CN103273704A - Composite film with high energy storage density, and preparation method thereof - Google Patents
Composite film with high energy storage density, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a composite film with a high energy storage density, and a preparation method thereof. The bottom layer and the upper layer of the composite film both are a lead-zirconate-based film layer, and the interface layer is a barium-titanate-based bicomponent-solid-solution film layer. The preparation method comprises: preparing a lead-zirconate-based precursor solution of the raw material of the lead-zirconate-based film layer, and a barium-titanate-based bicomponent-solid-solution precursor solution of the raw material of the barium-titanate-based bicomponent-solid-solution film layer; spin coating the prepared lead-zirconate-based precursor solution on a Pt(III)/Ti/SiO2/Si substrate to get a wet film, and baking, hydrolysis treating and annealing the film in oxygen atmosphere to get the lead-zirconate-based film layer; successively preparing the barium-titanate-based bicomponent-solid-solution film layer and another lead-zirconate-based film layer on the prepared lead-zirconate-based film layer in accordance with the preparation process of the lead-zirconate-based film layer; and thus the composite film is obtained. The composite film is high in energy storage density, good in polarization fatigue resistant performance, simple and practicable in the preparation and low in cost, and industrial production of the composite film can be realized.
Description
Technical field
The present invention relates to a kind of laminated film with high energy storage density and preparation method thereof, belong to the energy storage material technical field.
Background technology
Energy-storage capacitor occupies very big proportion as the key element of high power pulsed ion beams power supply in entire equipment, be very important critical component.The capacitor of development high energy storage density is for increasing pulse power power, reducing weight and volume important effect is arranged.Compare with ferroelectric material with the common dielectric material, the dielectric constant of antiferroelectric materials not only increase with the increase of extra electric field and also antiferroelectric-uprush during ferroelectric phase transition, thereby has a higher theoretical energy storage density, be particularly suitable for making the high power pulsed ion beams energy-storage capacitor, caused researcher's concern in recent years.
Computing formula J=∫ EdP=ε according to energy storage density
0(J is energy storage density to ∫ E ε (E) dE, and E is extra electric field intensity, and P is polarization intensity, ε
0Be permittivity of vacuum, ε (E) is relative dielectric constant) as can be known, the anti-electric field breakdown strengths or the polarization intensity that improve antiferroelectric materials all can effectively improve its energy storage density.Therefore, high anti-electric field breakdown strengths, high dielectric constant values and the big polarization intensity energy storage density that is very beneficial for improving antiferroelectric materials.
Lead zirconates is a kind of typical perovskite antiferroelectric materials.Compare other antiferroelectric materials, it has higher anti-electric field breakdown strengths and better fatigue durability, is the most promising high power pulsed ion beams power supply ferroelectric energy-accumulating medium material of novel trans.But at present the anti-ferroelectric thin film used energy storage density of the lead zirconates of Experiment Preparation is lower, can not satisfy practical application.There is the researcher to report, thereby the polarization intensity that improves the lead zirconates based antiferroelectric film by the method for mixing, introduce cushion or control thin film alignment has improved its energy storage density to a certain extent, although obtained certain improvement, it improves effect and also has very big gap from practical application.Therefore, the energy storage density that further improves the lead zirconates based antiferroelectric film becomes and realizes that the lead zirconates based antiferroelectric film is in the top priority of the application of high power pulsed ion beams power supply.
Summary of the invention
The present invention is directed to the low problem that can not satisfy the application requirements of high power pulsed ion beams power supply of antiferroelectric materials energy storage density in the prior art, purpose is to be to provide a kind of laminated film with high energy storage density and anti-polarization fatigue.
Another object of the present invention is the method that is to provide the above-mentioned laminated film of preparation that a kind of technology is simple, cost is low.
The invention provides a kind of laminated film with high energy storage density, this laminated film bottom and upper strata are lead zirconates base film layer; The intermediate layer is barium phthalate base binary solid solution thin layer; Described lead zirconates base film layer thickness is 50～300nm, and barium phthalate base binary solid solution thin layer thickness is 50～300nm.
Described lead zirconates base film layer is PbZrO
3Thin layer, or one or more doping PbZrO among La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti
3Thin layer.
Described barium phthalate base binary solid solution thin layer is (1-x) Bi (Mg, Ti) O
3– xBaTiO
3Thin layer, (1-x) Bi (Zn, Ti) O
3– xBaTiO
3Thin layer or (1-x) BiScO
3– xBaTiO
3Thin layer, wherein, 0.5≤x＜1.
The present invention also provides a kind of preparation method of laminated film as mentioned above, and this method is that lead zirconates base film layer raw material is mixed with solution, leaves standstill after 3～7 days to filter, and making concentration is the zirconic acid lead base precursor solution of 0.1～0.3mol/L; Barium phthalate base binary solid solution thin layer raw material is mixed with solution, leaves standstill after 3～7 days and filter, making concentration is the barium phthalate base binary solid solution precursor solution of 0.05～0.2mol/L; Be spin-coated on Pt (111)/Ti/SiO with the zirconic acid lead base precursor solution that makes by whirl coating
2Obtain wet film on the/Si substrate, again with the wet film that obtains under oxygen atmosphere through overbaking, pyrolysis, annealing in process, make lead zirconates base film layer; Preparation process according to above-mentioned lead zirconates base film layer prepares barium phthalate base binary solid solution thin layer and lead zirconates base film layer successively on the lead zirconates base film layer that has made again, namely.
Described annealing temperature is 600～800 ° of C, and the time is 2～5min.
Described pyrolysis temperature is 350～450 ° of C, and the time is 3～8min.
Described baking temperature is 150～200 ° of C, and the time is 2～5min.
Described whirl coating spin coating is to carry out at sol evenning machine, earlier even glue 5～12s under 300～800rpm rotating speed; Under 3000～5000rpm rotating speed, spare glue 20～50s again.
The heating rate of described baking, pyrolysis, annealing in process is 10～20 ° of C/s.
Organic salt (as acetate salt, normal propyl alcohol salt) or nitro salt that described lead zirconates base film layer raw material is Pb and Zr; One or more organic salt (as acetate salt, normal propyl alcohol salt) or nitro salt among the perhaps organic salt of Pb and Zr (as acetate salt, normal propyl alcohol salt) or nitro salt, and La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti.
Described barium phthalate base binary solid solution thin layer raw material is selected from organic salt (as acetate salt) or the nitro salt of Ba, Bi, Mg, Zn, Sc, and butyl titanate.
Described zirconic acid lead base precursor solution is PbZrO
3Solution, or one or more doping PbZrO among La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti
3Solution; Described barium phthalate base binary solid solution precursor solution is (1-x) Bi (Mg, Ti) O
3– xBaTiO
3Solution, (1-x) Bi (Zn, Ti) O
3– xBaTiO
3Solution or (1-x) BiScO
3– xBaTiO
3Solution, wherein 0.5≤x＜1.
In the said method in the zirconic acid lead base precursor solution solvent be EGME; Solvent in the barium phthalate base binary solid solution precursor solution is EGME and glacial acetic acid (volume ratio is about 1:1).
The number of repetition of the whirl coating spin coating of the thickness of the lead zirconates base film layer that makes in the said method by changing zirconic acid lead base precursor solution, baking, pyrolysis, annealing in process process is controlled; The thickness of the lead zirconates base film layer that makes in the repetitive process each time can be controlled by the concentration, viscosity, the rotating speed of whirl coating spin coating, the time that change zirconic acid lead base precursor solution; The barium phthalate base binary solid solution thin layer that makes is adopted its thickness of control that uses the same method.
Preparation method of composite film of the present invention may further comprise the steps:
Step a:
The preparation of zirconic acid lead base precursor solution: by stoichiometric proportion lead zirconates base film layer raw material is dissolved in EGME, is mixed with solution; After leaving standstill 3～7 days, filter and obtain the zirconic acid lead base precursor solution that concentration is 0.1～0.3mol/L;
Organic salt (as acetate salt, normal propyl alcohol salt) or nitro salt that described lead zirconates base film layer raw material is Pb and Zr; One or more organic salt (as acetate salt, normal propyl alcohol salt) or nitro salt among the perhaps organic salt of Pb and Zr (as acetate salt, normal propyl alcohol salt) or nitro salt, and La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti; Described zirconic acid lead base precursor solution is PbZrO
3Solution, or one or more doping PbZrO among La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti
3Solution;
Step b:
The preparation of barium phthalate base binary solid solution precursor solution: barium phthalate base binary solid solution thin layer raw material is dissolved in EGME and glacial acetic acid by stoichiometric proportion, be mixed with solution, after leaving standstill 3～7 days, filter and obtain the barium phthalate base binary solid solution precursor solution that concentration is 0.05～0.2mol/L;
Organic salt (as acetate salt) or nitro salt and butyl titanate that described barium phthalate base binary solid solution thin layer raw material is Ba, Bi, Mg, Zn, Sc; Described barium phthalate base binary solid solution precursor solution is (1-x) Bi (Mg, Ti) O
3– xBaTiO
3Solution, (1-x) Bi (Zn, Ti) O
3– xBaTiO
3Solution or (1-x) BiScO
3– xBaTiO
3Solution;
Step c:
The preparation of laminated film: the zirconic acid lead base precursor solution that step a is obtained carries out whirl coating at sol evenning machine, earlier even glue 5～12s under 300～800rpm rotating speed; Even glue 20～50s under 3000～5000rpm rotating speed is coated in Pt (111)/Ti/SiO equably again
2Obtain wet film on the/Si substrate; The wet film that obtains is placed in the quick anneal oven, under oxygen atmosphere, earlier at 150～200 ° of C baking 2～5min; Pyrolysis 3～8min under 350～450 ° of C again; Again at 600～800 ° of C, annealing in process 2～5min; Obtain individual layer lead zirconates base film layer; Repeat above-mentioned whirl coating spin coating, baking, pyrolysis, annealing process, up to obtaining desired thickness (50～300nm) lead zirconates base film layer; The heating rate of described baking, pyrolysis, annealing in process is 10～20 ° of C/s;
Steps d:
The barium phthalate base binary solid solution precursor solution that on the lead zirconates base film layer that has obtained step b is obtained is prepared into barium phthalate base binary solid solution thin layer according to the lead zirconates base film layer preparation process of step c; Process according to step c prepares lead zirconates base film layer on the barium phthalate base binary solid solution thin layer that makes again.
Laminated film with high energy storage density of the present invention can be widely used in the high power pulsed ion beams energy-storage capacitor.
Know-why of the present invention and innovative point: the present invention is by the research of inventor's repetition test, the result shows that laminated film that the barium phthalate base binary solid solution ferroelectric thin film layer that adopts the good lead zirconates base film layer of two-layer antiferroelectric performance up and down, centre to be mingled with big dielectric constant, high anti-electric field breakdown strengths is made has the performance of high energy storage density and anti-polarization fatigue; This laminated film combines Prepared by Sol Gel Method film and annealing process successively in preparation process, make laminated film have higher polarization intensity and better interfacial characteristics, thereby further improved its energy storage density and anti-polarization fatigue performance.
Beneficial effect of the present invention:
(1) laminated film of the present invention had both had high energy storage density, had good polarization fatigue performance again, experimental results show that: laminated film energy storage density of the present invention is up to 28.4J/cm
3, under the electric field of 500kv/cm through 1.45 * 10
8After the inferior upset, polarization intensity only reduces 3.19%, but the energy storage material of high power pulsed ion beams capacitor is made in extensive use;
(2) preparation method of the present invention is simple, cost is low, but suitability for industrialized production.
Description of drawings
[Fig. 1] is the PbZrO of embodiment 1
3/ 0.12Bi (Mg, Ti) O
3– 0.88BaTiO
3/ PbZrO
3The X-ray diffractogram of laminated film.
[Fig. 2] is the PbZrO of embodiment 1
3/ 0.12Bi (Mg, Ti) O
3– 0.88BaTiO
3/ PbZrO
3The ESEM surface topography map of laminated film.
[Fig. 3] is the Pb of embodiment 2
0.95Sr
0.05ZrO
3/ 0.3Bi (Mg, Ti) O
3– 0.7BaTiO
3/ Pb
0.95Sr
0.05ZrO
3The ESEM surface topography map of laminated film.
[Fig. 4] is the Pb of embodiment 3
0.92La
0.08(Zr
0.95Ti
0.05) O
3/ 0.5Bi (Mg, Ti) O
3– 0.5BaTiO
3/ Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3The ESEM surface topography map of laminated film.
[Fig. 5] is the laminated film of embodiment 1 and the single PbZrO of Comparative Examples
3The polarization intensity of film, energy storage density and extra electric field concern comparison diagram: (a) be the graph of a relation of polarization intensity and extra electric field; (b) be the graph of a relation of energy storage density and extra electric field.
[Fig. 6] is the PbZrO of embodiment 1
3/ 0.12Bi (Mg, Ti) O
3– 0.88BaTiO
3/ PbZrO
3The single PbZrO of laminated film and Comparative Examples
3The polarization fatigue comparison diagram of film.
The specific embodiment
Following example is intended to illustrate the present invention, rather than limitation of the invention further.
Embodiment 1
This experiment is preparation PbZrO
3/ (1-x) Bi (Mg, Ti) O
3– xBaTiO
3/ PbZrO
3Laminated film (x=0.88), concrete steps are as follows:
(1) preparation PbZrO
3Solution: taking by weighing mol ratio respectively is three water lead acetate 0.8345g and the zirconium-n-propylate 0.6551g of 1.1:1, adds EGME then and makes solvent, and the solution that will contain three water lead acetates naturally cools to normal temperature after 105 ° of C magnetic stir 30min, obtain solution A; The solution that will contain zirconium-n-propylate magnetic at normal temperatures is stirred to dissolving fully, obtains solution B; Limit agitating solution B, the limit dropwise is added to solution A in the solution B, and adds 3 acetylacetone,2,4-pentanediones, and the spent glycol methyl ether dilutes it then, and continues to stir 2h, obtains the solution 10mL of 0.2mol/L, leaves standstill to filter after 4 days to obtain faint yellow transparent PbZrO
3Precursor solution.
(2) preparation 0.12Bi (Mg, Ti) O
3– 0.88BaTiO
3Solution: take by weighing bismuth acetate (excessive 10%) 0.1529g and be dissolved in the 4mL EGME, after 60 ° of C stir 1min, dropwise add the 4mL glacial acetic acid, and continue to stir 20min to dissolving fully, obtain solution C; Take by weighing butyl titanate 0.9598g and be dissolved in EGME, Dropwise 5 drips acetylacetone,2,4-pentanedione, and stirring at normal temperature obtains solution D to dissolving fully; Solution C and solution D are mixed, stir and obtain solution E; Take by weighing barium acetate 0.6743g and four water acetic acid magnesium 0.0386g are dissolved in glacial acetic acid, stir 10min in 105 ° of C, obtain solution F; Solution E and solution F are mixed, and the spent glycol methyl ether dilutes it, and continues to stir 2h, obtains the solution 30mL of 0.1mol/L, leaves standstill to filter after 3 days to obtain rufous 0.12Bi (Mg
1/2, Ti
1/2) O
3– 0.88BaTiO
3Precursor solution.
(3) preparation PbZrO
3/ 0.12Bi (Mg, Ti) O
3– 0.88BaTiO
3/ PbZrO
3Laminated film: whirl coating on sol evenning machine, low rotation speed are 400rpm, and the even glue time is 8s, and the high speed rotating speed is 4000rpm, and the even glue time is 40s, directly at Pt (111)/Ti/SiO
2Deposit PbZrO on the/Si substrate
3Wet film; Wet film is placed in the quick anneal oven, under oxygen atmosphere, at 180 ° of C baking 3min, 400 ° of C pyrolysis 5min, 700 ° of C annealing 3min; Repeat above-mentioned whirl coating spin coating, baking, pyrolysis, annealing process, obtain the PbZrO that thickness is about the crystallization of 180nm
3Rete; The PbZrO that is obtaining again
3Prepare 0.12Bi (Mg, Ti) O that thickness is about 180nm on the film successively
3– 0.88BaTiO
3Film and thickness are about the PbZrO of 180nm
3Film, technical process and with preparation bottom PbZrO
3Film is identical.
This experiment is preparation Pb
0.95Sr
0.05ZrO
3/ (1-x) Bi (Mg, Ti) O
3– xBaTiO
3/ Pb
0.95Sr
0.05ZrO
3Laminated film (x=0.7), concrete steps are as follows:
(1) preparation Pb
0.95Sr
0.05ZrO
3Solution: press Pb
0.95Sr
0.05ZrO
3The mol ratio of Pb and Sr takes by weighing three water lead acetates (excessive 10%) 0.7928g respectively and strontium acetate 0.0206g is dissolved in the EGME in the formula, naturally cools to normal temperature after 105 ° of C magnetic stir 30min, obtains solution A; Mol ratio according to Pb, Sr and Zr is 0.95:0.05:1, and weighing zirconium-n-propylate 0.6551g puts into another container, adds EGME and makes solvent, and magnetic is stirred to dissolving fully at normal temperatures, obtains solution B; Limit agitating solution B, the limit dropwise is added to solution A in the solution B, and adds 3 acetylacetone,2,4-pentanediones, and the spent glycol methyl ether dilutes it then, and continues to stir 2h, obtains the solution 20mL of 0.1mol/L, leaves standstill to filter after 3 days to obtain faint yellow transparent Pb
0.95Sr
0.05ZrO
3Precursor solution.
(2) preparation 0.3Bi (Mg, Ti) O
3– 0.7BaTiO
3Solution: take by weighing bismuth acetate (excessive 10%) 0.1274g and be dissolved in the 3mL EGME, after 60 ° of C stir 1min, dropwise add the 3mL glacial acetic acid, and continue to stir 20min to dissolving fully, obtain solution C; Take by weighing butyl titanate 0.2893g and be dissolved in EGME, Dropwise 5 drips acetylacetone,2,4-pentanedione, and stirring at normal temperature obtains solution D to dissolving fully; Solution C and solution D are mixed, stir and obtain solution E; Take by weighing barium acetate 0.1788g and four water acetic acid magnesium 0.0322g are dissolved in glacial acetic acid, stir 10min in 105 ° of C, obtain solution F; Solution E and solution F are mixed, and the spent glycol methyl ether dilutes it, and continues to stir 2h, obtains the solution 20mL of 0.05mol/L, leaves standstill to filter after 3 days to obtain rufous 0.3Bi (Mg
1/2, Ti
1/2) O
3– 0.7BaTiO
3Precursor solution.
(3) preparation Pb
0.95Sr
0.05ZrO
3/ 0.3Bi (Mg, Ti) O
3– 0.7BaTiO
3/ Pb
0.95Sr
0.05ZrO
3Laminated film: whirl coating on sol evenning machine, low rotation speed are 300rpm, and the even glue time is 5s, and the high speed rotating speed is 3000rpm, and the even glue time is 30s, directly at Pt (111)/Ti/SiO
2Deposit Pb on the/Si substrate
0.95Sr
0.05ZrO
3Wet film; Wet film is placed in the quick anneal oven, under oxygen atmosphere, at 150 ° of C baking 3min, 350 ° of C pyrolysis 3min, 650 ° of C annealing 3min; Repeat above-mentioned whirl coating spin coating, baking, pyrolysis, annealing process, obtain the Pb that thickness is about the crystallization of 150nm
0.95Sr
0.05ZrO
3Rete; The Pb that is obtaining again
0.95Sr
0.05ZrO
3Prepare 0.3Bi (Mg, Ti) O that thickness is about 150nm on the film successively
3– 0.7BaTiO
3Film and thickness are about the Pb of 150nm
0.95Sr
0.05ZrO
3Film, technical process and preparation bottom Pb
0.95Sr
0.05ZrO
3Film is identical.
This Experiment Preparation Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3/ (1-x) Bi (Mg, Ti) O
3– xBaTiO
3/ Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Laminated film (x=0.5), concrete steps are as follows:
(1) preparation Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Solution: press Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3The mol ratio of Pb and La takes by weighing three water lead acetates (excessive 10%) 1.1516g respectively and lanthanum acetate 0.0758g is dissolved in the EGME in the formula, naturally cools to normal temperature after 105 ° of C magnetic stir 30min, obtains solution A; Mol ratio according to Pb, La, Zr and Ti is 0.92:0.08:0.95:0.05, and weighing zirconium-n-propylate 0.9336g and butyl titanate 0.0511g put into another container, adds EGME and makes solvent, and magnetic is stirred to dissolving fully at normal temperatures, obtains solution B; Limit agitating solution B, the limit dropwise is added to solution A in the solution B, and adds 3 acetylacetone,2,4-pentanediones, and the spent glycol methyl ether dilutes it then, and continues to stir 2h, obtains the solution 10mL of 0.3mol/L, leaves standstill to filter after 7 days to obtain faint yellow transparent Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Precursor solution.
(2) preparation 0.5Bi (Mg, Ti) O
3– 0.5BaTiO
3Solution: take by weighing bismuth acetate (excessive 10%) 0.6371g and be dissolved in the 3mL EGME, after 60 ° of C stir 1min, dropwise add the 3mL glacial acetic acid, and continue to stir 20min to dissolving fully, obtain solution C; Take by weighing butyl titanate 0.7658g and be dissolved in EGME, Dropwise 5 drips acetylacetone,2,4-pentanedione, and stirring at normal temperature obtains solution D to dissolving fully; Solution C and solution D are mixed, stir and obtain solution E; Take by weighing barium acetate 0.3831g and four water acetic acid magnesium 0.1608g are dissolved in glacial acetic acid, stir 10min in 105 ° of C, obtain solution F; Solution E and solution F are mixed, and the spent glycol methyl ether dilutes it, and continues to stir 2h, obtains the solution 20mL of 0.15mol/L, leaves standstill to filter after 5 days to obtain rufous 0.5Bi (Mg
1/2, Ti
1/2) O
3– 0.5BaTiO
3Precursor solution.
(3) preparation Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3/ 0.5Bi (Mg, Ti) O
3– 0.5BaTiO
3/ Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Laminated film: whirl coating on sol evenning machine, low rotation speed are 800rpm, and the even glue time is 10s, and the high speed rotating speed is 4500rpm, and the even glue time is 40s, directly at Pt (111)/Ti/SiO
2Deposit Pb on the/Si substrate
0.92La
0.08(Zr
0.95Ti
0.05) O
3Wet film; Wet film is placed in the quick anneal oven, under oxygen atmosphere, at 200 ° of C baking 5min, 420 ° of C pyrolysis 5min, 750 ° of C annealing 5min; Repeat above-mentioned whirl coating spin coating, baking, pyrolysis, annealing process, obtain the Pb that thickness is about the crystallization of 200nm
0.92La
0.08(Zr
0.95Ti
0.05) O
3Rete; The Pb that is obtaining again
0.92La
0.08(Zr
0.95Ti
0.05) O
3Prepare 0.5Bi (Mg, Ti) O that thickness is about 200nm on the film successively
3– 0.5BaTiO
3Film and thickness are about 200nm's and Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Film, technical process and preparation bottom Pb
0.92La
0.08(Zr
0.95Ti
0.05) O
3Film is identical.
Embodiment 4
This Experiment Preparation Pb
0.95Ba
0.05ZrO
3/ (1-x) Bi (Zn, Ti) O
3– xBaTiO
3/ Pb
0.95Ba
0.05ZrO
3Laminated film (x=0.8), concrete steps are as follows:
(1) preparation Pb
0.95Ba
0.05ZrO
3Solution: press Pb
0.95Ba
0.05ZrO
3The mol ratio of Pb and Ba takes by weighing three water lead acetates (excessive 10%) 0.7928g respectively and barium acetate 0.0255g is dissolved in the EGME in the formula, naturally cools to normal temperature after 105 ° of C magnetic stir 30min, obtains solution A; Mol ratio according to Pb, Ba and Zr is 0.95:0.05:1, and weighing zirconium-n-propylate 0.6551g puts into another container, adds EGME and makes solvent, and magnetic is stirred to dissolving fully at normal temperatures, obtains solution B; Limit agitating solution B, the limit dropwise is added to solution A in the solution B, and adds 3 acetylacetone,2,4-pentanediones, and the spent glycol methyl ether dilutes it then, and continues to stir 2h, obtains the solution 10mL of 0.2mol/L, leaves standstill to filter after 5 days to obtain faint yellow transparent Pb
0.95Ba
0.05ZrO
3Precursor solution.
(2) preparation 0.2Bi (Zn, Ti) O
3– 0.8BaTiO
3Solution: take by weighing bismuth acetate (excessive 10%) 0.2549g and be dissolved in the 4mL EGME, after 60 ° of C stir 1min, dropwise add the 4mL glacial acetic acid, and continue to stir 20min to dissolving fully, obtain solution C; Take by weighing butyl titanate 0.9189g and be dissolved in EGME, Dropwise 5 drips acetylacetone,2,4-pentanedione, and stirring at normal temperature obtains solution D to dissolving fully; Solution C and solution D are mixed, stir and obtain solution E; Take by weighing barium acetate 0.613g and zinc acetate 0.055g is dissolved in glacial acetic acid, stir 10min in 105 ° of C, obtain solution F; Solution E and solution F are mixed, and the spent glycol methyl ether dilutes it, and stirs 2h, obtains the solution 30mL of 0.1mol/L, leaves standstill to filter after 5 days to obtain rufous 0.2Bi (Zn, Ti) O
3– 0.8BaTiO
3Precursor solution.
(3) preparation Pb
0.95Ba
0.05ZrO
3/ 0.2Bi (Zn, Ti) O
3– 0.8BaTiO
3/ Pb
0.95Ba
0.05ZrO
3Laminated film, this step obtains Pb at last with the step among the embodiment 1 (3)
0.95Ba
0.05ZrO
3/ 0.2Bi (Zn, Ti) O
3– 0.8BaTiO
3/ Pb
0.95Ba
0.05ZrO
3Laminated film; The thickness of three-layer thin-film is about 180nm.
Embodiment 5
This Experiment Preparation Pb
0.97Eu
0.03ZrO
3/ (1-x) BiScO
3– xBaTiO
3/ Pb
0.97Eu
0.03ZrO
3Laminated film (x=0.6), concrete steps are as follows:
(1) preparation Pb
0.97Eu
0.03ZrO
3Solution: press Pb
0.97Eu
0.03ZrO
3The mol ratio of Pb and Eu takes by weighing three water lead acetates (excessive 10%) 0.8095g respectively and five water europium nitrate 0.0257g are dissolved in the EGME in the formula, naturally cools to normal temperature after 105 ° of C magnetic stir 30min, obtains solution A; Mol ratio according to Pb, Eu and Zr is 0.97:0.03:1, and weighing zirconium-n-propylate 0.6551g puts into another container, adds EGME and makes solvent, and magnetic is stirred to dissolving fully at normal temperatures, obtains solution B; Limit agitating solution B, the limit dropwise is added to solution A in the solution B, and adds 3 acetylacetone,2,4-pentanediones, and the spent glycol methyl ether dilutes it then, and continues to stir 2h, obtains the solution 10mL of 0.2mol/L, leaves standstill to filter after 5 days to obtain faint yellow transparent Pb
0.97Eu
0.03ZrO
3Precursor solution.
(2) preparation 0.4BiScO
3– 0.6BaTiO
3Solution: take by weighing bismuth acetate (excessive 10%) 0.5097g and be dissolved in the 4mL EGME, after 60 ° of C stir 1min, dropwise add the 4mL glacial acetic acid, and continue to stir 20min to dissolving fully, obtain solution C; Take by weighing butyl titanate 0.6126g and be dissolved in EGME, Dropwise 5 drips acetylacetone,2,4-pentanedione, and stirring at normal temperature obtains solution D to dissolving fully; Solution C and solution D are mixed, stir and obtain solution E; Take by weighing barium acetate 0.4598g and acetic acid scandium 0.2665g is dissolved in glacial acetic acid, stir 10min in 105 ° of C, obtain solution F; Solution E and solution F are mixed, and the spent glycol methyl ether dilutes it, and stirs 2h, obtains the solution 30mL of 0.1mol/L, leaves standstill to filter after 5 days to obtain rufous 0.4BiScO
3-0.6BaTiO
3Precursor solution.
(3) preparation Pb
0.97Eu
0.03ZrO
3/ 0.4BiScO
3– 0.6BaTiO
3/ Pb
0.97Eu
0.03ZrO
3Laminated film, this step obtains Pb at last with the step among the embodiment 1 (3)
0.97Eu
0.03ZrO
3/ 0.4BiScO
3– 0.6BaTiO
3/ Pb
0.97Eu
0.03ZrO
3Laminated film; The thickness of three-layer thin-film is about 180nm.
Comparative Examples
This experiment is the PbZrO of preparation one-component
3Film, concrete steps are as follows:
(1) preparation PbZrO
3Solution, this step is with the step among the embodiment 1 (1).
(2) preparation PbZrO
3Film: whirl coating on sol evenning machine, low rotation speed are 400rpm, and the even glue time is 8s, and the high speed rotating speed is 4000rpm, and the even glue time is 40s, directly at Pt (111)/Ti/SiO
2Deposit PbZrO on the/Si substrate
3Wet film.Wet film is placed in the quick anneal oven, at 180 ° of C baking 3min, 400 ° of C pyrolysis 5min, 700 ° of C annealing 3min.Repeat above-mentioned whirl coating spin coating, baking, pyrolytic process several times, obtain the PbZrO that thickness is 540nm
3Film.
As seen from Figure 1, laminated film of the present invention comprises each layer film X ray characteristic diffraction peak separately; By Fig. 2,3,4 as can be seen, laminated film surfacing of the present invention, densification, no hole crackle; Single PbZrO as seen from Figure 5 and in the Comparative Examples
3Film is compared, and the energy storage density of laminated film of the present invention is significantly improved, wherein, and single PbZrO in the Comparative Examples
3The ceiling capacity storage density of film is 13.5J/cm
3, the ceiling capacity storage density of laminated film of the present invention is 28.4J/cm
3In addition, single PbZrO in laminated film of the present invention and the Comparative Examples
3Film is compared, and its polarization fatigue performance is also obviously improved.As seen from Figure 6, single PbZrO in the Comparative Examples
3Film under the electric field of 500kv/cm through 1.45 * 10
8After the inferior upset, its polarization intensity reduces 25%, and the polarization intensity of laminated film of the present invention only reduces 3.19%.
More than show: laminated film of the present invention not only has high energy storage density but also have good fatigue behaviour, can use in the high power pulsed ion beams energy-storage capacitor.
Claims (10)
1. one kind has laminated film of high energy storage density and preparation method thereof, it is characterized in that, bottom and upper strata are lead zirconates base film layer; The intermediate layer is barium phthalate base binary solid solution thin layer; Described lead zirconates base film layer thickness is 50～300nm, and barium phthalate base binary solid solution thin layer thickness is 50～300nm.
2. laminated film as claimed in claim 1 is characterized in that, described lead zirconates base film layer is PbZrO
3Thin layer, or one or more doping PbZrO among La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti
3Thin layer.
3. laminated film as claimed in claim 1 is characterized in that, described barium phthalate base binary solid solution thin layer is (1-x) Bi (Mg, Ti) O
3– xBaTiO
3Thin layer, (1-x) Bi (Zn, Ti) O
3– xBaTiO
3Thin layer or (1-x) BiScO
3– xBaTiO
3Thin layer, wherein, 0.5≤x＜1.
4. the preparation method as claim 1～3 laminated film as described in each is characterized in that, lead zirconates base film layer raw material is mixed with solution, leaves standstill after 3～7 days and filters, and obtaining concentration is the zirconic acid lead base precursor solution of 0.1～0.3mol/L; Barium phthalate base binary solid solution thin layer raw material is mixed with solution, leaves standstill after 3～7 days and filter, making concentration is the barium phthalate base binary solid solution precursor solution of 0.05～0.2mol/L; Be spin-coated on Pt (111)/Ti/SiO with the zirconic acid lead base precursor solution that makes by whirl coating
2Obtain wet film on the/Si substrate, again with the wet film that obtains under oxygen atmosphere through overbaking, pyrolysis, annealing in process, make lead zirconates base film layer; Preparation process according to above-mentioned lead zirconates base film layer prepares barium phthalate base binary solid solution thin layer and lead zirconates base film layer successively on the lead zirconates base film layer that has made again, namely.
5. preparation method as claimed in claim 4 is characterized in that, described annealing temperature is 600～800 ° of C, and the time is 2～5min.
6. preparation method as claimed in claim 4 is characterized in that, described pyrolysis temperature is 350～450 ° of C, and the time is 3～8min.
7. preparation method as claimed in claim 4 is characterized in that, described baking temperature is 150～200 ° of C, and the time is 2～5min.
8. preparation method as claimed in claim 4 is characterized in that, the heating rate of described baking, pyrolysis, annealing in process is 10～20 ° of C/s.
9. preparation method as claimed in claim 4 is characterized in that, described whirl coating spin coating is to carry out at sol evenning machine, earlier even glue 5～12s under 300～800rpm rotating speed; Under 3000～5000rpm rotating speed, spare glue 20～50s again.
10. preparation method as claimed in claim 4 is characterized in that, described zirconic acid lead base precursor solution is PbZrO
3Solution, or one or more doping PbZrO among La, Mn, Ba, Sr, Nb, Eu, Pr, Sn, the Ti
3Solution; Described barium phthalate base binary solid solution precursor solution is (1-x) Bi (Mg, Ti) O
3– xBaTiO
3Solution, (1-x) Bi (Zn, Ti) O
3– xBaTiO
3Solution or (1-x) BiScO
3– xBaTiO
3Solution, wherein 0.5≤x＜1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220168A (en) * | 2016-07-07 | 2016-12-14 | 内蒙古科技大学 | The antiferroelectric membrane material negative electricity card refrigerating method of a kind of raising |
| CN110746185A (en) * | 2019-09-30 | 2020-02-04 | 中国科学院上海硅酸盐研究所 | Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof |
| CN111825447A (en) * | 2020-07-06 | 2020-10-27 | 武汉理工大学 | Barium titanate-based dielectric film with high energy storage density and preparation method thereof |
| CN113493346A (en) * | 2021-06-17 | 2021-10-12 | 哈尔滨理工大学 | Energy storage thin film with high breakdown field strength and preparation method thereof |
| CN114671680A (en) * | 2022-03-25 | 2022-06-28 | 南京卡巴卡电子科技有限公司 | Bismuth scandate-barium titanate-based core-shell structure ferroelectric film and preparation method thereof |
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| CN1342783A (en) * | 2001-09-14 | 2002-04-03 | 中国科学院上海硅酸盐研究所 | Process for preparing functional gradient film of lead zirconate titanate ceramics |
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| CN1342783A (en) * | 2001-09-14 | 2002-04-03 | 中国科学院上海硅酸盐研究所 | Process for preparing functional gradient film of lead zirconate titanate ceramics |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106220168A (en) * | 2016-07-07 | 2016-12-14 | 内蒙古科技大学 | The antiferroelectric membrane material negative electricity card refrigerating method of a kind of raising |
| CN110746185A (en) * | 2019-09-30 | 2020-02-04 | 中国科学院上海硅酸盐研究所 | Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof |
| CN110746185B (en) * | 2019-09-30 | 2021-11-02 | 中国科学院上海硅酸盐研究所 | Titanium oxide nanowire array/lead lanthanum zirconate antiferroelectric composite film material and preparation method thereof |
| CN111825447A (en) * | 2020-07-06 | 2020-10-27 | 武汉理工大学 | Barium titanate-based dielectric film with high energy storage density and preparation method thereof |
| CN113493346A (en) * | 2021-06-17 | 2021-10-12 | 哈尔滨理工大学 | Energy storage thin film with high breakdown field strength and preparation method thereof |
| CN114671680A (en) * | 2022-03-25 | 2022-06-28 | 南京卡巴卡电子科技有限公司 | Bismuth scandate-barium titanate-based core-shell structure ferroelectric film and preparation method thereof |
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