CN102515748B - Preparation method of bismuth titanate ferroelectric film - Google Patents
Preparation method of bismuth titanate ferroelectric film Download PDFInfo
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Abstract
The invention relates to a preparation method of a bismuth titanate ferroelectric film. Bismuth nitrate pentahydrate (Bi (NO3) 3 . 5 H2O) and tetrabutyl titanate (Ti (OC4H9) 4) are used as initial raw materials, ethylene glycol monomethyl ether and diacetone are used as a solvent and a stabilizer to prepare bismuth titanate precursor liquid, the bismuth titanate precursor liquid is put in Co60 for irradiation, the irradiated bismuth titanate precursor liquid is coated on a treated Pt/Ti/SiO2/Si substrate in a rotating mode, and then a single-layer amorphous bismuth titanate film is obtained after drying. The film is obtained after 6-8 times of repeated coating and drying, at the atmosphere of flowing oxygen, the room temperature is raised to an annealing temperature, the annealing temperature is kept, and then the film is cooled along with the furnace to obtain a casually oriented lamellar peroskite-structure bismuth titanate film. The invention aims to solve the problems of poor ferroelectric properties, low density and uneven particle distribution in bismuth titanate ferroelectric film preparation of the prior art, and provides a novel preparation method in which the bismuth titanate precursor liquid receives Co60 irradiation.
Description
Technical field
The present invention relates to functional film material field, specifically refer to a kind of preparation method of bismuth titanate ferro-electricity membrane.
Background technology
Traditional ferroelectric piezoelectric ceramics how leaded (as Pb-based lanthanumdoped zirconate titanates, lead lanthanum zirconate titanate), they are in preparation and use procedure, bring very large infringement all can to environment and human health.In recent years, along with the demand of environment protection, it is novel that a lot of country has started to be devoted to research and development, the ferroelectric piezoelectric ceramics material of toxicological harmless.Bismuth titanates (Bi
4ti
3o
12), as a kind of ferroelectric material of excellent property, because it has unique electricity, optics and photoelectronics performance, in modern microelectronic, MEMS (micro electro mechanical system), information storage etc., there is the trend replacing traditional material gradually.But the impact due to factors such as present production technique result in the shortcomings such as the thin anti-fatigue performance of bismuth titanates ferroelectric film own is poor, residual polarization value is little, the reliability of storage is low, have impact on the application of film to a certain extent.So people are devoted to improve the thin various performances of film by doping means all the time.Thus the raising that have ignored bismuth titanate ferro-electricity membrane self performance.
Summary of the invention
The present invention discloses a kind of bismuth titanate ferro-electricity membrane preparation method, its objective is to solve in prior art the poor ferroelectric property preparing bismuth titanate ferro-electricity membrane, the problem that density is low and size distribution is uneven, and a kind of new preparation method bismuth titanates precursor liquid being accepted Co60 and irradiate is provided.
For achieving the above object, the present invention is by the following technical solutions:
A kind of bismuth titanate ferro-electricity membrane preparation method, is characterized in that: said method comprising the steps of:
Step 1. is according to chemical formula Bi
4ti
3o
12, stoichiometrically take five water Bismuth trinitrate and tetrabutyl titanates, its ratio, for often to take 10 ~ 12g five water Bismuth trinitrate, should take 5 ~ 6ml tetrabutyl titanate;
Ethylene glycol monomethyl ether slowly joins in five water Bismuth trinitrates by step 2., and stirred at ambient temperature 20 ~ 40min obtains colourless transparent solution A, and its ratio adds 14 ~ 16ml ethylene glycol monomethyl ether in every 10 ~ 12g five water Bismuth trinitrate;
Tetrabutyl titanate slowly joins in methyl ethyl diketone by step 3., stirred at ambient temperature 20 ~ 40min, obtains clear solution B, and its ratio is that every 5 ~ 6ml tetrabutyl titanate joins in 20 ~ 25ml methyl ethyl diketone;
Solution B is slowly added drop-wise in solution A by step 4., stirred at ambient temperature 50 ~ 70min, leaves standstill 1 ~ 2 day, filters, obtains the bismuth titanates precursor liquid of homogeneous transparent;
Bismuth titanates precursor liquid is put in Co60 radioactive source and accepts irradiation by step 5.;
Step 6. is by Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, and ultrasonic cleaning 8 ~ 12min, then carries out drying respectively;
The bismuth titanates precursor liquid accepting Co60 irradiation is spun to the Pt/Ti/SiO processed through step 6 by step 7. by sol evenning machine
2on/Si substrate, under then substrate being placed in 90 ~ 120 DEG C of conditions, dry 3 ~ 10min, obtains film;
Film is placed in the environment oven dry 15 ~ 25min of 300 ~ 370 DEG C by step 8., organic solvent is volatilized, organic substance decomposing, obtains the unbodied bismuth titanate film of individual layer that thickness is 40 ~ 55nm;
The film of step 9. repeating step 7-8 and drying course 6 ~ 8 times, obtain the bismuth titanate film of desired thickness;
Bismuth titanate film is placed in quartz tube furnace by step 10., under the oxygen atmosphere of flowing, rise to the annealing temperature 650 ~ 750 DEG C of setting from room temperature, insulation 20 ~ 25min, furnace cooling, obtains the laminated perovskite structure bismuth titanate ferro-electricity membrane that final thickness is the random orientation of 350 ~ 450nm.
In step 7, bismuth titanates precursor liquid is spun to the Pt/Ti/SiO processed by sol evenning machine
2time on/Si substrate, first with 900 ~ 1500r/min spin coating 10s, then with 3500 ~ 4500r/min spin coating, 20 ~ 30s.
In step 10, temperature rise rate is 10 ~ 20 DEG C/min.
In step 5, the absorption metering of irradiation is 10 ~ 40kGy
In step 5, the absorption metering of irradiation is 40 ~ 60kGy.
In step 5, the absorption metering of irradiation is 60 ~ 100kGy.
The present invention compares with traditional bismuth titanate ferro-electricity membrane preparation process, and obtained film surface is more smooth, finer and close; Grain size evenly.Test its fatigue resistance and electric leakage performance, find that its anti-fatigue performance strengthens, leakage property reduces.
accompanying drawing illustrates:
Fig. 1 absorbs the XRD spectra that metering is the bismuth titanate ferro-electricity membrane of 10 ~ 40kGyCo60 irradiation;
Fig. 2 absorbs the XRD spectra that metering is the bismuth titanate ferro-electricity membrane of 40 ~ 60kGyCo60 irradiation;
Fig. 3 absorbs the XRD spectra that metering is the bismuth titanate ferro-electricity membrane of 60 ~ 100kGyCo60 irradiation;
Fig. 4 absorbs the SEM spectrogram that metering is the bismuth titanate ferro-electricity membrane of 10 ~ 40kGyCo60 irradiation;
Fig. 5 absorbs the SEM spectrogram that metering is the bismuth titanate ferro-electricity membrane of 40 ~ 60kGyCo60 irradiation;
Fig. 6 absorbs the SEM spectrogram that metering is the bismuth titanate ferro-electricity membrane of 60 ~ 1000kGyCo60 irradiation.
embodiment:
Below in conjunction with specific embodiment, the present invention is described in detail:
Embodiment 1:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 10.67gBi (NO
3)
35H
2o is dissolved in 15ml ethylene glycol monomethyl ether, and stirred at ambient temperature 30min obtains settled solution A; By 5.20mlTi (OC
4h
9)
4dissolve in 23ml methyl ethyl diketone, stirred at ambient temperature 30min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 60min, leave standstill and filter after 1 day, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 10min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 10 ~ 40kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1000r/min spin coating 10s, then with 4000 r/min spin coating 25s; Then dry 5min through 100 DEG C, then dry 20min through 350 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 700 DEG C of annealing 20min are risen to from room temperature with the temperature rise rate of 15 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 2:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 10.67gBi (NO
3)
35H
2o is dissolved in 15ml ethylene glycol monomethyl ether, and stirred at ambient temperature 30min obtains settled solution A; By 5.20mlTi (OC
4h
9)
4dissolve in 23ml methyl ethyl diketone, stirred at ambient temperature 30min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 60min, leave standstill and filter after 1 day, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 8min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 40 ~ 60kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 900r/min spin coating 10s, then with 3500 r/min spin coating 20s; Then dry 5min through 100 DEG C, then dry 20min through 350 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 700 DEG C of annealing 20min are risen to from room temperature with the temperature rise rate of 10 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 3:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 10.67gBi (NO
3)
35H
2o is dissolved in 15ml ethylene glycol monomethyl ether, and stirred at ambient temperature 30min obtains settled solution A; By 5.20mlTi (OC
4h
9)
4dissolve in 23ml methyl ethyl diketone, stirred at ambient temperature 30min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 60min, leave standstill and filter after 1 day, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 12min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 60 ~ 100kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1500r/min spin coating 10s, then with 4500 r/min spin coating 30s; Then dry 5min through 100 DEG C, then dry 20min through 350 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 700 DEG C of annealing 20min are risen to from room temperature with the temperature rise rate of 20 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 4:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 12gBi (NO
3)
35H
2o is dissolved in 16ml ethylene glycol monomethyl ether, and stirred at ambient temperature 20min obtains settled solution A; By 6mlTi (OC
4h
9)
4dissolve in 25ml methyl ethyl diketone, stirred at ambient temperature 20min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 50min, leave standstill and filter after 2 days, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 12min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 10 ~ 40kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1200r/min spin coating 10s, then with 4000 r/min spin coating 30s; Then dry 10min through 90 DEG C, then dry 15min through 300 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 650 DEG C of annealing 25min are risen to from room temperature with the temperature rise rate of 20 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 5:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 10gBi (NO
3)
35H
2o is dissolved in 14ml ethylene glycol monomethyl ether, and stirred at ambient temperature 40min obtains settled solution A; By 5mlTi (OC
4h
9)
4dissolve in 20ml methyl ethyl diketone, stirred at ambient temperature 40min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 70min, leave standstill and filter after 2 days, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 10min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 40 ~ 60kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1500r/min spin coating 10s, then with 4000 r/min spin coating 30s; Then dry 10min through 120 DEG C, then dry 25min through 370 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 750 DEG C of annealing 25min are risen to from room temperature with the temperature rise rate of 20 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 6:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 11.5gBi (NO
3)
35H
2o is dissolved in 14.5ml ethylene glycol monomethyl ether, and stirred at ambient temperature 35min obtains settled solution A; By 5.5mlTi (OC
4h
9)
4dissolve in 21ml methyl ethyl diketone, stirred at ambient temperature 35min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 65min, leave standstill and filter after 1 day, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 8min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 60 ~ 100kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1100r/min spin coating 10s, then with 4200 r/min spin coating 25s; Then dry 8min through 110 DEG C, then dry 20min through 320 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 730 DEG C of annealing 25min are risen to from room temperature with the temperature rise rate of 15 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 7:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 11.8gBi (NO
3)
35H
2o is dissolved in 15.5ml ethylene glycol monomethyl ether, and stirred at ambient temperature 40min obtains settled solution A; By 5.8mlTi (OC
4h
9)
4dissolve in 23ml methyl ethyl diketone, stirred at ambient temperature 25min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 65min, leave standstill and filter after 2 days, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 10min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 10 ~ 40kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1300r/min spin coating 10s, then with 4500 r/min spin coating 25s; Then dry 4min through 100 DEG C, then dry 20min through 320 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 730 DEG C of annealing 25min are risen to from room temperature with the temperature rise rate of 10 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 8:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 10.3gBi (NO
3)
35H
2o is dissolved in 14ml ethylene glycol monomethyl ether, and stirred at ambient temperature 40min obtains settled solution A; By 5mlTi (OC
4h
9)
4dissolve in 24ml methyl ethyl diketone, stirred at ambient temperature 40min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 55min, leave standstill and filter after 2 days, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 10min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 40 ~ 60kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1300r/min spin coating 10s, then with 3500 r/min spin coating 30s; Then dry 6min through 100 DEG C, then dry 15min through 310 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 680 DEG C of annealing 25min are risen to from room temperature with the temperature rise rate of 20 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
Embodiment 9:
With five water Bismuth trinitrate (Bi (NO
3)
35H
2and tetrabutyl titanate (Ti (OC O)
4h
9)
4) be initial feed, ethylene glycol monomethyl ether and methyl ethyl diketone are solvent and stablizer, prepare bismuth titanates precursor liquid.First by 11gBi (NO
3)
35H
2o is dissolved in 15ml ethylene glycol monomethyl ether, and stirred at ambient temperature 20min obtains settled solution A; By 6mlTi (OC
4h
9)
4dissolve in 20ml methyl ethyl diketone, stirred at ambient temperature 30min obtains settled solution B; Solution B is slowly joined in solution A, stirred at ambient temperature 60min, leave standstill and filter after 1 day, obtain the bismuth titanates precursor liquid of orange-yellow clear homogeneous.
By Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, respectively ultrasonic cleaning 10min, then dry, to remove Pt/Ti/SiO
2the on-chip impurity of/Si.
Precursor liquid is put into irradiation in Co60, absorption metering is 60 ~ 100kGy.Bismuth titanates precursor liquid after irradiation is spun to the Pt/Ti/SiO processed by sol evenning machine
2on/Si substrate, first with 1500r/min spin coating 10s, then with 4500 r/min spin coating 30s; Then dry 10min through 120 DEG C, then dry 20min through 350 DEG C, obtain the unbodied bismuth titanate film of individual layer.Repetition film and drying course obtain film 6 ~ 8 times, last in tube furnace, under the oxygen atmosphere of flowing, 700 DEG C of annealing 20min are risen to from room temperature with the temperature rise rate of 20 DEG C/min, furnace cooling, obtains the bismuth titanate film that final thickness is the laminated perovskite structure of the random orientation of 350nm ~ 450nm.
The present invention is by after carrying out difference and absorbing metering Co60 irradiation to bismuth titanates precursor liquid, obtained bismuth titanate ferro-electricity membrane compares research, finds bismuth titanate ferro-electricity membrane smooth surface, fine and close flawless obtained after Co60 irradiation.Especially absorbing metering is that the ferroelectric membranc size distribution of 40 ~ 60kGy is more even, and film is grown more intact, as shown in Fig. 2,5.And then the enhancing of test discovery anti-fatigue performance is carried out to its fatigue resistance and electric leakage performance, leakage property reduces.Illustrate that the performance of the bismuth titanate ferro-electricity membrane obtained when the metering of bismuth titanates precursor liquid absorption Co60 irradiation is 40 ~ 60kGy is best, absorbing metering 40 ~ 60kGy is optimal absorption metering.Present invention process is simple, easy to operate, can be compatible with microelectronics.
Can see from Fig. 1 ~ 3, all can obtain the bismuth titanate film of the laminated perovskite structure of single-phase through step 1 ~ 10.
Scanning electron microscope detection (Fig. 4 ~ 6) is carried out by the bismuth titanate film being 10 ~ 40kGy, 40 ~ 60kGy and 60 ~ 100kGy to the metering of Co60 irradiation, can see: although the bismuth titanate film grain size in Fig. 4 is more even, but compare with Fig. 5, intercrystalline space is comparatively large, not fine and close.And agglomeration appears in the bismuth titanate film in Fig. 6, crystal grain is less simultaneously, and degree of crystallinity is lower, and this also matches lower than the diffraction peak intensity in Fig. 1,2 with the diffraction peak intensity of the XRD in Fig. 3.Contrasted by above spectrogram, absorbing metering is the spectrogram that 40 ~ 60kGy bismuth titanate film is obviously better than that other absorbs metering.
Claims (1)
1. a bismuth titanate ferro-electricity membrane preparation method, is characterized in that: said method comprising the steps of:
Step 1. is according to chemical formula Bi
4ti
3o
12, stoichiometrically take five water Bismuth trinitrate and tetrabutyl titanates, its ratio, for often to take 10 ~ 12g five water Bismuth trinitrate, should take 5 ~ 6ml tetrabutyl titanate;
Ethylene glycol monomethyl ether slowly joins in five water Bismuth trinitrates by step 2., and stirred at ambient temperature 20 ~ 40min obtains colourless transparent solution A, and its ratio adds 14 ~ 16ml ethylene glycol monomethyl ether in every 10 ~ 12g five water Bismuth trinitrate;
Tetrabutyl titanate slowly joins in methyl ethyl diketone by step 3., stirred at ambient temperature 20 ~ 40min, obtains clear solution B, and its ratio is that every 5 ~ 6ml tetrabutyl titanate joins in 20 ~ 25ml methyl ethyl diketone;
Solution B is slowly added drop-wise in solution A by step 4., stirred at ambient temperature 50 ~ 70min, leaves standstill 1 ~ 2 day, filters, obtains the bismuth titanates precursor liquid of homogeneous transparent;
Bismuth titanates precursor liquid is put in Co60 radioactive source and accepts irradiation by step 5.;
Step 6. is by Pt/Ti/SiO
2/ Si substrate puts into acetone, dehydrated alcohol and deionized water successively, and ultrasonic cleaning 8 ~ 12min, then carries out drying respectively;
The bismuth titanates precursor liquid accepting Co60 irradiation is spun to the Pt/Ti/SiO processed through step 6 by step 7. by sol evenning machine
2on/Si substrate, under then substrate being placed in 90 ~ 120 DEG C of conditions, dry 3 ~ 10min, obtains film;
Film is placed in the environment oven dry 15 ~ 25min of 300 ~ 370 DEG C by step 8., organic solvent is volatilized, organic substance decomposing, obtains the unbodied bismuth titanate film of individual layer that thickness is 40 ~ 55nm;
The film of step 9. repeating step 7-8 and drying course 6 ~ 8 times, obtain the bismuth titanate film of desired thickness;
Bismuth titanate film is placed in quartz tube furnace by step 10., under the oxygen atmosphere of flowing, rise to the annealing temperature 650 ~ 750 DEG C of setting from room temperature, insulation 20 ~ 25min, furnace cooling, obtains the laminated perovskite structure bismuth titanate ferro-electricity membrane that final thickness is the random orientation of 350 ~ 450nm;
In described step 5, the absorption metering of irradiation is 40 ~ 60kGy.
2. a kind of bismuth titanate ferro-electricity membrane preparation method according to claim 1, is characterized in that: in step 7, bismuth titanates precursor liquid is spun to the Pt/Ti/SiO processed by sol evenning machine
2time on/Si substrate, first with 900 ~ 1500r/min spin coating 10s, then with 3500 ~ 4500r/min spin coating, 20 ~ 30s.
3. a kind of bismuth titanate ferro-electricity membrane preparation method according to claim 1, it is characterized in that: in step 10, temperature rise rate is 10 ~ 20 DEG C/min.
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| CN103265075B (en) * | 2013-06-05 | 2014-08-06 | 湘潭大学 | Preparation method of bismuth titanate microsphere with multilevel structure |
| CN104084699B (en) * | 2014-06-26 | 2016-01-06 | 天津大学 | The method of even organic-inorganic perovskite crystal film prepared by a kind of flexible substrate |
| CN104538176A (en) * | 2014-12-05 | 2015-04-22 | 黑龙江省科学院高技术研究院 | Method for crystallizing bismuth titanate ferroelectric film by high pressure |
| CN111416006B (en) * | 2020-02-27 | 2021-08-17 | 北京科技大学 | Two-dimensional layered perovskite ferroelectric multifunctional film and preparation process thereof |
| CN114133600B (en) * | 2021-11-22 | 2023-09-05 | 广西大学 | Method for preparing high-molecular magnetic composite film of friction nano generator |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269957A (en) * | 2008-05-14 | 2008-09-24 | 哈尔滨工业大学 | Low-temperature photo-irradiation preparation method for rare earth doped bismuth titanate ferro-electricity membrane |
| CN101798239A (en) * | 2010-04-06 | 2010-08-11 | 湘潭大学 | Method for improving performance of lead-free ferroelectric film and lead-free ferroelectric film prepared by same |
-
2011
- 2011-11-25 CN CN201110380734.3A patent/CN102515748B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269957A (en) * | 2008-05-14 | 2008-09-24 | 哈尔滨工业大学 | Low-temperature photo-irradiation preparation method for rare earth doped bismuth titanate ferro-electricity membrane |
| CN101798239A (en) * | 2010-04-06 | 2010-08-11 | 湘潭大学 | Method for improving performance of lead-free ferroelectric film and lead-free ferroelectric film prepared by same |
Non-Patent Citations (1)
| Title |
|---|
| 李东.铁电存储器薄膜材料的Sol-Gel制备及性能研究.《中国优秀博硕士学位论文全文数据库(硕士) 工程科技II辑》.2005,(第03期),第10-12、15页. * |
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