CN109192855A - BEFMO/ZnO composite heterojunction with resistance switching effect and preparation method thereof - Google Patents
BEFMO/ZnO composite heterojunction with resistance switching effect and preparation method thereof Download PDFInfo
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Abstract
The invention provides a BEFMO/ZnO composite heterojunction with resistance switching effect and a preparation method thereof, wherein the BEFMO/ZnO composite heterojunction comprises a lower layer film and an upper layer film which are compounded together; the chemical formula of the lower layer film is ZnO, and the lower layer film has a hexagonal wurtzite structure; the upper film has a chemical formula of Bi0.9Er0.1Fe0.99Mn0.01O3A twisted rhombohedral perovskite structure, space group R3 c. The preparation method comprises the following steps: preparing ZnO precursor solution; spin-coating ZnO precursor solution on an FTO/Glass substrate, baking, and annealing to obtain a crystalline ZnO film; preparing BEFMO precursor solution, spinning and coating the BEFMO precursor solution on a crystalline ZnO film, baking and annealing to obtain the BEFMO/ZnO composite heterojunction. The BEFMO/ZnO composite heterojunction provided by the invention shows a good resistance switching effect.
Description
Technical field
The invention belongs to field of functional materials, are related to a kind of BEFMO/ZnO composite heterogenous junction with resistance switch effect
And preparation method thereof.
Background technique
Multiferroic bismuth ferrite BiFeO3(writing a Chinese character in simplified form BFO) material is that currently the only in room temperature while having ferroelectricity and ferromagnetic
Multi-ferroic material has excellent ferroelectricity and magneto-electric coupled characteristic, in novel Nonvolatile Memory Device, Multifunction Sensor
The fields such as part, spin electric device, photovoltaic device have broad application prospects.Ferrous acid bismuthino resistive memory combines iron
The advantages of electrical storage and resistance-variable storing device, regulates and controls interface potential barrier and carrier transport characteristic by the reversion of iron electric polarization, with
This realizes the switching of high low resistance state, and non-defective regulation resistive behavior, shows unique advantage.
Since polarization reversal is very fast under external electric field by BFO, there is high-speed read-write advantage.However, BiFeO3In film
The volatile and part Fe of bismuth element3+To Fe2+Transformation, make to generate more Lacking oxygen in film, so as to cause BiFeO3
There is serious leakies and biggish coercive field for film, it is difficult to polarize, be difficult to obtain higher remanent polarization, therefore
Resistive mechanism is often different from the resistive structure of ideal iron electric polarization regulation, and the resistive characteristic of practical bismuth ferrite is restricted.
Summary of the invention
Aiming at the problems existing in the prior art, it is multiple to provide a kind of BEFMO/ZnO with resistance switch effect by the present invention
Hetero-junctions and preparation method thereof is closed, BEFMO/ZnO composite heterogenous junction ferroelectric properties obtained is good, and resistance switch effect is good.
The present invention is to be achieved through the following technical solutions:
A kind of BEFMO/ZnO composite heterogenous junction with resistance switch effect, including the lower membrane that is combined with each other and upper
Tunic；Lower membrane chemical formula is ZnO, hexagonal wurtzite structure；Upper layer film chemical formula is Bi0.9Er0.1Fe0.99Mn0.01O3, distortion
Water chestnut side's perovskite structure, space group R3c.
Preferably, high low resistance state on-off ratio RHRS/RLRSIt is 4.62~74.76.
Preferably, under the magnetic field 1kHz, under the voltage of 40~50V, remanent polarization PrFor 27~40 μ C/cm2, electricity
Hysteresis curves rectangular degree Rsq=0.99~1.05, coercive field strength is 384~466kV/cm.
A kind of preparation method of the BEFMO/ZnO composite heterogenous junction with resistance switch effect, which is characterized in that
The following steps are included:
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, is stirred evenly, and is obtained
ZnO precursor liquid；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is toasted to obtain at 280~300 DEG C afterwards, annealing obtains crystalline state ZnO film at 550~580 DEG C；
Step 3, after crystalline state ZnO film cooling after, on crystalline state ZnO film repeat step 2, reach preset thickness to get
To ZnO film；
Step 4, by Bi (NO3)3·5H2O、Er(NO3)3·6H2O、Fe(NO3)3·9H2O、C4H6MnO4·4H2O by mole
Than being dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride for 0.95:0.10:0.99:0.01, stir evenly, before obtaining BEFMO
Drive liquid；
Step 5, the spin coating BEFMO precursor liquid on crystalline state ZnO film, obtains BEFMO wet film, wet film is after spin coating 180
~200 DEG C are toasted to obtain dry film, are annealed at 530~550 DEG C, and crystalline state BEFMO film is obtained；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches preset thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Preferably, the concentration of metal ion is 0.5~0.6mol/L in ZnO precursor liquid in step 1.
Preferably, the total concentration of metal ion is 0.2~0.3mol/L in BEFMO precursor liquid in step 4.
Preferably, ethylene glycol monomethyl ether and the volume ratio of ethanol amine are (30~32) in ZnO precursor liquid: 1；BEFMO precursor liquid
Middle ethylene glycol monomethyl ether and the volume ratio of acetic anhydride are (2.9~3.2): 1.
Preferably, the spin coating revolving speed in step 2 and step 5 is 3800~4000r/min, and spin coating time is 12~15s.
Preferably, the baking time in step 2 after spin coating is 15~20min, and the baking time in step 5 after spin coating is 5
~10min.
Preferably, the annealing time in step 2 is 45~60min, and the annealing time in step 5 is 8~15min.
Compared with prior art, the invention has the following beneficial technical effects:
BEFMO/ZnO composite heterogenous junction of the present invention selects rare earth element er and transiting group metal elements Mn to carry out
The content of Lacking oxygen and defect can be effectively reduced in the position A, B codope of BFO, doping, reduces the leakage current density in film, from
And improve thin-film ferroelectric.ZnO belongs to broad stopband direct band-gap semicondictor at normal temperature, and forbidden bandwidth is about 3.37eV, oxidation
Zinc is used as channel material as extensive semiconductor material in thin film transistor (TFT) (Thin-FilmTransistor, TFT)
Material has application.The compound ZnO semiconductor of BEFMO constructs ferroelectric film/heterojunction semiconductor, and ZnO film belongs to N-type semiconductor, body
The transport property for revealing N-type carrier can form class p-n junction with the BFO of p-type conduction.Regulated and controled by control applied voltage
The polarization direction and polarization intensity of ferroelectric layer, so that intercoupling between ferroelectric layer and semiconductor layer causes in semiconductor layer
Interface carrier is exhausted or is accumulated, these carrier (defect and a large amount of space charge) meetings are so that compound membrane interface
Place generates a kind of intermediate layer, and hetero-junctions just produces different local conductivity states, so that hetero-junctions can be in height
Switch between resistance state, form more obvious resistive behavior, shows good resistance switch effect.In addition, in practical application
The application of the demand of pluralistic effect, single BFO is restricted.It is thin to bismuth ferrite in order to promote the resistive characteristic of bismuth ferrite
Film carry out oxide it is compound, bismuth ferrite material embodies the resistive characteristic of enhancing, be mainly derived from its enhancing ferroelectric properties and
Introduce the resistives mechanism such as Lacking oxygen.
Further, the high low resistance state on-off ratio R under positive electric fieldHRS/RLRSIt is 4.62~74.76, illustrates that it has very
Good resistance switch effect.
Further, BEFMO/ZnO composite heterogenous junction changes in 40~50V voltage range, and remanent polarization is 27~40 μ
C/cm2, ferroelectric hysteresis loop rectangular degree is Rsq=1.05, therefore it has stable ferroelectricity with applied voltage variation.
Method currently used for preparing BFO and ZnO film has very much, compared to other methods, colloidal sol that the present invention uses
Gel method chemical process is simpler, and the cost of equipment and maintenance is relatively low, the Uniform Doped on molecular level easy to accomplish, can be with
The thickness of effective control film.Ferroelectric layer and semiconductor layer it is good it is compound prepare BEFMO/ZnO composite heterogenous junction, be made
Composite heterogenous junction has good uniformity.
Detailed description of the invention
Fig. 1 is the XRD diagram of BEFMO/ZnO composite heterogenous junction prepared by the present invention；
Fig. 2 is the leakage current loop line of BFO/ZnO composite heterogenous junction and BEFMO/ZnO composite heterogenous junction prepared by the present invention
Figure；
Fig. 3 is the high low resistance state ratio of BFO/ZnO composite heterogenous junction and BEFMO/ZnO composite heterogenous junction prepared by the present invention
Change curve；
Fig. 4 is the ferroelectric hysteresis loop figure of BEFMO/ZnO composite heterogenous junction prepared by the present invention；
Specific embodiment
Below with reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
BEFMO/ZnO composite heterogenous junction of the present invention with resistance switch effect is bilayer film, including compound
Lower membrane and upper layer film together, wherein lower membrane is ZnO crystalline state film, hexagonal wurtzite structure；Upper layer film is
Bi0.9Er0.1Fe0.99Mn0.01O3(writing a Chinese character in simplified form BEFMO) crystalline state film, water chestnut side's perovskite structure of distortion, space group R3c.
The BEFMO/ZnO composite heterogenous junction with resistance switch effect, in the interface defect of BEFMO/ZnO and big
The space charge of amount produces one and is rich in Bi-Er-Mn-Zn intermediate layer, the high low resistance state on-off ratio under positive electric field
RHRS/RLRSIt is 4.62~74.76, composite heterogenous junction has resistance switch effect.
Under the voltage of 40~50V, the remanent polarization P of BEFMO/ZnO composite heterogenous junctionrFor 27~40 μ C/cm2, electricity
Hysteresis curves rectangular degree Rsq=0.99~1.05, coercive field strength is 384~466kV/cm, and hetero-junctions has good ferroelectricity.
The preparation method of the BEFMO/ZnO composite heterogenous junction, comprising the following steps:
Step 1: by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, is stirred evenly, and is obtained
ZnO precursor liquid；
Step 2: using spin-coating method spin coating ZnO precursor liquid on FTO/Glass substrate, obtain ZnO wet film, wet film is through spin coating
Dry film is toasted to obtain at 280~300 DEG C afterwards, annealing obtains crystalline state ZnO film at 550~580 DEG C；
Step 3: after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4: by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O、
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio, is stirred
It mixes uniformly, obtains BEFMO precursor liquid；
Step 5: the spin coating BEFMO precursor liquid on crystalline state ZnO film obtains BEFMO wet film, wet film is after spin coating 180
~200 DEG C are toasted to obtain dry film, are annealed at 530~550 DEG C, and crystalline state BEFMO film is obtained；
Step 6: after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
The total concentration of metal ion is 0.5~0.6mol/L in ZnO precursor liquid in the step 1.
The total concentration of metal ion is 0.2~0.3mol/L in BEFMO precursor liquid in the step 4.
Ethylene glycol monomethyl ether and the volume ratio of ethanol amine are (30~32) in the ZnO precursor liquid: 1；Second in BEFMO precursor liquid
The volume ratio of glycol methyl ether and acetic anhydride is (2.9~3.2): 1；The time of uniform stirring is 1.5~2h in step 1.
The step 2 first cleans FTO/glass substrate before progress, then treatment with irradiation under ultraviolet light, then
Spin coating ZnO precursor liquid；Before the step 5 first carries out ultraviolet light processing, then spin coating BEFMO to ZnO crystalline state film before progress
Drive liquid.
Spin coating revolving speed in the step 2 and step 5 is 3800~4000r/min, and spin coating time is 12~15s.
Baking time in the step 2 and step 5 after spin coating is respectively 15~20min and 5~10min.
Annealing time in the step 2 is 45~60min, and the annealing time in step 5 is 8~15min.
The number of plies of crystalline state ZnO film is 5~8 layers, and the number of plies of crystalline state BEFMO film is 8~13 layers.
Specific embodiment is as follows.
Embodiment 1
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.5mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 300 DEG C of baking 20min afterwards, the 60min that anneals at 550 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.3mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating,
Anneal 10min at 550 DEG C, obtains crystalline state BEFMO film；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 2
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.5mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 300 DEG C of baking 20min afterwards, the 60min that anneals at 550 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.3mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating,
Anneal 15min at 530 DEG C, obtains crystalline state BEFMO film；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 3
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.5mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 280 DEG C of baking 20min afterwards, the 60min that anneals at 560 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.3mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating,
Anneal 10min at 550 DEG C, obtains crystalline state BEFMO film；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 4
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.5mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 300 DEG C of baking 20min afterwards, the 60min that anneals at 550 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.2mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 180 DEG C of baking 8min after spin coating,
Anneal 10min at 550 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 4000r/min, spin coating time 15s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 5
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.6mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 300 DEG C of baking 20min afterwards, the 50min that anneals at 580 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.3mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating,
Anneal 10min at 550 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 4000r/min, spin coating time 15s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 6
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.6mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 31:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 280 DEG C of baking 20min afterwards, the 60min that anneals at 560 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.3mol/L, ethylene glycol monomethyl ether
Volume ratio with acetic anhydride is 2.9:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating,
Anneal 10min at 550 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 4000r/min, spin coating time 15s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 7
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.52mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is
32:1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 285 DEG C of baking 15min afterwards, the 45min that anneals at 555 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 3800r/
Min, spin coating time 12s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.22mol/L, ethylene glycol first
The volume ratio of ether and acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 185 DEG C of baking 5min after spin coating,
Anneal 8min at 535 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 3800r/min, spin coating time 12s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 8
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.54mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is
30:1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 290 DEG C of baking 16min afterwards, the 50min that anneals at 560 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 3900r/
Min, spin coating time 13s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.24mol/L, ethylene glycol first
The volume ratio of ether and acetic anhydride is 3.1:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 190 DEG C of baking 6min after spin coating,
Anneal 10min at 540 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 3900r/min, spin coating time 13s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 9
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.56mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is
30:1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 295 DEG C of baking 18min afterwards, the 55min that anneals at 570 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 14s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.26mol/L, ethylene glycol first
The volume ratio of ether and acetic anhydride is 3.2:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid to be distinguished on ZnO film, obtains BEFMO wet film, wet film obtains dry film in 195 DEG C of baking 9min after spin coating,
Anneal 12min at 545 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 4000r/min, spin coating time 14s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Embodiment 10
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.58mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is
30:1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 280 DEG C of baking 20min afterwards, the 58min that anneals at 560 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 3800r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%), Er (NO3)3·6H2O、Fe(NO3)3·9H2O and
C4H6MnO4·4H2O is that 0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride in molar ratio,
Even stirring 2h, obtains BEFMO precursor liquid, and wherein the concentration of metal ions in BEFMO precursor liquid is 0.28mol/L, ethylene glycol first
The volume ratio of ether and acetic anhydride is 3:1；
Step 5, prepared BEFMO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state
Spin coating BEFMO precursor liquid is distinguished on ZnO film, obtains BEFMO wet film, wet film must be done after spin coating in 200 DEG C of baking 10min
Film, anneal 14min at 550 DEG C, obtains crystalline state BEFMO film；Spin coating revolving speed is 3800r/min, spin coating time 15s；
Step 6, after crystalline state BEFMO film Temperature fall, step 5 is repeated on BEFMO film, reaches required thickness,
Obtain BEFMO/ZnO composite heterogenous junction.
Comparative example 1
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, and uniform stirring 2h is obtained
ZnO precursor liquid, the concentration of metal ion is 0.5mol/L in ZnO precursor liquid, and the volume ratio of ethylene glycol monomethyl ether and ethanol amine is 30:
1；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film is through spin coating
Dry film is obtained in 300 DEG C of baking 20min afterwards, the 60min that anneals at 550 DEG C obtains crystalline state ZnO film；Spin coating revolving speed is 4000r/
Min, spin coating time 15s；
Step 3, after crystalline state ZnO film Temperature fall, step 2 is repeated on crystalline state ZnO film, reaches required thickness,
Obtain ZnO film；
Step 4, by Bi (NO3)3·5H2O (bismuth nitrate excessive 5%) and Fe (NO3)3·9H2O is that 1.05:1 is molten in molar ratio
In the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride, uniform stirring 2h obtains BFO precursor liquid, wherein the metal in BFO precursor liquid
Ion concentration is 0.3mol/L, and the volume ratio of ethylene glycol monomethyl ether and acetic anhydride is 3:1；
Step 5, prepared BFO precursor liquid is stood for 24 hours, using ultraviolet irradiation ZnO crystalline state film 40min, in crystalline state ZnO
Spin coating BFO precursor liquid is distinguished on film, obtains BFO wet film, wet film obtains dry film in 200 DEG C of baking 8min after spin coating, then at 550
Anneal 10min at DEG C, obtains crystalline state BFO film；
Step 6, after crystalline state BFO film Temperature fall, on BFO film repeat step 5, reach required thickness to get
To BFO/ZnO composite heterogenous junction.
Using the object phase composition structure of XRD determining BEFMO/ZnO compound film hetero-junction；It is tested with Agilent B2900
The leakage current characteristic of BEFMO/ZnO compound film hetero-junction；It is different with TF2000 ferroelectricity analyzer test b EFMO/ZnO laminated film
The ferroelectric properties of matter knot.
Fig. 1 is that BEFMO/ZnO composite heterogenous junction is made in the embodiment of the present invention 1 and the BFO/ZnO of the preparation of comparative example 1 is compound different
The XRD diagram of matter knot.It can be seen that film 2 θ=22.5 °, 32 °, 39.5 °, 57.5 ° corresponding (101), (110),
(021), (122) crystallographic plane diffraction peak and BiFeO3Standard card (JCPDS No.20-0169) matches, and has the water chestnut side of distortion
Perovskite structure, space group R3c, film is in 2 θ=31.5 °, 34.5 ° and 36.5 ° corresponding (100), (002) and (101) crystal face
Diffraction maximum is consistent with ZnO standard card (JCPDS No.36-1415), and the characteristic peak of ZnO is weaker, is hexagonal wurtzite structure, multiple
The crystallinity for closing rear film is good.
Fig. 2 and Fig. 3 is the leakage current loop line figure and high low resistance state that BEFMO/ZnO compound film hetero-junction is made in embodiment 1
Ratio change curve.The defect of BEFMO/ZnO composite heterogenous junction interface and a large amount of space charge can make composite membrane circle
Bi-Er-Mn-Zn intermediate layer is generated at face, from Fig. 2 and 3 it can be seen that high low resistance state on-off ratio R under its positive electric fieldHRS/
RLRSIt is 74.76, composite membrane has resistance switch effect.BEFMO/ZnO composite heterogenous junction has biggish on-off ratio RHRS/RLRS
It is 74.76, as Er, Mn ion mix in the BFO of upper layer, the J-E loop line of film broadens, i.e., resistive effect should enhance, this shows
Interfacial effect enhancing between BEFMO and ZnO layer.
Fig. 4 is the ferroelectric hysteresis loop figure that BEFMO/ZnO composite heterogenous junction is made in embodiment 1, is measured at room temperature by figure in 1kHz
Ferroelectric hysteresis loop it is found that under the voltage of 40~50V, the remanent polarization P of BEFMO/ZnO hetero-junctionsrFor 27~40 μ C/cm2,
Its ferroelectric hysteresis loop rectangular degree Rsq=0.99~1.05, coercive field strength is 384~446kV/cm, and film has preferable ferroelectricity,
And there is stable ferroelectricity with applied voltage variation.
Above said content is that a further detailed description of the present invention in conjunction with specific preferred embodiments, is not
Whole or unique embodiment, those of ordinary skill in the art are by reading description of the invention to technical solution of the present invention
Any equivalent transformation taken, all are covered by the claims of the invention.
Claims (10)
1. a kind of BEFMO/ZnO composite heterogenous junction with resistance switch effect, which is characterized in that including being combined with each other down
Tunic and upper layer film；Lower membrane chemical formula is ZnO, hexagonal wurtzite structure；Upper layer film chemical formula is
Bi0.9Er0.1Fe0.99Mn0.01O3, water chestnut side's perovskite structure of distortion, space group R3c.
2. the BEFMO/ZnO composite heterogenous junction according to claim 1 with resistance switch effect, which is characterized in that high
Low resistance state on-off ratio RHRS/RLRSIt is 4.62~74.76.
3. the BEFMO/ZnO composite heterogenous junction according to claim 1 with resistance switch effect, which is characterized in that
Under the magnetic field 1kHz, under the voltage of 40~50V, remanent polarization PrFor 27~40 μ C/cm2, ferroelectric hysteresis loop rectangular degree Rsq=
0.99~1.05, coercive field strength is 384~466kV/cm.
4. a kind of preparation of the described in any item BEFMO/ZnO composite heterogenous junctions with resistance switch effect of claim 1-3
Method, which comprises the following steps:
Step 1, by C4H6O4Zn·2H2O is dissolved in the mixed liquor of ethylene glycol monomethyl ether and ethanol amine, is stirred evenly, and ZnO forerunner is obtained
Liquid；
Step 2, using spin-coating method on FTO/Glass substrate spin coating ZnO precursor liquid, obtain ZnO wet film, wet film after spin coating
280~300 DEG C are toasted to obtain dry film, and annealing obtains crystalline state ZnO film at 550~580 DEG C；
Step 3, after the cooling of crystalline state ZnO film, step 2 is repeated on crystalline state ZnO film, reaches preset thickness to get ZnO is arrived
Film；
Step 4, by Bi (NO3)3·5H2O、Er(NO3)3·6H2O、Fe(NO3)3·9H2O、C4H6MnO4·4H2O is in molar ratio
0.95:0.10:0.99:0.01 is dissolved in the mixed liquor of ethylene glycol monomethyl ether and acetic anhydride, is stirred evenly, and BEFMO precursor liquid is obtained；
Step 5, the spin coating BEFMO precursor liquid on crystalline state ZnO film, obtains BEFMO wet film, wet film is after spin coating 180~200
DEG C dry film is toasted to obtain, anneals at 530~550 DEG C, obtain crystalline state BEFMO film；
Step 6, after crystalline state BEFMO film Temperature fall, on BEFMO film repeat step 5, reach preset thickness to get
To BEFMO/ZnO composite heterogenous junction.
5. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect, special
Sign is that the concentration of metal ion is 0.5~0.6mol/L in ZnO precursor liquid in step 1.
6. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect, special
Sign is that the total concentration of metal ion is 0.2~0.3mol/L in BEFMO precursor liquid in step 4.
7. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect, special
Sign is that ethylene glycol monomethyl ether and the volume ratio of ethanol amine are (30~32) in ZnO precursor liquid: 1；Ethylene glycol in BEFMO precursor liquid
The volume ratio of methyl ether and acetic anhydride is (2.9~3.2): 1.
8. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect, special
Sign is that the spin coating revolving speed in step 2 and step 5 is 3800~4000r/min, and spin coating time is 12~15s.
9. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect, special
Sign is that the baking time in step 2 after spin coating is 15~20min, and the baking time in step 5 after spin coating is 5~10min.
10. the preparation method of the BEFMO/ZnO composite heterogenous junction according to claim 4 with resistance switch effect,
It is characterized in that, the annealing time in step 2 is 45~60min, and the annealing time in step 5 is 8~15min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104575907A (en) * | 2014-12-11 | 2015-04-29 | 陕西科技大学 | Bi1-xRExFe1-yTMyO3/CoFe2O4 multiferroic composite film and preparation method thereof |
| CN105369201A (en) * | 2015-11-12 | 2016-03-02 | 天津大学 | Method for preparing manganese-doped zinc oxide-bismuth ferrite epitaxial heterostructure having indoor-temperature electric-control magnetic property |
-
2018
- 2018-09-18 CN CN201811089163.6A patent/CN109192855B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104575907A (en) * | 2014-12-11 | 2015-04-29 | 陕西科技大学 | Bi1-xRExFe1-yTMyO3/CoFe2O4 multiferroic composite film and preparation method thereof |
| CN105369201A (en) * | 2015-11-12 | 2016-03-02 | 天津大学 | Method for preparing manganese-doped zinc oxide-bismuth ferrite epitaxial heterostructure having indoor-temperature electric-control magnetic property |
Non-Patent Citations (2)
| Title |
|---|
| YUMIN HAN 等: ""Enhancement of magnetic and ferroelectric properties of BiFeO3 by Er and transition element (Mn, Co) co-doping"", 《MATERIALS SCIENCE AND ENGINEERING B》 * |
| 贾湘江: ""ZnO/BiFeO3双层膜电阻开关特性的研究"", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技II辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110246958A (en) * | 2019-06-29 | 2019-09-17 | 河南大学 | A method of improving the photoelectric respone of BFO/ZnO heterojunction device |
| CN110246958B (en) * | 2019-06-29 | 2020-12-18 | 河南大学 | Method for improving photoelectric response of BFO/ZnO heterojunction device |
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