CN105198406A - Magnetic-phase-oriented barium titanate/Ni-Zn ferrite nanocrystalline complex-phase thin film and preparation method thereof - Google Patents
Magnetic-phase-oriented barium titanate/Ni-Zn ferrite nanocrystalline complex-phase thin film and preparation method thereof Download PDFInfo
- Publication number
- CN105198406A CN105198406A CN201510500941.6A CN201510500941A CN105198406A CN 105198406 A CN105198406 A CN 105198406A CN 201510500941 A CN201510500941 A CN 201510500941A CN 105198406 A CN105198406 A CN 105198406A
- Authority
- CN
- China
- Prior art keywords
- phase
- barium titanate
- sputtering
- nickel
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a ferromagnetic-phase-oriented growth barium titanate/Ni-Zn ferrite nanocrystalline complex-phase thin film material and a preparation method thereof. A barium titanate crystal phase in a complex-phase thin film grows randomly, crystalline-phase-oriented growth is carried out on a Ni-Zn ferrite, and two-phase disorder distribution is achieved. The thin film is prepared through the method combining radio frequency magnetron sputtering with heat treatment. The material has electric and magnetic double percolation thresholds, has low dielectric loss, high dielectric constant and high magnetic conductivity, and has a good phase-to-phase stress transfer effect and a coupling effect. The multiferroic complex-phase thin film material is simple in preparation technology, low in cost and capable of being used in multi-state memories and heterogeneous read-write capacitors, and can be widely used in the field of electromagnetic devices.
Description
Technical field
The present invention relates to a kind of complex phase film and preparation method thereof, particularly relate to a kind of nanocrystalline complex phase thin-film material of barium titanate/nickel-zinc ferrite and preparation method of only ferromagnetic phase oriented growth, belong to many ferroelectric material films technical field.
Background technology
In modern society, along with the infiltration of digitize and informationize in people's Working Life every field, development and the innovation of electromagnetic device have become one of current new and high technology be badly in need of most.But the large size electromagnetic material of traditional simple function can not adapt to people for electromagnetic device portability, polyfunctional requirement.In addition, along with the raising of socioeconomic fast development and state of the art, traditional single-material is more difficult meets the more and more higher requirement proposed many performances at present.Therefore, a kind of small size is prepared with a kind of method of relative ease and the material of excellent performance is significant.
Multi-iron material is a kind of multi-functional sensitive material, and multiferroic composite diphase material solves single phase multi-iron material scarcity at present and requires one of important materials improving constantly problem to multiple sensitive property.But according to compound law, with regard to ferroelectric/ferromagnetic many iron composite materials, the non-magnetic properties that ferroelectric phase contains can make magnetic decline owing to making ferromagnetic minimizing mutually in compound system; In like manner, ferromagnetic existence mutually can make ferroelectric, dielectric properties decline because of the minimizing of ferroelectric phase.And the problem that known seep effect is the degradation solved in composite diphase material provides a kind of resolving ideas.According to seepage theory, in a compound system be made up of insulative dielectric phase and conductive phase, when conductive phase content reaches a certain degree, namely during percolation threshold, conductive particle starts contact with each other and form a conductive channel.If insulation to be regarded mutually as the dielectric substance of an electrical condenser, conductive phase regards the electrode at electrical condenser two ends as, and this composite diphase material is exactly the system be made up of many micro-capacitances in series.Before conductive channel will be formed, the thickness of electrical condenser will reach mnm., and just now test gained capacitance very greatly, the apparent dielectric constant calculating matrix material also there will be very large value.That is, for ferroelectric-ferromagnetic complex phase, because the specific conductivity of ferromagnetic phase is much higher relative to ferroelectric phase, thus many iron compound system also there will be seep effect thus obtains larger specific inductivity at percolation threshold annex.
But as mentioned above, when percolation threshold, conductive phase passage is formed, and the specific conductivity of composite diphase material also can occur because of short circuit uprushing, and thus causes leakage current and finally causes the dielectric loss of material significantly to increase, thus affecting the dielectric properties of its entirety.Therefore, can the leakage conductance reducing material become a key that effectively utilize seep effect.The conductance of the crystalline phase transition of electric charge between defect structure ex vivo in a lot of situation, and this transition mechanism is easily destroyed thus makes its resistance improve on crystal boundary, so in crystalline phase body, the existence of crystal boundary serves the barrier function stoping flow of charge, is conducive to the leakage current of reduction system.Reduce the contact between the good ferromagnetic phase of conduction on the other hand, also namely utilize the ferroelectric phase isolation of comparatively insulating mutually by ferromagnetic as far as possible, be also conducive to the leakage current of reduction system.And nanocrystalline crystal boundary content is obviously greater than the crystal boundary content of large size crystal grain, so the formation of nano-crystal film will be one of the important means of the dielectric loss reducing many iron composite diphase material.
In addition, in ferroelectric-ferromagnetic multiphase system, the existence of non-magnetic phase can make ferromagnetic phase particle be isolated, and the magnetic flux news between magnetic-particle are blocked, thus produces the magnetic permeability that equivalent demagnetizing field also greatly inhibits material.That is, for traditional many iron composite diphase material, require that the ferromagnetic of good conductivity does not contact mutually each other to obtain lower dielectric loss, and well there is similar requirement to obtain high specific inductivity.Contradiction is created between obvious electricity, magnetic property requirements.Namely, when the specific inductivity of many iron composite diphase material arrives very high values and reduces dielectric loss near its percolation threshold as far as possible, its magnetic permeability can remain at low levels because being subject to the suppression of demagnetizing field.Obviously, make before the magnetic percolation threshold of composite diphase material can appear at its electroosmotic flow threshold value if can solve, namely still can make to realize good magnetic flux between magnetic-particle to interrogate when magnetic is isolated by non-magnetic, really making magnetic flux interrogate in other words and being cut off (magnetic percolation threshold point) is appear at the words in the corresponding system needing more non-magnetic phase than electroosmotic flow threshold value, so when the dielectric properties of excellence occur near electroosmotic flow threshold point (more ferromagnetic phase content), magnetic permeability not by the impact of demagnetizing field, thus keeps higher magnetic property to exist.In fact, the communication between magnetic signal is undertaken by inducedmagnetic field.Such communication modes can cross over certain non-magnetic area.According to bibliographical information before, the thickness of this non-magnetic area is approximately 20nm.That is, when the non-magnetic phase barrier layer thickness between magnetic phase is less than 20nm, the magnetic flux news between magnetic phase still can be carried out smoothly.Obviously, if when the ferroelectric non-magnetic particle size in many iron composite diphase material is less than 20nm, individual layer ferroelectric particle cannot cut off the magnetic flux news between ferromagnetic phase.At this moment magnetic percolation threshold point has been reached, but be not near electroosmotic flow threshold point, and electroosmotic flow threshold point will be reached must increase more nonmagnetic conductive phase in system, namely magnetic percolation threshold point is lower than electroosmotic flow threshold point, has certain composition deviation range between two threshold values.So both can realize utilizing electroosmotic flow effect to obtain height to be situated between and the object of low damage (now the conductive channel of ferromagnetic phase is not formed), the effective communication between magnetic particle can have been ensured again thus the object of acquisition high magnetic characteristics simultaneously.Therefore, crystalline phase particle size in many iron composite diphase material is controlled within 20nm, except aforementioned low-dielectric loss, the magnetic percolation threshold of material is more likely made to appear in the multiphase system with less ferromagnetic phase content relative to electroosmotic flow threshold value, make the composite diphase material being in electroosmotic flow Near Threshold not by the impact of demagnetizing field, also namely ensure that while there is the high low damage performance that is situated between, have high magnetic property exists, the many performances obtaining a kind of excellent performance coexist complex phase many ferroelectric material films system.
Further, effective electromagnetic coupled between complex phase multi-iron material, usually by piezoelectricity (volume change) characteristic of ferroelectric phase, the ferromagnetic respective change changing easy magnetization axis, angle etc. to realize magnetic property mutually by its effect generation lattice distortion is made by changing ferroelectric phase volume.But if be that homogeneous phase is same because ferromagnetic phase is subject to external stress in all directions, although then it there occurs corresponding volume change, its easy magnetization axis, angle etc. can't change under the effect of this uniform force field.Therefore, in the ferromagnetic composite diphase material of 0-0 Ferroelectric of two-phase mixtures, the volume change controlling ferroelectric phase is difficult to produce the change of effective ferromagnetic property, and namely this composite diphase material is difficult to produce coupling effect.And in fact, people only achieve magneto-electric coupled in 2-2 type multilayer crystalline phase composite film material and 1-1 molded line shape orderly complex phase film arranged vertically.This is because the stress that ferroelectric phase causes in these complex phase films is only applied on some specific directions of ferromagnetic crystalline phase, namely stress can make magneticsubstance produce anisotropic distortion, thus cause the ferromagnetic change comprising easy magnetization axis, angle etc. mutually, the couplings that final generation two is alternate.But these films all also exist respective problem, comprise coupling efficiency low and preparation very difficult.Such as, for 2-2 type film, need by extension induced growth layer by layer, and only in a direction by stress, both complex process and coupling efficiency is low; And for 1-1 type film, needed before masking, substrate is carried out a series of process such as etch and will induce two-phase simultaneously, technique is more complicated, although the Stress transmit of this film carries out in the peripheral direction of one dimension line simultaneously, Stress transmit coupling efficiency is relatively high.Comparatively speaking, the preparation technology of the 0-0 type film of two-phase random growth is obviously very simple, but as mentioned above, the two phase structure of this Homogeneous phase mixing distribution, its Stress transmit is uniformly distributed existence in surrounding, can not cause the change of ferromagnetic phase easy magnetization axis, angle etc.But, further analysis is known, if can realize the oriented growth of ferromagnetic phase, is then equivalent to 1-1 type two Entropy density deviation successfully achieving film on each microcell, and occurring in the peripheral direction being similar to one dimension crystal grain due to its stress, opposing coupler efficiency is also higher.Although at this moment also certain stress can be subject on the direction of this kind one-dimensional line, but because thin-film material itself is very thin, utilize the induction transmission effect that substrate is formed film crystalline phase orientation, the ferrite of this orientation is expected to induced synthesis on kind one-dimensional direction mutually.Therefore, in general, stress (stressed area) suffered on this kind one-dimensional line direction is more much smaller than the stress (stressed area) suffered by online surrounding, thus makes this oriented growth ferrite crystalline phase can be subject to effective anisotropic stress effect and produce coupling effect.Moreover when the grain-size of this oriented growth ferrite crystalline phase is controlled in nanoscale, the stress that ferroelectric phase produces is expected to the whole lattices passing to nanometer ferrite preferably, and also namely all ferrite lattice all produce distortion and participate in coupling.And and unlike larger ferrite crystal grains, be mainly subject to stress and make most of ferrite internal crystal framework cannot be subject to stress thus participating in coupling very well in contact surface part, thus coupling is reduced.Therefore, the Nanocrystalline Composite Films of ferrite oriented growth is expected to become a kind of magneto-electric coupled multiferroic complex phase film of good performance.
In a word, successfully prepare a kind of ferrite oriented growth, particularly ferroelectric phase/the application of ferromagnetic phase composite nanocrystalline multiferroic film to the magneto-electric coupled performance materials of Gao Jie, Gao Ci, low-loss and height of (100) orientation will play very important effect.
But, how efficiently prepare a kind of ferroelectric phase of satisfactory ferrite oriented growth, ferromagnetic phase two-phase composite film to be used widely being this film the required another key issue solved in field of electronic materials.
Summary of the invention
The object of the invention is to for existing relevant many iron complex phase thin-film dielectric loss high, magnetic permeability is low, the deficiency of the aspect such as magneto-electric coupled weak and preparation method is complicated, propose a kind of nanocrystalline complex phase thin-film material of barium titanate/nickel-zinc ferrite and preparation method of ferromagnetic phase oriented growth, barium titanate crystalline phase random growth in this complex phase film, nickel-zinc ferrite crystalline phase oriented growth and two-phase chaotic distribution, this kind of material has two (electricity, magnetic) percolation threshold, there is low-dielectric loss simultaneously, high-k and high magnetic permeability, there are two higher alternate Stress transmit effect and coupling effects, preparation is simple.
The nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite of the present invention, chemical formula is (1-x) BaTiO
3/ xNi
0.5zn
0.5fe
2o
4be made up of barium titanate (BTO) crystalline phase and nickel-zinc ferrite (NZFO) crystalline phase, in two-phase, crystal grain is chaotic distribution, and barium titanate is mutually without specific orientation, nickel-zinc ferrite hands down (100) oriented growth, the grain-size of two-phase is all less than 20nm.
The preparation method of the nanocrystalline complex phase film of above-mentioned barium titanate/nickel-zinc ferrite, comprises the steps:
1) silicon single crystal of (111) orientation is cleaned, remove surface oxide layer and dry, obtaining sputtering substrate;
2) radio-frequency magnetron sputter method is adopted, with barium titanate/nickel-zinc ferrite complex phase sputtering target material through step 1) monocrystalline silicon piece that processes sputters noncrystal membrane, concrete growth parameter(s) is: compare for the gas mixture of 3:7 ~ 6:4 is as sputtering atmosphere using oxygen and partial pressure of ar gas, total pressure is 0.6 × 10
-3~ 2 × 10
-3mbar, sputtering power 160 ~ 220W carry out 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) noncrystal membrane be deposited in (111) monocrystal silicon substrate that obtains heat-treats, first with the speed of 3 ~ 6 DEG C/min from room temperature to 560 ~ 600 DEG C, again with ramp to 780 ~ 820 DEG C of 8 ~ 10 DEG C/min, insulation 1 ~ 4h; Cool to room temperature with the furnace afterwards, obtain the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite of magnetic phase orientation.
Magnetron sputtering deposition is a kind of common method preparing thin-film material, and at high temperature sputtering obtains associated film usually, comprises oriented film.But in view of ferroelectric phase/ferrite phase laminated film itself characteristic to limit and magnetron sputtering deposition process is formed film and the control characteristic of orientation etc., the complex phase film wanting to utilize magnetron sputtering method to obtain the uniform close of ferrite edge (100) orientations also needs to design especially technique, and key how to avoid the direct control action kou of aura deposition process to crystalline formation and orientation etc.For this reason, this programme proposes: first control its at room temperature sputtering sedimentation, obtains amorphous phase basement membrane, and high-energy when eliminating deposition with this is to the direct control of film crystalline formation and influence; And then by specific treatment process, through at high temperature thermal treatment, utilize homogeneous nucleation crystallization principle, control nucleation crystallization in noncrystal substrate, the final film obtaining ferrite single-phase oriented growth.This scheme both make use of magnetically controlled sputter method, again in conjunction with Post isothermal treatment control techniques, prepared relevant multiferroic complex phase film.
The key that success obtains ferrite orientation crystallization in this two-phase composites is that controlling two-phase is forming influencing each other in crystalline phase and orientation process.For this reason, first select have (111) silicon single crystal of certain lattice match relation to be substrate with (100) crystal face of ferrite phase structure, and by specific clean technique, make substrate produce stronger orientation inducing action to rete crystallization, control ferrite relatively easy orientation in Crystallization Process in film.Secondly, consider that the crystallization condition of two kinds of crystalline phases is different, a kind of formation of crystalline phase can have an impact to another kind of crystalline phase, thus by controlling heat treatment process, utilize and be rapidly heated and the method for temperature-gradient method, avoid the optimum temps interval (600 ~ 700 DEG C) forming ferroelectric phase in system fast, ferroelectric phase to be decrystallized formation in the relatively high ferrite formation temperature stage, ferrite can be formed mutually and oriented growth produces the problem suppressed to the later stage to solve early origin ferroelectric phase.
In addition, as a kind of deposition of noncrystal membrane, effectively must control its as far as possible densification, with the close contact after the crystalline formation ensureing the later stage and mutual stress transfer.In fact, magnetron sputtering deposition is that argon ion bombardment target by being accelerated by electromagnetic field realizes.Sputtering power is low, and the momentum of bombarding ion and deposition and atomic is not enough, cannot reach the requirement of amorphous basement membrane densification; Sputtering power is high, improves sputtering power especially in certain power range, is conducive to improving deposition compact degree, but at this moment easily produces more defect, as a large amount of loss of oxygen, the adjustment of sputtering atmosphere thus must be coordinated to control sputtering power.Only guaranteed under relatively high oxygen atmosphere ratio, by higher sputtering power; Or by improving the concentration of bombarding ion argon under lower sputtering power, being just expected to deposition and obtaining dense uniform, the qualified amorphous basement membrane of less oxygen loss again.
Compared with prior art, the beneficial effect that the present invention has is:
Barium titanate crystalline phase random growth in film of the present invention, nickel-zinc ferrite crystalline phase oriented growth, two-phase chaotic distribution, compared with common complex phase film, has following superiority:
1, 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, thus makes that its dielectric loss is low reaches 0.008;
2, there is different electroosmotic flow threshold value and magnetic percolation threshold, there is between two threshold values the composition deviation range of about 15%, electroosmotic flow threshold value about NZFO content be 55mol% place, and magnetic percolation threshold is 38mol% place about NZFO content, achieve the film simultaneously with Gao Jie, high magnetic and low loss performance;
3, there are two higher alternate Stress transmit effects, and obtain higher electromagnetic coupling effect, magnetic induction density can be made to produce the sudden change of 10% in BTO Curie temperature;
4, the preparation technology of the present invention's many iron complex phase thin-film material is simple, with low cost, can be used for multi-state memory and heterogeneous read-write electrical condenser, and is expected to be used widely at electromagnetic device applications.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the complex phase thin-film material 0.6BTO/0.4NZFO that embodiment 1 obtains;
Fig. 2 is the TEM figure of the complex phase thin-film material 0.6BTO/0.4NZFO that embodiment 1 obtains;
Fig. 3 is the XRD figure of the complex phase thin-film material 0.4BTO/0.6NZFO that embodiment 2 obtains;
Fig. 4 is the XRD figure of the complex phase thin-film material 0.2BTO/0.8NZFO that embodiment 3 obtains;
Fig. 5 is the XRD figure of the complex phase thin-film material 0.5BTO/0.5NZFO that embodiment 4 obtains.
Embodiment
The nanocrystalline composite diphase material of barium titanate nickel-zinc ferrite of the present invention is polycrystal film, and wherein barium titanate is random growth, and nickel-zinc ferrite is along (100) oriented growth.The chemical formula of described many iron laminated film is BaTiO
3/ Ni
0.5zn
0.5fe
2o
4.
Consider and need being uniformly distributed of the simplicity of technique and two-phase particle, the preparation of this complex phase film takes and realizes industrialized radio-frequency magnetron sputter method already.Using (111) oriented single crystal silicon as thin film deposition substrate, elder generation's sputtering sedimentation on substrate is adopted to obtain noncrystal membrane, again to amorphous-nucleation two step formation method that noncrystal membrane is heat-treated, obtain the distribution of two-phase uniform crystal particles and the complex phase film of wherein ferrite phase (100) oriented growth.Wherein control sputtering power and 0.3 ~ 0.6 oxygen partial pressure of 160 ~ 220W, at room temperature deposit 2 ~ 6 hours; Control thermal treatment to carry out in air atmosphere, first with the speed of 3 ~ 6 DEG C/min from room temperature to 560 ~ 600 DEG C, then with ramp to 780 ~ 820 of 8 ~ 10 DEG C/min DEG C insulation 1 ~ 4h, last furnace cooling.Obtain the barium titanate nickel-zinc ferrite nanocrystalline many iron complex phase film meeting described properties requirement.
Utilize XRD and SEM to carry out microstructure and pattern test to the film prepared, utilize electric impedance analyzer and MPMS magnetic measurement system, vibrating sample magnetometer to carry out room temperature dielectric performance, agnetic property at room temperature m and alternating temperature magnetism testing to complex phase film.
Below in conjunction with specific embodiment, the present invention will be further described:
Embodiment 1:
1), after the silicon single crystal of (111) orientation tentatively being cleaned with deionized water, in hydrofluoric acid, soak 5min, then be placed in ethanol and carry out ultrasonic cleaning 10min; Monocrystalline silicon piece after cleaning is placed in vacuum drying oven dry, obtains sputtering substrate.
2) complex phase sputtering target material barium titanate, iron Zn ferrite obtained for 0.6:0.4 in molar ratio and (111) silicon single crystal sputtering substrate cleaned up are placed in the sputtering chamber of rf magnetron sputtering instrument; After sputtering chamber is vacuumized again logical oxygen partial pressure be 0.4 oxygen and the gas mixture of argon gas as sputtering atmosphere; The total pressure of gas mixture is controlled 8 × 10
-4after mbar, radio frequency power is adjusted to 200W, and at room temperature sputtering sedimentation 4h obtains the noncrystal membrane of even compact.
3) the even compact noncrystal membrane be deposited in (111) monocrystal silicon substrate is placed in retort furnace, with the speed of 3 DEG C/min after room temperature to 600 DEG C, 2h is incubated again with after the ramp to 800 of 10 DEG C/min DEG C, after cooling to room temperature with the furnace, obtain 0.6BTO/0.4NZFO many iron Nanocrystalline Composite Films.
Fig. 1 is the XRD figure spectrum of the barium titanate nickel-zinc ferrite complex phase film that the present embodiment obtains, and can see, in material, barium titanate is random growth mutually, and nickel-zinc ferrite is then along (100) oriented growth mutually.Fig. 2 is the TEM photo of the barium titanate nickel-zinc ferrite complex phase film that the present embodiment obtains, and can see, in material, barium titanate is completely unordered mutually, and nickel-zinc ferrite is then along (100) oriented growth mutually; Two-phase grain-size is all at below 20nm; Two-phase particle close contact and even chaotic distribution.
Embodiment 2:
1), after the silicon single crystal of (111) orientation tentatively being cleaned with deionized water, in hydrofluoric acid, soak 4min, then be placed in ethanol and carry out ultrasonic cleaning 15min; Monocrystalline silicon piece after cleaning is placed in vacuum drying oven dry, obtains sputtering substrate.
2) complex phase sputtering target material barium titanate, iron Zn ferrite obtained for 0.4:0.6 in molar ratio and (111) silicon single crystal sputtering substrate cleaned up are placed in the sputtering chamber of rf magnetron sputtering instrument; After sputtering chamber is vacuumized again logical oxygen partial pressure be 0.5 oxygen and the gas mixture of argon gas as sputtering atmosphere; The total pressure of gas mixture is controlled 2 × 10
-3after mbar, radio frequency power is adjusted to 220W, and at room temperature sputtering sedimentation 2h obtains the noncrystal membrane of even compact.
3) by the even compact noncrystal membrane be deposited in (111) monocrystal silicon substrate and be placed in retort furnace, with the speed of 5 DEG C/min after room temperature to 560 DEG C, 1h is incubated again with after the ramp to 820 of 8 DEG C/min DEG C, after cooling to room temperature with the furnace, obtain 0.4BTO/0.6NZFO many iron Nanocrystalline Composite Films.
Fig. 3 is the XRD figure spectrum of the barium titanate nickel-zinc ferrite complex phase film that the present embodiment obtains, and can see, in material, barium titanate is random growth mutually, and nickel-zinc ferrite is then along (100) oriented growth mutually.
Embodiment 3:
1), after the silicon single crystal of (111) orientation tentatively being cleaned with deionized water, in hydrofluoric acid, soak 6min, then be placed in ethanol and carry out ultrasonic cleaning 10min; Monocrystalline silicon piece after cleaning is placed in vacuum drying oven dry, obtains sputtering substrate.
2) the complex phase sputtering target material obtained for 0.1:0.9 in molar ratio by barium titanate iron Zn ferrite and (111) silicon single crystal sputtering substrate cleaned up are placed in the sputtering chamber of rf magnetron sputtering instrument; After sputtering chamber is vacuumized again logical oxygen partial pressure be 0.3 oxygen and the gas mixture of argon gas as sputtering atmosphere; The total pressure of gas mixture is controlled 0.6 × 10
-3after mbar, radio frequency power is adjusted to 160W, and at room temperature sputtering sedimentation 6h obtains the noncrystal membrane of even compact.
3) by the even compact noncrystal membrane be deposited in (111) monocrystal silicon substrate and be placed in retort furnace, with the speed of 6 DEG C/min after room temperature to 580 DEG C, 2h is incubated again with after the ramp to 800 of 10 DEG C/min DEG C, after cooling to room temperature with the furnace, obtain 0.1BTO/0.9NZFO many iron Nanocrystalline Composite Films.
Fig. 4 is the XRD figure spectrum of the barium titanate nickel-zinc ferrite complex phase film that the present embodiment obtains, and can see, in material, barium titanate is random growth mutually, and nickel-zinc ferrite is then along (100) oriented growth mutually.
Embodiment 4:
1), after the silicon single crystal of (111) orientation tentatively being cleaned with deionized water, in hydrofluoric acid, soak 8min, then be placed in ethanol and carry out ultrasonic cleaning 20min; Monocrystalline silicon piece after cleaning is placed in vacuum drying oven dry, obtains sputtering substrate.
2) be that 0.5:0.5 complex phase sputtering target material is placed in the sputtering chamber of rf magnetron sputtering instrument with (111) silicon single crystal sputtering substrate cleaned up by barium titanate iron Zn ferrite ratio; After sputtering chamber is vacuumized again logical oxygen partial pressure be 0.4 oxygen and the gas mixture of argon gas as sputtering atmosphere; The total pressure of gas mixture is controlled 1.2 × 10
-3after mbar, radio frequency power is adjusted to 180W, and at room temperature sputtering sedimentation 6h obtains the noncrystal membrane of even compact.
3) by the even compact noncrystal membrane be deposited in (111) monocrystal silicon substrate and be placed in retort furnace, with the speed of 5 DEG C/min after room temperature to 600 DEG C, be incubated 4h with after the ramp to 780 of 8 DEG C/min DEG C again, after cooling to room temperature with the furnace, obtain being met 0.5BTO/0.5NZFO many iron Nanocrystalline Composite Films of the unordered nickel-zinc ferrite ordering growth of barium titanate described in claim 1.
Fig. 5 is the XRD figure spectrum of the barium titanate nickel-zinc ferrite complex phase film that the present embodiment obtains, and can see, in material, barium titanate is random growth mutually, and nickel-zinc ferrite is then along (100) oriented growth mutually.
Embodiment 5:
1), after the silicon single crystal of (111) orientation tentatively being cleaned with deionized water, in hydrofluoric acid, soak 8min, then be placed in ethanol and carry out ultrasonic cleaning 20min; Monocrystalline silicon piece after cleaning is placed in vacuum drying oven dry, obtains sputtering substrate.
2) the complex phase sputtering target material obtained for 0.9:0.1 in molar ratio by barium titanate iron Zn ferrite and (111) silicon single crystal sputtering substrate cleaned up are placed in the sputtering chamber of rf magnetron sputtering instrument; After sputtering chamber is vacuumized again logical oxygen partial pressure be 0.6 oxygen and the gas mixture of argon gas as sputtering atmosphere; The total pressure of gas mixture is controlled 2 × 10
-3after mbar, radio frequency power is adjusted to 180W, and at room temperature sputtering sedimentation 6h obtains the noncrystal membrane of even compact.
3) by the even compact noncrystal membrane be deposited in (111) monocrystal silicon substrate and be placed in retort furnace, with the speed of 5 DEG C/min after room temperature to 600 DEG C, 4h is incubated again with after the ramp to 780 of 8 DEG C/min DEG C, after cooling to room temperature with the furnace, obtain 0.9BTO/0.1NZFO many iron Nanocrystalline Composite Films.
Claims (2)
1. the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite, is characterized in that, this film chemical formula is (1-x) BaTiO
3/ xNi
0.5zn
0.5fe
2o
4, wherein 0 < x < 1, is made up of barium titanate crystalline phase and nickel-zinc ferrite crystalline phase, in two-phase, crystal grain is chaotic distribution, barium titanate is mutually without specific orientation, and nickel-zinc ferrite hands down (100) oriented growth, the grain-size of two-phase is all less than 20nm.
2. the preparation method of the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite according to claim 1, is characterized in that, comprise the steps:
1) silicon single crystal of (111) orientation is cleaned, remove surface oxide layer and dry, obtaining sputtering substrate;
2) radio-frequency magnetron sputter method is adopted, with barium titanate/nickel-zinc ferrite complex phase sputtering target material through step 1) monocrystalline silicon substrate that processes sputters noncrystal membrane, concrete growth parameter(s) is: compare for the gas mixture of 3:7 ~ 6:4 is as sputtering atmosphere using oxygen and partial pressure of ar gas, total pressure is 0.6 × 10
-3~ 2 × 10
-3mbar, sputtering power 160 ~ 220W carry out 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) noncrystal membrane be deposited in (111) monocrystal silicon substrate that obtains heat-treats, first with the speed of 3 ~ 6 DEG C/min from room temperature to 560 ~ 600 DEG C, again with ramp to 780 ~ 820 DEG C of 8 ~ 10 DEG C/min, insulation 1 ~ 4h; Cool to room temperature with the furnace afterwards, obtain the nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite of magnetic phase orientation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510500941.6A CN105198406B (en) | 2015-08-14 | 2015-08-14 | Nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510500941.6A CN105198406B (en) | 2015-08-14 | 2015-08-14 | Nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105198406A true CN105198406A (en) | 2015-12-30 |
| CN105198406B CN105198406B (en) | 2017-08-15 |
Family
ID=54946434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510500941.6A Active CN105198406B (en) | 2015-08-14 | 2015-08-14 | Nanocrystalline complex phase film of barium titanate/nickel-zinc ferrite that magnetic is mutually orientated and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105198406B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112713238A (en) * | 2020-12-18 | 2021-04-27 | 浙江大学 | BTO/NZFO complex phase multiferroic film with (111) oriented growth NZFO crystalline phase column array and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050111147A1 (en) * | 2000-09-11 | 2005-05-26 | Matsushita Electric Industrial Co., Ltd. | Method for forming a compound magnetic thin film |
| CN102051582A (en) * | 2010-11-12 | 2011-05-11 | 北京工业大学 | Method for preparing highly (100) oriented BiFeO3 films on Si substrate |
| CN102584217A (en) * | 2012-02-06 | 2012-07-18 | 浙江大学 | BaTiO3-Ni0.5Zn0.5Fe2O4 ferroelectric-ferromagnetic composite ceramic thin film prepared by utilizing magnetron sputtering method and preparation method |
-
2015
- 2015-08-14 CN CN201510500941.6A patent/CN105198406B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050111147A1 (en) * | 2000-09-11 | 2005-05-26 | Matsushita Electric Industrial Co., Ltd. | Method for forming a compound magnetic thin film |
| CN102051582A (en) * | 2010-11-12 | 2011-05-11 | 北京工业大学 | Method for preparing highly (100) oriented BiFeO3 films on Si substrate |
| CN102584217A (en) * | 2012-02-06 | 2012-07-18 | 浙江大学 | BaTiO3-Ni0.5Zn0.5Fe2O4 ferroelectric-ferromagnetic composite ceramic thin film prepared by utilizing magnetron sputtering method and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| HAE SEOK CHO 等: "Preferred orientation and microstructure of Ni-Zn-Cu ferrite thin films deposited by rf magnetron sputtering", 《JOURNAL OF MATERIALS RESEARCH》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112713238A (en) * | 2020-12-18 | 2021-04-27 | 浙江大学 | BTO/NZFO complex phase multiferroic film with (111) oriented growth NZFO crystalline phase column array and preparation method thereof |
| CN112713238B (en) * | 2020-12-18 | 2022-05-17 | 浙江大学 | BTO/NZFO complex phase multiferroic film with (111) oriented growth NZFO crystalline phase column array and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105198406B (en) | 2017-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hu et al. | Structural Transition and Multiferroic Properties of Eu‐Doped BiFeO3 Thin Films | |
| CN105331942B (en) | Yttrium-iron garnet thin film material and preparation method thereof | |
| CN103274677B (en) | A kind of titanium doped barium ferrite stupalith and preparation method thereof | |
| Liao et al. | Microstructure and enhanced magnetic properties of low-temperature sintered LiZnTiMn ferrite ceramics with Bi2O3-Al2O3 additive | |
| Trukhanov et al. | Crystal structure, magnetic, and microwave properties of solid solutions BaFe 12–x Ga x O 19 (0.1≤ x≤ 1.2) | |
| Hossain et al. | Effect of Li substitution on the magnetic properties of LixMg0. 40Ni0. 60− 2xFe2+ xO4 ferrites | |
| Wang et al. | Low-temperature sintering and ferromagnetic properties of Li0. 35Zn0. 30Mn0. 05Ti0. 15Fe2. 15O4 ferrites co-fired with Bi2O3-MgO mixture | |
| CN105112868A (en) | Preparation method of topology insulator/ferromagnet heterostructure film | |
| Jia et al. | High-frequency properties of Si-doped Z-type hexaferrites | |
| Zou et al. | Room temperature ferromagnetism and ferroelectricity behavior of (Cu, Li) co-doped ZnO films deposited by reactive magnetron sputtering | |
| CN105198406A (en) | Magnetic-phase-oriented barium titanate/Ni-Zn ferrite nanocrystalline complex-phase thin film and preparation method thereof | |
| Zhang et al. | Magnetic properties of in-plane oriented barium hexaferrite thin films prepared by direct current magnetron sputtering | |
| Islam et al. | Influence of Mg substitution on structural, magnetic and electrical properties of Zn-Cu ferrites | |
| CN103255384A (en) | Preparation method of barium ferrite film with grain c-shaft perpendicular film surface in oriented growth | |
| Zhang et al. | Significantly improved multiferrioc properties of BiFeO3/Pb (Zr0. 52Ti0. 48) O3 bilayer films by magnetic field annealing | |
| CN109234678B (en) | Copper-doped barium titanate/nickel zinc ferrite multiphase film material and preparation method thereof | |
| CN110078131B (en) | C-axis oriented growth of Bi on Si substrate4Ti2.95Co0.05O12Multiferroic film and preparation method thereof | |
| CN103540904A (en) | Method used for preparation of T-phase BiFeO3 thin film | |
| CN103714942A (en) | Self-biased non-homogeneous microwave ferromagnetic thin film material and preparation method thereof | |
| CN102965633B (en) | Preparation method of M type barium ferrite thin film orientated by c axis vertical film surface | |
| KR102156117B1 (en) | Room-temperature multiferroic materials, preparing method of the same and electronic device comprising the same | |
| Ma et al. | Reduced leakage current and enhanced magnetic properties of (Bi, Nd) FeO3 thin films grown on (Ba, Sr) TiO3 bottom layer | |
| CN106835134B (en) | A kind of novel magnetic power tuning laminated film and preparation method thereof | |
| US8029921B2 (en) | Growth of high quality low-loss ferrite materials on wide bandgap semiconductor substrates | |
| CN105154826A (en) | Cu-doped-ZnO nano columnar crystal film with room-temperature ferromagnetism and preparing method of Cu-doped-ZnO nano columnar crystal film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |