CN109802033A - It is a kind of to induce BiFeO using ion implanting3The method of film reversible transition - Google Patents
It is a kind of to induce BiFeO using ion implanting3The method of film reversible transition Download PDFInfo
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Abstract
The present invention provides a kind of utilization ion implanting induction BiFeO3The method of film reversible transition, to BiFeO3Film injects helium ion, change its lattice gradually by rhombohedral phase → class tetragonal phase → tetragonal phase → super tetragonal phase sequence with the increase of He isotopic geochemistry amount, it is made annealing treatment again, changes its lattice by super tetragonal phase → tetragonal phase → class tetragonal phase → rhombohedral phase sequence.By the BiFeO for by He isotopic geochemistry including rhombohedral phase3In film, helium ion enters BiFeO3Interstitial void, to rhombohedral phase lattice the face ab provide stress, stretch c-axis, rhombohedral phase promoted to be gradually converted into class tetragonal phase and/or tetragonal phase and/or super tetragonal phase.Helium ion spilling interstitial void can be effectively excited using making annealing treatment and rationally controlling annealing temperature and annealing time, so that class tetragonal phase and/or tetragonal phase and/or super tetragonal phase is reverted to rhombohedral phase, realizes controllable, reversible transition between class tetragonal phase and/or tetragonal phase and/or super tetragonal phase and rhombohedral phase.
Description
Technical field
The invention belongs to semiconductor film material technical fields more particularly to a kind of utilization ion implanting to induce BiFeO3It is thin
The method of film reversible transition.
Background technique
Multi-iron material is the multifunctional material that one kind has both ferroelectricity (anti-ferroelectricity) and ferromagnetism (anti-ferromagnetism), can be real
Now electrically and magnetically between mutual regulation, be expected to be used for high density, low-power consumption, high speed, non-volatile magneto-electric coupled memory device.
BiFeO3(BFO) it is most hot one of the multi-iron material of current research, has both ferroelectricity and anti-ferromagnetism, ferroelectrie Curie temperature
(~1100K) and antiferromagnetic Neel temperature (~653K) be much higher than room temperature.The stable phase of BFO at room temperature is rhombohedral phase,
For the lattice constant ratio (c/a ratio) of c-axis and a axis close to 1, the polarization value in [001] direction is about 60 μ C/cm in lattice2.BFO's
In epitaxial film, other than intrinsic rhombohedral phase, there is also the class tetragonal phase, tetragonal phase and super tetragonal phase by strain inducing, tools
Have that spontaneous polarization is big, piezoelectric response is strong and the novel physics performance such as photovoltaic effect.
Existing induction BFO film forms class tetragonal phase, the main method of tetragonal phase and super tetragonal phase be using with substrate compared with
Big lattice mismatch (~4.5%) provides strain for the face ab of rhombohedral phase lattice, stretches c-axis, make c/a ratio close to 1.23 or
It is bigger.However as the increase of film thickness, the interface from film bottom and substrate is to maintain class tetragonal phase, tetragonal phase
It will be unable to keep with the restraining force of super tetragonal phase, especially tetragonal phase and super tetragonal phase, part BFO forms water chestnut side because of strain relief
Phase, the mixed phase state that a type tetragonal phase is presented in entire film and rhombohedral phase coexists.It therefore usually can not be biggish in thickness
Simple tetragonal phase or super tetragonal phase are obtained in BFO film, greatly limit its application.
Summary of the invention
Based on this, the present invention provides a kind of utilization ion implanting induction BiFeO3The method of film reversible transition, this method
Not by BiFeO3The influence of film thickness can make BiFeO3Film reversibly mutually conversion between tetragonal phase and mixed phase.
It is of the present invention to induce BiFeO using ion implanting3The method of film reversible transition is, to BiFeO3Film injection
Helium ion changes its lattice.
Further, the BiFeO containing rhombohedral phase3The lattice of film gradually presses water chestnut with the increase of He isotopic geochemistry amount
Square phase → class tetragonal phase → tetragonal phase → super tetragonal phase sequence changes, become containing class tetragonal phase and/or tetragonal phase and/
Or the BiFeO of super tetragonal phase3Film.
Compared with the existing technology, He isotopic geochemistry is included the BiFeO of rhombohedral phase by the present invention3In film, helium ion enters
BiFeO3Interstitial void, to rhombohedral phase lattice the face ab provide stress, stretch c-axis, rhombohedral phase promoted to be gradually converted into
Class tetragonal phase and/or tetragonal phase and/or super tetragonal phase.
Further, described to induce BiFeO using ion implanting3The method of film reversible transition further includes containing to described
The BiFeO of class tetragonal phase and/or tetragonal phase and/or super tetragonal phase3Film is made annealing treatment, make its lattice by super tetragonal phase →
Tetragonal phase → class tetragonal phase → rhombohedral phase sequence changes.By annealing, helium ion is from BiFeO3In interstitial void
It overflows, then BiFeO3Lattice loses stress brought by ion implanting, and tetragonal phase and/or super tetragonal phase become rhombohedral phase again.
Further, the BiFeO3Film thickness is 0~100nm.
Further, the implantation dosage of the helium ion is 5 × 1014~5 × 1015He/cm2.If the implantation dosage of helium ion
Greater than this range, BiFeO3Film meeting large area is amorphous；Phase transformation is not thorough if being less than this range, remains a large amount of water chestnuts
Fang Xiang.
Further, the annealing temperature is 550~650 DEG C.If annealing region is excessive, sample easily forms miscellaneous phase,
Pattern is easily destroyed, and temperature is too low, does not excite the helium ion in nested lattice to leave lattice enough.
Further, the annealing time is no less than 1h.Annealing 1h or more can allow helium ion to have time enough to overflow lattice.
Further, the annealing atmosphere is pure oxygen atmosphere.
Further, the partial pressure of oxygen is 1 × 103~1 × 105Pa.If the too low easy induction of partial pressure of oxygen generates in annealing process
Miscellaneous phase.
Further, the original BiFeO containing rhombohedral phase3Film is prepared using pulse laser deposition method, in temperature
Degree is 695~715 DEG C, oxygen pressure makes laser bombardment BiFeO under conditions of being 15~15.5Pa3Ceramic target, allows BiFeO3Atom is heavy
Product arrives LaAlO3In single crystalline substrate.
Detailed description of the invention
Fig. 1 is atomic force microscope (atomic force microscope, AFM) shape appearance figure；
Fig. 2 is reciprocal space figure (reciprocal space mapping, RSM) phenogram；
Fig. 3 is BiFeO3Lattice variations schematic diagram.
Specific embodiment
The present invention is BiFeO using He isotopic geochemistry technology3Film injection strain, brings it about phase transformation, specific to can induce
Rhombohedral phase arrives the phase transformation of super tetragonal phase to class tetragonal phase, tetragonal phase again；After being made annealing treatment again to the sample that ion implanting is crossed
Film can be made to be re-converted to initial rhombohedral phase.Illustrate technical solution of the present invention below by way of specific embodiment.
The present invention induces BiFeO using ion implanting3The method of film reversible transition is, first to BiFeO3Film injection
Helium ion makes its lattice with the increase of He isotopic geochemistry amount gradually by rhombohedral phase → class tetragonal phase → tetragonal phase → super tetragonal phase
Sequence changes, and obtains the BiFeO containing class tetragonal phase and/or tetragonal phase and/or super tetragonal phase3Film；Contain again to described
There is the BiFeO of class tetragonal phase and/or tetragonal phase and/or super tetragonal phase3Film is made annealing treatment, and makes its lattice by super tetragonal phase
→ tetragonal phase → class tetragonal phase → rhombohedral phase sequence changes.
Specifically, pulsed laser deposition is used under conditions of temperature is 695~715 DEG C, oxygen pressure is 15~15.5Pa
Make laser bombardment BiFeO3Ceramic target, allows BiFeO3Atomic deposition is to LaAlO3Thickness is prepared on (001) crystal face of single crystalline substrate
Degree is the original BiFeO containing rhombohedral phase of 70nm3Film is named as BiFeO for convenience of narration3Film one.Then will
BiFeO3Film one is placed in ion implantation apparatus, and is come down in torrents 7 ° to avoid channelling effect, is then mixed with helium ion scan
Phase BiFeO3Beam dimensions about 1mm is arranged in epitaxial film2, scan frequency 1kHz, injection rate infused respectively as 5 × 1014He/cm2It is (real
Apply example 1) and 5 × 1015He/cm2(embodiment 2), obtains BiFeO3Film two.It then is 1 × 10 in 550 DEG C, partial pressure of oxygen5Pa's
To BiFeO in oxygen atmosphere3Two insulation annealing 2h of film, obtains BiFeO3Film three.
Fig. 1 a is please referred to, is BiFeO3The AFM shape appearance figure of film one, wherein dark contrast region is rhombohedral phase, bright contrast
Region is non-rhombohedral phase.It can be seen from figure 1a that BiFeO3Rhombohedral phase and class tetragonal phase of the film one including the mixing that intersects,
And rhombohedral phase and class four directions Phase Proportion are close.It is BiFeO referring to Fig. 2 a3The RSM of film one schemes.Use XRD pairs
BiFeO3Film one is characterized and is obtained its RSM figure, M in figureCXiang represents class tetragonal phase, and R represents rhombohedral phase；The figure is further
It has been shown that, BiFeO3Film one has the feature of mixed phase, while including rhombohedral phase R and class tetragonal phase MC；And it calculates
BiFeO3The ratio (c/a) of c-axis and a axis lattice parameter is than being 1.23 in film one.
Fig. 1 b and Fig. 2 b is please referred to, is embodiment 1 in BiFeO35 × 10 are injected in film one14He/cm2Helium ion
The BiFeO obtained afterwards3The AFM shape appearance figure (Fig. 1 b) and RSM of film two scheme (Fig. 2 b).Fig. 1 b reflection, injection 5 × 1014He/cm2
Helium ion after BiFeO3Rhombohedral phase in film largely reduces, and Fig. 2 b shows the BiFeO of embodiment 13Rhombohedral phase in film two
The feature diffraction spot of R disappears, and tetragonal phase T occurs1, and tetragonal phase T1Diffraction spot it is mobile to-L axis direction, it means that
BiFeO3Lattice c-axis is stretching.It is computed, the tetragonal phase BiFeO of embodiment 13The c/a ratio of film be 1.24, compare injection helium from
It increased before son.
Fig. 1 c and Fig. 2 c is please referred to, is embodiment 2 in mixed phase BiFeO35 × 10 are injected in epitaxial film15He/cm2
Helium ion after obtained BiFeO3The AFM shape appearance figure (Fig. 1 c) and RSM of film two scheme (Fig. 2 c).Injection 5 × 1015He/cm2's
Dark contrast region is had no in helium ion rear film, is only shown bright contrast region, is illustrated that rhombohedral phase thoroughly disappears；And Fig. 2 c display is real
Apply the BiFeO of example 23The feature diffraction spot of rhombohedral phase disappears in film two, super tetragonal phase T occurs2Feature diffraction spot, and
Super tetragonal phase T2Diffraction spot it is further mobile to-L axis direction, illustrate BiFeO3The c-axis of lattice is further stretched.Through counting
It calculates, the BiFeO of embodiment 23The c/a ratio of film two be 1.29, relative to injection helium ion before and be only injected into 5 × 1014He/cm2
The c/a ratio of helium ion samples further increases.
To the BiFeO of embodiment 23After film two is made annealing treatment, gained BiFeO3The AFM shape appearance figure and RSM of film three
Figure is as shown in Fig. 1 d and Fig. 2 d.The reflection of Fig. 1 d AFM shape appearance figure, after annealing, the ratio of rhombohedral phase characteristic area in the film is big
Amplitude rises, while scheming from Fig. 2 d RSM it can also be seen that rhombohedral phase R and class tetragonal phase MCFeature diffraction spot, illustrate to pass through
It crosses the super tetragonal phase that annealing is induced by He isotopic geochemistry and partially reverts to rhombohedral phase.
Through the film after analyzing above-mentioned helium ion note front and back and annealing it is found that after He isotopic geochemistry, BiFeO3
Lattice is gradually transitioned into super tetragonal phase through class tetragonal phase, tetragonal phase from mixed phase, after annealing, super tetragonal phase converting be tetragonal phase,
Class tetragonal phase is finally gradually converted into rhombohedral phase again, as shown in Figure 3.
Compared with the existing technology, the present invention is by He isotopic geochemistry technology to BiFeO3Lattice apply strain, helium ion into
Enter rhombohedral phase and BiFeO that class tetragonal phase coexists3Interstitial void stretches c-axis, to generate rhombohedral phase-class tetragonal phase-four directions
The phase transition of the super tetragonal phase of phase-.By changing the implantation dosage of helium ion, degree of transformation can control.And using annealing
And rationally controlling annealing temperature and annealing time can effectively excite helium ion to overflow interstitial void, keep super tetragonal phase, tetragonal phase extensive
Again at rhombohedral phase, controllable, reversible transition between super tetragonal phase, tetragonal phase, class tetragonal phase and rhombohedral phase are realized.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.
Claims (10)
1. a kind of induce BiFeO using ion implanting3The method of film reversible transition, it is characterised in that: to BiFeO3Film injection
Helium ion changes its lattice.
2. inducing BiFeO using ion implanting according to claim 13The method of film reversible transition, it is characterised in that: institute
State BiFeO3The lattice of film gradually surpasses four by rhombohedral phase → class tetragonal phase → tetragonal phase → with the increase of He isotopic geochemistry amount
The sequence of square phase changes, and becomes the BiFeO containing class tetragonal phase and/or tetragonal phase and/or super tetragonal phase3Film.
3. inducing BiFeO using ion implanting according to claim 23The method of film reversible transition, it is characterised in that: right
The BiFeO containing class tetragonal phase and/or tetragonal phase and/or super tetragonal phase3Film is made annealing treatment, and makes its lattice by super
Tetragonal phase → tetragonal phase → class tetragonal phase → rhombohedral phase sequence changes.
4. inducing BiFeO using ion implanting according to claim 33The method of film reversible transition, it is characterised in that: institute
State BiFeO3Film thickness is 0~100nm.
5. inducing BiFeO using ion implanting according to claim 33The method of film reversible transition, it is characterised in that: institute
The implantation dosage for stating helium ion is 5 × 1014~5 × 1015He/cm2。
6. inducing BiFeO using ion implanting according to claim 33The method of film reversible transition, it is characterised in that: institute
Stating annealing temperature is 550~650 DEG C.
7. inducing BiFeO using ion implanting according to claim 63The method of film reversible transition, it is characterised in that: institute
It states annealing time and is no less than 1h.
8. inducing BiFeO using ion implanting according to claim 73The method of film reversible transition, it is characterised in that: institute
Stating annealing atmosphere is pure oxygen atmosphere.
9. inducing BiFeO using ion implanting according to claim 83The method of film reversible transition, it is characterised in that: institute
Stating partial pressure of oxygen is 1 × 103~1 × 105Pa。
10. any one is described according to claim 1~9 induces BiFeO using ion implanting3The method of film reversible transition, it is special
Sign is: the original BiFeO containing rhombohedral phase3Film is prepared using pulsed laser deposition, temperature be 695~
715 DEG C, oxygen pressure be 15~15.5Pa under conditions of make laser bombardment BiFeO3Ceramic target, allows BiFeO3Atomic deposition arrives
LaAlO3In single crystalline substrate.
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Citations (4)
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| JP2012219361A (en) * | 2011-04-13 | 2012-11-12 | Canon Anelva Corp | Method for producing spinel ferrite thin film |
| US20150129765A1 (en) * | 2013-03-25 | 2015-05-14 | Seiko Epson Corporation | Infrared sensor, heat sensing element, and heat sensing method using the same |
| WO2017031925A1 (en) * | 2015-08-24 | 2017-03-02 | 中国科学院上海微系统与信息技术研究所 | Phase-change type vanadium oxide material and preparation method therefor |
| CN108565336A (en) * | 2018-03-12 | 2018-09-21 | 华南师范大学 | A kind of BiFeO3Film and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012219361A (en) * | 2011-04-13 | 2012-11-12 | Canon Anelva Corp | Method for producing spinel ferrite thin film |
| US20150129765A1 (en) * | 2013-03-25 | 2015-05-14 | Seiko Epson Corporation | Infrared sensor, heat sensing element, and heat sensing method using the same |
| WO2017031925A1 (en) * | 2015-08-24 | 2017-03-02 | 中国科学院上海微系统与信息技术研究所 | Phase-change type vanadium oxide material and preparation method therefor |
| CN108565336A (en) * | 2018-03-12 | 2018-09-21 | 华南师范大学 | A kind of BiFeO3Film and preparation method thereof |
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| DEYANG CHEN等: "A Strain-Driven Antiferroelectric-to-Ferroelectric Phase Transition in La-Doped BiFeO3 Thin Films on Si", 《NANO LETTERS》 * |
| J. C. YANG等: "Orthorhombic BiFeO3", 《PHYSICAL REVIEW LETTERS》 * |
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