CN105198406B - Nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated and preparation method thereof - Google Patents
Nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated and preparation method thereof Download PDFInfo
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- CN105198406B CN105198406B CN201510500941.6A CN201510500941A CN105198406B CN 105198406 B CN105198406 B CN 105198406B CN 201510500941 A CN201510500941 A CN 201510500941A CN 105198406 B CN105198406 B CN 105198406B
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Abstract
The invention discloses the nanocrystalline complex phase thin-film material of barium titanate/nickel-zinc ferrite and preparation method of a kind of ferromagnetic phase oriented growth, barium titanate crystalline phase random growth in the complex phase film, nickel-zinc ferrite crystalline phase oriented growth and two-phase disorder distribution, this kind of film is made using rf magnetron sputtering combination heat-treating methods, this kind of material has electricity, the double percolation thresholds of magnetic, there is low-dielectric loss simultaneously, high-k and high magnetic permeability, with two higher alternate stress transmission effects and coupling effect, the preparation technology of many iron complex phase thin-film materials of the present invention is simple, it is with low cost, available for multi-state memory and heterogeneous read-write capacitor, and be expected to be used widely in electromagnetic device applications.
Description
Technical field
The present invention relates to a kind of complex phase film and preparation method thereof, more particularly to a kind of metatitanic acid of only ferromagnetic phase oriented growth
The nanocrystalline complex phase thin-film material of barium/nickel-zinc ferrite and preparation method, belong to many ferroelectric material film technical fields.
Background technology
In modern society, with digitlization and the information-based infiltration in people's Working Life every field, electromagnetic device
Development and innovation have become one of current new and high technology being most badly in need of.However, the large scale electromagnetism material of traditional simple function
Material has not adapted to people for electromagnetic device portability, multi-functional requirement.In addition, with the quick hair of social economy
Exhibition and the raising of technical merit, traditional homogenous material more difficult satisfaction many performances are proposed at present it is higher and higher
It is required that.Therefore, the material for preparing a kind of small size and excellent performance in a kind of method of relative ease is significant.
Multi-iron material is a kind of multi-functional sensitive material, and multiferroic composite diphase material is that current solution single phase multi-iron material is deficient
One of important materials weary and to multiple sensitive property requirement continuous improvement problem.However, according to compound law, with regard to ferroelectricity/iron
For many iron composite materials of magnetic, the nonmagnetic that ferroelectric phase contains can make under magnetic in compound system due to reducing ferromagnetic phase
Drop；Similarly, ferromagnetic phase presence can be such that ferroelectricity, dielectric properties declines because of the reduction of ferroelectric phase.And known seep effect is solution
A kind of resolving ideas is certainly provided the problem of hydraulic performance decline in composite diphase material.According to seepage theory, at one by insulative dielectric
Mutually and in the compound system of conductive phase composition, when conductive phase content reaches a certain degree, i.e. percolation threshold, conductive particle starts
Contact with each other and form a conductive channel.If by the dielectric substance for mutually regarding a capacitor as that insulate, conductive phase is regarded as
The electrode at capacitor two ends, the composite diphase material is exactly the system being composed in series by many micro- electric capacity.When conductive channel will be formed
Before, the thickness of capacitor reaches minimum, and now test gained capacitance is just very big, calculates the apparent of composite
Very big value also occurs in dielectric constant.That is, for ferroelectric-ferromagnetic complex phase, because the electrical conductivity of ferromagnetic phase is with respect to ferroelectricity
It is mutually much higher, thus many iron compound systems also occur seep effect so as to normal in the larger dielectric of percolation threshold annex acquisition
Number.
But, as described above, in percolation threshold, conductive phase passage is formed, the electrical conductivity of composite diphase material is as short
Road and uprush, thus cause leakage current and ultimately result in the dielectric loss of material and be significantly increased, so as to influence it overall
Dielectric properties.Therefore, can the leakage conductance of reduction material turns into effectively utilize a key of seep effect.It is brilliant in many cases
The conductance of phase ex vivo between defect sturcture electric charge transition, and on crystal boundary this transition mechanism be more easily damaged so that its
Resistance is improved, so in crystalline phase body, the presence of crystal boundary serves the barrier function for preventing electric charge from flowing, favorably
In the leakage current of reduction system.On the other hand the contact between conductive preferably ferromagnetic phase is reduced, namely as far as possible by ferromagnetic phase profit
It is isolated with the ferroelectricity of relatively insulation, is also beneficial to the leakage current of reduction system.And nanocrystalline crystal boundary content is substantially greater than greatly
The crystal boundary content of crystal sizes, so, the formation of nano-crystal film by be reduce many iron composite diphase materials dielectric loss it is important
One of means.
In addition, in ferroelectric-ferromagnetic multiphase system, the presence of non-magnetic phase can be isolated ferromagnetic phase particle, magnetic-particle it
Between magnetic flux news be blocked, so as to produce equivalent demagnetizing field and greatly inhibit the magnetic conductivity of material.That is, for passing
For many iron composite diphase materials of system, in order to which the ferromagnetic phase for obtaining lower dielectric loss requirement good conductivity is not contacted each other,
And there is well similar requirement in order to obtain high dielectric constant.Obviously contradiction is generated between electricity, magnetic property requirements.I.e. when many
When the dielectric constant of iron composite diphase material reaches very high values near its percolation threshold and reduces dielectric loss as far as possible, its magnetic conductivity meeting
Remained at low levels because of being suppressed by demagnetizing field.Obviously, if it is possible to which solution makes the magnetic percolation threshold of composite diphase material
It can appear in before its EOF threshold value, i.e., remain able to make when magnetic is isolated by non-magnetic to realize well between magnetic-particle
Magnetic flux interrogate, really make in other words magnetic flux news separate (magnetic percolation threshold point) occur from accordingly it is more more than EOF threshold value needs
Non-magnetic phase system in if, then when excellent dielectric properties are near EOF threshold point (more ferromagnetic phase content)
During appearance, magnetic conductivity is not influenceed by demagnetizing field, so as to keep higher magnetic property to exist.In fact, between magnetic signal
Communication is carried out by induced field.Such communication modes can cross over certain non-magnetic area.According to text before
Report is offered, the thickness of this non-magnetic area is about 20nm.That is, when the non-magnetic phase barrier layer thickness between magnetic phase is less than
During 20nm, the magnetic flux news between magnetic phase still can be smoothed out.Obviously, if ferroelectricity non-magnetic particle in many iron composite diphase materials
When size is less than 20nm, individual layer ferroelectric particle can not cut off the magnetic flux news between ferromagnetic phase.At this moment magnetic seepage flow has been reached
Threshold point, but be not near EOF threshold point, and it is more non-to reach that EOF threshold point must increase in system
Magnetic conductive phase, i.e. magnetic percolation threshold point, which are less than between EOF threshold point, two threshold values, has certain composition deviation range.So both
It can be achieved to obtain high Jie and the low purpose for damaging (now the conductive channel of ferromagnetic phase is not formed) using EOF effect, simultaneously
The effective communication between magnetic particle is ensured that to obtain the purpose of high magnetic characteristics.Therefore, by the crystalline substance in many iron composite diphase materials
Phase particle size is controlled within 20nm, in addition to foregoing low-dielectric loss, more likely makes the magnetic percolation threshold of material relative
EOF threshold value is appeared in the multiphase system with less ferromagnetic phase content, makes the composite diphase material in EOF Near Threshold
Do not influenceed by demagnetizing field, namely ensure that occurring while high Jie is low to damage performance there is high magnetic property to exist, obtain one
The many ferroelectric material film systems of complex phase coexist in many performances for planting excellent performance.
Further, effective electromagnetic coupled between complex phase multi-iron material, generally can be by the piezoelectricity (Volume Changes) of ferroelectric phase
Characteristic, by change ferroelectricity phase volume make it is ferromagnetic by its effect occur distortion of lattice and change direction of easy axis, angle etc. come
Realize the respective change of magnetic property.If however, because ferromagnetic phase is in all directions homogeneous phase by external stress
With if, although then it there occurs corresponding Volume Changes, the effect in this uniform force field such as its direction of easy axis, angle
Under can't change.Therefore, in the ferromagnetic composite diphase material of 0-0 Ferroelectrics of two-phase mixtures, the volume of control ferroelectric phase becomes
It is difficult to produce effective ferromagnetic property change to change, i.e., this composite diphase material is difficult to produce coupling effect.And in fact, people only exist
Realized in 2-2 types multilayer crystalline phase composite film material and the orderly complex phase film of 1-1 molded line shape vertical arrangement magneto-electric coupled.This is
Because stress caused by ferroelectric phase is applied only on some specific direction of ferromagnetic crystalline phase in these complex phase films, i.e. stress
Effect can make magnetic material produce anisotropic distortion, so that causing ferromagnetic phase includes the change of direction of easy axis, angle etc.
Change, it is final to produce two alternate couplings.But the problem of these films all have respective, including coupling efficiency is low and prepares
It is extremely difficult.For example, for 2-2 types film, it is necessary to by extension induced growth layer by layer, and only answered masterpiece in a direction
With both complex process and coupling efficiency is low；And for 1-1 types film, it is necessary to before film, one is performed etching etc. in substrate
Series of processes simultaneously will carry out inducing simultaneously to two-phase, and technique is increasingly complex, although the stress of this film is delivered in one dimensional line
Carried out simultaneously in peripheral direction, stress transmission coupling efficiency is of a relatively high.Comparatively, the 0-0 type films of two-phase random growth
Preparation technology it is obviously very simple, but as described above, the two phase structure of this uniform mixed distribution, the transmission of its stress be
Surrounding is uniformly distributed presence, can not cause the change of ferromagnetic phase direction of easy axis, angle etc..However, further analysis can
Know, if the oriented growth of ferromagnetic phase can be realized, equivalent to the 1-1 type two-phases that film is successfully realized on each microcell
Distribution, and because its stress occurs in the peripheral direction similar to one-dimensional crystal grain, opposing coupler efficiency is also higher.Although this
When also can be by certain stress on the direction of this kind one-dimensional line, but because thin-film material is very thin in itself, utilize base
Plate is orientated the induction transmission to be formed effect to film crystalline phase, and the ferrite of this orientation is mutually expected to induce shape on kind one-dimensional direction
Into.Therefore, in general, stress (lifting surface area) suffered on this kind one-dimensional line direction is than online surrounding institute
The stress (lifting surface area) being subject to is much smaller, so that this oriented growth ferrite crystalline phase can be answered by effective anisotropy
Power acts on and produces coupling effect.Moreover, when the crystallite dimension of this oriented growth ferrite crystalline phase is controlled in nanoscale
When, the stress that ferroelectric phase is produced is expected to preferably pass to whole lattices of nanometer ferrite, namely all ferrite lattices are all
Produce distortion and participate in coupling.And it is not as larger ferrite crystal grains like that, mainly it is stressed effect in contact surface part
And most of ferrite internal crystal framework can not be stressed effect thus coupling can not be participated in very well, so that coupling is made
With reduction.Therefore, the Nanocrystalline Composite Films of ferrite oriented growth are expected to turn into a kind of magneto-electric coupled many iron of good performance
Property complex phase film.
In a word, a kind of ferrite oriented growth is successfully prepared, the ferroelectric phase/ferromagnetic phase of particularly (100) orientation is compound to be received
The brilliant multiferroic film of rice will play very important work to Gao Jie, Gao Ci, low-loss and the application of high magneto-electric coupled performance materials
With.
It is combined however, how efficiently to prepare a kind of ferroelectric phase of satisfactory ferrite oriented growth, ferromagnetic phase two-phase
The another key issue that film will be this film to be solved required for field of electronic materials is used widely.
The content of the invention
It is low, magneto-electric coupled it is an object of the invention to which high, magnetic conductivity is lost for existing related many iron complex phase thin-film dielectrics
A kind of deficiency in terms of weak and preparation method is complicated, it is proposed that barium titanate of ferromagnetic phase oriented growth/nickel-zinc ferrite nanometer
Barium titanate crystalline phase random growth in brilliant complex phase thin-film material and preparation method, the complex phase film, the orientation life of nickel-zinc ferrite crystalline phase
Long and two-phase disorder distribution, this kind of material has double (electricity, magnetic) percolation thresholds, while having low-dielectric loss, high-k
With high magnetic permeability, with two higher alternate stress transmission effects and coupling effect, preparation is simple.
The nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite of the present invention, chemical formula is (1-x) BaTiO3/
xNi0.5Zn0.5Fe2O4, it is made up of barium titanate (BTO) crystalline phase and nickel-zinc ferrite (NZFO) crystalline phase, crystal grain is in unordered point in two-phase
Cloth, barium titanate is without specific orientation, and nickel-zinc ferrite hands down (100) oriented growth, and the crystallite dimension of two-phase is respectively less than 20nm.
The preparation method of the above-mentioned nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite, comprises the following steps：
1) monocrystalline silicon for being orientated (111) is cleaned, and is removed surface oxide layer and is dried, obtains sputtering substrate；
2) radio-frequency magnetron sputter method is used, with barium titanate/nickel-zinc ferrite complex phase sputtering target material through step 1) processing
Noncrystal membrane is sputtered on monocrystalline silicon piece, specific growth parameter(s) is：Using oxygen and partial pressure of ar gas ratio as 3:7~6:4 gaseous mixture is made
For sputtering atmosphere, total pressure is 0.6 × 10-3~2 × 10-3Mbar, 160~220W of sputtering power progress room temperature sputtering growth 2~
6h；Described target constitutive molar ratio is：BTO:NZFO=0.1:0.9~0.9:0.1；
3) by step 2) the obtained noncrystal membrane being deposited in (111) monocrystal silicon substrate is heat-treated, first with 3~6
DEG C/min speed is warming up to 780~820 DEG C, insulation from room temperature to 560~600 DEG C, then with 8~10 DEG C/min speed
1~4h；Cool to room temperature with the furnace afterwards, obtain the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated.
Magnetron sputtering deposition is a kind of common method for preparing thin-film material, and generally sputtering obtains related thin at high temperature
Film, including oriented film.But in view of the ferroelectric phase/characteristic of ferrite phase laminated film in itself is limited and magnetron sputtering deposition process
To the control characteristic of film formation and orientation etc., want to obtain ferrite along the equal of (100) orientations using magnetron sputtering method
Even close complex phase film also needs to be specifically designed technique, it is important to how to avoid aura deposition process to crystalline formation and
The direct control action of orientation etc..Therefore, what this programme was proposed：Its sputtering sedimentation at room temperature is controlled first, obtains amorphous phase
Basement membrane, direct control and influence of the high-energy to film crystalline formation when eliminating deposition with this；And then by specific
Handling process, by being heat-treated at high temperature, using homogeneous nucleation crystallization principle, control nucleation crystallization in noncrystal substrate,
The final film for obtaining ferrite single-phase oriented growth.This scheme both make use of magnetically controlled sputter method, and later stage heat is combined again
Control technology is handled, to prepare related multiferroic complex phase film.
Successfully obtain ferrite the key of crystallization is orientated in this two-phase composites and be to control two-phase forming brilliant
Influencing each other mutually and in orientation process.Therefore, selection and (100) crystal face of ferrite phase structure first has certain Lattice Matching
(111) monocrystalline silicon of relation is substrate, and by specific cleaning treatment technique, substrate is produced stronger take to film layer crystallization
To inducing action, ferrite is relatively easily orientated in Crystallization Process in control film.Secondly, it is contemplated that the analysis of two kinds of crystalline phases
Crystal bar part is different, and a kind of formation of crystalline phase can produce influence to another crystalline phase, thus by controlling heat treatment process, using fast
Speed heating and the method for temperature-gradient method, the optimum temperature for quickly avoiding being formed ferroelectric phase in system are interval (600~700 DEG C), make
Ferroelectric phase decrystallizes to be formed in of a relatively high ferrite formation temperature stage, can be to later stage shape to solve early formation ferroelectric phase
The problem of mutually simultaneously oriented growth produces suppression into ferrite.
In addition, being used as a kind of deposition of noncrystal membrane, it is necessary to its densification of trying one's best effectively is controlled, to ensure the crystalline phase in later stage
Close contact and mutual stress transfer after formation.In fact, magnetron sputtering deposition be by the argon accelerated by electromagnetic field from
Son bombards target to realize.Sputtering power is low, and the momentum of bombardment ion and deposition and atomic is not enough, it is impossible to reach that amorphous basement membrane is caused
The requirement of densification；Sputtering power is high, especially improves sputtering power in certain power bracket, is conducive to improving deposition compact
Degree, but more defect, a large amount of loss of such as oxygen are at this moment easily produced, thus the regulation of sputtering atmosphere must be coordinated to control to splash
Penetrate power.It is only guaranteed under of a relatively high oxygen atmosphere ratio, pass through higher sputtering power；Or in relatively low sputtering power
The lower concentration by improving bombardment ion argon, is just expected to deposition and obtains dense uniform, and the loss of less oxygen is qualified non-
Brilliant basement membrane.
Compared with prior art, the invention has the advantages that：
Barium titanate crystalline phase random growth in the film of the present invention, nickel-zinc ferrite crystalline phase oriented growth, two-phase disorder distribution,
Compared with common complex phase film, with following superiority：
1st, the ratio of crystal boundary is relative to the height of common crystalline phase, and the leakage current of material reduces more than two orders of magnitude, so that
Make its dielectric loss low up to 0.008；
2nd, there is about 15% composition deviation range, electricity with different EOF threshold values and magnetic percolation threshold, between two threshold values
Percolation threshold about NZFO contents be 55mol% locate, and magnetic percolation threshold about NZFO contents be 38mol% at, realize together
When there is Gao Jie, high magnetic and low loss performance film；
3rd, with two higher alternate stress transmission effects, and higher electromagnetic coupling effect is obtained, magnetic induction can be made strong
Spend the mutation in BTO curie points generation 10%；
4th, the preparation technology of many iron complex phase thin-film materials of the invention is simple, with low cost, available for multi-state memory and different
Matter reads and writes capacitor, and is expected to be used widely in electromagnetic device applications.
Brief description of the drawings
Fig. 1 is the XRD for the complex phase thin-film material 0.6BTO/0.4NZFO that embodiment 1 is obtained；
Fig. 2 is the TEM figures for the complex phase thin-film material 0.6BTO/0.4NZFO that embodiment 1 is obtained；
Fig. 3 is the XRD for the complex phase thin-film material 0.4BTO/0.6NZFO that embodiment 2 is obtained；
Fig. 4 is the XRD for the complex phase thin-film material 0.2BTO/0.8NZFO that embodiment 3 is obtained；
Fig. 5 is the XRD for the complex phase thin-film material 0.5BTO/0.5NZFO that embodiment 4 is obtained.
Embodiment
The nanocrystalline composite diphase material of metatitanic acid hexagonal ferrite of the present invention is polycrystal film, and wherein barium titanate is random raw
It is long, and nickel-zinc ferrite edge (100) oriented growth.The chemical formula of many iron laminated films is BaTiO3/Ni0.5Zn0.5Fe2O4。
In view of needing the simplicity of technique and being uniformly distributed for two-phase particle, the preparation of the complex phase film takes already
Realize industrialized radio-frequency magnetron sputter method.Using (111) oriented single crystal silicon as thin film deposition substrate, splashed using elder generation on substrate
Penetrate deposition and obtain noncrystal membrane, then the step forming method of amorphous-nucleation two being heat-treated to noncrystal membrane, obtain two-phase crystal grain
It is uniformly distributed and the wherein complex phase film of ferrite phase (100) oriented growth.Wherein control 160~220W sputtering power and
0.3~0.6 partial pressure of oxygen, is deposited 2~6 hours at room temperature；Control heat treatment is carried out in air atmosphere, first with 3~6 DEG C/min
Speed from room temperature to 560~600 DEG C, then with 8~10 DEG C/min speed be warming up to 780~820 DEG C insulation 1~4h,
Last furnace cooling.Obtain the nanocrystalline many iron complex phase films of metatitanic acid hexagonal ferrite for meeting the performance requirements.
Micro-structural and pattern test are carried out to the film prepared using XRD and SEM, electric impedance analyzer and MPMS is utilized
Magnetic measurement system, vibrating specimen magnetometer carry out room temperature dielectric performance, agnetic property at room temperature m and alternating temperature magnetic property to complex phase film
Test.
With reference to specific embodiment, the present invention will be further described：
Embodiment 1：
1) after the monocrystalline silicon for being orientated (111) is tentatively cleaned with deionized water, 5min is soaked in hydrofluoric acid, then be placed in second
Ultrasonic cleaning 10min is carried out in alcohol；Monocrystalline silicon piece after cleaning is placed in vacuum drying chamber and dried, obtains sputtering substrate.
2) it is 0.6 in molar ratio by barium titanate, iron Zn ferrite：Complex phase sputtering target material made from 0.4 and clean up
(111) monocrystalline silicon sputtering substrate is placed in the sputtering chamber of rf magnetron sputtering instrument；Lead to oxygen after being vacuumized to sputtering chamber again
Press for 0.4 oxygen and argon gas gaseous mixture as sputtering atmosphere；The total pressure of gaseous mixture is controlled 8 × 10-4After mbar, penetrate
Frequency power is adjusted to 200W, and sputtering sedimentation 4h obtains the noncrystal membrane of even compact at room temperature.
3) the even compact noncrystal membrane being deposited in (111) monocrystal silicon substrate is placed in Muffle furnace, with 3 DEG C/min's
Speed is incubated 2h from room temperature to after 600 DEG C, then after being warming up to 800 DEG C with 10 DEG C/min speed, cools to room temperature with the furnace
Afterwards, many iron Nanocrystalline Composite Films of 0.6BTO/0.4NZFO are obtained.
Fig. 1 is the XRD spectrum for the metatitanic acid hexagonal ferrite complex phase film that the present embodiment is obtained, it can be seen that in material
Barium titanate is mutually random growth, and Ni Zn ferrimagnet body phase is then along (100) oriented growth.Fig. 2 is that the present embodiment is obtained
The TEM photos of metatitanic acid hexagonal ferrite complex phase film, it can be seen that barium titanate is mutually completely unordered, and nickel zinc in material
Ferrite phase is then along (100) oriented growth；Two-phase crystallite dimension is all in below 20nm；Two-phase particle is in close contact and uniform
Disorder distribution.
Embodiment 2：
1) after the monocrystalline silicon for being orientated (111) is tentatively cleaned with deionized water, 4min is soaked in hydrofluoric acid, then be placed in second
Ultrasonic cleaning 15min is carried out in alcohol；Monocrystalline silicon piece after cleaning is placed in vacuum drying chamber and dried, obtains sputtering substrate.
2) it is 0.4 in molar ratio by barium titanate, iron Zn ferrite：Complex phase sputtering target material made from 0.6 and clean up
(111) monocrystalline silicon sputtering substrate is placed in the sputtering chamber of rf magnetron sputtering instrument；Lead to oxygen after being vacuumized to sputtering chamber again
Press for 0.5 oxygen and argon gas gaseous mixture as sputtering atmosphere；The total pressure of gaseous mixture is controlled 2 × 10-3After mbar, penetrate
Frequency power is adjusted to 220W, and sputtering sedimentation 2h obtains the noncrystal membrane of even compact at room temperature.
3) by the even compact noncrystal membrane being deposited in (111) monocrystal silicon substrate and it is placed in Muffle furnace, with 5 DEG C/min
Speed be incubated 1h from room temperature to after 560 DEG C, then after being warming up to 820 DEG C with 8 DEG C/min speed, cool to room temperature with the furnace
Afterwards, many iron Nanocrystalline Composite Films of 0.4BTO/0.6NZFO are obtained.
Fig. 3 is the XRD spectrum for the metatitanic acid hexagonal ferrite complex phase film that the present embodiment is obtained, it can be seen that in material
Barium titanate is mutually random growth, and Ni Zn ferrimagnet body phase is then along (100) oriented growth.
Embodiment 3：
1) after the monocrystalline silicon for being orientated (111) is tentatively cleaned with deionized water, 6min is soaked in hydrofluoric acid, then be placed in second
Ultrasonic cleaning 10min is carried out in alcohol；Monocrystalline silicon piece after cleaning is placed in vacuum drying chamber and dried, obtains sputtering substrate.
2) it is 0.1 in molar ratio by barium titanate iron Zn ferrite：The 0.9 complex phase sputtering target material obtained and clean up
(111) monocrystalline silicon sputtering substrate is placed in the sputtering chamber of rf magnetron sputtering instrument；Lead to oxygen after being vacuumized to sputtering chamber again
Press for 0.3 oxygen and argon gas gaseous mixture as sputtering atmosphere；The total pressure of gaseous mixture is controlled 0.6 × 10-3After mbar,
Radio-frequency power is adjusted to 160W, and sputtering sedimentation 6h obtains the noncrystal membrane of even compact at room temperature.
3) by the even compact noncrystal membrane being deposited in (111) monocrystal silicon substrate and it is placed in Muffle furnace, with 6 DEG C/min
Speed be incubated 2h from room temperature to after 580 DEG C, then after being warming up to 800 DEG C with 10 DEG C/min speed, cool to room with the furnace
Wen Hou, obtains many iron Nanocrystalline Composite Films of 0.1BTO/0.9NZFO.
Fig. 4 is the XRD spectrum for the metatitanic acid hexagonal ferrite complex phase film that the present embodiment is obtained, it can be seen that in material
Barium titanate is mutually random growth, and Ni Zn ferrimagnet body phase is then along (100) oriented growth.
Embodiment 4：
1) after the monocrystalline silicon for being orientated (111) is tentatively cleaned with deionized water, 8min is soaked in hydrofluoric acid, then be placed in second
Ultrasonic cleaning 20min is carried out in alcohol；Monocrystalline silicon piece after cleaning is placed in vacuum drying chamber and dried, obtains sputtering substrate.
2) it is 0.5 by barium titanate iron Zn ferrite ratio：0.5 complex phase sputtering target material and (111) monocrystalline silicon cleaned up
Sputtering substrate is placed in the sputtering chamber of rf magnetron sputtering instrument；Lead to the oxygen that partial pressure of oxygen is 0.4 after being vacuumized to sputtering chamber again
The gaseous mixture of gas and argon gas is used as sputtering atmosphere；The total pressure of gaseous mixture is controlled 1.2 × 10-3After mbar, radio-frequency power is adjusted
To 180W, sputtering sedimentation 6h obtains the noncrystal membrane of even compact at room temperature.
3) by the even compact noncrystal membrane being deposited in (111) monocrystal silicon substrate and it is placed in Muffle furnace, with 5 DEG C/min
Speed be incubated 4h from room temperature to after 600 DEG C, then after being warming up to 780 DEG C with 8 DEG C/min speed, cool to room temperature with the furnace
The many iron of 0.5BTO/0.5NZFO for obtaining being met the unordered nickel-zinc ferrite ordering growth of barium titanate described in claim 1 afterwards are received
The brilliant laminated film of rice.
Fig. 5 is the XRD spectrum for the metatitanic acid hexagonal ferrite complex phase film that the present embodiment is obtained, it can be seen that in material
Barium titanate is mutually random growth, and Ni Zn ferrimagnet body phase is then along (100) oriented growth.
Embodiment 5：
1) after the monocrystalline silicon for being orientated (111) is tentatively cleaned with deionized water, 8min is soaked in hydrofluoric acid, then be placed in second
Ultrasonic cleaning 20min is carried out in alcohol；Monocrystalline silicon piece after cleaning is placed in vacuum drying chamber and dried, obtains sputtering substrate.
2) it is 0.9 in molar ratio by barium titanate iron Zn ferrite：Complex phase sputtering target material made from 0.1 and clean up
(111) monocrystalline silicon sputtering substrate is placed in the sputtering chamber of rf magnetron sputtering instrument；Lead to oxygen after being vacuumized to sputtering chamber again
Press for 0.6 oxygen and argon gas gaseous mixture as sputtering atmosphere；The total pressure of gaseous mixture is controlled 2 × 10-3After mbar, penetrate
Frequency power is adjusted to 180W, and sputtering sedimentation 6h obtains the noncrystal membrane of even compact at room temperature.
3) by the even compact noncrystal membrane being deposited in (111) monocrystal silicon substrate and it is placed in Muffle furnace, with 5 DEG C/min
Speed be incubated 4h from room temperature to after 600 DEG C, then after being warming up to 780 DEG C with 8 DEG C/min speed, cool to room temperature with the furnace
Afterwards, many iron Nanocrystalline Composite Films of 0.9BTO/0.1NZFO are obtained.
Claims (2)
1. a kind of nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite, it is characterised in that the film chemical formula is (1-x)
BaTiO3/xNi0.5Zn0.5Fe2O4, wherein 0 ＜ x ＜ 1, are made up of, crystal grain in two-phase barium titanate crystalline phase and nickel-zinc ferrite crystalline phase
In disorder distribution, barium titanate is without specific orientation, and nickel-zinc ferrite hands down (100) oriented growth, and the crystallite dimension of two-phase is small
In 20nm.
2. the preparation method of the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite according to claim 1, its feature exists
In comprising the following steps：
1) monocrystalline silicon for being orientated (111) is cleaned, and is removed surface oxide layer and is dried, obtains sputtering substrate；
2) radio-frequency magnetron sputter method is used, with barium titanate/nickel-zinc ferrite complex phase sputtering target material through step 1) processing monocrystalline
Noncrystal membrane is sputtered on silicon substrate, specific growth parameter(s) is：Using oxygen and partial pressure of ar gas ratio as 3:7~6:4 gaseous mixture conduct
Sputtering atmosphere, total pressure is 0.6 × 10-3~2 × 10-3Mbar, 160~220W of sputtering power progress room temperature sputtering growth 2~
6h；Described target constitutive molar ratio is：BTO:NZFO=0.1:0.9~0.9:0.1；
3) by step 2) the obtained noncrystal membrane being deposited in (111) monocrystal silicon substrate is heat-treated, first with 3~6 DEG C/
Min speed is warming up to 780~820 DEG C from room temperature to 560~600 DEG C, then with 8~10 DEG C/min speed, and insulation 1~
4h；Cool to room temperature with the furnace afterwards, obtain the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated.
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