CN104072129A - B-position equivalent zirconium doped sodium bismuth titanate film - Google Patents
B-position equivalent zirconium doped sodium bismuth titanate film Download PDFInfo
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Abstract
The invention discloses a B-position equivalent zirconium doped sodium bismuth titanate film, and belongs to the field of functional film. The film is represented by a chemical general formula Na0.5Bi0.5(Ti(1-x)Zrx)O3, wherein x is mole mixing amount of zirconium ion, and x is not less than 0.01 and not more than 0.04. A film is spin-coated on a glass substrate plated with a bottom electrode in combination of a chemical solution method and a layer-by-layer annealing process, the thermal treatment is performed at low temperature of 500-550 DEG.C in nitrogen atmosphere to prepare a lead-free film with good electric insulativity, ferroelectricity and dielectricity. The film can be used for preparing a nonvolatile ferroelectric memory, developing a multifunctional material and apparatus with ferroelectric, piezoelectric, photoelectric, photorefraction and non-linear optical properties.
Description
Technical field
The present invention relates to a kind of B position zirconium ion doping with bismuth titanate sodium of equal value film, belong to perovskite structure environmental harmony type microelectronics field of new.
Background technology
Bismuth-sodium titanate (Na
0.5bi
0.5tiO
3) material is as the Relaxation Ferroelectrics of a kind of A position complex perovskite structure, have relatively high Curie temperature (
t c=320 ℃), stronger ferroelectricity (remnant polarization under room temperature
p r=38 μ C/cm
2).Yet in high temperature crystallization process, Na
0.5bi
0.5tiO
3in film, sodium, bismuth ion volatilization seriously, not only make to prepare single Perovskite Phase and become difficult, and make a large amount of defects of the inner generation of film, and leakage current increases.These problems cause Na
0.5bi
0.5tiO
3film is also being deposited certain gap compared with plumbum-based material aspect ferroelectric, piezoelectric property.For above-mentioned situation, on the one hand, we reduce the volatilization of A position sodium, bismuth ion as far as possible by low-temperature annealing, thereby reduce the quantity in oxygen room, improve electrical insulating property.On the other hand, at the Na of perovskite structure
0.5bi
0.5tiO
3in film, polarization comes from the (ionic radius: 0.605) with respect to the skew of central position of titanium ion in Ti-O hexahedron, mix the zirconium ion that ionic radius is larger (ionic radius: 0.72), lattice distortion certainly will make the polarization of film increase, and improves ferroelectricity.And it is feasible that this thinking has been proved to be in the research of lead zirconat-titanato material, B position zirconium ion replaces the mobility that titanium ion can strengthen electricdomain.
For film, good ferroelectric, dielectricity, and optical characteristics is very crucial in aspect application such as ferroelectric condenser, solar cell and intelligent glass for it.The glass substrate that is coated with the stannic oxide (FTO) of tin indium oxide (ITO), fluorine doping and zinc oxide (AZO) transparency conducting layer of aluminium doping has high conductivity, stability, and has good tack with film.Therefore, the employing that these are coated with bottom electrode glass substrate, is conducive to Na
0.5bi
0.5tiO
3based film material is ferroelectric, piezoelectricity, photoelectricity, light is sold off and the making full use of of linear optics feature, for the exploitation of multifunctional material and device provides possibility.
Summary of the invention
The present invention is directed to existing Na
0.5bi
0.5tiO
3the problem that thin-film electro insulativity and ferroelectricity are poor, provides a kind of B position Na that zirconium ion of equal value adulterates
0.5bi
0.5tiO
3film, i.e. Na
0.5bi
0.5(Ti
1-xzr
x) O
3film.Prepared Na
0.5bi
0.5(Ti
1-xzr
x) O
3film has the advantages such as electrical insulating property is good, residual polarization is high, dielectricity is stable.
The present invention passes through the precursor solution of preparation stable and uniform, spin coating plated film in the glass substrate that is coated with bottom electrode (ITO, FTO, AZO), and thermal treatment under the low temperature of 500 ~ 550 ℃ in nitrogen atmosphere, prepares the good Na of crystallinity
0.5bi
0.5(Ti
1-xzr
x) O
3film, its concrete technical scheme is as follows.
The Na of B of the present invention position zirconium ion doping of equal value
0.5bi
0.5tiO
3film, is characterized in that: chemical general formula is Na
0.5bi
0.5(Ti
1-xzr
x) O
3, wherein, mole volume that x is zirconium ion, and 0.01≤x≤0.04.
The substrate material that above-mentioned film adopts is for being coated with the glass substrate of bottom electrode (ITO, FTO, AZO).
The thickness of above-mentioned film is approximately 300 ~ 600nm.
The preparation method of the bismuth-sodium titanate film of zirconium doping of the present invention, is characterized in that comprising following steps:
(1), the preparation of precursor solution
1. take sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate, acetic acid zirconium or zirconium nitrate, tetra-n-butyl titanate or titanium isopropylate is raw material, according to Na
0.5bi
0.5(Ti
1-xzr
x) O
3stoichiometric ratio, accurately weigh various raw materials, wherein, sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate are slightly excessive, separately according to empirical value, weigh poly(oxyethylene glycol) 400 ~ 10000, standby;
2. measure tetra-n-butyl titanate or titanium isopropylate in beaker, methyl ethyl diketone is dropwise added, and be placed on magnetic stirring apparatus and under room temperature, stir the chelating that completes titanium for 3 ~ 6 hours, be defined as solution 1;
3. take acetic acid zirconium or zirconium nitrate and be placed in beaker, add a certain amount of ethylene glycol monomethyl ether and at the temperature of 40 ~ 80 ℃, be stirred to solution clarification, add again a certain amount of methyl ethyl diketone and be stirred to and mix, add after cooling in solution 1, at room temperature stir 0.5 ~ 2 hour, be defined as solution 2;
4. sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate are added in Glacial acetic acid, at the temperature of 40 ~ 80 ℃, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3;
5. polyoxyethylene glycol is added in ethylene glycol monomethyl ether, at the temperature of 40 ~ 80 ℃, heated and stirred is extremely dissolved, and is cooled to room temperature, is defined as solution 4;
6. solution 3,4 is added in solution 2 successively, at room temperature stir 8 ~ 12 hours, be made into the precursor solution that concentration is 0.1 ~ 0.5mol/L;
(2), the preparation of thin-film material: film is prepared in employing spin-coating method combination layer by layer annealing process
1. adopt spin-coating method that precursor solution is deposited on substrate.Under nitrogen atmosphere, film is heat-treated, treating processes is: first 280 ~ 320 ℃ of insulations 6 ~ 10 minutes, then 400 ~ 460 ℃ of insulations 4 ~ 6 minutes, then 500 ~ 550 ℃ of annealing 8 ~ 12 minutes;
2. repeat above-mentioned process in 1., until film thickness is approximately 300 ~ 600nm, obtain.
In above-mentioned preparation method, in order to make up the volatilization of sodium under high temperature, bismuth ion, SODIUMNITRATE or SODIUMNITRATE and bismuth acetate or Bismuth trinitrate be excessive 1 ~ 2mol%, 1 ~ 5mol% respectively.
In above-mentioned preparation method, in step (1), tetra-n-butyl titanate 2. or the volume ratio of titanium isopropylate and methyl ethyl diketone solution are 1:1.
In above-mentioned preparation method, the quality of poly(oxyethylene glycol) 400 ~ 10000 is 0.15 ~ 0.5g.
Spin coating proceeding described in above-mentioned preparation method, rotating speed is 3000～6000 revs/min, and the spin coating time is 20～30 seconds, and the precursor solution thickness of each spin coating is approximately 20～40nm.
In above-mentioned preparation method, described substrate material is for being coated with the glass substrate of bottom electrode (ITO, FTO, AZO).
The present invention has prepared the Na of different zirconium ion volumes first
0.5bi
0.5(Ti, Zr) O
3film.In research process, the precursor solution that contriver has good uniformity by preparation, under lower annealing temperature, has prepared the film with single perovskite structure.By doping zirconium ion, improved Na
0.5bi
0.5tiO
3the ferroelectric properties of film, makes it in unleaded Nonvolatile ferroelectric memory, have application prospect more widely.In addition, contriver is first by the Na of zirconium ion doping
0.5bi
0.5tiO
3thin film deposition is being coated with in the glass substrate of bottom electrode (ITO, FTO, AZO), is conducive to research and develop ferroelectric, piezoelectricity, photoelectricity, light is sold off and the Na of the multifrequency nature such as nonlinear optics
0.5bi
0.5tiO
3based film material.
Accompanying drawing explanation
Fig. 1 is zirconium ion doping with bismuth titanate sodium group membrane structure schematic diagram of the present invention.
Fig. 2 be embodiment 1 preparation at the Na being coated with in FTO bottom electrode glass substrate
0.5bi
0.5(Ti
0.99zr
0.01) O
3the XRD figure spectrum of film.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is diffracted intensity.
Fig. 3 be embodiment 3 preparation at the Na being coated with in ITO bottom electrode glass substrate
0.5bi
0.5(Ti
0.98zr
0.02) O
3the XRD figure spectrum of film.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is diffracted intensity.
Fig. 4 be embodiment 3 preparation at the Na being coated with in ITO bottom electrode glass substrate
0.5bi
0.5(Ti
0.98zr
0.02) O
3the sectional drawing of film.
Fig. 5 be embodiment 3 preparation at the Na being coated with in ITO bottom electrode glass substrate
0.5bi
0.5(Ti
0.98zr
0.02) O
3the ferroelectric hysteresis loop collection of illustrative plates of film.Wherein, X-coordinate is strength of electric field: kv/cm, ordinate zou is polarizability: microcoulomb/square centimeter.
Fig. 6 be embodiment 3 preparation at the Na being coated with in FTO bottom electrode glass substrate
0.5bi
0.5(Ti
0.98zr
0.02) O
3the ferroelectric hysteresis loop collection of illustrative plates of film.Wherein, X-coordinate is strength of electric field: kv/cm, ordinate zou is polarizability: microcoulomb/square centimeter.
Fig. 7 be embodiment 4 preparation at the Na being coated with in AZO bottom electrode glass substrate
0.5bi
0.5(Ti
0.975zr
0.025) O
3the XRD figure spectrum of film.Wherein, X-coordinate is diffraction angle 2 θ, and ordinate zou is diffracted intensity.
Fig. 8 be embodiment 7 preparation at the Na being coated with in FTO bottom electrode glass substrate
0.5bi
0.5(Ti
0.96zr
0.04) O
3the sectional drawing of film.
Fig. 9 be embodiment 7 preparation at the Na being coated with in ITO bottom electrode glass substrate
0.5bi
0.5(Ti
0.96zr
0.04) O
3the ferroelectric hysteresis loop collection of illustrative plates of film.Wherein, X-coordinate is strength of electric field: kv/cm, ordinate zou is polarizability: microcoulomb/square centimeter.
Figure 10 be embodiment 7 preparation at the Na being coated with in ITO bottom electrode glass substrate
0.5bi
0.5(Ti
0.96zr
0.04) O
3the dielectric spectrogram of film.Wherein, X-coordinate is frequency: hertz, left ordinate zou is relative permittivity, right ordinate zou is dissipation factor.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further elaborated; it should be explicitly made clear at this point, following explanation is only in order to explain the present invention, its content is not limited; so long as meet any technical scheme of spirit of the present invention, all should be in the scope of protection of present invention.
embodiment 1
(1), according to Na
0.5bi
0.5(Ti
0.99zr
0.01) O
3stoichiometric ratio, accurately take 0.3380g sodium-acetate (excessive 2mol%), 2.0578g Bismuth trinitrate (excessive 5mol%), 0.0347g zirconium nitrate, and to measure 2.8mL tetra-n-butyl titanate be raw material, separately weigh 0.5g poly(oxyethylene glycol) 400, standby; Tetra-n-butyl titanate is placed in to beaker, measures 2.8mL methyl ethyl diketone and dropwise add in tetra-n-butyl titanate, and be placed on magnetic stirring apparatus and under room temperature, stir 5 hours, to being fully uniformly mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 4mL ethylene glycol monomethyl ether and add wherein, at the temperature of 40 ℃, be stirred to completely and dissolve, add again 4mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 0.5 hour, be defined as solution 2; Sodium-acetate, Bismuth trinitrate are added in 8mL Glacial acetic acid, and at 40 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; 0.5g poly(oxyethylene glycol) 400 is added in 5mL ethylene glycol monomethyl ether and at the temperature of 40 ℃ and is stirred to dissolving, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 8 hours, being mixed with concentration is 0.3mol/L, and volume is about the precursor solution that 27mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited in the glass substrate that is coated with FTO bottom electrode, 3000 revs/min of spin speed, the spin coating time is 20 seconds; Under nitrogen atmosphere, film is heat-treated, treating processes is: first 280 ℃ of insulations 10 minutes, then 400 ℃ of insulations 6 minutes, then 500 ℃ of annealing 10 minutes; Repeat said process, until film thickness reaches about 600nm.
As shown in Figure 2, through x-ray diffractometer, (German Brooker, D8) to being deposited on the Na being coated with in FTO bottom electrode glass substrate
0.5bi
0.5(Ti
0.99zr
0.01) O
3film carries out structured testing, and prepared film has the single perovskite structure of polycrystalline.
embodiment 2
(1), according to Na
0.5bi
0.5(Ti
0.985zr
0.015) O
3stoichiometric ratio, accurately take 0.3468g SODIUMNITRATE (excessive 1mol%), 1.5756g bismuth acetate (excessive 1mol%), 0.0397g acetic acid zirconium, and to measure 2.4mL titanium isopropylate be raw material, separately weigh 0.4g Polyethylene Glycol-600, standby; Titanium isopropylate is placed in to beaker, measures 2.4mL methyl ethyl diketone and dropwise add in titanium isopropylate, and be placed on magnetic stirring apparatus and under room temperature, stir 4 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 15mL ethylene glycol monomethyl ether and add wherein, at 50 ℃ of temperature, be stirred to completely and dissolve, add again 15mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 1 hour, be defined as solution 2; SODIUMNITRATE, bismuth acetate are added in 25mL Glacial acetic acid, and at 50 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 20mL ethylene glycol monomethyl ether and at 50 ℃ of temperature extremely to dissolve 0.4g Polyethylene Glycol-600, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 9 hours, being mixed with concentration is 0.1mol/L, and volume is about the precursor solution that 80mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited in the glass substrate that is coated with ITO bottom electrode, 4000 revs/min of spin speed, the spin coating time is 25 seconds; Under nitrogen atmosphere, film is heat-treated, treating processes is: first 280 ℃ of insulations 10 minutes, then 400 ℃ of insulations 6 minutes, then 500 ℃ of annealing 12 minutes; Repeat said process, until film thickness reaches about 450nm.
Gained film has the single perovskite structure of polycrystalline, and electric property is good.
embodiment 3
(1), according to Na
0.5bi
0.5(Ti
0.98zr
0.02) O
3stoichiometric ratio, accurately take 0.3380g sodium-acetate (excessive 2mol%), 1.5756g Bismuth trinitrate (excessive 5mol%), 0.0639g zirconium nitrate, and to measure 2.7mL tetra-n-butyl titanate be raw material, separately weigh 0.4g Polyethylene Glycol-600, standby; Tetra-n-butyl titanate is placed in to beaker, measures 2.7mL methyl ethyl diketone and dropwise add in tetra-n-butyl titanate, and be placed on magnetic stirring apparatus and under room temperature, stir 5 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 10mL ethylene glycol monomethyl ether and add wherein, at 50 ℃ of temperature, be stirred to completely and dissolve, add again 10mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 1 hour, be defined as solution 2; Sodium-acetate, Bismuth trinitrate are added in 10mL Glacial acetic acid, and at 50 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 5mL ethylene glycol monomethyl ether and at 50 ℃ of temperature extremely to dissolve 0.4g Polyethylene Glycol-600, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 9 hours, being mixed with concentration is 0.2mol/L, and volume is about the precursor solution that 40mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited on respectively in the glass substrate that is coated with ITO, FTO bottom electrode, 4000 revs/min of spin speed, the spin coating time is 30 seconds; Under nitrogen atmosphere, film is heat-treated, treating processes is: first 300 ℃ of insulations 8 minutes, then 450 ℃ of insulations 5 minutes, then 525 ℃ of annealing 10 minutes; Repeat said process, until film thickness reaches about 500nm.
As shown in Figure 3, (German Brooker, D8) to being deposited on the Na in ITO bottom electrode glass substrate to utilize x-ray diffractometer
0.5bi
0.5(Ti
0.98zr
0.02) O
3film carries out structured testing, can find that prepared film has the single perovskite structure of polycrystalline.Utilize scanning electron microscope (S-2500) to be coated with ITO bottom electrode Na on glass to being deposited on
0.5bi
0.5(Ti
0.98zr
0.02) O
3thin-membrane section scans, and result as shown in Figure 4, can find out that membrane structure is even, fine and close, and and substrate between interface clear.Utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to be coated with Na on bottom electrode ito glass to being deposited on
0.5bi
0.5(Ti
0.98zr
0.02) O
3the ferroelectric hysteresis loop of film characterizes, result as shown in Figure 5, under about 1000kV/cm strength of electric field, residual polarization (
p r) be 11.6 μ C/cm
2, coercive field (E
c) be 264.9kV/cm.To being deposited on, be coated with bottom electrode FTO Na on glass
0.5bi
0.5(Ti
0.98zr
0.02) O
3the ferroelectric hysteresis loop of film characterizes, result as shown in Figure 6, under about 1000kV/cm strength of electric field, residual polarization (
p r) be 14.4 μ C/cm
2, coercive field (E
c) be 182.8kV/cm.
embodiment 4
(1), according to Na
0.5bi
0.5(Ti
0.975zr
0.025) O
3stoichiometric ratio, accurately take 0.3485g SODIUMNITRATE (excessive 1.5mol%), 1.5912g bismuth acetate (excessive 2mol%), 0.0661g acetic acid zirconium, and to measure 2.4mL titanium isopropylate be raw material, separately weigh 0.3g cetomacrogol 1000, standby; Titanium isopropylate is placed in to beaker, measures 2.4mL methyl ethyl diketone and dropwise add in titanium isopropylate, and be placed on magnetic stirring apparatus and under room temperature, stir 6 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 5mL ethylene glycol monomethyl ether and add wherein, at 60 ℃ of temperature, be stirred to completely and dissolve, add again 10mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 1.5 hours, be defined as solution 2; SODIUMNITRATE, bismuth acetate are added in 10mL Glacial acetic acid, and at 60 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 10mL ethylene glycol monomethyl ether and at 60 ℃ of temperature extremely to dissolve 0.3g cetomacrogol 1000, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 10 hours, being mixed with concentration is 0.2mol/L, and volume is about the precursor solution that 40mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited in the glass substrate that is coated with AZO bottom electrode, 5000 revs/min of spin speed, the spin coating time is 30 seconds; Under nitrogen atmosphere, film is heat-treated, treating processes is: first 300 ℃ of insulations 8 minutes, then 450 ℃ of insulations 5 minutes, then 500 ℃ of annealing 12 minutes; Repeat said process, until film thickness reaches about 400nm.
Through x-ray diffractometer, (German Brooker, D8) to being deposited on the Na being coated with in AZO bottom electrode glass substrate
0.5bi
0.5(Ti
0.975zr
0.025) O
3film carries out structured testing, and result as shown in Figure 7.Can find out that prepared film has the single perovskite structure of polycrystalline.
embodiment 5
(1), according to Na
0.5bi
0.5(Ti
0.97zr
0.03) O
3stoichiometric ratio, accurately take 0.3468g SODIUMNITRATE (excessive 1mol%), 1.6068g bismuth acetate (excessive 3mol%), 0.1041g zirconium nitrate, and to measure 2.3mL titanium isopropylate be raw material, separately weigh 0.2g Macrogol 4000, standby; Titanium isopropylate is placed in to beaker, measures 2.3mL methyl ethyl diketone and dropwise add in titanium isopropylate, and be placed on magnetic stirring apparatus in stirring at room 5 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 5mL ethylene glycol monomethyl ether and add wherein, at 60 ℃ of temperature, be stirred to completely and dissolve, add again 5mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 1.5 hours, be defined as solution 2; SODIUMNITRATE, bismuth acetate are added in 7mL Glacial acetic acid, and at 60 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 5mL ethylene glycol monomethyl ether and at 60 ℃ of temperature extremely to dissolve 0.2g polyethylene glycol 6000, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 10 hours, being mixed with concentration is 0.3mol/L, and volume is about the precursor solution that 27mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited in the glass substrate that is coated with FTO bottom electrode, 5000 revs/min of spin speed, the spin coating time is 30 seconds; Under nitrogen atmosphere, film is heat-treated, treating processes is: first 300 ℃ of insulations 8 minutes, then 450 ℃ of insulations 5 minutes, then 525 ℃ of annealing 12 minutes; Repeat said process, until film thickness reaches about 300nm.
Gained film has the single perovskite structure of polycrystalline, and electric property is good.
embodiment 6
(1), according to Na
0.5bi
0.5(Ti
0.965zr
0.035) O
3stoichiometric ratio, accurately take 0.3485g SODIUMNITRATE (excessive 1.5mol%), 1.6224g bismuth acetate (excessive 4mol%), 0.0926g acetic acid zirconium, and to measure 2.3mL titanium isopropylate be raw material, separately weigh 0.2g polyethylene glycol 6000, standby; Titanium isopropylate is placed in to beaker, measures 2.3mL methyl ethyl diketone and dropwise add in titanium isopropylate, and be placed on magnetic stirring apparatus and under room temperature, stir 3 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 4mL ethylene glycol monomethyl ether and add wherein, at 80 ℃ of temperature, be stirred to completely and dissolve, add again 2mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 2 hours, be defined as solution 2; SODIUMNITRATE, bismuth acetate are added in 4mL Glacial acetic acid, and at 80 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 2mL ethylene glycol monomethyl ether and at 80 ℃ of temperature extremely to dissolve 0.2g polyethylene glycol 6000, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 11 hours, being mixed with concentration is 0.5mol/L, and volume is about the precursor solution that 17mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited in the glass substrate that is coated with ITO bottom electrode, 6000 revs/min of spin speed, the spin coating time is 20 seconds; Under n 2 annealing atmosphere, film is heat-treated, treating processes is: first 320 ℃ of insulations 6 minutes, then 460 ℃ of insulations 4 minutes, then 550 ℃ of annealing 8 minutes; Repeat said process, until film thickness reaches about 400nm.
Gained film has the single perovskite structure of polycrystalline, and electric property is good.
embodiment 7
(1), according to Na
0.5bi
0.5(Ti
0.96zr
0.04) O
3stoichiometric ratio, accurately take 0.3380g sodium-acetate (excessive 2mol%), 2.0578g Bismuth trinitrate (excessive 5mol%), 0.1388g zirconium nitrate, and to measure 2.3mL tetra-n-butyl titanate be raw material, separately weigh 0.15g PEG20000, standby; Tetra-n-butyl titanate is placed in to beaker, measures 2.3mL methyl ethyl diketone and dropwise add in tetra-n-butyl titanate, and be placed on magnetic stirring apparatus and under room temperature, stir 6 hours, to fully having mixed the chelating of titanium, be defined as solution 1; Zirconium nitrate is placed in to beaker, and measures 4mL ethylene glycol monomethyl ether and add wherein, at 80 ℃ of temperature, be stirred to completely and dissolve, add again 3mL methyl ethyl diketone and be stirred to and mix, after solution is cooling, add in solution 1, at room temperature stir 2 hours, be defined as solution 2; Sodium-acetate, Bismuth trinitrate are added in 5mL Glacial acetic acid, and at 80 ℃ of temperature, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3; Add heated and stirred in 3mL ethylene glycol monomethyl ether and at 80 ℃ of temperature extremely to dissolve 0.15g PEG20000, to be cooled to room temperature, be defined as solution 4; Solution 3,4 is added in solution 2 successively; At room temperature stir 12 hours, being mixed with concentration is 0.4mol/L, and volume is about the precursor solution that 20mL is even, transparent;
(2), adopt spin-coating method precursor solution to be deposited on respectively in the glass substrate that is coated with ITO, FTO bottom electrode, 5500 revs/min of spin speed, the spin coating time is 25 seconds; Under n 2 annealing atmosphere, film is heat-treated, treating processes is: first 320 ℃ of insulations 6 minutes, then 460 ℃ of insulations 4 minutes, then 550 ℃ of annealing 8 minutes; Repeat said process, until film thickness reaches about 500nm.
As shown in Figure 8, utilize scanning electron microscope (S-2500) to being deposited on the Na being coated with in FTO bottom electrode glass substrate
0.5bi
0.5(Ti
0.96zr
0.04) O
3thin-membrane section scans, and can see that membrane structure is even, fine and close, and and substrate between interface clear.As shown in Figure 9, utilize ferroelectric test macro (Precision Pro. Radiant Technologies) to be coated with Na on bottom electrode ito glass to being deposited on
0.5bi
0.5(Ti
0.96zr
0.04) O
3the ferroelectric hysteresis loop of film characterizes, under about 1000kV/cm strength of electric field, residual polarization (
p r) be 11.6 μ C/cm
2, coercive field (E
c) be 457.9kV/cm.As shown in figure 10, use Agilent 4294A to be coated with Na on bottom electrode ito glass to being deposited on
0.5bi
0.5(Ti
0.96zr
0.04) O
3the dielectric properties of film are tested, and relative permittivity is along with the overall trend of frequency change reduces gradually, and meanwhile the variation overall trend of dissipation factor first reduces rear increase.When frequency is 100kHz, specific inductivity and dissipation factor are respectively 540,0.11.
Claims (12)
1. a bismuth-sodium titanate film for B position zirconium ion doping of equal value, is characterized in that: with chemical general formula Na
0.5bi
0.5(Ti
1-xzr
x) O
3represent, wherein, Na
0.5bi
0.5tiO
3for matrix, zirconium ion is dopant ion.
2. the bismuth-sodium titanate film of zirconium ion doping according to claim 1, is characterized in that: 0.01≤x≤0.04.
3. the bismuth-sodium titanate film of zirconium ion doping according to claim 1, is characterized in that: the total thickness of film is approximately 300 ~ 600nm.
4. the bismuth-sodium titanate film that B claimed in claim 1 position zirconium ion of equal value adulterates, is characterized in that comprising the following steps:
(1), the preparation of precursor solution
1. take sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate, acetic acid zirconium or zirconium nitrate, tetra-n-butyl titanate or titanium isopropylate is raw material, according to Na
0.5bi
0.5(Ti
1-xzr
x) O
3stoichiometric ratio, accurately weigh each raw material, wherein, sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate are slightly excessive, separately according to empirical value, weigh poly(oxyethylene glycol) 400 ~ 10000, standby;
2. measure tetra-n-butyl titanate or titanium isopropylate in beaker, methyl ethyl diketone is dropwise added, and be placed on magnetic stirring apparatus and under room temperature, stir the chelating that completes titanium for 3 ~ 6 hours, be defined as solution 1;
3. take acetic acid zirconium or zirconium nitrate in beaker, add a certain amount of ethylene glycol monomethyl ether and at the temperature of 40 ~ 80 ℃, be stirred to solution clarification, then add a certain amount of methyl ethyl diketone and be stirred to and mix, add after cooling in solution 1, at room temperature stir 0.5 ~ 2 hour, be defined as solution 2;
4. sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate are joined in Glacial acetic acid, at the temperature of 40 ~ 80 ℃, heated and stirred is extremely dissolved completely, and is cooled to room temperature, is defined as solution 3;
5. polyoxyethylene glycol is added in ethylene glycol monomethyl ether, at the temperature of 40 ~ 80 ℃, heated and stirred is extremely dissolved, and is cooled to room temperature, is defined as solution 4;
6. solution 3,4 is added in solution 2 successively, at room temperature stir 8 ~ 12 hours, be mixed with the precursor solution that concentration is 0.1 ~ 0.5mol/L.
5. the preparation of (2), thin-film material: prepare film in conjunction with annealing process layer by layer with spin-coating method
1. adopt spin-coating method that precursor solution is deposited on substrate.
6. under nitrogen atmosphere, film is heat-treated, treating processes is: first 280 ~ 320 ℃ of insulations 6 ~ 10 minutes, then 400 ~ 460 ℃ of insulations 4 ~ 6 minutes, finally 500 ~ 550 ℃ of annealing 8 ~ 12 minutes;
2. repeat above-mentioned process in 1., until film thickness is approximately 300 ~ 600nm, obtain.
7. preparation method according to claim 4, is characterized in that: while preparing precursor solution, sodium-acetate or SODIUMNITRATE, bismuth acetate or Bismuth trinitrate be excessive 1 ~ 2mol%, 1 ~ 5mol% respectively.
8. preparation method according to claim 4, is characterized in that: in step (1) tetra-n-butyl titanate 2. or titanium isopropylate with the liquor capacity of methyl ethyl diketone than being 1:1.
9. preparation method according to claim 4, is characterized in that: in step (1), poly(oxyethylene glycol) 400 ~ 10000 quality is 0.15 ~ 0.5g.
10. preparation method according to claim 4, is characterized in that: in described spin coating proceeding, rotating speed is 3000～6000 revs/min, and the spin coating time is 20～30 seconds, and every layer film thickness is approximately 20～40nm.
11. preparation methods according to claim 4, is characterized in that: described substrate material is for being coated with the glass substrate of bottom electrode (ITO, FTO, AZO).
12. preparation methods according to claim 4, is characterized in that: heat-treating atmosphere is nitrogen.
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| CN104844197A (en) * | 2015-05-08 | 2015-08-19 | 济南大学 | Method for growing (100) preferred orientation sodium bismuth titanate-based thin film on silicon chip |
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