CN117945459A - Bismuth zinc niobate composite sol and preparation method thereof, bismuth zinc niobate composite film and preparation method thereof - Google Patents
Bismuth zinc niobate composite sol and preparation method thereof, bismuth zinc niobate composite film and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 90
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000011701 zinc Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 143
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 55
- 239000011575 calcium Substances 0.000 claims description 53
- 239000002243 precursor Substances 0.000 claims description 46
- 239000010955 niobium Substances 0.000 claims description 42
- 239000002244 precipitate Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 28
- 239000012445 acidic reagent Substances 0.000 claims description 27
- 239000002738 chelating agent Substances 0.000 claims description 27
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 26
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 26
- 229910052797 bismuth Inorganic materials 0.000 claims description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 26
- 229910052791 calcium Inorganic materials 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 25
- 239000011975 tartaric acid Substances 0.000 claims description 20
- 235000002906 tartaric acid Nutrition 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 229910019800 NbF 5 Inorganic materials 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims 1
- 238000012360 testing method Methods 0.000 abstract description 8
- 239000003989 dielectric material Substances 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 238000003756 stirring Methods 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 101000827703 Homo sapiens Polyphosphoinositide phosphatase Proteins 0.000 description 2
- 102100023591 Polyphosphoinositide phosphatase Human genes 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000002525 ultrasonication Methods 0.000 description 2
- 101001121408 Homo sapiens L-amino-acid oxidase Proteins 0.000 description 1
- 102100026388 L-amino-acid oxidase Human genes 0.000 description 1
- 101100012902 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) FIG2 gene Proteins 0.000 description 1
- 101100233916 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) KAR5 gene Proteins 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000005433 ionosphere Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
- C01G33/006—Compounds containing niobium, with or without oxygen or hydrogen, and containing two or more other elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0004—Preparation of sols
- B01J13/0047—Preparation of sols containing a metal oxide
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2006/40—Electric properties
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- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/23—Mixtures
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- C03—GLASS; MINERAL OR SLAG WOOL
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- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
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Abstract
Description
技术领域Technical Field
本发明属于介电材料技术领域，具体涉及一种铌酸铋锌复合溶胶及其制备方法、铌酸铋锌复合薄膜及其制备方法。The invention belongs to the technical field of dielectric materials, and specifically relates to a bismuth zinc niobate composite sol and a preparation method thereof, a bismuth zinc niobate composite film and a preparation method thereof.
背景技术Background technique
微波技术是近代科学技术发展的重大成就之一，微波具有很多优势，比如波长短、频率高、方向性强、信息容量大、能穿透电离层等特点，因此在雷达、微波通讯、卫星通讯、移动电话等领域得到了广泛应用。由于谐振器、耦合器、滤波器等新型的电场调谐器件在高频条件下的应用要求，使得可调介电薄膜的研究成为热点。通过研究和开发可调介电薄膜，可以提高微波器件的性能和效率，进一步推动微波技术的发展和应用。这对于军事、工业和民用领域都具有重要意义，有助于改善通信和雷达系统的性能，提高数据传输速率，促进无线通信技术的发展等。Microwave technology is one of the major achievements in the development of modern science and technology. Microwaves have many advantages, such as short wavelength, high frequency, strong directivity, large information capacity, and the ability to penetrate the ionosphere. Therefore, they have been widely used in radar, microwave communication, satellite communication, mobile phones and other fields. Due to the application requirements of new electric field tuning devices such as resonators, couplers, filters, etc. under high frequency conditions, the research on tunable dielectric films has become a hot topic. By researching and developing tunable dielectric films, the performance and efficiency of microwave devices can be improved, further promoting the development and application of microwave technology. This is of great significance to the military, industrial and civilian fields, and helps to improve the performance of communication and radar systems, increase data transmission rates, and promote the development of wireless communication technology.
基于以上需求，研究人员对钙钛矿结构的(BaxSr1-x)TiO3(BST)铁电薄膜进行了较多研究，但仍需要研究新型高性能的介电调谐薄膜材料，以解决BST铁电薄膜因内部本征特性引起的介电损耗过高的问题。铌酸铋锌Bi1.5ZnNb1.5O7(BZN)介电调谐薄膜材料不仅具有较低的介电损耗也展现出优异的介电可调性，与BST薄膜相比有较小的的介电损耗。但是为获得较高的介电调谐率需要在薄膜上加载很高的偏压电场，这限制了BZN薄膜的集成化应用。Based on the above requirements, researchers have conducted a lot of research on the perovskite structured (Ba x Sr 1-x )TiO 3 (BST) ferroelectric thin films, but new high-performance dielectric tuning thin film materials are still needed to solve the problem of excessive dielectric loss caused by the internal intrinsic characteristics of BST ferroelectric thin films. Bismuth zinc niobate Bi 1.5 ZnNb 1.5 O 7 (BZN) dielectric tuning thin film materials not only have low dielectric loss but also show excellent dielectric tunability, and have smaller dielectric loss than BST thin films. However, in order to obtain a higher dielectric tuning rate, a very high bias electric field needs to be loaded on the film, which limits the integrated application of BZN thin films.
发明内容Summary of the invention
本发明的目的在于提供一种铌酸铋锌复合溶胶及其制备方法、铌酸铋锌复合薄膜及其制备方法，由本发明提供的铌酸铋锌复合溶胶制备得到的复合薄膜具有优异的介电性能。The purpose of the present invention is to provide a bismuth zinc niobate composite sol and a preparation method thereof, a bismuth zinc niobate composite film and a preparation method thereof. The composite film prepared from the bismuth zinc niobate composite sol provided by the present invention has excellent dielectric properties.
为了实现上述目的，本发明提供如下技术方案：In order to achieve the above object, the present invention provides the following technical solutions:
本发明提供了一种铌酸铋锌复合溶胶，所述铌酸铋锌复合溶胶的化学组成为Bi1.5CaxZn1-xNbO7，所述x的取值范围为0.1～0.25。The present invention provides a bismuth zinc niobate composite sol. The chemical composition of the bismuth zinc niobate composite sol is Bi 1.5 Ca x Zn 1-x NbO 7 , and the value range of x is 0.1-0.25.
本发明还提供了上述技术方案所述的铌酸铋锌复合溶胶的制备方法，包括以下步骤：The present invention also provides a method for preparing the bismuth zinc niobate composite sol described in the above technical solution, comprising the following steps:
将含铌源的溶液和沉淀剂混合，得到Nb(OH)5沉淀；Mixing a solution containing a niobium source and a precipitant to obtain a Nb(OH) 5 precipitate;
将所述Nb(OH)5沉淀和螯合剂混合，得到前驱体溶液；Mixing the Nb(OH) 5 precipitate and the chelating agent to obtain a precursor solution;
将所述前驱体溶液、含铋源的溶液、含钙源的溶液和含锌源的溶液混合，调节所得混合液的pH值为酸性后，进行凝胶反应，得到所述铌酸铋锌复合溶胶。The precursor solution, the solution containing a bismuth source, the solution containing a calcium source and the solution containing a zinc source are mixed, the pH value of the obtained mixed solution is adjusted to be acidic, and then a gel reaction is performed to obtain the bismuth zinc niobate composite sol.
优选的，所述含铌源的溶液为NbF5溶液；Preferably, the solution containing a niobium source is a NbF 5 solution;
所述NbF5溶液的制备方法包括以下步骤：将Nb2O5与氢氟酸混合，进行反应，得到所述NbF5溶液；The method for preparing the NbF 5 solution comprises the following steps: mixing Nb 2 O 5 with hydrofluoric acid, reacting to obtain the NbF 5 solution;
所述氢氟酸的质量浓度为99.99％，所述Nb2O5与氢氟酸的摩尔比为1：10～15；所述反应的温度为150℃，时间为2～3h。The mass concentration of the hydrofluoric acid is 99.99%, the molar ratio of Nb2O5 to hydrofluoric acid is 1:10-15; the reaction temperature is 150°C, and the reaction time is 2-3 hours.
优选的，所述沉淀剂包括碳酸氢铵与浓氨水，所述碳酸氢铵与浓氨水的摩尔比为1：3～5。Preferably, the precipitant comprises ammonium bicarbonate and concentrated aqueous ammonia, and the molar ratio of the ammonium bicarbonate to the concentrated aqueous ammonia is 1:3-5.
优选的，所述螯合剂包括酒石酸和柠檬酸，所述酒石酸和柠檬酸的摩尔比为1：4；Preferably, the chelating agent comprises tartaric acid and citric acid, and the molar ratio of tartaric acid to citric acid is 1:4;
以铌的摩尔量计，所述Nb(OH)5沉淀和螯合剂的摩尔比为1：6～8。Calculated on the molar amount of niobium, the molar ratio of the Nb(OH) 5 precipitate to the chelating agent is 1:6-8.
优选的，所述含铋源的溶液中的铋源包括BiCl3或Bi(NO3)3·5H2O；所述含铋源的溶液的溶剂为酸性试剂；所述铋源和酸性试剂的摩尔比为1：1.2～1.5；Preferably, the bismuth source in the bismuth source-containing solution includes BiCl 3 or Bi(NO 3 ) 3 ·5H 2 O; the solvent of the bismuth source-containing solution is an acidic reagent; the molar ratio of the bismuth source to the acidic reagent is 1:1.2-1.5;
所述含钙源的溶液中的钙源包括CaCl2或Ca(NO3)2·4H2O；所述含钙源的溶液的溶剂为酸性试剂；所述钙源和酸性试剂的摩尔比为1：1.2～1.5；The calcium source in the solution containing the calcium source includes CaCl 2 or Ca(NO 3 ) 2 ·4H 2 O; the solvent of the solution containing the calcium source is an acidic reagent; the molar ratio of the calcium source to the acidic reagent is 1:1.2-1.5;
所述含锌源的溶液中的锌源包括ZnCl2或Zn(NO3)2·6H2O；所述含锌源的溶液的溶剂为酸性试剂；所述锌源和酸性试剂的摩尔比为1：1.2～1.5。The zinc source in the solution containing the zinc source includes ZnCl 2 or Zn(NO 3 ) 2 ·6H 2 O; the solvent of the solution containing the zinc source is an acidic reagent; and the molar ratio of the zinc source to the acidic reagent is 1:1.2-1.5.
优选的，所述酸性的pH值为3～5；Preferably, the acidic pH value is 3 to 5;
所述凝胶反应的温度为70～80℃。The temperature of the gel reaction is 70-80°C.
本发明还提供了一种铌酸铋锌复合薄膜，以溶胶为原料经涂覆得到，所述溶胶为上述技术方案所述的铌酸铋锌复合溶胶或上述技术方案所述的制备方法制备得到的铌酸铋锌复合溶胶。The present invention also provides a bismuth zinc niobate composite film, which is obtained by coating with a sol as a raw material, wherein the sol is the bismuth zinc niobate composite sol described in the above technical scheme or the bismuth zinc niobate composite sol prepared by the preparation method described in the above technical scheme.
本发明还提供了上述技术方案所述的铌酸铋锌复合薄膜的制备方法，包括以下步骤：The present invention also provides a method for preparing the bismuth zinc niobate composite film described in the above technical solution, comprising the following steps:
将溶胶涂覆在基底的表面，依次进行干燥和结晶化处理，得到所述铌酸铋锌复合薄膜。The sol is coated on the surface of the substrate, and drying and crystallization treatments are performed in sequence to obtain the bismuth zinc niobate composite film.
优选的，所述干燥的温度为110～150℃，时间为10min；Preferably, the drying temperature is 110-150°C and the drying time is 10 minutes;
所述结晶化处理的温度为600～650℃，保温时间为1h。The temperature of the crystallization treatment is 600-650° C., and the insulation time is 1 hour.
本发明提供了一种铌酸铋锌复合溶胶，所述铌酸铋锌复合溶胶的化学组成为Bi1.5CaxZn1-xNbO7，所述x的取值范围为0.1～0.25。本发明利用Ca2+掺杂Bi1.5ZnNbO7介质材料。其中，Ca2+离子与Zn2+离子的离子半径、离子极化率大小相近，即离子匹配性较好，使用Ca2+进行掺杂，可提高纯相Bi1.5ZnNbO7介质材料的介电性能。根据实施例的测试结果可知，由本发明提供的铌酸铋锌复合溶胶制备得到的介电薄膜在1MHz频率下介电常数为110～120，介电损耗≤0.008，具有优异的介电性能。The present invention provides a bismuth zinc niobate composite sol, wherein the chemical composition of the bismuth zinc niobate composite sol is Bi 1.5 Ca x Zn 1-x NbO 7 , and the value range of x is 0.1 to 0.25. The present invention utilizes Ca 2+ to dope Bi 1.5 ZnNbO 7 dielectric material. Among them, the ionic radius and ionic polarizability of Ca 2+ ions and Zn 2+ ions are similar in size, that is, the ion matching is good, and the use of Ca 2+ for doping can improve the dielectric properties of the pure phase Bi 1.5 ZnNbO 7 dielectric material. According to the test results of the embodiment, the dielectric film prepared by the bismuth zinc niobate composite sol provided by the present invention has a dielectric constant of 110 to 120 at a frequency of 1 MHz, a dielectric loss of ≤0.008, and has excellent dielectric properties.
本发明还提供了上述技术方案所述的铌酸铋锌复合溶胶的制备方法，包括以下步骤：将含铌源的溶液和沉淀剂混合，得到Nb(OH)5沉淀；将所述Nb(OH)5沉淀和螯合剂混合，得到前驱体溶液；将所述前驱体溶液、含铋源的溶液、含钙源的溶液和含锌源的溶液混合，调节所得混合液的pH值为酸性后，进行凝胶反应，得到所述铌酸铋锌复合溶胶。本发明使用溶胶-凝胶法制铌酸铋锌复合溶胶，相较于现有技术来说，制备工艺简单，可制得组分均匀、纯度高的介质材料。The present invention also provides a method for preparing the bismuth zinc niobate composite sol described in the above technical solution, comprising the following steps: mixing a solution containing a niobium source and a precipitant to obtain a Nb(OH) 5 precipitate; mixing the Nb(OH) 5 precipitate and a chelating agent to obtain a precursor solution; mixing the precursor solution, a solution containing a bismuth source, a solution containing a calcium source, and a solution containing a zinc source, adjusting the pH value of the obtained mixed solution to be acidic, and then performing a gel reaction to obtain the bismuth zinc niobate composite sol. The present invention uses a sol-gel method to prepare the bismuth zinc niobate composite sol. Compared with the prior art, the preparation process is simple, and a dielectric material with uniform components and high purity can be obtained.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
图1为实施例1～4得到的铌酸铋锌复合薄膜的XRD图；FIG1 is an XRD diagram of the bismuth zinc niobate composite film obtained in Examples 1 to 4;
图2为实施例1～4得到的铌酸铋锌复合薄膜的SEM图；FIG2 is a SEM image of the bismuth zinc niobate composite film obtained in Examples 1 to 4;
图3为实施例1～4得到的铌酸铋锌复合薄膜的介电性能测试结果；FIG3 is a test result of dielectric properties of bismuth zinc niobate composite films obtained in Examples 1 to 4;
图4为本发明提供的制备方法的流程示意图。FIG4 is a schematic flow chart of the preparation method provided by the present invention.
具体实施方式Detailed ways
本发明提供了一种铌酸铋锌复合溶胶，所述铌酸铋锌复合溶胶的化学组成为Bi1.5CaxZn1-xNbO7，所述x的取值范围为0.1～0.25。The present invention provides a bismuth zinc niobate composite sol. The chemical composition of the bismuth zinc niobate composite sol is Bi 1.5 Ca x Zn 1-x NbO 7 , and the value range of x is 0.1-0.25.
在本发明中，所述x的取值范围为0.1～0.25，进一步优选为0.15～0.2。In the present invention, the value range of x is 0.1 to 0.25, and more preferably 0.15 to 0.2.
在本发明中，所述铌酸铋锌复合溶胶优选具有立方焦绿石结构，空间群优选为Fd-3m(227)。In the present invention, the bismuth zinc niobate composite sol preferably has a cubic pyrochlore structure, and the space group is preferably Fd-3m (227).
本发明还提供了上述技术方案所述的铌酸铋锌复合溶胶的制备方法，包括以下步骤：The present invention also provides a method for preparing the bismuth zinc niobate composite sol described in the above technical solution, comprising the following steps:
将含铌源的溶液和沉淀剂混合，得到Nb(OH)5沉淀；Mixing a solution containing a niobium source and a precipitant to obtain a Nb(OH) 5 precipitate;
将所述Nb(OH)5沉淀和螯合剂混合，得到前驱体溶液；Mixing the Nb(OH) 5 precipitate and the chelating agent to obtain a precursor solution;
将所述前驱体溶液、含铋源的溶液、含钙源的溶液和含锌源的溶液混合，调节所得混合液的pH值为酸性后，进行凝胶反应，得到所述铌酸铋锌复合溶胶材料。The precursor solution, the solution containing a bismuth source, the solution containing a calcium source and the solution containing a zinc source are mixed, the pH value of the obtained mixed solution is adjusted to be acidic, and then a gel reaction is performed to obtain the bismuth zinc niobate composite sol material.
在本发明中，若无特殊说明，所有制备原料均为本领域技术人员熟知的市售产品。In the present invention, unless otherwise specified, all preparation raw materials are commercially available products well known to those skilled in the art.
本发明将含铌源的溶液和沉淀剂混合，得到Nb(OH)5沉淀。The present invention mixes a solution containing a niobium source and a precipitant to obtain a Nb(OH) 5 precipitate.
在本发明中，所述含铌源的溶液优选为NbF5溶液。在本发明中，所述NbF5溶液的制备方法优选包括以下步骤：将Nb2O5和氢氟酸混合，进行反应，得到所述NbF5溶液。在本发明中，所述Nb2O5的纯度优选为99.99％。在本发明中，所述氢氟酸的质量浓度优选为99.99％；所述Nb2O5和氢氟酸的摩尔比优选为1：10～15。在本发明中，所述反应的温度优选为150℃，时间优选为2～3h。In the present invention, the solution containing niobium source is preferably NbF 5 solution. In the present invention, the method for preparing the NbF 5 solution preferably comprises the following steps: mixing Nb 2 O 5 and hydrofluoric acid, reacting to obtain the NbF 5 solution. In the present invention, the purity of Nb 2 O 5 is preferably 99.99%. In the present invention, the mass concentration of hydrofluoric acid is preferably 99.99%; the molar ratio of Nb 2 O 5 to hydrofluoric acid is preferably 1:10-15. In the present invention, the reaction temperature is preferably 150°C, and the reaction time is preferably 2-3h.
在本发明中，所述沉淀剂优选包括碳酸氢铵与浓氨水，所述浓氨水的质量浓度优选为25～28％；所述碳酸氢铵与浓度氨水的摩尔比优选为1：3～5。在本发明中，所述沉淀剂的制备方法优选包括以下步骤：将饱和碳酸氢铵溶液和氨水混合，得到所述沉淀剂。In the present invention, the precipitant preferably comprises ammonium bicarbonate and concentrated ammonia water, the mass concentration of the concentrated ammonia water is preferably 25-28%, and the molar ratio of the ammonium bicarbonate to the concentrated ammonia water is preferably 1:3-5. In the present invention, the preparation method of the precipitant preferably comprises the following steps: mixing a saturated ammonium bicarbonate solution and ammonia water to obtain the precipitant.
本发明对所述含铌源的溶液和沉淀剂的比例没有特殊的限定，能够将所述混合得到的混合液的pH值调整到8～10即可。The present invention has no particular limitation on the ratio of the solution containing the niobium source and the precipitant, and the pH value of the mixed solution can be adjusted to 8-10.
所述混合后，本发明还优选包括将得到的混合体系进行离心和固液分离。After the mixing, the present invention preferably further comprises centrifuging the obtained mixed system and performing solid-liquid separation.
得到所述Nb(OH)5沉淀后，本发明将所述Nb(OH)5沉淀和螯合剂混合，得到前驱体溶液。After obtaining the Nb(OH) 5 precipitate, the present invention mixes the Nb(OH) 5 precipitate with a chelating agent to obtain a precursor solution.
在本发明中，所述螯合剂优选包括酒石酸(TA)和柠檬酸(CA)，所述酒石酸和柠檬酸的摩尔比优选为1：4。在本发明中，以铌的摩尔量计，所述Nb(OH)5沉淀和螯合剂的摩尔比优选为1：6～8。在本发明中，所述螯合剂的制备方法优选包括以下步骤：将酒石酸和柠檬酸溶于去离子水中得到复合螯合剂。本发明对所述去离子水的用量没有特殊的限定，采用本领域技术人员熟知的即可。本发明在制备溶胶时使用络合能力更强的柠檬酸和酒石酸作为复合螯合剂，有利于溶胶稳定性的提高，进而使制备出的薄膜的介电性能更优。In the present invention, the chelating agent preferably includes tartaric acid (TA) and citric acid (CA), and the molar ratio of tartaric acid to citric acid is preferably 1:4. In the present invention, the molar ratio of the Nb(OH) 5 precipitate to the chelating agent is preferably 1:6-8 based on the molar amount of niobium. In the present invention, the preparation method of the chelating agent preferably includes the following steps: dissolving tartaric acid and citric acid in deionized water to obtain a composite chelating agent. The present invention has no special limitation on the amount of deionized water, and the amount familiar to those skilled in the art can be used. In the present invention, citric acid and tartaric acid with stronger complexing ability are used as composite chelating agents when preparing the sol, which is beneficial to improving the stability of the sol, thereby making the dielectric properties of the prepared film better.
在本发明中，所述Nb(OH)5沉淀和螯合剂混合优选在搅拌的条件下进行；所述搅拌的温度优选为70～80℃。本发明对所述搅拌的时间没有特殊的限定，直至所述Nb(OH)5沉淀完全溶解即可。In the present invention, the Nb(OH) 5 precipitate and the chelating agent are preferably mixed under stirring; the stirring temperature is preferably 70-80° C. The present invention has no particular limitation on the stirring time, as long as the Nb(OH) 5 precipitate is completely dissolved.
得到所述前驱体溶液后，本发明将所述前驱体溶液、含铋源的溶液、含钙源的溶液和含锌源的溶液混合，调节所得混合液的pH值为酸性后，进行凝胶反应，得到所述铌酸铋锌复合溶胶材料。After obtaining the precursor solution, the present invention mixes the precursor solution, a solution containing a bismuth source, a solution containing a calcium source and a solution containing a zinc source, adjusts the pH value of the obtained mixed solution to be acidic, and then performs a gel reaction to obtain the bismuth zinc niobate composite sol material.
在本发明中，所述含铋源的溶液中的铋源优选包括BiCl3或Bi(NO3)3·5H2O；所述铋源的纯度优选为99.99％；所述含铋源的溶液的溶剂优选为酸性试剂；当所述铋源为BiCl3时，所述酸性试剂优选为盐酸，所述盐酸的质量浓度优选为37％；当所述铋源为Bi(NO3)3·5H2O时，所述酸性试剂优选为硝酸；所述硝酸的质量浓度优选为65％；所述铋源和酸性试剂的摩尔比优选为1：1.2～1.5。在本发明中，所述含铋源的溶液的制备方法优选包括：将铋源溶解在酸性试剂中，得到所述含铋源的溶液。In the present invention, the bismuth source in the solution containing the bismuth source preferably includes BiCl 3 or Bi(NO 3 ) 3 ·5H 2 O; the purity of the bismuth source is preferably 99.99%; the solvent of the solution containing the bismuth source is preferably an acidic reagent; when the bismuth source is BiCl 3 , the acidic reagent is preferably hydrochloric acid, and the mass concentration of the hydrochloric acid is preferably 37%; when the bismuth source is Bi(NO 3 ) 3 ·5H 2 O, the acidic reagent is preferably nitric acid; the mass concentration of the nitric acid is preferably 65%; the molar ratio of the bismuth source to the acidic reagent is preferably 1:1.2-1.5. In the present invention, the method for preparing the solution containing the bismuth source preferably includes: dissolving the bismuth source in the acidic reagent to obtain the solution containing the bismuth source.
在本发明中，所述含钙源的溶液中的钙源优选包括CaCl2或Ca(NO3)2·4H2O；所述钙源的纯度优选为99.99％；所述含钙源的溶液的溶剂优选为酸性试剂；当所述钙源为CaCl2时，所述酸性试剂优选为盐酸，所述盐酸的质量浓度优选为37％；当所述钙源为Ca(NO3)2·4H2O时，所述酸性试剂优选为硝酸；所述硝酸的质量浓度优选为65％；所述钙源和酸性试剂的摩尔比优选为1：1.2～1.5。在本发明中，所述含钙源的溶液的制备方法优选包括：将钙源溶解在酸性试剂中，得到所述含钙源的溶液。In the present invention, the calcium source in the solution containing the calcium source preferably includes CaCl 2 or Ca(NO 3 ) 2 ·4H 2 O; the purity of the calcium source is preferably 99.99%; the solvent of the solution containing the calcium source is preferably an acidic reagent; when the calcium source is CaCl 2 , the acidic reagent is preferably hydrochloric acid, and the mass concentration of the hydrochloric acid is preferably 37%; when the calcium source is Ca(NO 3 ) 2 ·4H 2 O, the acidic reagent is preferably nitric acid; the mass concentration of the nitric acid is preferably 65%; the molar ratio of the calcium source to the acidic reagent is preferably 1:1.2-1.5. In the present invention, the method for preparing the solution containing the calcium source preferably includes: dissolving the calcium source in the acidic reagent to obtain the solution containing the calcium source.
在本发明中，所述含锌源的溶液中的锌源优选包括ZnCl2和/或Zn(NO3)2·6H2O；所述锌源的纯度优选为99.99％；所述含锌源的溶液的溶剂优选为酸性试剂；当所述锌源为ZnCl2时，所述酸性试剂优选为盐酸，所述盐酸的质量浓度优选为37％；当所述锌源为ZnCl2时，所述酸性试剂优选为硝酸；所述硝酸的质量浓度优选为65％；所述锌源和酸性试剂的摩尔比优选为1：1.2～1.5。在本发明中，所述含锌源的溶液的制备方法优选包括：将锌源溶解在酸性试剂中，得到所述含锌源的溶液。In the present invention, the zinc source in the solution containing the zinc source preferably includes ZnCl 2 and/or Zn(NO 3 ) 2 ·6H 2 O; the purity of the zinc source is preferably 99.99%; the solvent of the solution containing the zinc source is preferably an acidic reagent; when the zinc source is ZnCl 2 , the acidic reagent is preferably hydrochloric acid, and the mass concentration of the hydrochloric acid is preferably 37%; when the zinc source is ZnCl 2 , the acidic reagent is preferably nitric acid; the mass concentration of the nitric acid is preferably 65%; the molar ratio of the zinc source to the acidic reagent is preferably 1:1.2-1.5. In the present invention, the method for preparing the solution containing the zinc source preferably includes: dissolving the zinc source in the acidic reagent to obtain the solution containing the zinc source.
在本发明中，所述将前驱体溶液、含铋源的溶液、含钙源的溶液和含锌源的溶液混合的过程优选为：在搅拌的条件下，将含铋源的溶液、含钙源的溶液和含锌源的溶液滴入所述前驱体溶液中；所述搅拌的温度优选为70～80℃。In the present invention, the process of mixing the precursor solution, the solution containing a bismuth source, the solution containing a calcium source and the solution containing a zinc source is preferably: under stirring, the solution containing a bismuth source, the solution containing a calcium source and the solution containing a zinc source are dripped into the precursor solution; the stirring temperature is preferably 70-80°C.
在本发明中，所述酸性的pH值优选为3～5；所述调节采用的试剂优选为氨水。在本发明中，所述凝胶反应的温度优选为70～80℃。在本发明中，当所述含铋源的溶液、含钙源的溶液和含锌源的溶液滴入所述前驱提溶液时，即开始发生凝胶反应；所述滴加完毕后，还优选包括进行持续搅拌；所述持续搅拌的时间优选为1～2h，即本申请的凝胶反应时间包括滴入时间和持续搅拌时间。In the present invention, the acidic pH value is preferably 3 to 5; the reagent used for the adjustment is preferably ammonia water. In the present invention, the temperature of the gel reaction is preferably 70 to 80°C. In the present invention, when the solution containing the bismuth source, the solution containing the calcium source and the solution containing the zinc source are dripped into the precursor solution, the gel reaction begins to occur; after the dripping is completed, it is also preferably included to continue stirring; the continuous stirring time is preferably 1 to 2 hours, that is, the gel reaction time of the present application includes the dripping time and the continuous stirring time.
所述凝胶反应后，本发明还优选包括将得到的溶胶进行陈化，所述陈化的时间优选为24h。在本发明中，所述陈化优选在密封的条件下进行。After the gel reaction, the present invention also preferably includes aging the obtained sol, and the aging time is preferably 24 hours. In the present invention, the aging is preferably carried out under sealed conditions.
本发明还提供了一种铌酸铋锌复合薄膜，以溶胶为原料经涂覆得到，所述溶胶为上述技术方案所述的铌酸铋锌复合溶胶或上述技术方案所述的制备方法制备得到的铌酸铋锌复合溶胶。The present invention also provides a bismuth zinc niobate composite film, which is obtained by coating with a sol as a raw material, wherein the sol is the bismuth zinc niobate composite sol described in the above technical scheme or the bismuth zinc niobate composite sol prepared by the preparation method described in the above technical scheme.
在本发明中，所述铌酸铋锌复合薄膜优选具有立方焦绿石结构。In the present invention, the bismuth zinc niobate composite film preferably has a cubic pyrochlore structure.
本发明还提供了上述技术方案所述的铌酸铋锌复合薄膜的制备方法，包括以下步骤：The present invention also provides a method for preparing the bismuth zinc niobate composite film described in the above technical solution, comprising the following steps:
将溶胶涂覆在基底的表面，依次进行干燥和结晶化处理，得到所述铌酸铋锌复合薄膜。The sol is coated on the surface of the substrate, and drying and crystallization treatments are performed in sequence to obtain the bismuth zinc niobate composite film.
在本发明中，所述基底优选包括ITO基片。所述涂覆前，本发明还优选包括对所述基底进行预处理；所述预处理优选包括：将所述基底依次放入去离子水、丙酮、无水乙醇和去离子水中进行超声，每种溶剂中的超声时间均优选为15min，通过预处理以去除基底表面的杂质。In the present invention, the substrate preferably includes an ITO substrate. Before the coating, the present invention also preferably includes pre-treating the substrate; the pre-treatment preferably includes: placing the substrate in deionized water, acetone, anhydrous ethanol and deionized water in sequence for ultrasonication, and the ultrasonication time in each solvent is preferably 15 minutes, and the impurities on the surface of the substrate are removed by pre-treatment.
在本发明中，所述涂覆的方式优选为真空旋涂。本发明对所述真空旋涂的过程没有特殊的限定，采用本领域技术人员熟知的即可。In the present invention, the coating method is preferably vacuum spin coating. The present invention has no special limitation on the vacuum spin coating process, and any method known to those skilled in the art can be used.
在本发明中，所述干燥的温度优选为110～150℃，时间优选为10min。在本发明中，所述结晶化处理的温度优选为600～650℃，保温时间优选为1h。In the present invention, the drying temperature is preferably 110-150° C., and the drying time is preferably 10 min. In the present invention, the crystallization temperature is preferably 600-650° C., and the holding time is preferably 1 h.
在本发明中，优选重复进行上述的涂覆、干燥和结晶化处理过程，直至得到所需厚度的铌酸铋锌复合薄膜；所述重复的次数优选为5～7次。In the present invention, the above-mentioned coating, drying and crystallization treatment processes are preferably repeated until a bismuth zinc niobate composite film of a desired thickness is obtained; the number of repetitions is preferably 5 to 7 times.
本发明提供的制备方法的流程示意图如图4所示。The schematic flow diagram of the preparation method provided by the present invention is shown in FIG4 .
为了进一步说明本发明，下面结合附图和实施例对本发明提供的一种铌酸铋锌复合溶胶及其制备方法、铌酸铋锌复合薄膜及其制备方法进行详细地描述，但不能将它们理解为对本发明保护范围的限定。In order to further illustrate the present invention, a bismuth zinc niobate composite sol and its preparation method, a bismuth zinc niobate composite film and its preparation method provided by the present invention are described in detail below in combination with the drawings and examples, but they should not be understood as limiting the scope of protection of the present invention.
实施例1Example 1
本实施例得到的铌酸铋锌复合溶胶的化学组成为Bi1.5Ca0.1Zn0.9NbO7，根据化学计量比称取所需的原料；The chemical composition of the bismuth zinc niobate composite sol obtained in this example is Bi 1.5 Ca 0.1 Zn 0.9 NbO 7 , and the required raw materials are weighed according to the stoichiometric ratio;
称取高纯度(99.99％)的Nb2O5，将Nb2O5与氢氟酸(HF，质量浓度为99.99％)按1：10的摩尔比放入反应釜中，在150℃反应2h得到NbF5溶液；Weigh high-purity (99.99%) Nb 2 O 5 , put Nb 2 O 5 and hydrofluoric acid (HF, mass concentration of 99.99%) into a reaction kettle at a molar ratio of 1:10, and react at 150° C. for 2 h to obtain a NbF 5 solution;
配制沉淀剂：沉淀剂为饱和碳酸氢铵与浓氨水的混合液，摩尔比为1：3；Preparation of precipitant: The precipitant is a mixture of saturated ammonium bicarbonate and concentrated ammonia water, with a molar ratio of 1:3;
将沉淀剂加入上述NbF5溶液中，调节pH值到8；将上述得到的溶液进行离心、固液分离后得到Nb(OH)5沉淀；Adding a precipitant to the NbF 5 solution, adjusting the pH value to 8; centrifuging the solution obtained above, and performing solid-liquid separation to obtain Nb(OH) 5 precipitate;
将酒石酸(TA)与柠檬酸(CA)溶于去离子水中制成复合螯合剂，其中酒石酸与柠檬酸的摩尔比为1：4；Tartaric acid (TA) and citric acid (CA) are dissolved in deionized water to prepare a composite chelating agent, wherein the molar ratio of tartaric acid to citric acid is 1:4;
将Nb(OH)5沉淀加入复合螯合剂中，在70℃下水浴加热搅拌至沉淀溶解，得到前驱液溶液，其中Nb5+与复合螯合剂的摩尔比为1：6；The Nb(OH) 5 precipitate was added to the composite chelating agent, and heated in a water bath at 70°C with stirring until the precipitate was dissolved to obtain a precursor solution, wherein the molar ratio of Nb 5+ to the composite chelating agent was 1:6;
称取高纯度(99.99％)的BiCl3，将其溶于质量浓度为37％的HCl中，为保证溶解完全，氯化铋与HCl的摩尔比为1：1.2，得到Bi3+前驱液；Weigh high-purity (99.99%) BiCl 3 and dissolve it in 37% HCl. To ensure complete dissolution, the molar ratio of bismuth chloride to HCl is 1:1.2 to obtain a Bi 3+ precursor solution.
称取高纯度(99.99％)的ZnCl2，将其溶于质量浓度为37％的HCl中，氯化锌与HCl的摩尔比为1：1.2，得到Zn2+前驱液；Weigh high-purity (99.99%) ZnCl 2 and dissolve it in 37% HCl, with the molar ratio of zinc chloride to HCl being 1:1.2, to obtain a Zn 2+ precursor solution;
称取高纯度(99.99％)的CaCl2，将其溶于质量浓度为37％的HCl中，氯化钙与HCl的摩尔比为1：1.2，得到Ca2+前驱液；Weigh high-purity (99.99%) CaCl 2 and dissolve it in 37% HCl, with the molar ratio of calcium chloride to HCl being 1:1.2, to obtain a Ca 2+ precursor solution;
将Bi3+前驱液、Zn2+前驱液和Ca2+前驱液逐滴缓慢加入前驱体溶液中，全程在70℃下水浴加热搅拌，滴加完毕后，使用氨水将溶液pH值调至3；继续加热搅拌1h后取出得到溶胶，为提高溶胶的纯度，溶胶密封陈化24h得到所述铌酸铋锌复合溶胶；The Bi 3+ precursor solution, the Zn 2+ precursor solution and the Ca 2+ precursor solution are slowly added dropwise to the precursor solution, and the solution is heated and stirred in a water bath at 70° C. throughout the process. After the addition is completed, the pH value of the solution is adjusted to 3 with ammonia water; the solution is heated and stirred for 1 hour and then taken out to obtain a sol. In order to improve the purity of the sol, the sol is sealed and aged for 24 hours to obtain the bismuth zinc niobate composite sol;
将ITO玻璃基底依次放入去离子水、丙酮、无水乙醇、去离子水中超声各清洗15min以去除基底表面的杂质；将得到的铌酸铋锌复合溶胶，使用真空旋涂机涂覆在经预处理的ITO玻璃基底上，覆有湿膜的基底置于加热板上，在150℃干燥处理10min后，放入管式炉中在600℃下结晶化处理1h，在基底上获得一层掺杂铌酸铋锌(BCZN)薄膜。重复以上操作5次直至获得所需厚度，最终获得具有立方焦绿石结构的BCZN复合薄膜。The ITO glass substrate was sequentially placed in deionized water, acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning for 15 minutes each to remove impurities on the substrate surface; the obtained bismuth zinc niobate composite sol was coated on the pretreated ITO glass substrate using a vacuum spin coater, and the substrate covered with the wet film was placed on a heating plate, dried at 150°C for 10 minutes, and then placed in a tube furnace for crystallization at 600°C for 1 hour to obtain a layer of doped bismuth zinc niobate (BCZN) film on the substrate. The above operation was repeated 5 times until the desired thickness was obtained, and finally a BCZN composite film with a cubic pyrochlore structure was obtained.
实施例2Example 2
本实施例得到的铌酸铋锌复合溶胶的化学组成为Bi1.5Ca0.15Zn0.85NbO7，根据化学计量比称取所需的原料；The chemical composition of the bismuth zinc niobate composite sol obtained in this example is Bi 1.5 Ca 0.15 Zn 0.85 NbO 7 , and the required raw materials are weighed according to the stoichiometric ratio;
称取高纯度(99.99％)的Nb2O5，将Nb2O5与氢氟酸(HF，质量浓度为99.99％)按1：12的摩尔比放入反应釜中，在150℃反应2h得到NbF5溶液；Weigh high-purity (99.99%) Nb 2 O 5 , put Nb 2 O 5 and hydrofluoric acid (HF, mass concentration of 99.99%) into a reaction kettle at a molar ratio of 1:12, and react at 150° C. for 2 h to obtain a NbF 5 solution;
配制沉淀剂：沉淀剂为饱和碳酸氢铵与浓氨水的混合液，摩尔比为1：5；Preparation of precipitant: The precipitant is a mixture of saturated ammonium bicarbonate and concentrated ammonia water, with a molar ratio of 1:5;
将沉淀剂加入上述NbF5溶液中，调节pH值到9；将上述得到的溶液进行离心、固液分离后得到Nb(OH)5沉淀；Adding a precipitant to the NbF 5 solution, adjusting the pH value to 9; centrifuging the solution obtained above, and performing solid-liquid separation to obtain Nb(OH) 5 precipitate;
将酒石酸(TA)与柠檬酸(CA)溶于去离子水中制成复合螯合剂，其中酒石酸与柠檬酸的摩尔比为1：4；Tartaric acid (TA) and citric acid (CA) are dissolved in deionized water to prepare a composite chelating agent, wherein the molar ratio of tartaric acid to citric acid is 1:4;
将Nb(OH)5沉淀加入复合螯合剂中，在75℃下水浴加热搅拌至沉淀溶解，得到前驱液溶液，其中Nb5+与复合螯合剂的摩尔比为1：6；The Nb(OH) 5 precipitate was added to the composite chelating agent, and heated in a water bath at 75°C with stirring until the precipitate was dissolved to obtain a precursor solution, wherein the molar ratio of Nb 5+ to the composite chelating agent was 1:6;
称取高纯度(99.99％)的BiCl3，将其溶于质量浓度为37％的HCl中，为保证溶解完全，氯化铋与HCl的摩尔比为1：1.3，得到Bi3+前驱液；Weigh high-purity (99.99%) BiCl 3 and dissolve it in 37% HCl. To ensure complete dissolution, the molar ratio of bismuth chloride to HCl is 1:1.3 to obtain a Bi 3+ precursor solution.
称取高纯度(99.99％)的ZnCl2，将其溶于质量浓度为37％的HCl中，氯化锌与HCl的摩尔比为1：1.3，得到Zn2+前驱液；Weigh high-purity (99.99%) ZnCl 2 and dissolve it in 37% HCl, with the molar ratio of zinc chloride to HCl being 1:1.3, to obtain a Zn 2+ precursor solution;
称取高纯度(99.99％)的CaCl2，将其溶于质量浓度为37％的HCl中，氯化钙与HCl的摩尔比为1：1.3，得到Ca2+前驱液；Weigh high-purity (99.99%) CaCl 2 and dissolve it in 37% HCl, with the molar ratio of calcium chloride to HCl being 1:1.3, to obtain a Ca 2+ precursor solution;
将Bi3+前驱液、Zn2+前驱液和Ca2+前驱液逐滴缓慢加入前驱体溶液中，全程在75℃下水浴加热搅拌，滴加完毕后，使用氨水将溶液pH值调至4；继续加热搅拌1.5h后取出得到溶胶，为提高溶胶的纯度，溶胶密封陈化24h得到所述铌酸铋锌复合溶胶；The Bi 3+ precursor solution, the Zn 2+ precursor solution and the Ca 2+ precursor solution are slowly added dropwise to the precursor solution, and the solution is heated and stirred in a water bath at 75° C. throughout the process. After the addition is completed, the pH value of the solution is adjusted to 4 with ammonia water; the solution is heated and stirred for 1.5 hours and then taken out to obtain the sol. In order to improve the purity of the sol, the sol is sealed and aged for 24 hours to obtain the bismuth zinc niobate composite sol;
将ITO玻璃基底依次放入去离子水、丙酮、无水乙醇、去离子水中超声各清洗15min以去除基底表面的杂质；将得到的铌酸铋锌复合溶胶，使用真空旋涂机涂覆在经预处理的ITO玻璃基底上，覆有湿膜的基底置于加热板上，在120℃干燥处理10min后，放入管式炉中在625℃下结晶化处理1h，在基底上获得一层掺杂铌酸铋锌(BCZN)薄膜。重复以上操作6次直至获得所需厚度，最终获得具有立方焦绿石结构的BCZN复合薄膜。The ITO glass substrate was placed in deionized water, acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning for 15 minutes each to remove impurities on the substrate surface; the obtained bismuth zinc niobate composite sol was coated on the pretreated ITO glass substrate using a vacuum spin coater, and the substrate covered with the wet film was placed on a heating plate, dried at 120°C for 10 minutes, and then placed in a tube furnace for crystallization at 625°C for 1 hour to obtain a layer of doped bismuth zinc niobate (BCZN) film on the substrate. The above operation was repeated 6 times until the desired thickness was obtained, and finally a BCZN composite film with a cubic pyrochlore structure was obtained.
实施例3Example 3
本实施例得到的铌酸铋锌复合溶胶的化学组成为Bi1.5Ca0.2Zn0.8NbO7，根据化学计量比称取所需的原料；The chemical composition of the bismuth zinc niobate composite sol obtained in this example is Bi 1.5 Ca 0.2 Zn 0.8 NbO 7 , and the required raw materials are weighed according to the stoichiometric ratio;
称取高纯度(99.99％)的Nb2O5，将Nb2O5与氢氟酸(HF，质量浓度为99.99％)按1：15的摩尔比放入反应釜中，在150℃反应2h得到NbF5溶液；Weigh high-purity (99.99%) Nb 2 O 5 , put Nb 2 O 5 and hydrofluoric acid (HF, mass concentration of 99.99%) into a reaction kettle at a molar ratio of 1:15, and react at 150° C. for 2 h to obtain a NbF 5 solution;
配制沉淀剂：沉淀剂为饱和碳酸氢铵与浓氨水的混合液，摩尔比为1：4；Preparation of precipitant: The precipitant is a mixture of saturated ammonium bicarbonate and concentrated ammonia water, with a molar ratio of 1:4;
将沉淀剂加入上述NbF5溶液中，调节pH值到9；将上述得到的溶液进行离心、固液分离后得到Nb(OH)5沉淀；Adding a precipitant to the NbF 5 solution, adjusting the pH value to 9; centrifuging the solution obtained above, and performing solid-liquid separation to obtain Nb(OH) 5 precipitate;
将酒石酸(TA)与柠檬酸(CA)溶于去离子水中制成复合螯合剂，其中酒石酸与柠檬酸的摩尔比为1：4；Tartaric acid (TA) and citric acid (CA) are dissolved in deionized water to prepare a composite chelating agent, wherein the molar ratio of tartaric acid to citric acid is 1:4;
将Nb(OH)5沉淀加入复合螯合剂中，在80℃下水浴加热搅拌至沉淀溶解，得到前驱液溶液，其中Nb5+与复合螯合剂的摩尔比为1：8；The Nb(OH) 5 precipitate was added to the composite chelating agent, and heated in a water bath at 80°C with stirring until the precipitate was dissolved to obtain a precursor solution, wherein the molar ratio of Nb 5+ to the composite chelating agent was 1:8;
称取高纯度(99.99％)的BiCl3，将其溶于质量浓度为37％的HCl中，为保证溶解完全，氯化铋与HCl的摩尔比为1：1.5，得到Bi3+前驱液；Weigh high-purity (99.99%) BiCl 3 and dissolve it in 37% HCl. To ensure complete dissolution, the molar ratio of bismuth chloride to HCl is 1:1.5 to obtain a Bi 3+ precursor solution.
称取高纯度(99.99％)的ZnCl2，将其溶于质量浓度为37％的HCl中，氯化锌与HCl的摩尔比为1：1.5，得到Zn2+前驱液；Weigh high-purity (99.99%) ZnCl 2 and dissolve it in 37% HCl, with the molar ratio of zinc chloride to HCl being 1:1.5, to obtain a Zn 2+ precursor solution;
称取高纯度(99.99％)的CaCl2，将其溶于质量浓度为37％的HCl中，氯化钙与HCl的摩尔比为1：1.5，得到Ca2+前驱液；Weigh high-purity (99.99%) CaCl 2 and dissolve it in 37% HCl, with the molar ratio of calcium chloride to HCl being 1:1.5, to obtain a Ca 2+ precursor solution;
将Bi3+前驱液、Zn2+前驱液和Ca2+前驱液逐滴缓慢加入前驱体溶液中，全程在75℃下水浴加热搅拌，滴加完毕后，使用氨水将溶液pH值调至5；继续加热搅拌1.5h后取出得到溶胶，为提高溶胶的纯度，溶胶密封陈化24h得到所述铌酸铋锌复合溶胶；The Bi 3+ precursor solution, the Zn 2+ precursor solution and the Ca 2+ precursor solution are slowly added dropwise to the precursor solution, and the solution is heated and stirred in a water bath at 75° C. throughout the process. After the addition is completed, the pH value of the solution is adjusted to 5 with ammonia water; the solution is heated and stirred for 1.5 hours and then taken out to obtain the sol. In order to improve the purity of the sol, the sol is sealed and aged for 24 hours to obtain the bismuth zinc niobate composite sol;
将ITO玻璃基底依次放入去离子水、丙酮、无水乙醇、去离子水中超声各清洗15min以去除基底表面的杂质；将得到的铌酸铋锌复合溶胶，使用真空旋涂机涂覆在经预处理的ITO玻璃基底上，覆有湿膜的基底置于加热板上，在130℃干燥处理10min后，放入管式炉中在625℃下结晶化处理1h，在基底上获得一层掺杂铌酸铋锌(BCZN)薄膜。重复以上操作6次直至获得所需厚度，最终获得具有立方焦绿石结构的BCZN复合薄膜。The ITO glass substrate was placed in deionized water, acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning for 15 minutes each to remove impurities on the substrate surface; the obtained bismuth zinc niobate composite sol was coated on the pretreated ITO glass substrate using a vacuum spin coater, and the substrate covered with the wet film was placed on a heating plate, dried at 130°C for 10 minutes, and then placed in a tube furnace for crystallization at 625°C for 1 hour to obtain a layer of doped bismuth zinc niobate (BCZN) film on the substrate. The above operation was repeated 6 times until the desired thickness was obtained, and finally a BCZN composite film with a cubic pyrochlore structure was obtained.
实施例4Example 4
本实施例得到的铌酸铋锌复合溶胶的化学组成为Bi1.5Ca0.25Zn0.75NbO7，根据化学计量比称取所需的原料；The chemical composition of the bismuth zinc niobate composite sol obtained in this example is Bi 1.5 Ca 0.25 Zn 0.75 NbO 7 , and the required raw materials are weighed according to the stoichiometric ratio;
称取高纯度(99.99％)的Nb2O5，将Nb2O5与氢氟酸(HF，质量浓度为99.99％)按1：15的摩尔比放入反应釜中，在150℃反应2h得到NbF5溶液；Weigh high-purity (99.99%) Nb 2 O 5 , put Nb 2 O 5 and hydrofluoric acid (HF, mass concentration of 99.99%) into a reaction kettle at a molar ratio of 1:15, and react at 150° C. for 2 h to obtain a NbF 5 solution;
配制沉淀剂：沉淀剂为饱和碳酸氢铵与浓氨水的混合液，摩尔比为1：4；Preparation of precipitant: The precipitant is a mixture of saturated ammonium bicarbonate and concentrated ammonia water, with a molar ratio of 1:4;
将沉淀剂加入上述NbF5溶液中，调节pH值到9；将上述得到的溶液进行离心、固液分离后得到Nb(OH)5沉淀；Adding a precipitant to the NbF 5 solution, adjusting the pH value to 9; centrifuging the solution obtained above, and performing solid-liquid separation to obtain Nb(OH) 5 precipitate;
将酒石酸(TA)与柠檬酸(CA)溶于去离子水中制成复合螯合剂，其中酒石酸与柠檬酸的摩尔比为1：4；Tartaric acid (TA) and citric acid (CA) are dissolved in deionized water to prepare a composite chelating agent, wherein the molar ratio of tartaric acid to citric acid is 1:4;
将Nb(OH)5沉淀加入复合螯合剂中，在70℃下水浴加热搅拌至沉淀溶解，得到前驱液溶液，其中Nb5+与复合螯合剂的摩尔比为1：8；The Nb(OH) 5 precipitate was added to the composite chelating agent, and heated in a water bath at 70°C with stirring until the precipitate was dissolved to obtain a precursor solution, wherein the molar ratio of Nb 5+ to the composite chelating agent was 1:8;
称取高纯度(99.99％)的BiCl3，将其溶于质量浓度为37％的HCl中，为保证溶解完全，氯化铋与HCl的摩尔比为1：1.4，得到Bi3+前驱液；Weigh high-purity (99.99%) BiCl 3 and dissolve it in 37% HCl. To ensure complete dissolution, the molar ratio of bismuth chloride to HCl is 1:1.4 to obtain a Bi 3+ precursor solution.
称取高纯度(99.99％)的ZnCl2，将其溶于质量浓度为37％的HCl中，氯化锌与HCl的摩尔比为1：1.4，得到Zn2+前驱液；Weigh high-purity (99.99%) ZnCl 2 and dissolve it in 37% HCl, with the molar ratio of zinc chloride to HCl being 1:1.4, to obtain a Zn 2+ precursor solution;
称取高纯度(99.99％)的CaCl2，将其溶于质量浓度为37％的HCl中，氯化钙与HCl的摩尔比为1：1.4，得到Ca2+前驱液；Weigh high-purity (99.99%) CaCl 2 and dissolve it in 37% HCl, with the molar ratio of calcium chloride to HCl being 1:1.4, to obtain a Ca 2+ precursor solution;
将Bi3+前驱液、Zn2+前驱液和Ca2+前驱液逐滴缓慢加入前驱体溶液中，全程在80℃下水浴加热搅拌，滴加完毕后，使用氨水将溶液pH值调至4；继续加热搅拌1h后取出得到溶胶，为提高溶胶的纯度，溶胶密封陈化24h得到所述铌酸铋锌复合溶胶；The Bi 3+ precursor solution, the Zn 2+ precursor solution and the Ca 2+ precursor solution are slowly added dropwise to the precursor solution, and the solution is heated and stirred in a water bath at 80° C. during the whole process. After the addition is completed, the pH value of the solution is adjusted to 4 with ammonia water; the solution is heated and stirred for 1 hour and then taken out to obtain the sol. In order to improve the purity of the sol, the sol is sealed and aged for 24 hours to obtain the bismuth zinc niobate composite sol;
将ITO玻璃基底依次放入去离子水、丙酮、无水乙醇、去离子水中超声各清洗15min以去除基底表面的杂质；将得到的铌酸铋锌复合溶胶，使用真空旋涂机涂覆在经预处理的ITO玻璃基底上，覆有湿膜的基底置于加热板上，在150℃干燥处理10min后，放入管式炉中在650℃下结晶化处理1h，在基底上获得一层掺杂铌酸铋锌(BCZN)薄膜。重复以上操作7次直至获得所需厚度，最终获得具有立方焦绿石结构的BCZN复合薄膜。The ITO glass substrate was placed in deionized water, acetone, anhydrous ethanol, and deionized water for ultrasonic cleaning for 15 minutes each to remove impurities on the substrate surface; the obtained bismuth zinc niobate composite sol was coated on the pretreated ITO glass substrate using a vacuum spin coater, and the substrate covered with the wet film was placed on a heating plate, dried at 150°C for 10 minutes, and then placed in a tube furnace for crystallization at 650°C for 1 hour to obtain a layer of doped bismuth zinc niobate (BCZN) film on the substrate. The above operation was repeated 7 times until the desired thickness was obtained, and finally a BCZN composite film with a cubic pyrochlore structure was obtained.
性能测试Performance Testing
测试例1Test Example 1
图1为实施例1～4得到的铌酸铋锌复合薄膜的XRD图，其中BC0.1Z0.9N为实施例1、BC0.25Z0.85N为实施例2、BC0.2Z0.8N为实施例3、BC0.25Z0.75N为实施例4；从图1可以看出BZN仍保持立方焦绿石结构结构，Ca2+的掺入未破坏其原有晶体结构。Figure 1 is the XRD diagram of the bismuth zinc niobate composite films obtained in Examples 1 to 4, wherein BC 0.1 Z 0.9 N is Example 1, BC 0.25 Z 0.85 N is Example 2, BC 0.2 Z 0.8 N is Example 3, and BC 0.25 Z 0.75 N is Example 4; it can be seen from Figure 1 that BZN still maintains a cubic pyrochlore structure, and the incorporation of Ca 2+ does not destroy its original crystal structure.
图1为实施例1～4得到的铌酸铋锌复合薄膜的SEM图，从图2可以看出薄膜均匀致密无裂纹，随着Ca2+掺杂浓度增大，样品平均晶粒尺寸增大，Ca2+掺入一定程度上可促进晶粒的生长。Figure 1 is a SEM image of the bismuth zinc niobate composite film obtained in Examples 1 to 4. From Figure 2, it can be seen that the film is uniform, dense and crack-free. As the Ca 2+ doping concentration increases, the average grain size of the sample increases. Ca 2+ incorporation can promote grain growth to a certain extent.
测试例2Test Example 2
对实施例1～4得到的铌酸铋锌复合薄膜的介电性能进行测试，测试方法为：通过真空蒸镀法在复合薄膜表面制备直径为400μm的Au电极，进行介电性能测试。The dielectric properties of the bismuth zinc niobate composite films obtained in Examples 1 to 4 were tested. The testing method was as follows: an Au electrode with a diameter of 400 μm was prepared on the surface of the composite film by vacuum evaporation, and the dielectric properties were tested.
在1MHz频率下，所得到的测试结果如表1和图3所示：At a frequency of 1MHz, the test results are shown in Table 1 and Figure 3:
表1实施例1～4得到的铌酸铋锌复合薄膜的介电性能Table 1 Dielectric properties of bismuth zinc niobate composite films obtained in Examples 1 to 4
从表1和图3可以看出Ca2+的掺入使BZN材料具有较低的介电损耗，其在1MHz频率下介电常数为110～120，介电损耗≤0.008。It can be seen from Table 1 and Figure 3 that the incorporation of Ca 2+ makes the BZN material have lower dielectric loss. Its dielectric constant is 110-120 at a frequency of 1 MHz, and the dielectric loss is ≤0.008.
尽管上述实施例对本发明做出了详尽的描述，但它仅仅是本发明一部分实施例，而不是全部实施例，还可以根据本实施例在不经创造性前提下获得其他实施例，这些实施例都属于本发明保护范围。Although the above embodiment describes the present invention in detail, it is only a part of the embodiments of the present invention, not all of the embodiments. Other embodiments can be obtained based on this embodiment without creativity, and these embodiments all fall within the protection scope of the present invention.
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