, 2min, 3min, 4min, 5min, 7min, 9min or 10min, and the annealing may crystallize the thin film to obtain pure-phase AgNbO₃The inventors have found that, if the annealing temperature is too low, crystallization is insufficient and an amorphous thin film is easily obtained, while if the annealing temperature is too high, a hetero phase such as Ag is easily generated₂Nb₄O₁₁Etc., thereby forming a polycrystalline thin film; on the other hand, the film is easy to crack, and the pure-phase AgNbO is more favorably formed by controlling the annealing conditions₃A base film. Further, the cooling speed after annealing can be 0.5-1 ℃/s, and the slow cooling process can avoid film cracking caused by large thermal stress generated due to too high cooling speed.

According to another embodiment of the present invention, the pyrolysis and annealing are preferably performed in a flowing oxygen atmosphere, and the flow rate of the oxygen may be 1.5 to 3.5L/min, for example, may be 3L/min, and the inventors have found that by controlling the above-mentioned flow rate of the oxygen, it is more beneficial to obtain a pure phase silver niobate-based lead-free antiferroelectric film, and avoid the occurrence of oxygen-deficient phase impurities.

According to another embodiment of the present invention, the pyrolysis temperature may be 400 to 500 ℃, the annealing temperature may be 700 to 850 ℃, and the inventors have found that controlling the pyrolysis temperature and the annealing temperature to the above ranges is more favorable for obtaining a pure-phase, uniform and dense silver niobate-based lead-free antiferroelectric thin film.

According to an embodiment of the present invention, referring to fig. 2, the method of preparing a silver niobate-based lead-free antiferroelectric film may further include: and step S700.

S700: repeating the operations of the steps (5) to (6) on the silver niobate-based antiferroelectric film with the substrate obtained in the step S600 to obtain a silver niobate-based antiferroelectric film with a desired thickness

According to the embodiments of the present invention, the inventors found that, during the heat treatment process, if the thickness of the gel film is too thick, it is difficult to ensure the uniformity and the compactness of the finally prepared silver niobate-based lead-free antiferroelectric film, and to obtain the silver niobate-based antiferroelectric film with the desired thickness, the operations of steps S500 to S600 may be repeated, and the AgNbO is annealed layer by layer₃And (3) carrying out heat treatment on the film, namely drying, pyrolyzing and annealing the film after each layer of film is subjected to spin coating until the silver niobate-based antiferroelectric film with the required thickness is obtained.

According to still another embodiment of the present invention, the final thickness of the silver niobate-based antiferroelectric film prepared in the present invention is not particularly limited, and those skilled in the art can select the final thickness according to actual needs, and specifically, the desired thickness can be obtained by controlling the number of times of repeating the steps S500 to S600, and the inventors found that the thickness of the silver niobate-based antiferroelectric film obtained can be increased by 20 to 40nm each time the operations of the steps S500 to S600 are performed, so that the number of times of repeating the steps S500 to S600 can be determined according to the desired thickness of the silver niobate-based antiferroelectric film. The number of times of the repeated operations in steps S500 to S600 may be not greater than 20, for example, the number of times of the repeated operations may be 2, 3, 4, 5, 8, 10, 15, or 20. The number of times of repeating the operation determines the thickness of the finally obtained film, but the inventors found that if the number of times of repeating is too large, the film may be cracked.

In summary, the method for preparing a silver niobate-based lead-free antiferroelectric film according to the above embodiment of the present invention employs a sol-gel method, and compared with the prior art, the method at least has the following advantages: 1) the solvent used for preparing the silver niobium sol is non-toxic and harmless, and heating is not needed in the sol synthesis process; 2) by pre-forming a mixed solution of ethylene glycol monomethyl ether and ethylene glycol, respectively dissolving silver nitrate and niobium ethoxide solution in a part of mixed solvent, and then mixing, the uniform and stable silver niobium sol can be formed, and the film forming property can be improved; 3) can deposit pure-phase (perovskite structure) silver niobate-based antiferroelectric film on a substrate; 4) the prepared silver niobate-based antiferroelectric film has controllable thickness, compact structure and better uniformity; 5) the preparation process is safe, high in reliability, simple in equipment, material-saving, low in cost and easy to realize industrial production.

According to still another aspect of the present invention, there is provided a silver niobate-based lead-free antiferroelectric film. According to an embodiment of the present invention, the silver niobate-based lead-free antiferroelectric film is obtained by the above-described method for preparing a silver niobate-based lead-free antiferroelectric film. Compared with the prior art, the silver niobate-based lead-free antiferroelectric film has low cost, is easy to obtain, has pure phase of perovskite structure, has compact film structure and better uniformity, and can be widely used in dielectric capacitors. It should be noted that the features and effects described for the above method for preparing a silver niobate-based lead-free antiferroelectric film of the present invention are also applicable to the silver niobate-based lead-free antiferroelectric film, and are not described in detail herein.

According to yet another aspect of the present invention, a capacitor is provided. According to an embodiment of the present invention, the capacitor has the above silver niobate-based lead-free antiferroelectric film or the silver niobate-based lead-free antiferroelectric film obtained by the above method for producing a silver niobate-based lead-free antiferroelectric film. Compared with the prior art, the energy storage material adopted by the capacitor has less harm to human bodies and environment. It should be noted that the features and effects described for the silver niobate-based lead-free antiferroelectric film and the method for preparing the silver niobate-based lead-free antiferroelectric film of the present invention are also applicable to the capacitor, and are not described in detail herein.

The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.

Example 1

a) Preparing 2.570mL of mixed solvent of ethylene glycol monomethyl ether and ethylene glycol, wherein the volume fraction of the ethylene glycol is 30%, and adding 0.3168g (1.5mol multiplied by 10%) of the mixed solvent^-3) 0.080mL of acetic acid was added to adjust the pH of the citric acid monohydrate powder, and the mixed solution was stirred until dissolved, and 0.2553g (1.5 mol. times.10 g) were weighed out in the dark^-3) Adding silver nitrate powder into the mixed solution, and stirring for 40min without air until completely dissolving.

b) Preparing 1.285mL of mixed solvent of ethylene glycol monomethyl ether and ethylene glycol, wherein the volume fraction of the ethylene glycol is 30%, and adding 0.155mL (1.5 × 10)^-3mol) of acetylacetone as a chelating agent, stirring the mixed solution until the mixed solution is uniformly mixed, adding 1mL of 1.5mol/L niobium ethoxide solution dissolved in ethylene glycol monomethyl ether into the mixed solution, and stirring for 20min without air until the niobium ethoxide solution is completely dissolved.

c) Adding the silver-containing solution obtained in the step (a) into the niobium-containing solution obtained in the step (b), stirring for 3h at room temperature without air, sealing the obtained mixed solution in a glass bottle, and aging for 48h for later use.

d) The aged silver niobium sol (as shown in FIG. 3) was coated on cleaned 6mm X6 mm Pt (111)/Ti/SiO₂Setting the glue homogenizing program to 600r/min at low speed, 10s at high speed, 5500r/min at high speed and 30s at time on a/Si (100) substrate, and coating the sol on the substrate to form a uniform gel film containing silver and niobium.

e) And (3) placing the substrate coated with the gel film on a gel drying table, drying for 20s at 200 ℃, pyrolyzing for 60s at 450 ℃ in a rapid annealing furnace in an oxygen atmosphere, annealing for 120s at 750 ℃, then carrying out programmed cooling, and cooling to 400 ℃ from 750 ℃ in 500s along with the furnace to room temperature.

f) Repeating the steps of whirl coating, drying, pyrolysis and annealing, and annealing 10 layers layer by layer to obtain AgNbO with certain thickness₃A film.

For the prepared AgNbO₃The base film is subjected to crystal structure, section and surface appearance characterization, and a Pt top electrode is plated on the surface of the film by utilizing magnetron sputtering to perform electrical performance test. The test results were as follows:

FIG. 3 is a diagram of the product of the aged silver-containing niobium sol, and it can be seen from FIG. 3 that the sol prepared by the sol-gel method is clear, bright, uniform and stable.

FIG. 4 is a diagram for AgNbO finally obtained₃The XRD pattern obtained by X-ray diffraction analysis of the film was as shown in FIG. 4, and the AgNbO thus obtained₃The film is a pure phase film with a perovskite structure.

FIG. 5 shows AgNbO finally obtained₃Scanning Electron Microscope (SEM) photographs of the cross section and surface of the thin film sample, in which AgNbO is shown in FIG. 5(a) and FIG. 5(b), respectively₃The scanning electron microscope images show that the film has a compact structure and uniform grain distribution, and the images in fig. 5(c) - (e) show the surface scanning of the energy spectrums of the three elements of Ag, Nb and O, which shows that the three elements are uniformly distributed and no obvious phenomenon of segregation and enrichment of metal elements is caused.

FIG. 6 shows AgNbO finally obtained₃FIG. 6 shows the dielectric constant of the film as a function of temperature₃The film showed a dielectric constant versus temperature relationship similar to that of silver niobate bulk ceramic, indicating that the silver niobate film may undergo a similar phase transition in the silver niobate bulk from room temperature to 600 ℃, i.e., a phase transition of M1-M2-M3-O-T-C; unlike bulk ceramics, the dielectric anomaly peak for the transition from the M1 phase to the M2 phase occurs at a lower temperature (0 ℃). Therefore, the dielectric temperature spectrum indicates that the silver niobate thin film at room temperature may be an antiferroelectric phase (M2).

FIG. 7 shows the AgNbO finally obtained₃The change of the film polarization intensity with the external electric field is shown in the figure, which shows AgNbO₃The thin film sample shows a hysteresis loop which shows a linear trend at a low electric field strength (100kV/cm) and almost no residual polarization, which conforms to the linear characteristic of the antiferroelectric phase at a low field. However, at higher electric field strengths (120kV/cm) as shown in FIG. 7(b), two consecutive hysteresis loops do not coincide,and the residual polarization is larger, which may be due to the increase of leakage current, the breakdown performance is reduced, and it is not beneficial to continue the voltage-applying test. FIG. 8 is AgNbO₃The piezoelectric response diagram of the thin film in the ON state under the flip piezoelectric force microscope (SS-PFM) is shown in fig. 8, and it can be seen from fig. 8 that the piezoelectric response curve of the ON state of the flip piezoelectric force microscope (SS-PFM) of the thin film rises and then falls under low voltage, and the response is small, showing a response curve different from the butterfly curve of the normal ferroelectric body and having antiferroelectric characteristics. By combining the test results of the dielectric temperature spectrum, the electric hysteresis loop and the SS-PFM, the silver niobate film at room temperature can be judged to be an antiferroelectric phase.

Comparative example 1

The difference from example 1 is that in step e), the pyrolysis temperature is 350 ℃ and the annealing time is 650 ℃.

Comparative example 2

The difference from example 1 is that in step e), the pyrolysis temperature is 400 ℃ and the annealing time is 650 ℃.

Comparative example 3

The difference from example 1 is that in step e), the pyrolysis temperature is 450 ℃ and the annealing time is 650 ℃.

AgNbO prepared by contrast ratio of 1-3₃The films were subjected to X-ray diffraction analysis. AgNbO prepared in comparative examples 1-3₃XRD of the thin film is shown in FIG. 9, from which it can be seen that AgNbO is formed when the annealing temperature is too low₃Presence of hetero-phase Ag in the film₂NbO₁₁And Ag.

In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.