CN110395768A - A kind of preparation method of flexibility self poling ferrous acid bismuth-based thin films - Google Patents
A kind of preparation method of flexibility self poling ferrous acid bismuth-based thin films Download PDFInfo
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Abstract
The invention belongs to microelectronics new material technology fields, and in particular to a kind of preparation method of flexibility self poling ferrous acid bismuth-based thin films.For this method using high-temperature-resistant flexible mica as substrate material, metallic film or sull grow ferrous acid bismuth-based thin films as hearth electrode material after pre-processing to hearth electrode.Ferrous acid bismuth-based thin films of the direct high growth temperature with self poling effect, chemical composition are Bi (Fe to the present invention on flexible substrates for the first time1‑x‑yMnxTiy)O3, wherein 0 < x≤0.05,0 y≤0.05 <.Present invention process is simple and effective, prepared ferrous acid bismuth-based thin films are resistant to bending, electrical polarization characteristics are superior, charge retention is strong, anti-fatigue performance is good, and good piezoelectric property is just shown without artificial polarization, there is very big application potential in the technical fields such as the storage of flexible ferroelectricity, flexible piezoelectric sensing.
Description
Technical field
The invention belongs to microelectronics new material technology fields, and in particular to a kind of system of flexibility self poling ferrous acid bismuth-based thin films
Preparation Method.
Background technique
Ferroelectric material is a kind of important functional material, with characteristics such as excellent ferroelectricity, piezoelectricity, pyroelectricity, dielectrics,
It can be widely applied to Nonvolatile ferroelectric random access memory, piezoelectric transducer, PZT (piezoelectric transducer), pyroelectric infrared sensor, electricity
Container etc. has important application value in technical fields such as microelectronics.With the development of New Generation of Intelligent electronics, can wear
The rise of the flexible electronics technologies such as wearing electronic fabric, Flexible Displays, deformable sensing is to the semiconductor function based on ferroelectric material
Device proposes that lightweight, portable, flexible, extensible etc. require.It is soft that common flexible ferroelectric thin film is mostly deposited on organic polymer
Property substrate on ferroelectric polymer thin-film material such as polyvinylidene fluoride (PVDF), although have good flexibility, phase
Than in inorganic ferroelectric thin-flim materials, electrical properties are ideal not enough, there are polarization intensities it is small, anti-fatigue performance is poor the defects of.
Recently, two-dimentional mica (Mica) is because having good flexibility and thermal stability (~ 1000 DEG C), it is sufficient to it is thin to bear inorganic functional
High crystallization temperature needed for film (usually >=500 DEG C), it is considered to be it is suitble to the imaginable flexibility lining of the inorganic ferroelectric thin film of high growth temperature
Bottom material.Currently, being mostly with lead zirconate titanate (PZT) using inorganic iron voltage electrical part prepared by high-temperature-resistant flexible mica substrate
Functional layer (bibliography: J. Jiang, Y. Bitla, C.-W. Huang, T.H. Do, H.-J. Liu, Y.-H.
Hsieh, C.-H. Ma, C.-Y. Jang, Y.-H. Lai, P.-W. Chiu, W.-W. Wu, Y.-C. Chen,Y.-
C. Zhou, Y.-H. Chu, Flexible ferroelectric element based on van der Waals
Heteroepitaxy, Science Advances, 2017,3, e1700121.), but after producing, using and is discarded
Lead contamination during reason can seriously endanger human health and natural environment.
Bismuth ferrite (BiFeO3) be a kind of typical Ferroelectrics, leadless environment-friendly, Curie temperature it is high (T c ~830
DEG C), iron electric polarization intensity it is big (P s ~100 μC/cm2), it is the hot spot material (bibliography: J. of ferroelectric material scientific research personnel concern
Wang, J.B. Neaton, H. Zheng, V. Nagarajan, S.B. Ogale, B. Liu, D. Viehland,
V. Vaithyanathan, D.G. Schlom, U.V. Waghmare, N.A. Spaldin, K.M. Rabe, M.
Wuttig and R. Ramesh, Epitaxial BiFeO3 multiferroic thin film
heterostructures, Science, 2003, 299 (5613), 1719-1722.).However, currently with BiFeO3
Electronic device prepared by the excellent ferroelectricity of base film, piezoelectric property is based on BiFeO using hard material as substrate3Base film
Flexible ferroelectric piezoelectric device not yet has been reported that.Therefore, by BiFeO3The excellent ferroelectricity of base film, piezoelectric property and flexible electronic skill
Art combines, and is current promotion BiFeO3The urgent need of base film device industry.
But for BiFeO3For film, material leakage current with higher itself and biggish coercive field, so that its
Be difficult to be polarized (i.e. poling) when being applied to piezoelectricity MEMS and pyroelectric infrared sensor, i.e., it is enabled to be polarized
Very high energy consumption can be brought.If BiFeO3Just there is a degree of self poling effect after base film preparation, that is, do not need
The excitation in any external world and spontaneously form ferroelectric polarization, then can solve film in flexibility of research and development integrated piezoelectric chip
It is difficult to the problem of polarizing, to prepare high performance flexibility BiFeO3Base film piezoelectric device lays a good foundation.
Summary of the invention
The purpose of the present invention is can not be bent and ferrous acid bismuthino for bismuth ferrite based film material in existing hard substrates
Film is difficult to the problem of polarizing, and provides a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films.The present invention is using chemistry
Solution deposition techniques directly grow BiFeO in high-temperature-resistant flexible mica substrate3Base film, and the BiFeO prepared3Base is thin
Film is resistant to bending, electrical polarization characteristics are superior, charge retention is strong, anti-fatigue performance is good, and just shows well without artificial polarization
Piezoelectric property, can be used as flexible electronic device of new generation and the critical material of information collection and data storage be provided, in flexible iron
There is very big application potential in the technical fields such as electricity storage, flexible piezoelectric sensing.
The present invention is achieved by the following technical solutions:
A kind of preparation method of flexibility self poling ferrous acid bismuth-based thin films, this method comprises: using high-temperature-resistant flexible mica as lining
It is thin that bottom material, metallic film or sull grow ferrous acid bismuthino as hearth electrode material, after pre-processing to hearth electrode
Film.Wherein, the preprocessing process of the hearth electrode is N2Atmosphere, anneal at 300 ~ 650 DEG C 5 ~ 20 min, the ferrous acid bismuthino
The heat treatment process of film is 250 ~ 325 DEG C and anneals 2 ~ 5 minutes that 480 ~ 540 DEG C are annealed 5 ~ 10 minutes.
In the preparation method of above-mentioned flexible self poling ferrous acid bismuth-based thin films, hearth electrode material can be Pt, SrRuO3Or
LaNiO3Film.When hearth electrode is Pt metal film, it is made by the method for magnetron sputtering, with a thickness of 30 ~ 150 nm；When
Hearth electrode material is oxide S rRuO3When film, it is made by the method for magnetron sputtering, with a thickness of 10 ~ 50 nm；Hearth electrode
Material is oxide LaNiO3When film, it is made by chemical solution deposition technique, with a thickness of 20 ~ 60 nm.
In the preparation method of above-mentioned flexible self poling ferrous acid bismuth-based thin films, the chemical composition of film is Bi (Fe1-x- yMnxTiy)O3, wherein 0 < x≤0.05,0 y≤0.05 <；Film thickness is 300 ~ 800 nm to keep single spontaneous polarization
Orientation.
Preferably, the process of ferrous acid bismuth-based thin films is grown after hearth electrode is pre-processed are as follows: preparation Bi (Fe1-x-yMnxTiy)
O3Precursor solution is deposited on pretreated hearth electrode using spin-coating method, then dries material, move back by precursor solution
Fire repeats the process of " spin coating-drying-heat treatment ", until film thickness is 300 ~ 800 nm.When spin coating revolving speed be 3000 ~
4000 revs/min, the time is 20 ~ 40 seconds；The condition of drying is 200 ~ 350 DEG C 2 ~ 5 minutes dry；The condition of heat treatment is 250
~ 325 DEG C pre-process 2 ~ 5 minutes, and 480 ~ 540 DEG C are annealed 5 ~ 10 minutes.
Beneficial effect
The present invention for the first time combines the excellent ferroelectricity of ferrous acid bismuth-based thin films, piezoelectric property with flexible electronic technology, in flexible cloud
Direct high growth temperature has the ferrous acid bismuth-based thin films of self poling effect on female substrate, solves ferrous acid bismuthino in existing hard substrates
Thin-film material can not be bent and ferrous acid bismuth-based thin films are difficult to the problem of polarizing.Preparation method of the invention is simple and effective, and makes
Standby ferrous acid bismuth-based thin films are resistant to bending, electrical polarization characteristics are superior, charge retention is strong, anti-fatigue performance is good, and are not necessarily to artificial pole
Change just shows good piezoelectric property, has good reality in the technical fields such as the storage of flexible ferroelectricity, flexible piezoelectric sensing
Use prospect.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of flexible self poling ferrous acid bismuth-based thin films prepared by the present invention.
Fig. 2 is the Bi (Fe being deposited on Mica/Pt electrode prepared by embodiment 10.93Mn0.02Ti0.05)O3The X of film is penetrated
Ray diffraction diagram spectrum.
Fig. 3 (a) is the Bi (Fe being deposited on Mica/Pt electrode prepared by embodiment 20.90Mn0.05Ti0.05)O3Film
Atomic force microscopy surface shape appearance figure, Fig. 3 (b) are the Bi being deposited on Mica/Pt electrode prepared by embodiment 2
(Fe0.90Mn0.05Ti0.05)O3The scanning electron microscope cross-section morphology figure of film.
Fig. 4 (a) is the Bi (Fe being deposited on Mica/Pt electrode prepared by embodiment 30.93Mn0.05Ti0.02)O3Film
Phase image outside piezoelectricity force microscope face, Fig. 4 (b) are the Bi being deposited on Mica/Pt electrode prepared by embodiment 3
(Fe0.93Mn0.05Ti0.02)O3The piezoelectricity amplitude curve of film.
Fig. 5 (a) is the Bi (Fe being deposited on Mica/Pt electrode prepared by embodiment 40.93Mn0.05Ti0.02)O3Film exists
Ferroelectric hysteresis loop figure under differently curved degree, Fig. 5 (b) are the Bi being deposited on Mica/Pt electrode prepared by embodiment 4
(Fe0.93Mn0.05Ti0.02)O3The polarization intensity of film and coercive field with bending radius change curve.
Fig. 6 is deposited on Mica/SrRuO for prepared by embodiment 53Bi (Fe on electrode0.93Mn0.02Ti0.05)O3The X of film
Ray Energy Spectrum Analysis spectrogram.
Fig. 7 is deposited on Mica/SrRuO for prepared by embodiment 63Bi (Fe on electrode0.90Mn0.05Ti0.05)O3Film exists
Leakage current density under formation state with electric field change curve.
Fig. 8 is deposited on Mica/SrRuO for prepared by embodiment 73Bi (Fe on electrode0.93Mn0.05Ti0.02)O3Film exists
It is bent the retention performance curve of front and back.
Fig. 9 is deposited on Mica/LaNiO for prepared by embodiment 83Bi (Fe on electrode0.93Mn0.02Ti0.05)O3Film exists
Ferroelectric hysteresis loop figure under formation state.
Figure 10 is deposited on Mica/LaNiO for prepared by embodiment 93Bi (Fe on electrode0.90Mn0.05Ti0.05)O3Film exists
Fatigue properties curve under formation state.
Figure 11 is deposited on Mica/LaNiO for prepared by embodiment 103Bi (Fe on electrode0.93Mn0.05Ti0.02)O3Film
Retention performance curve under differently curved number.
Specific embodiment
The present invention will be further elaborated combined with specific embodiments below, it should be noted that following the description is only
In order to explain the present invention, its content is not limited.
Embodiment 1
Pt hearth electrode is deposited in 50 μm of thickness < of mica substrate, prepares Bi (Fe0.93Mn0.02Ti0.05)O3Film, specific mistake
Journey is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate Pt film bottom electricity
Pole, thickness are about 150 nm.Then it will be put in quick anneal oven in N2Atmosphere, 10 min of pre-burning at 350 DEG C.
(3) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.3 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/Pt electrode by spin-coating method, and revolving speed is 3000 rpm, and the time is 30 s；So
Material is placed on afterwards on 250 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, it is first pre- at 300 DEG C
5 min are handled, then are warming up to 480 DEG C of 8 min of annealing.Repeat " spin coating-drying-heat treatment " process, until film thickness about
For 400 nm.
The X ray diffracting spectrum of the film is as shown in Figure 2.Wherein, abscissa is 2 θ of the angle of diffraction, and ordinate is that diffraction is strong
Degree.As can be seen that the BiFeO of pure phase has been made on Mica/Pt electrode3Base film, without miscellaneous peak.
Embodiment 2
Pt hearth electrode is deposited in 50 μm of thickness < of mica substrate, prepares Bi (Fe0.90Mn0.05Ti0.05)O3Film, specific mistake
Journey is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate Pt film bottom electricity
Pole, thickness are about 30 nm.Then it will be put in quick anneal oven in N2Atmosphere, 8 min of pre-burning at 480 DEG C.
(3) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 3 days use
Precursor solution is deposited on pretreated Mica/Pt electrode by spin-coating method, and revolving speed is 4000 rpm, and the time is 30 s；So
Material is placed on afterwards on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, it is first pre- at 325 DEG C
5 min are handled, then are warming up to 500 DEG C of 10 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film thickness
About 700 nm.
Shown in atomic force microscopy surface shape appearance figure such as Fig. 3 (a) of the film, it can be seen that on Mica/Pt electrode
Bi (Fe obtained0.90Mn0.05Ti0.05)O3Roughness of film is larger.Scanning electron microscope cross-section morphology figure such as Fig. 3 of the film
(b) shown in, it can be seen that interface is clear between film and Pt electrode, in conjunction with preferable.
Embodiment 3
Pt hearth electrode is deposited in 50 μm of thickness < of mica substrate, prepares Bi (Fe0.93Mn0.05Ti0.02)O3Film, specific mistake
Journey is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate Pt film bottom electricity
Pole, thickness are about 50 nm.Then it will be put in quick anneal oven in N2Atmosphere, 8 min of pre-burning at 450 DEG C.
(3) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 4.5 precursor solution.
(4) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/Pt electrode by spin-coating method, and revolving speed is 4000 rpm, and the time is 30 s；So
Material is placed on afterwards on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, it is first pre- at 300 DEG C
5 min are handled, then are warming up to 500 DEG C of 8 min of annealing.Repeat " spin coating-drying-heat treatment " process, until film thickness about
For 500 nm.
Outside the piezoelectricity force microscope face of the film shown in phase image such as Fig. 4 (a), piezoelectricity amplitude curve such as Fig. 4 (b) institute
Show.As can be seen that Bi (the Fe obtained on Mica/Pt electrode0.93Mn0.05Ti0.02)O3Film show it is consistent it is upward from
Send out polarization orientation, calculate the film piezoelectric modulusd 33 For 313 pm/V.
Embodiment 4
Pt hearth electrode is deposited in 50 μm of thickness < of mica substrate, prepares Bi (Fe0.93Mn0.05Ti0.02)O3Film, specific mistake
Journey is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate Pt film bottom electricity
Pole, thickness are about 30 nm.Then it will be put in quick anneal oven in N2Atmosphere, 8 min of pre-burning at 480 DEG C.
(3) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/Pt electrode by spin-coating method, and revolving speed is 4000 rpm, and the time is 30 s；So
Material is placed on afterwards on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, it is first pre- at 300 DEG C
5 min are handled, then are warming up to 500 DEG C of 8 min of annealing.Repeat " spin coating-drying-heat treatment " process, until film thickness about
For 300 nm.
Shown in the ferroelectric hysteresis loop figure such as Fig. 5 (a) of the film under differently curved degree, polarization intensity and coercive field with
Shown in the change curve of bending radius such as Fig. 5 (b).As can be seen that the Bi obtained on Mica/Pt electrode
(Fe0.93Mn0.05Ti0.02)O3Film its polarization intensity and coercive field under various deformation bending condition have no significant change.
Embodiment 5
SrRuO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.93Mn0.02Ti0.05)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate SrRuO3Film
Hearth electrode, thickness are about 30 nm.Then it will be put in quick anneal oven in N2Atmosphere, 10 min of pre-burning at 600 DEG C.
(3) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.3 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/SrRuO by spin-coating method3On electrode, revolving speed is 3000 rpm, time 30
s；Then material is placed on 250 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 300
DEG C 5 min of pretreatment, then are warming up to 480 DEG C of 8 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film thickness
Degree is about 400 nm.
The X-ray energy spectrum analysis of spectra of the film is as shown in Figure 6.
Embodiment 6
SrRuO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.90Mn0.05Ti0.05)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate SrRuO3Film
Hearth electrode, thickness are about 20 nm.Then it will be put in quick anneal oven in N2Atmosphere, 10 min of pre-burning at 600 DEG C.
(3) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 3 days use
Precursor solution is deposited on pretreated Mica/SrRuO by spin-coating method3On electrode, revolving speed is 4000 rpm, time 30
s；Then material is placed on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 325
DEG C 5 min of pretreatment, then are warming up to 500 DEG C of 10 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film
Thickness is about 400 nm.
Leakage current density of the film under formation state is as shown in Figure 7 with the change curve of electric field.As can be seen that in electricity
When field is 400 kV/cm, in Mica/SrRuO3Bi (Fe obtained on electrode0.90Mn0.05Ti0.05)O3The leakage current density of film
About 1*10-4 A/cm2。
Embodiment 7
SrRuO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.93Mn0.05Ti0.02)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material: using the method for magnetron sputtering in flexible mica deposition on substrate SrRuO3Film
Hearth electrode, thickness are about 20 nm.Then it will be put in quick anneal oven in N2Atmosphere, 10 min of pre-burning at 600 DEG C.
(3) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/SrRuO by spin-coating method3On electrode, revolving speed is 4000 rpm, time 30
s；Then material is placed on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 300
DEG C 5 min of pretreatment, then are warming up to 500 DEG C of 8 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film thickness
Degree is about 400 nm.
Retention performance curve of the film before and after bending is as shown in Figure 8.As can be seen that in Mica/SrRuO3On electrode
Bi (Fe obtained0.93Mn0.05Ti0.02)O3Film charge retention with higher.
Embodiment 8
LaNiO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.93Mn0.02Ti0.05)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material:
A. chemical solution deposition is used, accurately weighs La (NO according to molar ratio 1:13)3·6H2O and Ni (NO3)3·6H2O,
It is dissolved in ethylene glycol monomethyl ether, compound concentration is the precursor solution of 0.1 mol/L；
B. it is combined and is annealed layer by layer in flexible mica deposition on substrate LaNiO using spin-coating method3Film hearth electrode.Revolving speed when spin coating
For 3000 rpm, the time is 30 s；Then material is placed on 300 DEG C of hot plate and dries 5 min, the film after drying is put
In quick anneal oven in N2Atmosphere, anneal at 620 DEG C 15 min.The process for repeating " spin coating-drying-heat treatment ", until
LaNiO3Film thickness is about 60 nm.
(3) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.3 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.02Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/LaNiO by spin-coating method3On electrode, revolving speed is 3000 rpm, time 30
s；Then material is placed on 250 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 300
DEG C 5 min of pretreatment, then are warming up to 480 DEG C of 8 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film thickness
Degree is about 500 nm.
Ferroelectric hysteresis loop of the film under formation state is as shown in Figure 9.As can be seen that in Mica/ LaNiO3It is made on electrode
Bi (the Fe obtained0.93Mn0.02Ti0.05)O3The ferroelectric hysteresis loop presentation of film significantly deviates to the right.
Embodiment 9
LaNiO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.90Mn0.05Ti0.05)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to a thickness of 50 μ of < with double-sided adhesive
m。
(2) preparation of hearth electrode material:
A. chemical solution deposition is used, accurately weighs La (NO according to molar ratio 1:13)3·6H2O and Ni (NO3)3·6H2O,
It is dissolved in ethylene glycol monomethyl ether, compound concentration is the precursor solution of 0.1 mol/L；
B. it is combined and is annealed layer by layer in flexible mica deposition on substrate LaNiO using spin-coating method3Film hearth electrode.Revolving speed when spin coating
For 3000 rpm, the time is 30 s；Then material is placed on 300 DEG C of hot plate and dries 5 min, the film after drying is put
In quick anneal oven in N2Atmosphere, anneal at 620 DEG C 15 min.The process for repeating " spin coating-drying-heat treatment ", until
LaNiO3Film thickness is about 40 nm.
(3) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.90Mn0.05Ti0.05)O3The preparation of film: the precursor solution of preparation still aging 3 days use
Precursor solution is deposited on pretreated Mica/LaNiO by spin-coating method3On electrode, revolving speed is 4000 rpm, time 30
s；Then material is placed on 250 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 325
DEG C 5 min of pretreatment, then are warming up to 500 DEG C of 10 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film
Thickness is about 400 nm.
Fatigue properties curve of the film under formation state is as shown in Figure 10.As can be seen that in Mica/ LaNiO3Electricity
Extremely upper Bi (Fe obtained0.90Mn0.05Ti0.05)O3Film has good resistance to polarization fatigue.
Embodiment 10
LaNiO is deposited in 50 μm of thickness < of mica substrate3Hearth electrode prepares Bi (Fe0.93Mn0.05Ti0.02)O3Film, tool
Body process is as follows:
(1) Substrate treatment: selecting the Fluororystal mica piece of surfacing, it is successively thinned to 50 μm of thickness < with double-sided adhesive.
(2) preparation of hearth electrode material:
A. chemical solution deposition is used, accurately weighs La (NO according to molar ratio 1:13)3·6H2O and Ni (NO3)3·6H2O,
It is dissolved in ethylene glycol monomethyl ether, compound concentration is the precursor solution of 0.1 mol/L；
B. it is combined and is annealed layer by layer in flexible mica deposition on substrate LaNiO using spin-coating method3Film hearth electrode.Revolving speed when spin coating
For 3000 rpm, the time is 30 s；Then material is placed on 300 DEG C of hot plate and dries 5 min, the film after drying is put
In quick anneal oven in N2Atmosphere, anneal at 620 DEG C 15 min.The process for repeating " spin coating-drying-heat treatment ", until
LaNiO3Film thickness is about 40 nm.
(3) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of thin film precursor solution: Bi is accurately weighed according to molar ratio
(NO3)3·5H2O (excessive 5 %), Fe (NO3)3·9H2O、(CH3COO)2Mn·4H2O is stirred at room temperature and is dissolved in 30 ml ethylene glycol
In, tetra-n-butyl titanate is instilled according still further to molar ratio, the acetylacetone,2,4-pentanedione of 2 ml is added as stabilizer, using acetic acid as pH value of solution
Regulator, compound concentration be 0.4 mol/L, pH be about 5 precursor solution.
(4) Bi(Fe0.93Mn0.05Ti0.02)O3The preparation of film: the precursor solution of preparation still aging 2 days use
Precursor solution is deposited on pretreated Mica/LaNiO by spin-coating method3On electrode, revolving speed is 4000 rpm, time 30
s；Then material is placed on 300 DEG C of hot plate and dries 2 min, the film after drying is put in quick anneal oven, first 300
DEG C 5 min of pretreatment, then are warming up to 500 DEG C of 8 min of annealing.The process for repeating " spin coating-drying-heat treatment ", until film thickness
Degree is about 400 nm.
Retention performance curve of the film under differently curved number is as shown in figure 11.As can be seen that in Mica/
LaNiO3Bi (Fe obtained on electrode0.93Mn0.05Ti0.02)O3Film resist bending all has under the conditions of different bending deformation
Good charge retention.
Claims (9)
1. a kind of preparation method of flexibility self poling ferrous acid bismuth-based thin films, which comprises the following steps: with resistant to high temperature
Flexible mica as substrate material, metallic film or sull as hearth electrode material, after being pre-processed to hearth electrode
Grow ferrous acid bismuth-based thin films.
2. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 1, which is characterized in that bottom
Electrode material is Pt, SrRuO3Or LaNiO3Film.
3. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 1, which is characterized in that iron
The chemical composition of sour bismuth-based thin films is Bi (Fe1-x-yMnxTiy)O3, wherein 0 < x≤0.05,0 y≤0.05 <, film thickness are
300~800 nm。
4. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 3, which is characterized in that bottom
Electrode grows the process of ferrous acid bismuth-based thin films after being pre-processed are as follows: preparation Bi (Fe1-x-yMnxTiy)O3Precursor solution uses
Precursor solution is deposited on pretreated hearth electrode by spin-coating method, then dries material, and annealing repeats " spin coating-baking
The process of dry-heat treatment ", until film thickness is 300 ~ 800nm.
5. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 4, which is characterized in that rotation
Revolving speed is 3000 ~ 4000 revs/min when painting, and the time is 20 ~ 40 seconds；The condition of drying is 200 ~ 350 DEG C 2 ~ 5 minutes dry；Heat
The condition of processing is 250 ~ 325 DEG C and pre-processes 2 ~ 5 minutes that 480 ~ 540 DEG C are annealed 5 ~ 10 minutes.
6. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 2, which is characterized in that bottom
Electrode is Pt metal film, is made by the method for magnetron sputtering, with a thickness of 30 ~ 150 nm.
7. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 2, which is characterized in that bottom
Electrode material is oxide S rRuO3Film, the method for crossing magnetron sputtering is made, with a thickness of 10 ~ 50 nm.
8. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 2, which is characterized in that bottom
Electrode material is oxide LaNiO3Film is made, with a thickness of 20 ~ 60 nm by chemical solution deposition technique.
9. a kind of preparation method of flexible self poling ferrous acid bismuth-based thin films according to claim 1, which is characterized in that institute
The preprocessing process for stating hearth electrode is N2Atmosphere, anneal at 300 ~ 650 DEG C 5 ~ 20 min.
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| CN115579424A (en) * | 2022-10-31 | 2023-01-06 | 内蒙古工业大学 | Preparation method of flexible bismuth ferrite film |
| WO2024061152A1 (en) * | 2022-09-20 | 2024-03-28 | 中国石油天然气股份有限公司 | Ultrasonic sensing device and manufacturing method therefor |
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