CN113121221B - Preparation method of high-dielectric-property calcium copper titanate epitaxial film - Google Patents
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Abstract
The invention provides a preparation method of a high dielectric property calcium copper titanate epitaxial film, which comprises the steps of firstly preparing a solution of calcium, copper and titanium by using a sol-gel method, and then synthesizing calcium copper titanate sol; next, SrTiO is cleaned3(001) Preparing a calcium copper titanate gel film on a substrate by using a dip-coating method; finally, the single-orientation CCTO film is obtained by heat treatment under different atmospheres and temperatures. The invention utilizes the sol-gel method with simple equipment and low cost to prepare SrTiO3(001) The single-orientation calcium copper titanate film is prepared on the substrate to improve the dielectric constant of the film and reduce the dielectric loss, thereby realizing the high dielectric property of the calcium copper titanate film. The method obviously reduces the requirements on film making equipment, has high repeatability, and is suitable for preparing high-quality copper calcium titanate films on substrates with different shapes. The dielectric constant of the film material reaches 104The dielectric loss is as low as 0.01.
Description
Technical Field
The invention relates to the field of functional material research and technical development, in particular to a preparation method of a high-dielectric-property calcium copper titanate epitaxial film.
Background
High quality dielectric films, which determine the level of volumetric efficiency and charge storage capability of passive components, have been one of the important issues in the microelectronics industry and related research fields. Tunnel due to quantum mechanicsThe vertical dimension of the capacitor is limited to around 2 nm by the punch-through effect, and therefore the capacitance must be increased by alternately increasing the dielectric constant. In recent years, calcium copper titanate (CaCu)3Ti4O12CCTO for short) is considered as the material of choice for nanoscale capacitor devices due to its large dielectric constant and no structural phase change at temperatures and frequencies in the range of 100-600K and 1kHz-1 MHz. The dielectric response of a CCTO is closely related to its microstructure and crystallinity. The dielectric constant of CCTO ceramic is 104Of the order of magnitude, while the dielectric constant in the form of a thin film is generally 103Within the range. From the application point of view, CCTO thin films are expected to have high dielectric constant and low dielectric loss, while dielectric loss in CCTO materials is large; increasing the dielectric constant is often accompanied by an increase in losses; therefore, the dielectric loss of the CCTO material is expected to be controlled below 0.05 to achieve the application purpose, and a high-quality CCTO film is guaranteed to obtain high dielectric performance.
At present, the preparation method of the CCTO film mainly comprises a pulse laser deposition method, a magnetron sputtering method, a molecular beam epitaxy method, a sol-gel method and the like; most of the methods need expensive equipment and complex process, which is not beneficial to industrial production; therefore, there is a need for a method of preparing high quality CCTO thin films at low cost. The film prepared by the sol-gel method has the advantages of good uniformity, accurate component control, large film coating area, simple equipment and operation, low cost, no need of high vacuum and the like.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a high-dielectric-property calcium copper titanate epitaxial film, which does not need expensive film-making equipment, and prepares a single-oriented high-dielectric-property CCTO film by using a sol-gel method, thereby laying a good foundation for the preparation and application of high-quality electronic components.
The technical scheme for realizing the invention is as follows:
a preparation method of a high dielectric property calcium copper titanate epitaxial film comprises the steps of firstly preparing a solution of calcium, copper and titanium by a sol-gel method, and then synthesizing CCTO sol; next, SrTiO is cleaned3(001) Substrate, preparing gel on the substrate by dipping and pulling methodA film; finally, the single-orientation CCTO film is obtained by heat treatment under different atmospheres and temperatures.
The preparation method comprises the following specific steps:
(1) preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) Taking propionic acid as a precursor, taking methanol as a solvent to prepare calcium acetate sol, adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, stirring for 2 hours under the heating condition of 40-80 ℃ to obtain a clear transparent solution A, wherein the calcium acetate in the solution: propionic acid: the molar ratio of methanol is 1: (2-4): (10-40).
With copper acetate (Cu (CH)3COO)2) Taking propionic acid as a precursor, taking methanol as a solvent to prepare copper acetate sol, adding copper acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, stirring for 2 hours under the heating condition of 40-90 ℃ to obtain a blue-green transparent solution B, wherein the copper acetate in the solution: propionic acid: the molar ratio of methanol is 1: (3-10): (10-40).
With tetrabutyl titanate (C)16H36O4Ti) as a precursor, methanol as a solvent to prepare titanium sol, adding tetrabutyl titanate into the methanol in a glove box with the humidity of less than 30%, and stirring for 2 hours to obtain a transparent solution C, wherein the tetrabutyl titanate in the sol: the molar ratio of methanol is 1: (10-30).
Mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+：Cu2+：Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1-2 mol/L;
wherein propionic acid may be replaced by methacrylic acid; the methanol can be replaced by ethanol and ethylene glycol monomethyl ether;
(2) preparation of CCTO gel film
The substrate cleaning process comprises the following steps: firstly, soaking the substrate in dilute hydrochloric acid for 1 hour to remove surface stains; then respectively ultrasonically shaking and cleaning in deionized water and alcohol for 10-15 min, and drying for later use;
taking the sol D containing calcium, copper and titanium obtained in the step one as precursor sol, slowly immersing the cleaned and dried substrate into the prepared CCTO sol through a drawing machine, standing for 20-30 s at a drawing speed of 5-10cm/min, drawing the substrate out of the sol liquid surface at a constant speed to prepare a copper calcium titanate gel film, then putting the copper calcium titanate gel film into a drying oven at 200-300 ℃, keeping the temperature for 20-30min, and repeating the steps to reach a proper film thickness;
(3) heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 0.5-1 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: (1-2); heating to 700 deg.C at 2 deg.C/min, maintaining for 1-1.5 hr, introducing nitrogen-oxygen mixed gas B at volume ratio of N2：O2=1: (2-3); then heating to 800-2：O2=1: (3-4); then, the temperature of the mixed gas C was lowered to 500 ℃ at 5 ℃/min while keeping the mixed gas C constant, and then, the gas was stopped to be introduced and cooled to room temperature in the furnace, and the gas pressure in the furnace was maintained at 1atm during the above treatment.
Wherein the nitrogen may be replaced by argon.
The CCTO film with single epitaxial orientation prepared by the invention has the dielectric constant of 104，103Dielectric loss at Hz is as low as 0.01.
The invention has the beneficial effects that: the invention utilizes the sol-gel method with simple equipment and low cost to prepare SrTiO3(001) A high-quality CCTO film with single orientation is prepared on the substrate to improve the dielectric constant of the film and reduce the dielectric loss, thereby realizing the high dielectric property of the CCTO film; the invention obviously reduces the requirements on film making equipment, has high repeatability and is suitable for preparing high-quality CCTO films on substrates with different shapes. The dielectric constant of the film material reaches 104Dielectric loss as low as 0.01; the performance of the film material of the invention is obviously superior to that of the film material prepared by other similar methodsThe CCTO film material has important application value.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is XRD of the CCTO thin film prepared in example 1 of the present invention.
FIG. 2 is an Փ scan of the (103) crystal plane of a CCTO film prepared in example 1 of the present invention.
Fig. 3 is an SEM image of the CCTO thin film prepared in example 1 of the present invention.
Fig. 4 is a graph of the dielectric constant of the CCTO thin film prepared in example 1 of the present invention as a function of frequency.
Fig. 5 and 6 are graphs showing the dielectric loss of the CCTO thin film prepared in example 1 of the present invention as a function of frequency.
Fig. 7 is an XRD pattern of the CCTO thin film prepared in the comparative example.
Fig. 8 is an SEM of a CCTO thin film prepared in the comparative example.
Fig. 9 is a change of dielectric constant with frequency of the CCTO thin film prepared in the comparative example.
Fig. 10 is a graph of dielectric loss versus frequency for CCTO films prepared in comparative examples.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) Taking propionic acid as a precursor, taking methanol as a solvent to prepare calcium acetate sol, adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, stirring for 2 hours under the heating condition of 40 ℃ to dissolve to obtain a clear transparent solution A, wherein the calcium acetate in the solution: propionic acid: the molar ratio of methanol is 1: 2: 10;
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a precursor, taking methanol as a solvent to prepare copper acetate sol, adding copper acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, stirring for 2 hours under the heating condition of 40 ℃ to obtain a blue-green transparent solution B, wherein the copper acetate in the solution: propionic acid: the molar ratio of methanol is 1:3: 10;
with tetrabutyl titanate (C)16H36O4Ti) as a precursor, methanol as a solvent to prepare a titanium solution, adding tetrabutyl titanate into the methanol in a glove box with the humidity of less than 30%, and stirring for 2 hours to obtain a transparent solution C, wherein the content of tetrabutyl titanate in the solution is as follows: the molar ratio of methanol is 1: 10.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 2 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) On the substrate, a CCTO gel film is prepared and then placed into an oven at 200 ℃ for heat preservation and drying for 20 minutes. The above steps were repeated four times.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 0.5 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: 1; then heating to 700 deg.C at 2 deg.C/minThe temperature is 1 hour, the nitrogen-oxygen mixed gas B is introduced in the whole process, and the volume ratio of the gas is N2：O2=1: 2.1; heating to 800 ℃ at the speed of 1 ℃/min, preserving heat for 1 hour, introducing nitrogen-oxygen mixed gas C in the whole process, wherein the volume ratio of the gas is N2：O2=1: 3.2; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
The XRD pattern of the CCTO high dielectric film prepared in example 1 is shown in figure 1, which shows that the CCTO film and the substrate have good epitaxial relationship and show pure c-axis single orientation growth; FIG. 2 is a Փ scan of the crystal plane of (103) CCTO film of example 1, in which the diffraction peaks are uniformly spaced at 90 deg. intervals and have the same intensity, and the full width at half maximum of the diffraction peak is about 0.5 deg., showing that the prepared CCTO film is along SrTiO3Of substrate (00)l) Epitaxially grown in a direction and having good single orientation. An SEM image of the CCTO thin film prepared in example 1 is shown in fig. 3, which indicates that the thin film has a very dense structure and good uniformity of grain size. The graph of the dielectric constant of the CCTO film prepared in example 1 changing with frequency is shown in FIG. 4, and the frequency is 105When the dielectric constant is below Hz, the dielectric constant of the CCTO film is all 104The above; the dielectric loss of the CCTO thin film prepared in example 1 varies with frequency as shown in fig. 5 and 6, from which it can be seen that the dielectric loss of the thin film is small and the minimum dielectric loss is 103A minimum value of 0.01 is reached at Hz.
Example 2
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is prepared by using propionic acid as complexing agent and methanol as solvent. Adding calcium acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring for 2 hr under heating at 80 deg.C to obtain clear transparent solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1: 4: 40.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare a copper acetate solution.Adding copper acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring at 40-90 deg.C for 2 hr to obtain blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 10: 40.
with tetrabutyl titanate (C)16H36O4Ti) is taken as a precursor, and methanol is taken as a solvent to prepare a titanium solution. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in solution: the molar ratio of methanol is 1: 30.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) On the substrate, preparing the copper calcium titanate gel film, then putting the film into an oven with the temperature of 200 ℃ and 300 ℃ for heat preservation for 30min for drying, and repeating the steps for four times.
Step three: heat treatment of CCTO films
The heat treatment process of the calcium copper titanate film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 1 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: 1.8; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1.5 hr, introducing nitrogen-oxygen mixed gas B at volume ratio of N2：O2=1: 2.8 of; heating to 850 deg.C at 1 deg.C/min, maintaining for 2 hr, introducing mixed nitrogen-oxygen gas C at volume ratio of N2：O2=1: 3.7; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Example 3
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is prepared by using propionic acid as complexing agent and methanol as solvent. Adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, and stirring for 2 hours under the heating condition of 60 ℃ to dissolve to obtain a clear and transparent solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1:3: 25.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare copper acetate sol. Adding copper acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, and stirring for 2 hours under the heating condition of 60 ℃ to obtain a blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 6.5: 25.
with tetrabutyl titanate (C)16H36O4Ti) is taken as a precursor, and methanol is taken as a solvent to prepare a titanium solution. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent, and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in solution: the molar ratio of methanol is 1: 20.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1.5 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) And preparing a copper calcium titanate gel film on the substrate, then putting the film into a drying oven at 250 ℃ for heat preservation for 25min for drying, and repeating the steps to obtain the film with proper thickness.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature at 2 deg.C/min to 500 deg.C, maintaining for 0.75 hr, introducing dry nitrogen-oxygen mixed gas A, gasIn a volume ratio of N2：O2=1: 1.5; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1.25 hr, introducing nitrogen-oxygen mixed gas B at a volume ratio of N2：O2=1: 2.5; heating to 830 deg.C at 1 deg.C/min, maintaining for 1.5 hr, introducing nitrogen-oxygen mixed gas C at volume ratio of N2：O2=1: 3.5; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Example 4
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is propionic acid as complexing agent and methanol as solvent to prepare calcium acetate solution. Adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, and stirring for 2 hours under the heating condition of 50 ℃ to dissolve to obtain a clear transparent solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1: 2.5: 20.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare a copper acetate solution. Adding copper acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring at 50 deg.C for 2 hr to obtain blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 5: 20.
with tetrabutyl titanate (C)16H36O4Ti) is taken as a precursor, and methanol is taken as a solvent to prepare a titanium solution. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in solution: the molar ratio of methanol is 1: 15.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of the three metal ions of calcium, copper and titanium in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1.8 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) On the substrate, a CCTO gel film is prepared and then is put into an oven at 220 ℃ to be heated for 25 minutes for drying, and the steps are repeated twice.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min for 0.5-1 hr, introducing dry nitrogen-oxygen mixed gas A at volume ratio of N2：O2=1: 1.2; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1.2 hr, introducing nitrogen-oxygen mixed gas B at a volume ratio of N2：O2=1: 2.2; heating to 810 ℃ at the rate of 1 ℃/min, preserving the heat for 1.2 hours, introducing nitrogen-oxygen mixed gas C in the whole process, wherein the volume ratio of the gas is N2：O2=1: 3.2; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Example 5
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is propionic acid as complexing agent and methanol as solvent to prepare calcium acetate solution. Adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, and stirring for 2 hours under the heating condition of 70 ℃ to dissolve to obtain a clear transparent solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1: 3.5: 30.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare a copper acetate solution. Adding copper acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring at 70 deg.C for 2 hr to obtain blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 7.5: 30.
titanium solution is prepared by taking tetrabutyl titanate as a precursor and methanol as a solvent. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in the sol: the molar ratio of methanol is 1: 25.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1.2 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) Preparing a CCTO gel film on the substrate, then putting the CCTO gel film into an oven with the temperature of 200-300 ℃ for heat preservation for 20-30min for drying, and repeating the steps twice.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 0.8 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: 1.8; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1.3 hr, introducing nitrogen-oxygen mixed gas B at a volume ratio of N2：O2=1: 2.8 of; then heating to 800-2：O2=1: 3.6; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Example 6
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is prepared by using propionic acid as complexing agent and methanol as solvent. Adding calcium acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, stirring at 45 deg.C for 2 hr to dissolveClear solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1: 2.2: 15.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare a copper acetate solution. Adding copper acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring at 55 deg.C for 2 hr to obtain blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 4: 20.
with tetrabutyl titanate (C)16H36O4Ti) is taken as a precursor, and methanol is taken as a solvent to prepare a titanium solution. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in solution: the molar ratio of methanol is 1: 15.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of calcium ions, copper ions and titanium ions in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1.6 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) On the substrate, a CCTO gel film is prepared and then is put into an oven with the temperature of 280 ℃ for heat preservation for 30min for drying. The above steps were repeated twice.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 1 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: 1; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1.5 hr, introducing nitrogen-oxygen mixed gas B at volume ratio of N2：O2=1: 3; heating to 840 ℃ at the rate of 1 ℃/min, preserving heat for 2 hours, introducing nitrogen-oxygen mixed gas C in the whole process, wherein the volume ratio of the gas is N2：O2=1: 4; then holdThe temperature of the mixed gas C is reduced to 500 ℃ at the speed of 5 ℃/minute without changing, then the ventilation is stopped, and the mixed gas C is cooled to the room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Example 7
The method comprises the following steps: preparation of CCTO sols
With calcium acetate (Ca (CH)3COO)2) The precursor is propionic acid as complexing agent and methanol as solvent to prepare calcium acetate solution. Adding calcium acetate into methanol in a glove box with the humidity of less than 30%, dripping propionic acid, and stirring for 2 hours under the heating condition of 70 ℃ to dissolve to obtain a clear and transparent solution A. Calcium acetate in solution: propionic acid: the molar ratio of methanol is 1: 4: 300.
with copper acetate (Cu (CH)3COO)2) Taking propionic acid as a complexing agent and methanol as a solvent to prepare a copper acetate solution. Adding copper acetate into methanol in a glove box with humidity less than 30%, dripping propionic acid, and stirring under heating at 85 deg.C for 2 hr to obtain blue-green transparent solution B. Copper acetate in solution: propionic acid: the molar ratio of methanol is 1: 9: 30.
with tetrabutyl titanate (C)16H36O4Ti) is taken as a precursor, and methanol is taken as a solvent to prepare a titanium solution. Tetrabutyl titanate is added into methanol in a glove box with the humidity of less than 30 percent and stirred for 2 hours to obtain a transparent solution C. Tetrabutyl titanate in solution: the molar ratio of methanol is 1: 30.
mixing the solution A, the solution B and the solution C, uniformly stirring, and aging for 24 hours to obtain sol D; controlling the molar ratio of the three metal ions of calcium, copper and titanium in the solution to be Ca2+:Cu2+:Ti4+1:3:4, and controlling the total concentration of metal ions in the solution to be 1.3 mol/L;
step two: preparation of CCTO gel film
Taking the sol D containing calcium, copper and titanium obtained in the step one as a precursor sol, combining a dipping and pulling method, and then adding the precursor sol into SrTiO3(001) Preparing a CCTO gel film on a substrate, then putting the CCTO gel film into an oven at 260 ℃ for heat preservation and drying for 20 minutes, and repeating the steps for three times.
Step three: heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 500 deg.C at 2 deg.C/min, keeping the temperature for 1 hr, introducing dry nitrogen-oxygen mixed gas A in the whole process, wherein the volume ratio of gas is N2：O2=1: 2; heating to 700 deg.C at a rate of 2 deg.C/min, maintaining for 1 hr, introducing nitrogen-oxygen mixed gas B at a volume ratio of N2：O2=1: 2.6; heating to 850 deg.C at 1 deg.C/min, maintaining for 1.4 hr, introducing mixed nitrogen-oxygen gas C at volume ratio of N2：O2=1: 3.2; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace. During the above treatment, the pressure in the furnace was maintained at 1 atm.
Comparative example
The CCTO film is prepared by a method in a literature report and a sol-gel method, and the structure and the performance of the film are detected.
(1) Preparation of CCTO sols
Calcium acetate, copper nitrate and butyl titanate are used as precursors, deionized water is used as a complexing agent, ethanol is used as a solvent, the pH value of the solution is adjusted to 2-3 by using a mixed solution of hydrochloric acid and sulfuric acid, and the molar ratio of calcium ions, copper ions and titanium ions in the solution is controlled to be Ca2+:Cu2 +:Ti4+Aging at room temperature for 24 hours to prepare calcium copper titanate sol with the total metal ion concentration controlled at 1 mol/L;
(2) preparation of CCTO gel film
Firstly, SrTiO3(001) Soaking the substrate in dilute sulfuric acid to remove surface stains; then ultrasonic vibration cleaning is carried out in acetone and alcohol respectively, and drying is carried out for standby. Preparing a CCTO gel film by using CCTO sol precursor sol and a dip-coating method, then putting the CCTO gel film into a drying oven at 400 ℃ for drying for 5 minutes, and repeating the steps for four times.
(3) Heat treatment of CCTO films
The heat treatment process of the CCTO film comprises the following steps: heating from room temperature to 750 ℃ at the speed of 5 ℃/minute and preserving heat for 1 hour; and then cooling to room temperature along with the furnace, and finishing the treatment process in air.
Fig. 7 is an XRD pattern of the CCTO thin film prepared in the comparative example, from which it can be seen that the thin film is well crystallized, exhibiting polycrystalline growth in different directions. Fig. 8 is an SEM of a CCTO thin film prepared in a comparative example, and it can be seen that some pores are clearly present in the thin film and the grain size is fine. FIG. 9 is a graph showing the change of dielectric constant with frequency of a CCTO thin film prepared in a comparative example, from which it can be seen that the maximum dielectric constant of the thin film is 103. FIG. 10 shows the variation of dielectric loss with frequency for CCTO film prepared by comparative example, the minimum dielectric loss of the film is 1030.04 at Hz.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (4)
1. A preparation method of a high dielectric property calcium copper titanate epitaxial film is characterized by comprising the following steps: firstly, preparing a solution of calcium, copper and titanium by using a sol-gel method, and then synthesizing CCTO sol; secondly, SrTiO is cleaned3(001) A substrate, and a CCTO gel film is prepared on the substrate by using a dip-coating method; finally, heat treatment is carried out under different atmospheres and temperatures to obtain the single-orientation CCTO film, and the specific steps are as follows:
(1) preparation of CCTO sols
Respectively preparing calcium, copper and titanium solutions, uniformly mixing the three solutions, and then aging for 24 hours to obtain precursor sol; wherein calcium acetate is used as a precursor, and propionic acid or methacrylic acid is used as a complexing agent; copper takes copper acetate as a precursor, and propionic acid or methacrylic acid as a complexing agent; titanium is prepared into titanium sol by taking tetrabutyl titanate as a precursor and alcohol as a solvent;
(2) preparation of CCTO gel film
Precursor sol is dipped and pulled on SrTiO3(001) Preparing a CCTO gel film on a substrate, then putting the CCTO gel film into an oven for drying, and repeating the steps to a proper film thickness;
(3) heat treatment of CCTO films
Carrying out heat treatment on the film obtained in the step (2) at different nitrogen-oxygen mixed gases and temperatures to obtain a single-orientation CCTO film;
the preparation steps of the calcium solution in the step (1) are as follows: adding calcium acetate into an alcohol solvent in a glove box with the humidity of less than 30%, dripping a complexing agent, stirring for 2 hours under the heating condition of 40-80 ℃ to dissolve to obtain a clear transparent solution A, wherein the content of calcium acetate in the solution is as follows: complexing agent: the molar ratio of the alcohol solvent is 1: (2-4): (10-40), wherein the alcohol solvent is any one of methanol, ethanol or ethylene glycol monomethyl ether;
the preparation method of the copper solution in the step (1) comprises the following steps: adding copper acetate into an alcohol solvent in a glove box with the humidity of less than 30%, dripping a complexing agent, and stirring for 2 hours under the heating condition of 40-90 ℃ to obtain a blue-green transparent solution B; copper acetate in solution: complexing agent: the molar ratio of the alcohol solvent is 1: (3-10): (10-40), wherein the alcohol solvent is any one of methanol, ethanol or ethylene glycol monomethyl ether;
the preparation method of the titanium solution in the step (1) comprises the following steps: adding tetrabutyl titanate into an alcohol solvent in a glove box with the humidity of less than 30%, stirring for 2h to obtain a transparent solution, wherein the mass ratio of tetrabutyl titanate in the sol: the molar ratio of the alcohol solvent is 1: (10-30), wherein the alcohol solvent is any one of methanol, ethanol or ethylene glycol monomethyl ether;
the heat treatment in the step (3) comprises the following specific steps:
heating from room temperature to 500 deg.c at 2 deg.c/min for 0.5-1 hr, and introducing dry mixed nitrogen-oxygen gas A;
heating from 500 deg.c to 700 deg.c at 2 deg.c/min, maintaining for 1-1.5 hr and introducing mixed nitrogen-oxygen gas B;
thirdly, heating from 700 ℃ at 1 ℃/min to 800-; then keeping the mixed gas C unchanged, cooling to 500 ℃ at the speed of 5 ℃/min, stopping ventilation, and cooling to room temperature along with the furnace;
n in the nitrogen-oxygen mixed gas A2And O2Is 1: (1 to 2)N in the nitrogen-oxygen mixed gas B2And O2Is 1: (2-3) N in the nitrogen-oxygen mixed gas C2And O2Is 1: (3-4).
2. The preparation method according to claim 1, wherein the molar ratio of the three metal ions of calcium, copper and titanium in the precursor sol in step (1) is 1:3:4, and the total concentration of the metal ions in the solution is controlled to be 1-2 mol/L.
3. The preparation method according to claim 2, wherein in the step (2), the cleaned and dried substrate is slowly immersed into the prepared precursor sol through a drawing machine, the precursor sol is kept still for 20 to 30 seconds, the drawing rate is 5 to 10cm/min, the substrate is uniformly drawn out of the surface of the sol, and then the substrate is placed into an oven at 200-300 ℃ for heat preservation for 20 to 30 min.
4. The production method according to any one of claims 1 to 3, characterized in that: the prepared film has single epitaxial orientation and dielectric constant up to 104，103The dielectric loss in Hz is as low as 0.01.
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