CN111876755B - BMN multilayer dielectric film and preparation method thereof - Google Patents

BMN multilayer dielectric film and preparation method thereof Download PDF

Info

Publication number
CN111876755B
CN111876755B CN202010679349.8A CN202010679349A CN111876755B CN 111876755 B CN111876755 B CN 111876755B CN 202010679349 A CN202010679349 A CN 202010679349A CN 111876755 B CN111876755 B CN 111876755B
Authority
CN
China
Prior art keywords
mixing
niobium
citric acid
dielectric film
multilayer dielectric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010679349.8A
Other languages
Chinese (zh)
Other versions
CN111876755A (en
Inventor
石锋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qilu University of Technology
Original Assignee
Qilu University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN202010679349.8A priority Critical patent/CN111876755B/en
Publication of CN111876755A publication Critical patent/CN111876755A/en
Application granted granted Critical
Publication of CN111876755B publication Critical patent/CN111876755B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • 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
    • C23C18/1225—Deposition of multilayers of inorganic material
    • 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
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material

Abstract

The invention provides a BMN multilayer dielectric film and a preparation method thereof, belonging to the technical field of microelectronics. The preparation method provided by the invention comprises the following steps: mixing Nb with2O5Mixing hydrofluoric acid and ammonia water, and carrying out precipitation reaction to obtain niobium hydroxide precipitate; mixing the niobium hydroxide precipitate, citric acid and water, and performing a complex reaction to obtain a niobium-CA solution; mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain a BMN precursor sol; deposition on Pt/Ti/SiO by laser pulse deposition2Depositing MgO on the surface of the/Si substrate to obtain a MgO seed crystal layer; after coating the BMN precursor sol on the surface of the MgO seed crystal layer, carrying out annealing heat treatment under the condition of oxygen to obtain a single-layer film; and repeating the coating and annealing heat treatment processes on the single-layer film to obtain the BMN multilayer dielectric film.

Description

BMN multilayer dielectric film and preparation method thereof
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to a BMN multilayer dielectric film and a preparation method thereof.
Background
With the increasing communication frequency, the wireless communication technology enters the microwave field, and accordingly, higher requirements are put on various communication devices, and agile radio frequency terminals must be designed and prepared to adapt to different microwave communication frequency bands. Adjustable microwave devices such as phase shifters, electrically tunable filters, voltage controlled oscillators, microwave switches, etc. which can be used in these communication devices, have a wide application in microwave communication systems because their frequency agility can improve the operating efficiency of the circuits and their environmental adaptability. Varactors are the core of the construction of various adjustable microwave devices, and currently used adjustable microwave devices are mainly based on the following varactor technologies: semiconductor varactor, MEMS varactor, ferromagnetic material varactor, multilayer dielectric film varactor. The research on the multilayer dielectric film voltage-controlled varactor is mainly based on Bi1.5MgNb1.5O7(BMN) multilayer dielectric thin film material having a cubic pyrochlore structureLow dielectric loss, good thermal stability and large dielectric tuning rate, and is a dielectric tunable material with great development prospect.
The preparation method of the BMN multilayer dielectric thin film material mainly comprises physical deposition and chemical deposition, wherein the chemical deposition is divided into chemical vapor deposition and chemical solution deposition. The most common method in chemical solution deposition is a sol-gel method, in which several metal alkoxides, organic salts or inorganic compounds are dissolved in the same solvent to form a solution, a highly uniformly dispersed complex sol containing metal ions is formed through hydrolysis and complexation, the sol is coated on the surface of a substrate to obtain a wet film, the solvent is volatilized under heating or normal temperature, the wet film forms a gel film, and the gel film is crystallized after high-temperature treatment to obtain a multilayer dielectric film. In the prior art, the expensive raw material niobium ethoxide is mostly used as the source of Nb in the BMN multilayer dielectric film, and the production cost is high.
Disclosure of Invention
In view of the above, the present invention aims to provide a BMN multilayer dielectric thin film and a method for preparing the same, wherein the method for preparing the BMN multilayer dielectric thin film uses an inorganic component Nb2O5As a source of Nb in the BMN multilayer dielectric film, the production cost is low.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a Bi1.5MgNb1.5O7The preparation method of the multilayer dielectric film comprises the following steps:
(1) mixing Nb with2O5Mixing hydrofluoric acid and ammonia water, and carrying out precipitation reaction to obtain Nb (OH)5Precipitating;
(2) reacting said Nb (OH)5Mixing the precipitate, citric acid and water, and performing a complex reaction to obtain a niobium-CA solution;
(3) mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain Bi-Mg-Ni precursor sol;
(4) deposition on Pt (111)/Ti/SiO by laser pulse deposition2Depositing MgO on the surface of the/Si (100) substrate to obtain MgO seed with (111) orientationA seed layer;
(5) coating the Bi-Mg-Ni precursor sol on the surface of the MgO seed crystal layer oriented to (111), and then carrying out annealing heat treatment under the condition of oxygen to obtain a single-layer film;
(6) repeating the coating and annealing heat treatment on the single-layer film to obtain Bi oriented to (222)1.5MgNb1.5O7A multilayer dielectric film;
the temperature of the annealing heat treatment is independently 500-800 ℃, and the time is independently 20-60 min;
the step (4) and the steps (1) to (3) have no time sequence.
Preferably, the Nb2O5And hydrofluoric acid at a molar ratio of 1: (8-15).
Preferably, the temperature of the precipitation reaction is 70-100 ℃, and the pH value is more than 8.
Preferably, the temperature of the complexation reaction in the step (2) is 75-90 ℃ and the time is 1-6 h.
Preferably, the temperature of the complexation reaction in the step (3) is 60-100 ℃, and the time is 1-8 h.
Preferably, the coating mode is spin coating, and the rotation speed of the spin coating is 3600-5400 r/min independently.
Preferably, after the complexation reaction in step (3), the method further comprises mixing the obtained complexation reaction product with ethylene glycol, and performing purification treatment.
The invention also provides Bi prepared by the preparation method in the technical scheme1.5MgNb1.5O7The thickness of the multilayer dielectric film is 300-400 nm, the orientation of crystal grains is (222), and the loss tan delta is less than or equal to 5 multiplied by 10-3@1MHz, Bi in the multilayer dielectric film1.5MgNb1.5O7The average grain size of the crystal grains is 40 to 80 nm.
The preparation method provided by the invention comprises the following steps: (1) mixing Nb with2O5Mixing hydrofluoric acid and ammonia water, and carrying out precipitation reaction to obtain Nb (OH)5Precipitating; (2) reacting said Nb (OH)5Precipitate, citric acid and waterMixing, and carrying out a complex reaction to obtain a niobium-CA solution; (3) mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain Bi-Mg-Ni precursor sol; (4) deposition on Pt (111)/Ti/SiO by laser pulse deposition2Depositing MgO on the surface of a/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111); (5) coating the Bi-Mg-Ni precursor sol on the surface of the MgO seed crystal layer oriented to (111), and then carrying out annealing heat treatment under the condition of oxygen to obtain a single-layer film; (6) repeating the coating and annealing heat treatment on the single-layer film to obtain Bi oriented to (222)1.5MgNb1.5O7A multilayer dielectric film; the temperature of the annealing heat treatment is independently 500-800 ℃, and the time is independently 20-60 min; the step (4) and the steps (1) to (3) have no time sequence. In the present invention, Nb is used as an inorganic component2O5The source of Nb is used for replacing expensive niobium ethoxide to prepare the BMN multilayer dielectric film, so that the production cost can be reduced. And Nb (OH) prepared by precipitation reaction5Precipitating the particles uniformly, adding Nb (OH)5The precipitate, the citric acid and the water are subjected to a complex reaction, so that the particle size of the niobium-CA can be effectively controlled; performing complex reaction on the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and controlling the particle size of the Bi-Mg-Ni precursor sol through temperature and time; the thickness and grain size of the BMN multilayer dielectric film can be effectively controlled by combining the annealing treatment layer by layer. Therefore, the preparation method provided by the invention can solve the problems of high raw material price and high production cost in the prior art.
Drawings
FIG. 1 is a process flow diagram of an example preparation of a BMN precursor sol;
FIG. 2 is a process flow diagram of an example process for preparing a BMN multilayer dielectric film.
Detailed Description
The invention provides a Bi1.5MgNb1.5O7The preparation method of the multilayer dielectric film comprises the following steps:
(1) mixing Nb with2O5Mixing hydrofluoric acid and ammonia water, and precipitatingReaction to obtain Nb (OH)5Precipitating;
(2) reacting said Nb (OH)5Mixing the precipitate, citric acid and water, and performing a complex reaction to obtain a niobium-CA solution;
(3) mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain Bi-Mg-Ni precursor sol;
(4) deposition on Pt (111)/Ti/SiO by laser pulse deposition2Depositing MgO on the surface of a/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111);
5) coating the Bi-Mg-Ni precursor sol on the surface of the MgO seed crystal layer oriented to (111), and then carrying out annealing heat treatment under the condition of oxygen to obtain a single-layer film;
(6) repeating the coating and annealing heat treatment on the single-layer film to obtain Bi oriented to (222)1.5MgNb1.5O7A multilayer dielectric film.
In the present invention, the raw materials used are all commercial products which are conventional in the art, unless otherwise specified.
In the invention, Nb2O5Mixing hydrofluoric acid and ammonia water, and carrying out precipitation reaction to obtain Nb (OH)5And (4) precipitating.
In the present invention, the Nb2O5And hydrofluoric acid are preferably present in a molar ratio of 1: (8-15), more preferably 1: (10-14). In the present invention, the mass concentration of the ammonia water is preferably 20 to 30%. The amount of the ammonia water used is not particularly limited in the present invention, and is determined by the actual Nb content2O5And hydrofluoric acid, adjusting the pH value of the mixture to>And 8, obtaining the product. In the present invention, Nb is used as an inorganic component2O5The source of Nb is used for replacing expensive niobium ethoxide to prepare the BMN multilayer dielectric film, so that the production cost can be reduced.
In the present invention, the Nb2O5The mixing order of hydrofluoric acid and ammonia water is preferably: mixing Nb with2O5Mixing with hydrofluoric acid, dissolving, and mixing with ammonia water. In the present invention, the mixing and dissolving are preferably carried out in a water bath,the temperature of the water bath is preferably 65-100 ℃; the mixing and dissolving time is preferably 1-8 h. The precipitation reaction is preferably carried out while adding ammonia water. In the invention, the temperature of the precipitation reaction is preferably 70-100 ℃, and is further preferably 80-90 ℃; the pH value of the precipitation reaction is preferably>8, and more preferably 10, to ensure complete precipitation.
After the precipitation reaction, the obtained precipitation product is preferably sequentially filtered and washed to obtain Nb (OH)5And (4) precipitating. The invention has no special limitation on the specific operation mode of the suction filtration and the washing, and ensures that the residual F in the precipitated product is removed-And NH4 +And (4) finishing.
Obtaining Nb (OH)5After precipitation, the invention converts the Nb (OH)5And mixing the precipitate, citric acid and water, and performing a complex reaction to obtain a niobium-CA solution.
In the present invention, the Nb (OH)5The order of mixing the precipitate, citric acid and water is preferably: mixing citric acid with water to obtain citric acid aqueous solution, and mixing with Nb (OH)5And mixing the precipitates, and performing a complex reaction. In the present invention, the mixing is preferably performed by magnetic stirring. The magnetic stirring method is not particularly limited, and Nb (OH) can be satisfied5And carrying out a complex reaction on the precipitate and a citric acid aqueous solution. The present invention preferably performs the complexing reaction while mixing. In the invention, the temperature of the complexation reaction is preferably 75-90 ℃, and more preferably 85 ℃; the time of the complex reaction is preferably 1-6 h. In the present invention, the citric acid and Nb (OH)5The molar ratio of the precipitates is preferably 1:2 to 5, and more preferably 1: 3. In the present invention, the molar ratio of citric acid to water is preferably 1:10 to 30. In the present invention, the water is preferably deionized water.
After the complexation reaction is completed, the obtained complexation reaction product is preferably magnetically stirred at 85 ℃ to obtain a niobium-CA solution, and the time of the magnetic stirring is preferably 1-3 h.
After obtaining the niobium-CA solution, mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain the Bi-Mg-Ni precursor sol.
In the present invention, the mixing order of the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water is preferably: mixing citric acid with water to obtain a citric acid aqueous solution, and then mixing the citric acid aqueous solution with a niobium-CA solution, bismuth nitrate and magnesium nitrate to perform a complex reaction. The mixing mode is not particularly limited, and the raw materials can be dissolved and subjected to a complex reaction, such as stirring. The present invention preferably performs the complexing reaction while mixing. In the invention, the temperature of the complex reaction is preferably 60-100 ℃, and more preferably 70-90 ℃; the time of the complex reaction is preferably 1-8 h, and more preferably 120-180 min.
In the present invention, the Nb2O5The mass ratio of bismuth nitrate to magnesium nitrate is preferably Bi1.5MgNb1.5O7The stoichiometric ratio of Bi, Mg and Nb. In the present invention, the molar ratio of the total molar number of niobium-CA, bismuth nitrate and magnesium nitrate to citric acid in the niobium-CA solution is preferably 1:2 to 8, and more preferably 1:4 to 6. In the present invention, the sum of niobium-CA, bismuth nitrate and magnesium nitrate in the niobium-CA solution refers to the molar sum of niobium-CA, bismuth nitrate and magnesium nitrate in the niobium-CA solution. In the present invention, the Nb2O5The purity of the bismuth nitrate and magnesium nitrate is preferably greater than 99.5%. In the present invention, the magnesium nitrate is preferably magnesium nitrate hexahydrate, and the bismuth nitrate is preferably bismuth nitrate pentahydrate. In the present invention, the molar ratio of citric acid to water is preferably 1:10 to 30. In the present invention, the water is preferably deionized water.
Nb (OH) prepared by precipitation reaction5Precipitating the particles uniformly, adding Nb (OH)5The precipitate and the citric acid aqueous solution are subjected to a complex reaction to generate a niobium-CA solution, which replaces niobium ethoxide, so that the cost can be effectively reduced; the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water are subjected to complex reaction, so that the cost of the Bi-Mg-Ni precursor sol can be further reduced.
After the complexing reaction, the invention preferably further comprises mixing the obtained complexing reaction product with ethylene glycol for purification treatment. In the present invention, the volume ratio of the Bi — Mg — Ni precursor sol to ethylene glycol is preferably 1: (2-3). In the invention, the purification treatment temperature is preferably 400-800 ℃, and more preferably 400-500 ℃; the pH value of the purification treatment is preferably not less than 8, and more preferably 10; the time of the purification treatment is preferably 1-3 h. The purification treatment can remove impurities, improve the purity of the Bi-Mg-Ni precursor sol and contribute to reducing the dielectric loss of the BMN multilayer dielectric film.
The invention uses laser pulse deposition method to deposit Pt (111)/Ti/SiO2MgO is deposited on the surface of the/Si (100) substrate to obtain a MgO seed crystal layer with the orientation of (111).
The invention is about the Pt (111)/Ti/SiO2The source of the/Si (100) substrate is not particularly limited, and may be any of those conventionally available commercially or those conventionally prepared in the art. In the present invention, the Pt (111)/Ti/SiO2The dimensions of the/Si (100) substrate are preferably 4cm by 4 cm. The Pt (111)/Ti/SiO is preferably used in the invention2the/Si (100) substrate is subjected to ultrasonic cleaning and then laser pulse deposition. In the present invention, the ultrasonic cleaning is preferably performed in the following manner: ultrasonic cleaning is carried out in deionized water for 10-30 min, acetone for 10-30 min, ethanol for 10-30 min and deionized water for 10-30 min in sequence. The power of the ultrasonic cleaning is not specially limited, and Pt (111)/Ti/SiO can be used2And cleaning the/Si (100) substrate.
After the ultrasonic cleaning, the cleaned Pt (111)/Ti/SiO are preferably cleaned2the/Si (100) substrate is dried, and the drying mode is preferably infrared lamp drying.
In the invention, the pulse energy of the laser pulse deposition is preferably 300-500 mJ, and is further preferably 400 mJ; the pulse frequency of the laser pulse deposition is preferably 3-6 Hz, and further preferably 4 Hz; the pulse time of the laser pulse deposition is preferably 30-60 min, and further preferably 45 min. The invention preferably takes MgO as a target material and utilizes laser pulse to deposit on the Pt (111)/Ti/SiO2Surface deposition of M on/Si (100) substratesG O seed crystal layer. In the present invention, the thickness of the MgO seed crystal layer having the orientation (111) is preferably 20 to 50 nm. In the invention, a laser pulse deposition method is utilized to obtain a (111) -oriented MgO seed crystal layer, and the seed crystal layer can induce the preferential orientation of BMN multilayer dielectric film crystal grains to prepare the (222) -oriented BMN multilayer dielectric film.
After the MgO seed crystal layer oriented to (111) is obtained, the Bi-Mg-Ni precursor sol is coated on the surface of the MgO seed crystal layer oriented to (111), and annealing heat treatment is carried out to obtain a single-layer film.
In the invention, the coating mode is preferably spin coating; in the embodiment of the invention, the spin coating is preferably carried out in a table spin coater, and the rotating speed of the table spin coater is preferably 3600-5400 r/min independently. In the invention, the coating amount of the coating is preferably 0.5-0.8 mL of the Bi-Mg-Ni precursor sol per time.
In the invention, the temperature of the annealing heat treatment is preferably 550-800 ℃, and more preferably 550-700 ℃; the time of the annealing heat treatment is preferably 20 to 60min, and more preferably 30 to 50 min. In the present invention, the annealing heat treatment can remove the organic matter in the Bi-Mg-Ni precursor sol. In the present invention, the annealing heat treatment is preferably performed in oxygen.
The invention anneals the prepared single-layer film layer by layer, each layer of film is heated uniformly, the thickness of the prepared BMN multilayer medium film is controllable and uniform, and the BMN particle size is controllable and uniform.
After obtaining the single-layer film, the invention repeats the coating and annealing heat treatment on the single-layer film to obtain Bi with the orientation of (222)1.5MgNb1.5O7A multilayer dielectric film.
In the present invention, the order of repeating the coating and annealing heat treatments is preferably coating-annealing heat treatment-coating. In the invention, the temperature of the annealing heat treatment is preferably 550-800 ℃ independently, and is further preferably 550-700 ℃ independently; the time of the annealing heat treatment is preferably 20 to 60min independently, and is further preferably 30 to 50min independently. According to the invention, after each annealing treatment, the obtained film is cooled to room temperature and then the coating and annealing heat treatment processes are repeated. The cooling method of the present invention is not particularly limited, and a cooling method known to those skilled in the art may be used. The number of times of the coating and annealing heat treatment process is not particularly limited, and the process is repeated until the thickness of the BMN multilayer dielectric film with the orientation (222) reaches the required thickness.
The invention also provides Bi prepared by the preparation method in the technical scheme1.5MgNb1.5O7The multilayer dielectric film has a thickness of 300-400 nm, a crystal grain orientation of (222), and a loss tan delta less than or equal to 5 multiplied by 10-3@1MHz, said Bi1.5MgNb1.5O7Bi in multilayer dielectric film1.5MgNb1.5O7The average grain size of the crystal grains is 40 to 80 nm.
The following examples are given to illustrate Bi according to the present invention1.5MgNb1.5O7The multilayer dielectric film and the method for preparing the same are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing Pt (111)/Ti/SiO2The method comprises the following steps that/Si (100) substrates are sequentially subjected to ultrasonic cleaning in deionized water for 10min, acetone for 10min, ethanol for 10min and deionized water for 10min, and then dried under an infrared lamp;
according to Bi1.5MgNb1.5O7Weighing 30.8974g of bismuth nitrate pentahydrate, 10.8883g of magnesium nitrate hexahydrate and 8.4656gNb2O5(ii) a The purity of the raw material is calculated according to 99.5 percent;
mixing Nb with2O5Mixing with hydrofluoric acid at a molar ratio of 1:10, dissolving in 85 deg.C water bath for 1 hr, adding ammonia water (25% by mass), and adjusting pH to>8, carrying out a precipitation reaction at the temperature of 85 ℃ to generate Nb (OH)5Precipitating;
reacting Nb (OH)5The precipitate is sequentially filtered and washed to remove F-And NH4+；
Citric acid and water in a molar ratio of 1: 20 to obtain citric acid aqueous solution;
removing impurities from Nb (OH)5Precipitating with the obtained citric acid aqueous solution, Nb (OH)5The molar ratio of the precipitate to the citric acid in the citric acid aqueous solution is 1: 2;
magnetically stirring at 60 ℃ to perform a complex reaction for 1h to obtain a niobium-CA solution;
mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate and the obtained citric acid aqueous solution, and carrying out a complex reaction at 70 ℃ for 3 hours to obtain a complex reaction product; the molar ratio of the sum of niobium-CA, bismuth nitrate and magnesium nitrate to citric acid in the niobium-CA solution is 1: 4;
mixing the complex reaction product and ethylene glycol according to the volume ratio of 1:2, purifying at 400 ℃ under the condition that the pH value is 8, and obtaining pure Bi-Mg-Ni precursor sol after 2 hours;
under the conditions of pulse energy of 400mJ and pulse frequency of 4Hz, after laser pulse deposition for 30min, Pt (111)/Ti/SiO with the size of 4cm multiplied by 4cm2Depositing MgO on the surface of the/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111), wherein the thickness is 30 nm;
spin-coating the purified Bi-Mg-Ni precursor sol on the surface of a (111) -oriented MgO seed crystal layer under the condition of 3600 r/min by spin coating, annealing for 45min at 550 ℃ in an oxygen atmosphere, and removing organic matters to obtain a single-layer film;
repeating the coating and annealing heat treatment processes on the basis of the single-layer film to obtain (222) oriented multilayer BMN multilayer dielectric film with the thickness of 390nm and the loss of 4 multiplied by 10 at 1MHz-3BMN, mean particle size 50 nm.
FIG. 1 is a process flow diagram of preparing a BMN precursor sol according to the example of Nb2O5Mixing and dissolving the Nb-HF solution and hydrofluoric acid under the condition of water bath to obtain an Nb-HF solution; adding ammonia water into the obtained Nb-HF solution, neutralizing with HF, and carrying out precipitation reaction to generate Nb (OH)5Precipitating; the produced Nb (OH)5Dissolving the precipitate in citric acid aqueous solution to obtain Nb-CA solution; mixing the obtained Nb-CA solution, bismuth nitrate and magnesium nitrate and a citric acid aqueous solution to carry out a complex reaction to obtain a complex reaction product; and mixing the complex reaction product with ethylene glycol, controlling the temperature and the pH value, and purifying to obtain the BMN precursor sol.
FIG. 2 is a flow chart of a process for preparing a BMN multi-layer dielectric film according to an embodiment of the present invention using laser pulse deposition on Pt (111)/Ti/SiO2Depositing MgO on the surface of a/Si (100) substrate to obtain a MgO seed crystal layer, spin-coating a purified BMN precursor sol on the surface of the MgO seed crystal layer, carrying out annealing heat treatment under the condition of oxygen, and repeating the spin-coating-annealing heat treatment process, namely carrying out annealing treatment layer by layer to obtain the BMN multilayer dielectric film.
Example 2
Mixing Pt (111)/Ti/SiO2The method comprises the following steps that/Si (100) substrates are sequentially subjected to ultrasonic cleaning in deionized water for 10min, acetone for 10min, ethanol for 10min and deionized water for 10min, and then dried under an infrared lamp;
according to Bi1.5MgNb1.5O715.4487gBi (NiO) was weighed in the stoichiometric ratio of (2)3)3·5H2O，5.4441gMg(NiO3)2·6H2O and 4.2328gNb2O5；
Mixing Nb with2O5Mixing with hydrofluoric acid at a molar ratio of 1:15, dissolving in 70 deg.C water bath for 1 hr, adding ammonia (28% by mass), and adjusting pH to>8, carrying out a precipitation reaction at 70 ℃ to generate Nb (OH)5Precipitating;
reacting Nb (OH)5The precipitate is sequentially filtered and washed to remove F-And NH4+；
Citric acid and water in a molar ratio of 1:10 to obtain a citric acid aqueous solution;
removing impurities from Nb (OH)5Precipitating with the obtained citric acid aqueous solution, Nb (OH)5Precipitating with citric acid waterThe molar ratio of citric acid in the solution is 2: 5;
magnetically stirring at 75 ℃ to perform a complex reaction for 1h to obtain a niobium-CA solution;
mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate and the obtained citric acid aqueous solution, and carrying out a complex reaction at 70 ℃ for 3 hours to obtain a complex reaction product; the molar ratio of the sum of niobium-CA, bismuth nitrate and magnesium nitrate to citric acid in the niobium-CA solution is 1: 5;
mixing the complex reaction product and ethylene glycol according to the volume ratio of 1:2.5, purifying at 450 ℃ under the condition that the pH value is 9, and obtaining Bi-Mg-Ni precursor sol after 2.5 h;
depositing Pt (111)/Ti/SiO with 4cm × 4cm size after laser pulse deposition for 40min under the conditions of pulse energy of 350mJ and pulse frequency of 5Hz2Depositing MgO on the surface of the/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111), wherein the thickness is 25 nm;
spin-coating the purified Bi-Mg-Ni precursor sol on the surface of a (111) -oriented MgO seed crystal layer under the condition of 5400 r/min by spin coating, annealing and heat treating for 30min at 600 ℃ in an oxygen atmosphere, and removing organic matters to obtain a single-layer film;
repeating the coating and annealing heat treatment processes on the basis of the single-layer film to obtain (222) oriented multilayer BMN multilayer dielectric film with the thickness of 360nm and the loss of 4.5 multiplied by 10 at 1MHz-3BMN, average particle size 60 nm.
Example 3
Mixing Pt (111)/Ti/SiO2The method comprises the following steps that/Si (100) substrates are sequentially subjected to ultrasonic cleaning in deionized water for 10min, acetone for 10min, ethanol for 10min and deionized water for 10min, and then dried under an infrared lamp;
according to Bi1.5MgNb1.5O712.3589gBi (NiO) was weighed in the stoichiometric ratio of (2)3)3·5H2O，4.3553gMg(NiO3)2·6H2O and 3.3862gNb2O5；
Mixing Nb with2O5The hydrofluoric acid is mixed with the hydrofluoric acid according to the molar ratio of 1:10Mixing and dissolving at 80 deg.C in water bath for 1 hr, adding ammonia water (30 wt%), and adjusting pH to>8, carrying out a precipitation reaction at the temperature of 80 ℃ to generate Nb (OH)5Precipitating;
reacting Nb (OH)5The precipitate is sequentially filtered and washed to remove F-And NH4+；
Citric acid and water in a molar ratio of 1:10 to obtain a citric acid aqueous solution;
removing impurities from Nb (OH)5Precipitating with the obtained citric acid aqueous solution, Nb (OH)5The molar ratio of the precipitate to the citric acid in the citric acid aqueous solution is 1: 3;
magnetically stirring at 80 ℃ to perform a complex reaction for 1h to obtain a niobium-CA solution;
mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate and the obtained citric acid aqueous solution, and carrying out a complex reaction at 70 ℃ for 3 hours to obtain a complex reaction product; the molar ratio of the sum of niobium-CA, bismuth nitrate and magnesium nitrate to citric acid in the niobium-CA solution is 1: 6;
mixing the complex reaction product and ethylene glycol according to the volume ratio of 1:3, purifying at 500 ℃ under the condition that the pH value is 9, and obtaining Bi-Mg-Ni precursor sol after 3 hours;
under the conditions of pulse energy of 400mJ and pulse frequency of 3Hz, after laser pulse deposition for 30min, Pt (111)/Ti/SiO with the size of 4cm multiplied by 4cm2Depositing MgO on the surface of the/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111), wherein the thickness is 20 nm;
spin-coating the purified Bi-Mg-Ni precursor sol on the surface of a (111) -oriented MgO seed crystal layer under the condition of 3600 r/min by spin coating, annealing and heat treating for 30min at 650 ℃ in an oxygen atmosphere, and removing organic matters to obtain a single-layer film;
repeating the coating and annealing heat treatment processes on the basis of the single-layer film to obtain (222) oriented multilayer BMN multilayer dielectric film with the thickness of 350nm and the loss of 4.5 multiplied by 10 at 1MHz-3BMN, average particle size 70 nm.
Example 4
Mixing Pt (111)/Ti/SiO2The method comprises the following steps that/Si (100) substrates are sequentially subjected to ultrasonic cleaning in deionized water for 10min, acetone for 10min, ethanol for 10min and deionized water for 10min, and then dried under an infrared lamp;
according to Bi1.5MgNb1.5O712.3589gBi (NiO) was weighed in the stoichiometric ratio of (2)3)3·5H2O，4.3553gMg(NiO3)2·6H2O and 3.3862gNb2O5；
Mixing Nb with2O5Mixing with hydrofluoric acid at a molar ratio of 1:10, dissolving in 80 deg.C water bath for 1 hr, adding ammonia water (30% by mass), and adjusting pH to>8, carrying out a precipitation reaction at the temperature of 80 ℃ to generate Nb (OH)5Precipitating;
reacting Nb (OH)5The precipitate is sequentially filtered and washed to remove F-And NH4+；
Citric acid and water in a molar ratio of 1:10 to obtain a citric acid aqueous solution;
removing impurities from Nb (OH)5Precipitating with the obtained citric acid aqueous solution, Nb (OH)5The molar ratio of the precipitate to the citric acid in the citric acid aqueous solution is 2: 3;
magnetically stirring at 80 ℃ to perform a complex reaction for 1h to obtain a niobium-CA solution;
mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate and the obtained citric acid aqueous solution, and carrying out a complex reaction at 70 ℃ for 3 hours to obtain a complex reaction product; the molar ratio of the sum of the niobium-CA, the bismuth nitrate and the magnesium nitrate in the niobium-CA solution to the citric acid is 1: 6;
under the conditions of pulse energy of 400mJ and pulse frequency of 3Hz, after laser pulse deposition for 30min, Pt (111)/Ti/SiO with the size of 4cm multiplied by 4cm2Depositing MgO on the surface of the/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111), wherein the thickness is 20 nm;
spin-coating a Bi-Mg-Ni precursor sol on the surface of a (111) -oriented MgO seed crystal layer under the condition of 3600 r/min by spin coating, annealing for 30min at 650 ℃ in an oxygen atmosphere, and removing organic matters to obtain a single-layer film;
repeating the coating and annealing heat treatment processes on the basis of the single-layer film to obtain (222) oriented multilayer BMN multilayer dielectric film with the thickness of 380nm and the loss of 5 x 10 at 1MHz-3BMN, average particle size 80 nm.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (6)

1. Bi1.5MgNb1.5O7The preparation method of the multilayer dielectric film comprises the following steps:
(1) mixing Nb with2O5Mixing hydrofluoric acid and ammonia water, and carrying out precipitation reaction to obtain Nb (OH)5Precipitating;
(2) reacting said Nb (OH)5Mixing the precipitate, citric acid and water, and performing a complex reaction to obtain a niobium-CA solution;
(3) mixing the niobium-CA solution, bismuth nitrate, magnesium nitrate, citric acid and water, and carrying out a complex reaction to obtain Bi-Mg-Ni precursor sol;
(4) deposition on Pt (111)/Ti/SiO by laser pulse deposition2Depositing MgO on the surface of a/Si (100) substrate to obtain an MgO seed crystal layer with the orientation of (111);
(5) coating the Bi-Mg-Ni precursor sol on the surface of the MgO seed crystal layer oriented to (111), and then carrying out annealing heat treatment under the condition of oxygen to obtain a single-layer film;
(6) repeating the coating and annealing heat treatment on the single-layer film to obtain Bi oriented to (222)1.5MgNb1.5O7A multilayer dielectric film;
the temperature of the complexation reaction in the step (3) is 70-90 ℃, and the time is 120-180 min;
the pulse energy of the laser pulse deposition is 400mJ, the pulse frequency is 4Hz, and the pulse time is 45 min;
the thickness of the MgO seed crystal layer is 20-50 nm;
bi in the multilayer dielectric film1.5MgNb1.5O7The average grain diameter of the crystal grains is 40-80 nm;
the temperature of the annealing heat treatment is independently 500-800 ℃, and the time is independently 20-60 min;
citric acid and Nb (OH) in step (2)5The molar ratio of the precipitate is 1: 2-5;
in the step (3), the molar ratio of the total molar number of the niobium-CA, the bismuth nitrate and the magnesium nitrate in the niobium-CA solution to the citric acid is 1: 2-8;
after the complexation reaction in the step (3), mixing the obtained complexation reaction product with ethylene glycol, and purifying;
the step (4) and the steps (1) to (3) have no time sequence.
2. The method of manufacturing according to claim 1, wherein the Nb is2O5And hydrofluoric acid at a molar ratio of 1: (8-15).
3. The method according to claim 1, wherein the precipitation reaction is carried out at a temperature of 70 to 100 ℃ and a pH of > 8.
4. The preparation method according to claim 1, wherein the temperature of the complexation reaction in step (2) is 75-90 ℃ and the time is 1-6 h.
5. The preparation method according to claim 1, wherein the coating is spin coating, and the spin coating speed is 3600-5400 rpm.
6. Bi produced by the production method according to any one of claims 1 to 51.5MgNb1.5O7The thickness of the multilayer dielectric film is 300-400 nm, the orientation of crystal grains is (222), and the loss tan delta is less than or equal to 5 multiplied by 10-3@1MHzIn the multilayer dielectric film, Bi1.5MgNb1.5O7The average grain size of the crystal grains is 40 to 80 nm.
CN202010679349.8A 2020-07-15 2020-07-15 BMN multilayer dielectric film and preparation method thereof Active CN111876755B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010679349.8A CN111876755B (en) 2020-07-15 2020-07-15 BMN multilayer dielectric film and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010679349.8A CN111876755B (en) 2020-07-15 2020-07-15 BMN multilayer dielectric film and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111876755A CN111876755A (en) 2020-11-03
CN111876755B true CN111876755B (en) 2022-02-18

Family

ID=73151263

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010679349.8A Active CN111876755B (en) 2020-07-15 2020-07-15 BMN multilayer dielectric film and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111876755B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113402275B (en) * 2021-08-12 2022-09-02 齐鲁工业大学 Multilayer BMN dielectric thin film material and preparation method thereof
CN117486608A (en) * 2023-11-16 2024-02-02 齐鲁工业大学(山东省科学院) BMZN film material with adjustable dielectric and low dielectric loss, and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002743A (en) * 2001-06-20 2003-01-08 Ngk Spark Plug Co Ltd Dielectric ceramic composition
CN102249307A (en) * 2011-05-06 2011-11-23 天津大学 Preparation method of Bi1.5MgNb1.5O7 (BMN) dielectric film
CN102795891A (en) * 2012-08-23 2012-11-28 同济大学 Preparation method for barium strontium titanate film taking MgO as buffer layer
CN103397303A (en) * 2013-07-31 2013-11-20 天津大学 Preparation method of voltage-controlled varactor made of transparent bismuth magnesium niobate thin films
CN104073790A (en) * 2014-06-26 2014-10-01 天津大学 Preparation method of oriented BMN film
CN105420672A (en) * 2015-11-25 2016-03-23 盐城工学院 Method for preparing Bi1.5MgNb1.5O7 (BMN) thin film
CN105734541A (en) * 2016-04-05 2016-07-06 新乡学院 Method for preparing high-temperature superconducting film transition layer on aluminum oxide crystalline substrate

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003002743A (en) * 2001-06-20 2003-01-08 Ngk Spark Plug Co Ltd Dielectric ceramic composition
CN102249307A (en) * 2011-05-06 2011-11-23 天津大学 Preparation method of Bi1.5MgNb1.5O7 (BMN) dielectric film
CN102795891A (en) * 2012-08-23 2012-11-28 同济大学 Preparation method for barium strontium titanate film taking MgO as buffer layer
CN103397303A (en) * 2013-07-31 2013-11-20 天津大学 Preparation method of voltage-controlled varactor made of transparent bismuth magnesium niobate thin films
CN104073790A (en) * 2014-06-26 2014-10-01 天津大学 Preparation method of oriented BMN film
CN105420672A (en) * 2015-11-25 2016-03-23 盐城工学院 Method for preparing Bi1.5MgNb1.5O7 (BMN) thin film
CN105734541A (en) * 2016-04-05 2016-07-06 新乡学院 Method for preparing high-temperature superconducting film transition layer on aluminum oxide crystalline substrate

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Influence of interface structure on microstructure and dielectric properties of bismuth magnesium niobate thin films;Helei Dong et al.;《Ceramics International》;20190211;第45卷(第8期);第10056-10062页 *
蓝宝石衬底上外延生长MgO薄膜过程中的应力研究;刘莹莹等;《全国薄膜技术学术研讨会论文摘要集》;20090818;第95页 *

Also Published As

Publication number Publication date
CN111876755A (en) 2020-11-03

Similar Documents

Publication Publication Date Title
CN111876755B (en) BMN multilayer dielectric film and preparation method thereof
CN101224907B (en) Method for preparing nano lanthanum-strontium-manganese oxide
CN106803601A (en) A kind of preparation method of solid electrolyte lithium lanthanum titanium oxide film
Choi et al. Sol-gel-derived magnesium oxide precursor for thin-film fabrication
CN111876756B (en) BMN multilayer dielectric film and preparation method thereof
CN111348683B (en) Method for synthesizing high-crystalline tin niobate by solid phase method
US10232335B2 (en) Method for producing β-eucryptite fine particles
CN113121221B (en) Preparation method of high-dielectric-property calcium copper titanate epitaxial film
CN101804967B (en) Low temperature controllable preparation method of double metal oxide semiconductor nanocrystalline sol
CN113402275B (en) Multilayer BMN dielectric thin film material and preparation method thereof
WO2012093658A1 (en) Method for producing conductive zinc oxide film
CN108558401B (en) Preparation of Bi by sol-gel method2/3Cu2Ta2Ti2O12Method for producing ceramic powder
CN103204551A (en) Controllable preparation method of micron-order Fe3O4
CN105669197A (en) Method for preparing SBN (Sr0.5Ba0.5Nb2O6) nano-powder with improved sol-gel method
US6086957A (en) Method of producing solution-derived metal oxide thin films
CN107601917B (en) Preparation method of titanium dioxide-based self-cleaning glass
KR20130056016A (en) Method of prepararing sodium vanadate nanowire
CN115323361B (en) Nanometer flake VO that can change phase 2 Method for producing film
CN101186329A (en) Method for preparing micron-level ZnO of octahedral structure
CN1843934A (en) Method for preparing zinc oxide film
JP2003326637A (en) Manganic acid nano-sheet ultrathin film and manufacturing method therefor
CN100341817C (en) Preparation method of barium strontium titanate film material
Tsai et al. The preparation of ITO films via a chemical solution deposition process
Paik et al. Ba titanate and barium/strontium titanate thin films from hydroxide precursors: Preparation and ferroelectric behavior
CN111647848A (en) Preparation of large-area CsPbBr by magnetron sputtering3Method and application of photoelectric film

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant