CN117328046B - BZN/BMN dielectric tuning composite film with heterostructure and preparation method thereof - Google Patents
BZN/BMN dielectric tuning composite film with heterostructure and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 abstract description 18
- 239000011975 tartaric acid Substances 0.000 claims abstract description 18
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 18
- 230000000737 periodic effect Effects 0.000 claims abstract description 17
- 230000005684 electric field Effects 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 98
- 239000002243 precursor Substances 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 85
- 238000010438 heat treatment Methods 0.000 claims description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 32
- 239000002244 precipitate Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 238000004528 spin coating Methods 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010668 complexation reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 abstract description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003980 solgel method Methods 0.000 abstract description 6
- 231100000086 high toxicity Toxicity 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 75
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 15
- 239000011777 magnesium Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229940095064 tartrate Drugs 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910010252 TiO3 Inorganic materials 0.000 description 1
- ONVGHWLOUOITNL-UHFFFAOYSA-N [Zn].[Bi] Chemical compound [Zn].[Bi] ONVGHWLOUOITNL-UHFFFAOYSA-N 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SKKNACBBJGLYJD-UHFFFAOYSA-N bismuth magnesium Chemical compound [Mg].[Bi] SKKNACBBJGLYJD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1254—Sol or sol-gel processing
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
- H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
- H01G7/025—Electrets, i.e. having a permanently-polarised dielectric having an inorganic dielectric
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a BZN/BMN dielectric tuning composite film with a heterostructure and a preparation method thereof, wherein the composite film comprises a substrate and a composite layer which is laminated on the substrate and is repeatedly arranged by taking the BZN/BMN as a periodic unit, and the composite layer comprises 2-3 periodic units; the dielectric tuning rate of the multilayer composite dielectric adjustable film is more than or equal to 60% under a bias electric field of 1.5MV/cm, and the dielectric loss is less than or equal to 0.006. The composite film provided by the invention combines the performance characteristics of the BZN film and the BMN film, has high dielectric tuning rate under lower bias voltage, and has smaller dielectric loss and stronger performance stability. In addition, the sol-gel method is used for preparing the composite film, and sulfuric acid is used for replacing hydrofluoric acid with high toxicity and volatility when the BZN film and the BMN film are prepared, so that the requirements on equipment materials and the pollution on the environment are reduced, and the preparation process and the preparation cost are also saved; the tartaric acid is used for replacing citric acid, which is favorable for improving the stability of sol and ensures that the prepared film has better performance.
Description
Technical Field
The invention relates to the technical field of film materials of electronic components, in particular to a BZN/BMN dielectric tuning composite film with a heterostructure and a preparation method thereof.
Background
The modern mobile communication technology is rapidly developed, and the microwave tunable device applied to 5G/6G communication is developed towards the trend of multifrequency, microminiaturization and high reliability. The microwave devices such as dielectric tunable thin film varactors and the like made of dielectric tunable thin film materials and related materials thereof have great market potential in the future military and civil markets.
The research on dielectric tunable materials is mainly focused on (Ba xSr1-x)TiO3 (BST) ferroelectric thin films with perovskite structures, but dielectric loss caused by intrinsic characteristics inside the materials is too high, which severely limits the wider application thereof.
The bismuth zinc niobate (Bi 1.5ZnNb1.5O7, BZN) dielectric tuning film material with the pyrochlore structure not only has lower dielectric loss, but also has excellent dielectric adjustability, and has lower dielectric loss compared with a BST film. However, when the BZN dielectric tuning film material is used, a higher dielectric tuning rate can be obtained only by loading a very high bias electric field, which limits the integrated application of the BZN film. Some researchers try to improve the problem by using different preparation methods, but the defects of the BZN film are caused by intrinsic characteristics of the material, and only changing the preparation method cannot make the performance of the BZN film break through greatly.
Bismuth magnesium niobate (Bi 1.5MgNb1.5O7, BMN) dielectric materials also have dielectric tunability and lower dielectric loss than BST. The BMN film has small dielectric loss, moderate dielectric constant and good temperature stability, is a novel microwave dielectric adjustable material with very promising prospect, but has relatively small tuning rate, and is also unfavorable for being independently used in actual products.
The preparation method of the dielectric film mainly comprises radio frequency magnetron sputtering (RF-Magnetronsputtering), pulse Laser Deposition (PLD), metal Organic Chemical Vapor Deposition (MOCVD) and Sol-Gel method (Sol-Gel); compared with other methods, the sol-gel method for preparing the film has the advantages of good uniformity, easy control of stoichiometric ratio, simple equipment and the like, and has been widely used for preparing the medium film; meanwhile, when preparing BMN and BZN films by a traditional sol-gel method, most of the prior art uses hydrofluoric acid to dissolve Nb 2O5 when preparing precursor liquid containing Nb, but the hydrofluoric acid has high toxicity and volatility, has high requirements on equipment materials and is easy to cause serious pollution to the environment, and Nb (OH) 5 can be obtained only by adjusting the pH value by using ammonia water or ammonium carbonate after dissolving Nb 2O5, so that the process is complicated and the precision is difficult to control.
At present, the preparation and performance research of a multilayer heterostructure film material are not reported in the prior art, so that a novel high-performance dielectric tuning film material is developed, and an improved sol-gel preparation method is provided, which has great significance, on one hand, the cost can be reduced, the experimental equipment requirement can be lowered, and on the other hand, the research blank of the multilayer composite heterostructure film material can be filled.
Disclosure of Invention
Aiming at the technical problems, the invention provides a BZN/BMN dielectric tuning composite film with a heterostructure and a preparation method thereof, wherein the BZN/BMN heterostructure dielectric tuning film has the characteristics of low dielectric loss, high dielectric tuning rate and good stability.
The invention provides a BZN/BMN dielectric tuning composite film with a heterostructure, which is characterized by comprising a substrate and a composite layer which is stacked on the substrate and is repeatedly arranged by taking the BZN/BMN as a periodic unit, wherein the composite layer comprises 2-3 periodic units; the dielectric tuning rate of the multilayer composite dielectric adjustable film is more than or equal to 60% under a bias electric field of 1.5MV/cm, and the dielectric loss is less than or equal to 0.006.
The second object of the present invention is to provide a method for preparing the BZN/BMN dielectric tuning composite film having a heterostructure, comprising the steps of:
S1, spin-coating BZN sol on a substrate by using a vacuum spin-coating machine, placing the spin-coated substrate on a heating plate for drying treatment, and then moving the substrate into a tube furnace for crystallization treatment; repeating the spin coating, drying and crystallization processes until the thickness of BZN formed on the substrate reaches 100nm;
s2, spin-coating BMN sol on the BZN film prepared in the step 1, then placing the BZN film on a heating plate for drying treatment, and then moving the BZN film into a tube furnace for crystallization treatment; repeating spin coating, drying and crystallization processes until the thickness of the BMN film formed on the substrate reaches 100nm to obtain a BZN/BMN periodic unit;
S3, repeatedly arranging the BZN/BMN periodic units prepared in the step 2 on the same substrate for 2-3 times, and then placing the BZN/BMN periodic units in a tube furnace for annealing heat treatment to obtain the BZN/BMN dielectric tuning composite film with the heterostructure.
Specifically, the preparation method of the BZN sol in step S1 comprises the following steps:
S11 preparation of Nb-TA-EG precursor solution
Placing Nb 2O5 and sulfuric acid with the concentration of 15mol/L in a beaker, uniformly mixing, then placing in an oven, heating for 2-3 h at 200 ℃, then heating to 300 ℃, and preserving heat for 0.5-1 h to obtain a product a; adding deionized water into the product a, heating to 80-90 ℃ in a water bath, and carrying out hydrolysis reaction to obtain Nb (OH) 5 solution; centrifuging and separating the Nb (OH) 5 solution to obtain Nb (OH) 5 precipitate; adding tartaric acid into Nb (OH) 5 precipitate, heating in water bath at 65-85 ℃, stirring until the precipitate is dissolved to obtain a mixed solution a, adding ethylene glycol into the mixed solution a, heating in water bath at 70-80 ℃ and stirring for 10min to carry out complexation reaction to obtain Nb-TA-EG precursor solution;
wherein, the mole ratio of Nb 2O5 to sulfuric acid is 1 (12-18), the mass ratio of the product a to deionized water is 1 (100-150), the mole ratio of Nb (OH) 5 to tartaric acid is 1 (5-8), and the mole ratio of tartaric acid to ethylene glycol is 1.5:1;
S12 preparation of Bi-EG precursor solution
Dissolving Bi (NO 3)3·5H2 O) in glycol to obtain Bi-EG precursor solution, wherein the mol ratio of Bi (NO 3)3·5H2 O to glycol is 1 (1.5-2.5);
S13 preparation of Zn-EG precursor liquid
Zn (NO 3)2·6H2 O) is dissolved in ethylene glycol to obtain Zn-EG precursor solution, wherein the mol ratio of Zn (NO 3)2·6H2 O) to ethylene glycol is 1 (1.5-2.5);
S14 preparation of BZN sol
Sequentially dripping the Bi-EG precursor solution prepared in the step S12 and the Zn-EG precursor solution prepared in the step S13 into the Nb-TA-EG precursor solution prepared in the step S11, stirring under water bath heating at 70-80 ℃, continuing heating and stirring for 1-3 h after dripping is finished to obtain sol a, and sealing and aging the sol a for 48-56h to obtain BZN sol; wherein the mol ratio of Bi-EG precursor solution to Zn-EG precursor solution to Nb-TA-EG precursor solution is 1.5:1:1.5.
Specifically, the preparation method of the BMN sol in step S2 includes:
s21 preparation of Nb-TA-EG precursor solution
Placing Nb 2O5 and sulfuric acid with the concentration of 15mol/L in a beaker, uniformly mixing, then placing in an oven, heating for 2-3 h at 200 ℃, then heating to 300 ℃, and preserving heat for 0.5-1 h to obtain a product b; adding deionized water into the product b, heating to 80-90 ℃ in a water bath, and carrying out hydrolysis reaction to obtain Nb (OH) 5 solution; centrifuging and separating the Nb (OH) 5 solution to obtain Nb (OH) 5 precipitate; adding tartaric acid into Nb (OH) 5 precipitate, heating in water bath at 65-85 ℃, stirring until the precipitate is dissolved to obtain a mixed solution b, adding ethylene glycol into the mixed solution b, heating in water bath at 70-80 ℃ and stirring for 10min to carry out complexation reaction to obtain Nb-TA-EG precursor solution;
Wherein, the mole ratio of Nb 2O5 to sulfuric acid is 1 (12-18), the mass ratio of the product b to deionized water is 1 (100-150), the mole ratio of Nb (OH) 5 to tartaric acid is 1 (5-8), and the mole ratio of tartaric acid to ethylene glycol is 1.5:1;
s22 preparation of Bi-EG precursor solution
Dissolving Bi (NO 3)3·5H2 O) in glycol to obtain Bi-EG precursor solution, wherein the mol ratio of Bi (NO 3)3·5H2 O to glycol is 1 (1.5-2.5);
s23 preparation of Mg-EG precursor liquid
Dissolving Mg (NO 3)2·6H2 O) in ethylene glycol to obtain Mg-EG precursor solution, wherein the mol ratio of Mg (NO 3)2·6H2 O to ethylene glycol is 1 (1.5-2.5);
S24 preparation of BMN sol
Sequentially dripping the Bi-EG precursor solution prepared in the step S22 and the Mg-EG precursor solution prepared in the step S23 into the Nb-TA-EG precursor solution prepared in the step S21, stirring under water bath heating at 70-80 ℃, continuing heating and stirring for 1-3 h after the dripping is finished to obtain sol b, and sealing and aging the sol b for 48-56h to obtain BMN sol; wherein the mol ratio of Bi-EG precursor liquid to Mg-EG precursor liquid to Nb-TA-EG precursor liquid is 1.5:1:1.5.
Specifically, the drying treatment in the steps S1 and S2 is carried out at a treatment temperature of 120-150 ℃ for 1-2min; the crystallization treatment is carried out at 600-700 ℃ for 1h.
Specifically, the treatment temperature of the annealing heat treatment in the step S3 is 600-700 ℃, and the treatment time is 2h.
Specifically, the substrate is any one of an ITO substrate and a P-type Si substrate.
The beneficial effects of the invention are as follows:
(1) The invention forms a novel complex heterostructure dielectric adjustable composite film on the substrate by using the periodic arrangement mode of BZN/BMN, integrates the performance characteristics of the BZN film and the BMN film, has high dielectric tuning rate under lower bias voltage, and has smaller dielectric loss and stronger performance stability.
(2) The BZN/BMN composite film is prepared by a sol-gel method, so that uniformity of film components is facilitated; in addition, when preparing Nb-TA-EG precursor liquid, sulfuric acid is used for replacing hydrofluoric acid with high toxicity and volatility, nb (OH) 5 is directly obtained through hydrolysis, so that the requirement on equipment materials is reduced, the pollution to the environment is improved, and the preparation process and cost are saved;
(3) In the preparation of the BZN/BMN composite film, tartaric acid with stronger complexing ability is used for replacing common citric acid in the preparation of the Nb-TA-EG precursor liquid, so that the stability of the sol is improved, and the prepared film has better performance.
Drawings
FIG. 1 is a schematic diagram of a BZN/BMN dielectric tuning composite film having a heterostructure according to the present invention;
FIG. 2 is a flow chart of the preparation of a BZN/BMN dielectric tuning composite film with heterostructure according to the present invention;
FIG. 3 is a graph showing the dielectric properties of a BZN/BMN dielectric tuning composite film having a heterostructure according to example 1 of the present invention;
FIG. 4 is an XRD pattern of a BZN/BMN dielectric tuned composite film having a heterostructure according to example 1 of the present invention
Fig. 5 is an SEM image of a BZN/BMN dielectric tuning composite film having a heterostructure in example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
And all that is not described in detail in this specification is well known to those skilled in the art.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Example 1
(One) preparation of BZN sol
1) Preparation of Nb-TA-EG precursor liquid
Weighing 0.0075mol of Nb 2O5 with purity of 99.99% and 0.1125mol of sulfuric acid with concentration of 15mol/L, uniformly mixing in a beaker, putting into an oven, heating at 200 ℃ for 2h, and then heating to 300 ℃ and preserving heat for 0.5h to obtain a product a1; adding 300ml of deionized water into 2g of a product a1, heating to 80 ℃ in a water bath to carry out hydrolysis reaction to generate Nb (OH) 5 solution; centrifuging the Nb (OH) 5 solution, and carrying out solid-liquid separation to obtain Nb (OH) 5 precipitate; adding 0.075mol of tartaric acid into 0.015mol of Nb (OH) 5 precipitate, heating in a water bath at 80 ℃ and stirring until the precipitate is dissolved to obtain a mixed solution a1; adding 0.05mol of ethylene glycol into the mixed solution a1, heating and stirring in a water bath at 70 ℃ for 10min to promote the polymerization of tartrate, and obtaining the Nb-TA-EG precursor solution.
2) Preparation of Bi-EG precursor solution and Zn-EG precursor solution
0.015Mol of Bi (NO 3)3·5H2 O is dissolved in 0.03mol of glycol to obtain a Bi-EG precursor solution a, and 0.01mol of Zn (NO 3)2·6H2 O is dissolved in 0.02mol of glycol to obtain a Zn-EG precursor solution).
3) Preparation of BZN sol
Slowly adding 0.015mol of Bi-EG precursor solution a and 0.01mol of Zn-EG precursor solution into 0.015mol of Nb-TA-EG precursor solution a dropwise, heating and stirring in a water bath at 70 ℃, continuously heating and stirring for 1h after the dripping is finished, obtaining sol a1, and sealing and aging the sol a1 for 48h to improve the purity of BZN sol, thereby obtaining the BZN sol.
(II) preparation of BMN sol
1) Preparation of Nb-TA-EG precursor liquid
Weighing 0.0075mol of Nb 2O5 with purity of 99.99% and 0.1125mol of sulfuric acid with concentration of 15mol/L, uniformly mixing in a beaker, putting into an oven, heating at 200 ℃ for 2h, and then heating to 300 ℃ and preserving heat for 0.5h to obtain a product b1; adding 300ml of deionized water into 2g of the product b1, heating to 80 ℃ in a water bath to carry out hydrolysis reaction to generate Nb (OH) 5 solution; centrifuging the Nb (OH) 5 solution, and carrying out solid-liquid separation to obtain Nb (OH) 5 precipitate; adding 0.075mol of tartaric acid into 0.015mol of Nb (OH) 5 precipitate, heating in a water bath at 80 ℃ and stirring until the precipitate is dissolved to obtain a mixed solution b1; adding 0.05mol of ethylene glycol into the mixed solution b1, heating and stirring in a water bath at 70 ℃ for 10min to promote the polymerization of tartrate, and obtaining the Nb-TA-EG precursor solution.
2) Preparation of Bi-EG precursor solution and Mg-EG precursor solution
0.015Mol of Bi (NO 3)3·5H2 O is dissolved in 0.03mol of ethylene glycol to obtain Bi-EG precursor b, and 0.01mol of Mg (NO 3)2·6H2 O is dissolved in 0.02mol of ethylene glycol to obtain Mg-EG precursor b).
3) Preparation of BMN sols
Slowly adding 0.015mol of Bi-EG precursor solution b and 0.01mol of Mg-EG precursor solution into 0.015mol of Nb-TA-EG precursor solution b dropwise, heating and stirring in a water bath at 70 ℃, continuously heating and stirring for 1h after the dripping is finished, obtaining sol b1, and sealing and aging the sol b1 for 48h to improve the purity of BZN sol, thus obtaining BMN sol.
(III) preparing BZN/BMN dielectric tuning composite film
Spin-coating BZN sol on a clean and dry ITO substrate by using a vacuum spin-coating machine, drying the substrate coated with a wet film on a heating plate at 150 ℃ for 2min, placing the substrate into a tubular furnace for crystallization treatment at 600 ℃ for 1h, obtaining a layer of BZN film on the substrate, and repeating the spin-coating, drying and crystallization treatment processes until the thickness of the BZN film formed on the substrate reaches 100nm.
And coating BMN sol on the BZN film by using a vacuum spin coater, drying at 150 ℃ for 2min on a heating plate, then placing the BZN film into a tubular furnace for crystallization at 600 ℃ for 1h, obtaining a layer of BMN film on the BZN film, and repeating spin coating, drying and crystallization processes until the thickness of the BMN film formed on the substrate reaches 100nm, thus obtaining the BZN/BMN periodic unit.
And repeating the steps for 2 times by taking BZN/BMN as a periodic unit on a substrate, and then placing the substrate in a tube furnace for homogenizing annealing at 600 ℃ for 2 hours to obtain the BZN/BMN dielectric tuning composite film prepared in the example 1.
Example 2
(One) preparation of BZN sol
1) Preparation of Nb-TA-EG precursor liquid
Weighing 0.0075mol of Nb 2O5 with purity of 99.99% and 0.135mol of sulfuric acid with concentration of 15mol/L, uniformly mixing in a beaker, putting into an oven, heating at 200 ℃ for 3h, and then heating to 300 ℃ and preserving heat for 1h to obtain a product a2; adding 200ml of deionized water into 2g of a product a2, heating to 90 ℃ in a water bath to carry out hydrolysis reaction to generate Nb (OH) 5 solution; centrifuging the Nb (OH) 5 solution, and carrying out solid-liquid separation to obtain Nb (OH) 5 precipitate; adding 0.12mol of tartaric acid into 0.015mol of Nb (OH) 5 precipitate, heating in a water bath at 80 ℃ and stirring until the precipitate is dissolved to obtain a mixed solution a2; adding 0.08mol of ethylene glycol into the mixed solution a2, heating and stirring in a water bath at 80 ℃ for 10min to promote the polymerization of tartrate, and obtaining the Nb-TA-EG precursor solution a.
2) Preparation of Bi-EG precursor solution and Zn-EG precursor solution
0.015Mol of Bi (NO 3)3·5H2 O is dissolved in 0.0375mol of ethylene glycol to obtain a Bi-EG precursor solution a, and 0.01mol of Zn (NO 3)2·6H2 O is dissolved in 0.025mol of ethylene glycol to obtain a Zn-EG precursor solution).
3) Preparation of BZN sol
Slowly adding 0.015mol of Bi-EG precursor solution and 0.01mol of Zn-EG precursor solution into 0.015mol of Nb-TA-EG precursor solution a dropwise, heating and stirring in a water bath at 80 ℃, continuously heating and stirring for 3 hours after the dripping is finished, obtaining sol a2, and sealing and aging the sol a2 for 56 hours to improve the purity of BZN sol, thus obtaining BZN sol.
(II) preparation of BMN sol
1) Preparation of Nb-TA-EG precursor liquid
Weighing 0.0075mol of Nb 2O5 with purity of 99.99% and 0.135mol of sulfuric acid with concentration of 15mol/L, uniformly mixing in a beaker, putting into an oven, heating at 200 ℃ for 3h, and then heating to 300 ℃ and preserving heat for 1h to obtain a product b2; adding 200ml of deionized water into 2g of the product b2, heating to 90 ℃ in a water bath to carry out hydrolysis reaction to generate Nb (OH) 5 solution; centrifuging the Nb (OH) 5 solution, and carrying out solid-liquid separation to obtain Nb (OH) 5 precipitate; adding 0.12mol of tartaric acid into 0.015mol of Nb (OH) 5 precipitate, heating in a water bath at 80 ℃ and stirring until the precipitate is dissolved to obtain a mixed solution b2; adding 0.08mol of ethylene glycol into the mixed solution b2, heating and stirring in a water bath at 80 ℃ for 10min to promote the polymerization of tartrate, and obtaining Nb-TA-EG precursor liquid b, wherein the preparation method is consistent with the preparation of Nb-TA-EG precursor liquid a when BZN sol is prepared.
2) Preparation of Bi-EG precursor solution and Mg-EG precursor solution
0.015Mol of Bi (NO 3)3·5H2 O is dissolved in 0.0375mol of ethylene glycol to obtain Bi-EG precursor b, and 0.01mol of Mg (NO 3)2·6H2 O is dissolved in 0.025mol of ethylene glycol to obtain Mg-EG precursor b).
3) Preparation of BMN sols
Slowly adding 0.015mol of Bi-EG precursor solution b and 0.01mol of Mg-EG precursor solution into 0.015mol of Nb-TA-EG precursor solution b dropwise, heating and stirring in a water bath at 80 ℃, continuously heating and stirring for 3 hours after the dripping is finished, obtaining sol b2, and sealing and aging the sol b2 for 56 hours to improve the purity of BZN sol, thus obtaining BZN sol.
(III) preparing BZN/BMN dielectric tuning composite film
Spin-coating BZN sol on a clean and dry P-type Si substrate by using a vacuum spin-coating machine, drying the substrate coated with a wet film on a heating plate at 120 ℃ for 1min, placing the substrate into a tubular furnace for crystallization at 700 ℃ for 1h, obtaining a BZN film on the substrate, and repeating the spin-coating, drying and crystallization processes until the thickness of the BZN film formed on the substrate reaches 100nm.
And coating BMN sol on the BZN film by using a vacuum spin coater, drying the BMN sol on a heating plate at 120 ℃ for 2min, then placing the BMN sol into a tubular furnace at 700 ℃ for crystallization for 1h, obtaining a layer of BMN film on the BZN film, and repeating spin coating, drying and crystallization processes until the thickness of the BMN film formed on the substrate reaches 100nm, thus obtaining the BZN/BMN periodic unit.
Repeating the steps for 3 times by taking BZN/BMN as a periodic unit on a substrate, and then placing the substrate in a tube furnace for homogenizing annealing at 700 ℃ for 2 hours to obtain the BZN/BMN dielectric tuning composite film prepared in the example 2.
Performance testing
A dielectric property tester, model Agilent4294A, manufactured by Agilent corporation; an X-ray diffractometer, model D8 ADVANCE, manufactured by Bruker, germany; SEM scanning electron microscope, model S4800, manufactured by Hitachi Corp;
The BZN/BMN dielectric tuning composite film prepared in example 1 was subjected to a dielectric property test by preparing an Au electrode having a diameter of 600 μm on the surface of the BZN/BMN dielectric tuning composite film by vacuum evaporation. Referring to fig. 3, fig. 3 is a dielectric property diagram of a BZN/BMN dielectric tuning composite film with heterostructure prepared in example 1 of the present invention; as can be seen from the graph, the BZN/BMN dielectric tuning composite film prepared in the example 1 has a dielectric tuning rate of 62% and a dielectric loss of 0.0052 under a bias electric field of 1.5 MV/cm.
The BZN/BMN dielectric tuning composite film with the heterostructure prepared in the example 1 is subjected to a dielectric property test by preparing a Pt electrode with the diameter of 500 mu m on the surface of the BZN/BMN heterostructure through vacuum evaporation, and the dielectric tuning rate of the prepared BZN/BMN dielectric tuning composite film is 60% under a bias electric field of 1.5MV/cm, and the dielectric loss is 0.0055.
Therefore, under a lower bias electric field, the high dielectric tuning rate is obtained, and meanwhile, the low dielectric loss is achieved, so that the dielectric property of the composite film is improved.
In order to prove the excellent performance of the BZN/BMN dielectric tuning composite film with a heterostructure prepared in the embodiment of the invention, performance detection is performed on the BMN multilayer dielectric film prepared in the embodiment 1 of the invention, fig. 4 is an XRD pattern of the BZN/BMN dielectric tuning composite film with a heterostructure in the embodiment 1 of the invention, it can be seen from fig. 4 that an XRD diffraction peak of the BZN/BMN dielectric tuning composite film with a heterostructure has obvious characteristics, and the BZN/BMN composite film (222) prepared on an ITO substrate has high diffraction peak intensity, and the (222) oriented BZN/BMN film is a key to obtain good dielectric performance.
Fig. 5 is an SEM image of a BZN/BMN dielectric tuning composite film having a heterostructure in example 1 of the present invention, and it can be seen from fig. 5 that the film has a uniform growth distribution, a good film crystallization, no occurrence of cracks, and a superior film quality.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be apparent to one skilled in the art that modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some of the technical features thereof; such modifications and substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (7)
1. The BZN/BMN dielectric tuning composite film with the heterostructure is characterized by comprising a substrate and a composite layer which is stacked on the substrate and is repeatedly arranged by taking the BZN/BMN as a periodic unit, wherein the composite layer comprises 2-3 periodic units; the dielectric tuning rate of the multilayer composite dielectric adjustable film is more than or equal to 60% under a bias electric field of 1.5MV/cm, and the dielectric loss is less than or equal to 0.006.
2. A method of preparing a BZN/BMN dielectric tuning composite film having a heterostructure according to claim 1, comprising the steps of:
S1, spin-coating BZN sol on a substrate by using a vacuum spin-coating machine, placing the spin-coated substrate on a heating plate for drying treatment, and then moving the substrate into a tube furnace for crystallization treatment; repeating the spin coating, drying and crystallization processes until the thickness of BZN formed on the substrate reaches 100nm;
s2, spin-coating BMN sol on the BZN film prepared in the step 1, then placing the BZN film on a heating plate for drying treatment, and then moving the BZN film into a tube furnace for crystallization treatment; repeating spin coating, drying and crystallization processes until the thickness of the BMN film formed on the substrate reaches 100nm to obtain a BZN/BMN periodic unit;
S3, repeatedly arranging the BZN/BMN periodic units prepared in the step 2 on the same substrate for 2-3 times, and then placing the BZN/BMN periodic units in a tube furnace for annealing heat treatment to obtain the BZN/BMN dielectric tuning composite film with the heterostructure.
3. The method for preparing the BZN/BMN dielectric tuning composite film having a heterostructure according to claim 2, wherein the preparing method of the BZN sol in step S1 is as follows:
S11 preparation of Nb-TA-EG precursor solution
Placing Nb 2O5 and sulfuric acid with the concentration of 15mol/L in a beaker, uniformly mixing, then placing in an oven, heating for 2-3 h at 200 ℃, then heating to 300 ℃, and preserving heat for 0.5-1 h to obtain a product a; adding deionized water into the product a, heating to 80-90 ℃ in a water bath, and carrying out hydrolysis reaction to obtain Nb (OH) 5 solution; centrifuging and separating the Nb (OH) 5 solution to obtain Nb (OH) 5 precipitate; adding tartaric acid into Nb (OH) 5 precipitate, heating in water bath at 65-85 ℃, stirring until the precipitate is dissolved to obtain a mixed solution a, adding ethylene glycol into the mixed solution a, heating in water bath at 70-80 ℃ and stirring for 10min to carry out complexation reaction to obtain Nb-TA-EG precursor solution;
wherein, the mole ratio of Nb 2O5 to sulfuric acid is 1 (12-18), the mass ratio of the product a to deionized water is 1 (100-150), the mole ratio of Nb (OH) 5 to tartaric acid is 1 (5-8), and the mole ratio of tartaric acid to ethylene glycol is 1.5:1;
S12 preparation of Bi-EG precursor solution
Dissolving Bi (NO 3)3·5H2 O in glycol to obtain Bi-EG precursor solution, wherein,
The mol ratio of Bi (NO 3)3·5H2 O to glycol is 1 (1.5-2.5);
S13 preparation of Zn-EG precursor liquid
Zn (NO 3)2·6H2 O) is dissolved in ethylene glycol to obtain Zn-EG precursor solution, wherein the mol ratio of Zn (NO 3)2·6H2 O) to ethylene glycol is 1 (1.5-2.5);
S14 preparation of BZN sol
Sequentially dripping the Bi-EG precursor solution prepared in the step S12 and the Zn-EG precursor solution prepared in the step S13 into the Nb-TA-EG precursor solution prepared in the step S11, stirring under water bath heating at 70-80 ℃, continuing heating and stirring for 1-3 h after dripping is finished to obtain sol a, and sealing and aging the sol a for 48-56h to obtain BZN sol; wherein the mol ratio of Bi-EG precursor solution to Zn-EG precursor solution to Nb-TA-EG precursor solution is 1.5:1:1.5.
4. The method for preparing a BZN/BMN dielectric tuning composite film having a heterostructure according to claim 2, wherein the method for preparing the BMN sol in step S2 is as follows:
s21 preparation of Nb-TA-EG precursor solution
Placing Nb 2O5 and sulfuric acid with the concentration of 15mol/L in a beaker, uniformly mixing, then placing in an oven, heating for 2-3 h at 200 ℃, then heating to 300 ℃, and preserving heat for 0.5-1 h to obtain a product b; adding deionized water into the product b, heating to 80-90 ℃ in a water bath, and carrying out hydrolysis reaction to obtain Nb (OH) 5 solution; centrifuging and separating the Nb (OH) 5 solution to obtain Nb (OH) 5 precipitate; adding tartaric acid into Nb (OH) 5 precipitate, heating in water bath at 65-85 ℃, stirring until the precipitate is dissolved to obtain a mixed solution b, adding ethylene glycol into the mixed solution b, heating in water bath at 70-80 ℃ and stirring for 10min to carry out complexation reaction to obtain Nb-TA-EG precursor solution;
Wherein, the mole ratio of Nb 2O5 to sulfuric acid is 1 (12-18), the mass ratio of the product b to deionized water is 1 (100-150), the mole ratio of Nb (OH) 5 to tartaric acid is 1 (5-8), and the mole ratio of tartaric acid to ethylene glycol is 1.5:1;
s22 preparation of Bi-EG precursor solution
Dissolving Bi (NO 3)3·5H2 O in glycol to obtain Bi-EG precursor solution, wherein,
The mol ratio of Bi (NO 3)3·5H2 O to glycol is 1 (1.5-2.5);
s23 preparation of Mg-EG precursor liquid
Dissolving Mg (NO 3)2·6H2 O) in ethylene glycol to obtain Mg-EG precursor solution, wherein the mol ratio of Mg (NO 3)2·6H2 O) to ethylene glycol is 1 (1.5-2.5);
S24 preparation of BMN sol
Sequentially dripping the Bi-EG precursor solution prepared in the step S22 and the Mg-EG precursor solution prepared in the step S23 into the Nb-TA-EG precursor solution prepared in the step S21, stirring under water bath heating at 70-80 ℃, continuing heating and stirring for 1-3 h after the dripping is finished to obtain sol b, and sealing and aging the sol b for 48-56h to obtain BMN sol; wherein the mol ratio of Bi-EG precursor liquid to Mg-EG precursor liquid to Nb-TA-EG precursor liquid is 1.5:1:1.5.
5. The method for preparing the BZN/BMN dielectric tuning composite film with the heterostructure according to claim 2, wherein the drying treatment in the steps S1 and S2 is carried out at a treatment temperature of 120-150 ℃ for 1-2min; the crystallization treatment is carried out at 600-700 ℃ for 1h.
6. The method for preparing a BZN/BMN dielectric tuning composite film having a heterostructure according to claim 2, wherein the annealing heat treatment in step S3 is performed at a treatment temperature of 600 to 700 ℃ for a treatment time of 2 hours.
7. The BZN/BMN dielectric tuning composite film having a heterostructure according to claim 1, wherein the substrate is any one of an ITO, P-type Si substrate.
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