CN117144305A - Preparation method of calcium-doped bismuth ferrite film system material - Google Patents
Preparation method of calcium-doped bismuth ferrite film system material Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 37
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 69
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000919 ceramic Substances 0.000 claims abstract description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 28
- 239000001301 oxygen Substances 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000010408 film Substances 0.000 claims description 87
- 238000010438 heat treatment Methods 0.000 claims description 46
- 238000005245 sintering Methods 0.000 claims description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000499 gel Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- 230000005291 magnetic effect Effects 0.000 claims description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 22
- 239000013077 target material Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000000227 grinding Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000004093 laser heating Methods 0.000 claims description 14
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 claims description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 238000004544 sputter deposition Methods 0.000 claims description 12
- 239000011858 nanopowder Substances 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 239000010409 thin film Substances 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011240 wet gel Substances 0.000 claims description 8
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 6
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 5
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 5
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 230000005290 antiferromagnetic effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a calcium-doped bismuth ferrite (Bi) 1‑ x Ca x FeO 3 ) The preparation method of the film system material specifically comprises the following steps: solution preparation, gel and powder preparation, target preparation, bottom electrode target preparation, target and substrate treatment, film growth environment regulation and control and film preparation; the invention adoptsThe solvent gel method ensures the mixing of all components at molecular level, the density of the ceramic target is high, and the phase purity of the epitaxially grown film is high; according to the invention, oxygen vacancies with different concentrations are introduced by adjusting the calcium doping proportion, so that the conductivity of the film is enhanced, and the film has great potential application value; the invention is characterized by introducing Bi 1‑x Ca x FeO 3 La with small difference in lattice constant 0.5 Sr 0.5 MnO 3 The electrode material is used as a bottom electrode, so that the epitaxially grown film has an atomic level flat step, which is beneficial to epitaxial growth, reduces defect density, has good film crystallization quality, and improves the performance and service life of the device.
Description
Technical Field
The invention belongs to the technical field of inorganic functional film materials, and particularly relates to a preparation method of a calcium-doped bismuth ferrite film system material.
Background
With the rapid development of industries such as ferroelectric memories, photocatalytic degradation, high-temperature piezoelectric devices, energy storage dielectrics, ferroelectric photovoltaics and the like in recent years, thin film materials with excellent ferroelectric and piezoelectric properties have become one of the hot spots in the current research field.
The multiferroic magnetoelectric material is a material with ferroelectric (antiferroelectric) and ferromagnetic (antiferromagnetic) properties, and has wide application prospect in the fields of ferroelectric memories, photocatalytic degradation, high-temperature piezoelectric devices, energy storage dielectrics, ferroelectric photovoltaics and the like 3 ) Because the material has room-temperature multiferroics (the ferroelectric Curie temperature is 1103K, the antiferromagnetic Neer temperature is 643K), the material becomes a lead-free environment-friendly material which can be compared favorably with lead materials, and provides great application possibility for developing novel information storage processing and magneto-electric devices based on ferroelectric-magnetic integration effect. However BiFeO 3 Lattice defects (such as ionic oxygen vacancies) in thin films are of great concern because their presence affects physical properties such as electron transport, magnetism, and ferroelectricity. Therefore, the invention proposes to adopt an electric field to regulate and control Bi 1-x Ca x FeO 3 The conductive state of the film can increase oxygen vacancy and maintain Fe by adding divalent calcium ions 3+ Valence state. Specifically, the concentration of oxygen vacancies and the conductivity of the film are regulated by controlling the calcium doping proportion. In addition, when PLD is used in LaAlO 3 On monocrystalline substratesGrowth of Bi 1-x Ca x FeO 3 When the crystal layer is formed, stress is generated near a growth interface due to large lattice constant difference of the two substances, so that crystal defects are generated to influence the epitaxial growth of crystals, a large number of defects are generated in the epitaxial layer, even single crystals cannot be grown, and the performance and the service life of a device are influenced, which is also a problem to be solved urgently.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a calcium-doped ferrite film system material capable of adjusting oxygen vacancies and conductivity. The method comprises synthesizing powder by sol-gel method, sintering into ceramic target, and sputter depositing the ceramic target on LaAlO by pulse laser deposition 3 Bi is prepared on the substrate 1-x Ca x FeO 3 A system film. The invention adjusts the oxygen vacancy concentration by controlling the calcium doping proportion, improves the conductivity of the film, and simultaneously introduces Bi into the film 1-x Ca x FeO 3 La with small difference in lattice constant 0.5 Sr 0.5 MnO 3 Electrode material, first grow a layer of La 0.5 Sr 0.5 MnO 3 Bottom electrode, regrowth Bi 1-x Ca x FeO 3 The film is favorable for epitaxial growth, reduces defect density, has good crystallization quality, and improves the performance and service life of the device.
The preparation method of the calcium-doped bismuth ferrite film system material comprises the following steps:
(1) Solution preparation
The calcium nitrate tetrahydrate, bismuth nitrate pentahydrate and ferric nitrate nonahydrate are prepared according to Bi 1-x Ca x FeO 3 Weighing the element chemical molar ratio, then weighing citric acid, sequentially dissolving the weighed mixture in a mixed solvent beaker of methanol and ethylene glycol, putting a magnetic stirrer into the beaker, putting the beaker on a constant-temperature magnetic force uniform table, uniformly stirring, controlling the magnetic rotation speed, and obtaining uniform solution after a period of time;
(2) Gel and powder preparation
Moving the solution which is uniform in the step (1) to a heating magnetic force uniform table for stirring and heating for a period of time, placing the beaker in a drying constant temperature oven for fully foaming for a period of time to obtain gel, taking the gel out of the beaker, fully grinding the gel in a pre-cleaned mortar to obtain calcium-doped bismuth ferrite ceramic powder, placing the calcium-doped bismuth ferrite ceramic powder in a box-type furnace for presintering treatment, and controlling the heating rate, the primary sintering time and the sintering temperature to obtain primary calcined powder;
(3) Target preparation
Placing the primary calcined powder in the step (2) into a specific die, performing pressurization treatment to prepare a calcium-doped bismuth ferrite ceramic block, and placing the obtained ceramic block into a box-type furnace for calcination to obtain a calcium-doped bismuth ferrite ceramic target;
(4) Preparation of bottom electrode target material
Dissolving strontium nitrate, lanthanum nitrate and manganese nitrate in deionized water solvent by using a sol-gel method, heating and stirring to form wet gel, and putting into a drying oven for drying; finally grinding the gel, and presintering to obtain nano powder; grinding the nano powder, tabletting, and sintering for the second time to obtain La 0.5 Sr 0.5 MnO 3 A bottom electrode target;
(5) Target and substrate processing
Bi is mixed with 1-x Ca x FeO 3 And La (La) 0.5 Sr 0.5 MnO 3 Polishing target material with sand paper, cleaning with alcohol and dust-free paper, and LaAlO 3 Placing the substrate into a box-type furnace for sintering under normal pressure and air atmosphere; laAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated by an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target;
(6) Thin film growth environment regulation
Vacuumizing the PLD cavity, shielding the cavity by using a baffle when the vacuum degree of the cavity reaches a certain value, setting parameters of a pulse laser, performing pre-sputtering, and starting to heat by using infrared laser after the sputtering is finished;
(7) Film preparation
First grow a layer of La 0.5 Sr 0.5 MnO 3 Bottom electrode according to the practiceAdjusting the growth condition of the bottom electrode according to the situation of need, setting the infrared laser heating temperature of the cavity, closing the molecular pump, adjusting the oxygen pressure of the cavity and the growth rate of the film, and growing Bi after growing the bottom electrode 1-x Ca x FeO 3 Setting the infrared laser heating temperature of the cavity, adjusting the oxygen pressure of the cavity and the growth rate of the film, introducing oxygen for annealing after the growth is finished, and controlling the cooling rate and the annealing time to obtain Bi 1-x Ca x FeO 3 A film.
According to the invention, in the step (1), x=0.02-0.30, the molar ratio of citric acid to metal cations of calcium-doped bismuth ferrite is 1:1, the volume ratio of methanol to glycol is 5:1-3:1, the stirring time is 30-60 min, and the magnetic rotation speed is 200-400 r/min.
According to the invention, the heating temperature of the mixed solution in the step (2) is 80-100 ℃, the heating time is 0.5-2 h, the drying temperature of an oven is 50-100 ℃, the drying time is 12-24 h, the grinding time is 0.5-1 h, the heating rate is 2-4 ℃ per minute, the primary sintering temperature is 400-600 ℃, the primary sintering time is 2-4 h, and the sintering conditions are normal pressure and air atmosphere.
The pressure of the tablet press in the step (3) is 1-2 mpa, the pressurizing time is 20-30 min, the calcining temperature is 700-900 ℃, the heating time is 2-12 h, and the sintering conditions are normal pressure and air atmosphere.
In the step (4), the secondary calcination temperature is 1200-1450 ℃, the heating time is 2-12 h, and the sintering condition is normal pressure and air atmosphere.
Bi is added in the step (5) of the invention 1-x Ca x FeO 3 Polishing the target material by using 500-3000 mesh sand paper, then cleaning by using alcohol and dust-free paper, and LaAlO 3 Placing the substrate into a box-type furnace, and sintering for 0.5-2 hours at 1000-1450 ℃ under normal pressure and air atmosphere; laAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated for 3-5 min by using an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target.
The vacuum degree of the cavity in the step (6) is 1 multiplied by 10 -4 ~2×10 -4 In Pa, setting the voltage of the pulse laser to be 19-20 kV and the frequency to be 3-5 Hz,the energy is 200-350 mJ, and pre-sputtering is carried out for 500-1000 pulses.
In the step (7), the infrared laser heating temperature of the growth bottom electrode is 700-750 ℃, a molecular pump is turned off, and the oxygen pressure of the cavity is regulated to 15-20 Pa; the film growth rate is 80-100 nm/h, and Bi is grown after the bottom electrode is grown 1- x Ca x FeO 3 Setting the infrared laser heating temperature of the cavity to be 600-700 ℃ and adjusting the oxygen pressure of the cavity to be 13.3-26.6 Pa; the film growth rate is 120-140 nm/h, and after the growth is finished, 1X 10 is introduced 4 ~2×10 4 Annealing by Pa oxygen at a cooling rate of 10-15 ℃/min for 45-60 min to obtain Bi 1-x Ca x FeO 3 A film.
The invention has the beneficial effects that:
(1) The invention adopts the solvent gel method to prepare the target material, the target material has high density, good crystallization quality and good chemical stability, ensures the mixing of all components at molecular level, and has good quality, good crystallinity and high phase purity of the epitaxially grown film;
(2) The target material has the advantages of simple preparation process, good repeatability, low price and high yield of the selected chemical reagent, and provides a favorable precondition for preparing the film with excellent performance; meanwhile, bi 1-x Ca x FeO 3 The system film sample observes an atomic level flattening morphology graph, and has good ferroelectric domain overturning property and high film quality, and good hysteresis loop and butterfly curve.
(3) The method introduces oxygen vacancies with different concentrations by adjusting the calcium doping proportion, enhances the conductivity of the film, has great potential application value, and is expected to be applied to industries such as information storage, mobile communication, electronic appliances, aviation and the like.
(4) The film preparation method of the invention uses Bi 1-x Ca x FeO 3 Relatively matched electrode material La 0.5 Sr 0.5 MnO 3 When LaAlO 3 Growth of Bi on monocrystalline substrates 1-x Ca x FeO 3 By introducing Bi into the single crystal layer 1-x Ca x FeO 3 Lattice constant differenceSmall La 0.5 Sr 0.5 MnO 3 The electrode material ensures that the epitaxially grown film has an atomic level flat step, is beneficial to epitaxial growth, reduces defect density, has good film crystallization quality, and improves the performance and service life of devices.
Drawings
FIG. 1 is a drawing of example 1Bi 0.90 Ca 0.10 FeO 3 XRD pattern of the thin film system material;
FIG. 2 is a drawing of example 1Bi 0.90 Ca 0.10 FeO 3 AFM topography of the film system material;
FIG. 3 is a drawing of example 1Bi 0.90 Ca 0.10 FeO 3 I-V graph of the film system material;
FIG. 4 is a block diagram of example 1Bi 0.90 Ca 0.10 FeO 3 A hysteresis loop and butterfly graph of the film system material;
FIG. 5 is a drawing of example 2Bi 0.85 Ca 0.15 FeO 3 AFM topography of the film system material;
FIG. 6 is example 2Bi 0.85 Ca 0.15 FeO 3 I-V graph of the film system material;
FIG. 7 is example 2Bi 0.85 Ca 0.15 FeO 3 A hysteresis loop and butterfly graph of the film system material;
FIG. 8 is a drawing of example 4Bi 0.70 Ca 0.30 FeO 3 XRD pattern of the thin film system material;
FIG. 9 is a drawing of example 4Bi 0.70 Ca 0.30 FeO 3 AFM topography of the film system material;
FIG. 10 is a drawing of example 4Bi 0.70 Ca 0.30 FeO 3 I-V graph of the film system material;
FIG. 11 is a drawing of example 4Bi 0.70 Ca 0.30 FeO 3 A hysteresis loop and butterfly graph of the film system material;
FIG. 12 is a drawing of example 5Bi 0.95 Ca 0.05 FeO 3 AFM topography of the film system material;
FIG. 13 is a drawing of example 5Bi 0.95 Ca 0.05 FeO 3 Film systemI-V plot of material;
FIG. 14 is a drawing of example 5Bi 0.95 Ca 0.05 FeO 3 Hysteresis loop and butterfly graph of the film system material.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific embodiments, but the scope of the invention is not limited to the description.
Example 1
(1) Solution preparation
The calcium nitrate tetrahydrate, bismuth nitrate pentahydrate and ferric nitrate nonahydrate are prepared according to Bi 1-x Ca x FeO 3 Weighing the element chemical molar ratio, wherein x=0.10, then weighing citric acid, sequentially dissolving the weighed mixture in a mixed solvent beaker of methanol and glycol, wherein the volume ratio of the methanol to the glycol is 3:1, placing a magnetic stirrer in the beaker, placing the beaker on a constant-temperature magnetic force uniform table for uniform stirring, controlling the magnetic rotation speed, obtaining uniform solution after a period of time, and stirring for 30min, wherein the magnetic rotation speed is 200r/min;
(2) Gel and powder preparation
Moving the solution which is uniform in the step (1) to a heating magnetic force uniform table for stirring and heating for a period of time, wherein the heating temperature is 80 ℃, the heating time is 0.5h, when the solvent evaporates to form a large number of bubbles, placing the beaker in a drying constant-temperature oven for fully foaming for a period of time to obtain gel, the drying temperature of the oven is 100 ℃, the drying time is 24h, taking the gel out of the beaker, placing the gel in a pre-cleaned mortar for fully grinding for 0.5h to obtain calcium-doped bismuth ferrite ceramic powder, placing the calcium-doped bismuth ferrite ceramic powder in a box-type furnace for presintering treatment, the heating rate is 2 ℃ per min, the primary sintering temperature is 500 ℃, the primary sintering time is 2h, and the sintering conditions are normal pressure and air atmosphere to obtain primary calcined powder;
(3) Target preparation
Placing the primary calcined powder in the step (2) into a circular mold for pressurization treatment, wherein the pressure of a tablet press is 1-2 mpa, the pressurization time is 20min, preparing a calcium-doped bismuth ferrite ceramic block, placing the obtained ceramic block into a box-type furnace for calcination, wherein the calcination temperature is 900 ℃, the heating time is 2h, and the sintering conditions are normal pressure and air atmosphere, so as to obtain the calcium-doped bismuth ferrite ceramic target;
(4) Preparation of bottom electrode target material
Heating and stirring strontium nitrate, lanthanum nitrate and manganese nitrate raw materials in deionized water solvent by using a sol-gel method to form wet gel, and putting the wet gel into a drying oven for drying; finally grinding the gel, and presintering to obtain nano powder; grinding the nano powder, tabletting, sintering in a box furnace at 1450 deg.C for 2 hr under normal pressure and air atmosphere to obtain La 0.5 Sr 0.5 MnO 3 A bottom electrode target;
(5) Target and substrate processing
Bi is mixed with 0.90 Ca 0.10 FeO 3 Polishing target material with 3000 mesh sand paper, cleaning with alcohol and dust-free paper, and LaAlO 3 The substrate is put into a box-type furnace to be sintered for 2 hours at 1000 ℃ under normal pressure and air atmosphere. LaAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated for 5min by an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target;
(6) Thin film growth environment regulation
Firstly, vacuumizing the cavity, when the vacuum degree of the cavity reaches 1 multiplied by 10 -4 When Pa, shielding by using a baffle, setting the voltage of a pulse laser to be 19kV, setting the frequency to be 3Hz, setting the energy to be 200mJ, performing pre-sputtering to 500pulse, and starting to heat by using infrared laser after sputtering is finished;
(7) Film preparation
First grow a layer of La 0.5 Sr 0.5 MnO 3 The bottom electrode is used for adjusting the growth condition of the bottom electrode according to the actual requirement, setting the infrared laser heating temperature of the cavity to 700 ℃, closing the molecular pump and adjusting the oxygen pressure of the cavity to 20Pa; the film growth rate is 80nm/h, and Bi is grown after the bottom electrode is grown 0.90 Ca 0.10 FeO 3 Setting the infrared laser heating temperature of the cavity to 660 ℃ and adjusting the oxygen pressure of the cavity to 13.3Pa; the film growth rate is 120nm/h, and after the growth is finished, 2X 10 is introduced 4 Annealing with Pa oxygen at a cooling rate of 10deg.C/minThe fire time is 45min, and Bi is obtained 0.90 Ca 0.10 FeO 3 A film.
Bi prepared in this example 0.90 Ca 0.10 FeO 3 The XRD patterns of the films are shown in FIG. 1, which shows relatively pure patterns.
Bi prepared in this example 0.90 Ca 0.10 FeO 3 The AFM profile of the film is shown in fig. 2, and it can be seen that the film grows flat.
Bi prepared in this example 0.90 Ca 0.10 FeO 3 The I-V graph of the film is shown in fig. 3, and it can be seen that the film has good conductivity.
Bi prepared in this example 0.90 Ca 0.10 FeO 3 The hysteresis loop and butterfly curve of the film are shown in fig. 4, and good hysteresis loop and butterfly curve can be seen.
Example 2
(1) Solution preparation
The calcium nitrate tetrahydrate, bismuth nitrate pentahydrate and ferric nitrate nonahydrate are prepared according to Bi 1-x Ca x FeO 3 Weighing the element chemical molar ratio, wherein x=0.15, then weighing citric acid, sequentially dissolving the weighed mixture in a mixed solvent beaker of methanol and glycol, wherein the volume ratio of the methanol to the glycol is 3:1, placing a magnetic stirrer in the beaker, placing the beaker on a constant-temperature magnetic force uniform table for uniform stirring, controlling the magnetic rotation speed, obtaining uniform solution after a period of time, and stirring for 30min, wherein the magnetic rotation speed is 300r/min;
(2) Gel and powder preparation
Moving the solution which is uniform in the step (1) to a heating magnetic force uniform table for stirring and heating for a period of time, wherein the heating temperature is 100 ℃, the heating time is 0.5h, when the solvent evaporates to form a large number of bubbles, placing the beaker in a drying constant-temperature oven for fully foaming for a period of time to obtain gel, the drying temperature of the oven is 100 ℃, the drying time is 12h, taking the gel out of the beaker, placing the gel in a pre-cleaned mortar for fully grinding for 0.5h to obtain calcium-doped bismuth ferrite ceramic powder, placing the calcium-doped bismuth ferrite ceramic powder in a box-type furnace for presintering treatment, the heating rate is 2 ℃ per min, the primary sintering temperature is 600 ℃, the primary sintering time is 2h, and the sintering conditions are normal pressure and air atmosphere to obtain primary calcined powder;
(3) Target preparation
Placing the primary calcined powder in the step (2) into a circular mold for pressurization treatment, wherein the pressure of a tablet press is 1-2 mpa, the pressurization time is 30min, preparing a calcium-doped bismuth ferrite ceramic block, placing the obtained ceramic block into a box-type furnace for calcination, wherein the calcination temperature is 900 ℃, the heating time is 2h, and the sintering conditions are normal pressure and air atmosphere, so as to obtain the calcium-doped bismuth ferrite ceramic target;
(4) Preparation of bottom electrode target material
Heating and stirring strontium nitrate, lanthanum nitrate and manganese nitrate raw materials in deionized water solvent by using a sol-gel method to form wet gel, and putting the wet gel into a drying oven for drying; finally grinding the gel, and presintering to obtain nano powder; grinding the nano powder, tabletting, sintering in a box furnace at 1300 deg.C for 8 hr under normal pressure and air atmosphere to obtain La 0.5 Sr 0.5 MnO 3 A bottom electrode target;
(5) Target and substrate processing
Bi is mixed with 0.85 Ca 0.15 FeO 3 Polishing target material with 3000 mesh sand paper, cleaning with alcohol and dust-free paper, and LaAlO 3 The substrate is put into a box-type furnace to be sintered for 1h at 1000 ℃ under normal pressure and air atmosphere. LaAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated for 5min by an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target;
(6) Thin film growth environment regulation
Firstly, vacuumizing the cavity, when the vacuum degree of the cavity reaches 2 multiplied by 10 -4 During Pa, shielding by using a baffle, setting the voltage of a pulse laser to be 19kV, setting the frequency to be 5Hz, setting the energy to be 250mJ, performing pre-sputtering for 1000pulse, and starting to heat by using infrared laser after sputtering is finished;
(7) Film preparation
First grow a layer of La 0.5 Sr 0.5 MnO 3 Bottom electrode according to the practiceThe growth condition of the bottom electrode is regulated according to the situation of need, the infrared laser heating temperature of the cavity is set to 700 ℃, the molecular pump is turned off, and the oxygen pressure of the cavity is regulated to 20Pa; the film growth rate is 80nm/h, and Bi is grown after the bottom electrode is grown 0.85 Ca 0.15 FeO 3 Setting the infrared laser heating temperature of the cavity to 660 ℃ and adjusting the oxygen pressure of the cavity to 13.3Pa; the film growth rate is 120nm/h, and after the growth is finished, 2X 10 is introduced 4 Annealing with Pa oxygen at a cooling rate of 10deg.C/min for 45min to obtain Bi 0.85 Ca 0.15 FeO 3 A film.
Bi prepared in this example 0.85 Ca 0.15 FeO 3 The AFM profile of the film is shown in fig. 5, and it can be seen that the film grows flat.
Bi prepared in this example 0.85 Ca 0.15 FeO 3 The I-V graph of the film is shown in fig. 6, and it can be seen that the film has good conductivity. Conductivity was further improved relative to the 10% calcium doped sample.
Bi prepared in this example 0.85 Ca 0.15 FeO 3 The hysteresis loop and butterfly curve of the film are shown in fig. 7, and good hysteresis loop and butterfly curve can be seen.
Example 3
(1) Solution preparation
The calcium nitrate tetrahydrate, bismuth nitrate pentahydrate and ferric nitrate nonahydrate are prepared according to Bi 1-x Ca x FeO 3 Weighing the element chemical molar ratio, wherein x=0.02, then weighing citric acid, wherein the molar ratio of citric acid to metal cations of calcium-doped bismuth ferrite is 1:1, sequentially dissolving the weighed mixture in a mixed solvent beaker of methanol and glycol, wherein the volume ratio of the methanol to the glycol is 5:1, placing a magnetic stirrer in the beaker, placing the beaker on a constant-temperature magnetic force uniform table for uniform stirring, controlling the magnetic rotation speed, obtaining uniform solution after a period of time, stirring for 60min, and setting the magnetic rotation speed to 400r/min;
(2) Gel and powder preparation
The solution which is uniform in the step (1) is moved to a heating magnetic force uniform table to be stirred and heated for a period of time, the heating temperature is 90 ℃, the heating time is 2 hours, a large amount of bubbles are formed by evaporating a solvent, a beaker is placed in a drying constant-temperature oven to be fully foamed for a period of time to obtain gel, the drying temperature of the oven is 50 ℃, the drying time is 24 hours, the gel is taken out of the beaker, the gel is placed in a pre-cleaned mortar to be fully ground for 1 hour to obtain calcium-doped bismuth ferrite ceramic powder, the calcium-doped bismuth ferrite ceramic powder is placed in a box-type furnace to be subjected to presintering treatment, the heating rate is 4 ℃ per minute, the primary sintering temperature is 400 ℃, the primary sintering time is 4 hours, and the sintering conditions are normal pressure and air atmosphere to obtain primary calcined powder;
(3) Target preparation
Placing the primary calcined powder in the step (2) into a circular mold for pressurization treatment, wherein the pressure of a tablet press is 1Mpa, the pressurization time is 30min, preparing a calcium-doped bismuth ferrite ceramic block, placing the obtained ceramic block into a box-type furnace for calcination, wherein the calcination temperature is 700 ℃, the heating time is 12h, and the sintering conditions are normal pressure and air atmosphere, so as to obtain the calcium-doped bismuth ferrite ceramic target;
(4) Preparation of bottom electrode target material
Heating and stirring strontium nitrate, lanthanum nitrate and manganese nitrate raw materials in deionized water solvent by using a sol-gel method to form wet gel, and putting the wet gel into a drying oven for drying; finally grinding the gel, and presintering to obtain nano powder; grinding the nano powder, tabletting, sintering in a box furnace at 1200deg.C for 12 hr under normal pressure and air atmosphere to obtain La 0.5 Sr 0.5 MnO 3 A bottom electrode target;
(5) Target and substrate processing
Bi is mixed with 0.98 Ca 0.02 FeO 3 Polishing target material with 3000 mesh sand paper, cleaning with alcohol and dust-free paper, and LaAlO 3 The substrate is put into a box-type furnace to be sintered for 1h at 1000 ℃ under normal pressure and air atmosphere. LaAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated for 5min by an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target;
(6) Thin film growth environment regulation
Firstly, vacuumizing the cavity, when the vacuum degree of the cavity reaches 2 multiplied by 10 -4 During Pa, shielding by using a baffle, setting the voltage of a pulse laser to be 19kV, setting the frequency to be 5Hz, setting the energy to be 250mJ, performing pre-sputtering for 1000pulse, and starting to heat by using infrared laser after sputtering is finished;
(7) Film preparation
First grow a layer of La 0.5 Sr 0.5 MnO 3 The bottom electrode is used for adjusting the growth condition of the bottom electrode according to the actual requirement, setting the infrared laser heating temperature of the cavity to 700 ℃, closing the molecular pump and adjusting the oxygen pressure of the cavity to 20Pa; the film growth rate is 80nm/h, and Bi is grown after the bottom electrode is grown 0.98 Ca 0.02 FeO 3 Setting the infrared laser heating temperature of the cavity to 660 ℃ and adjusting the oxygen pressure of the cavity to 13.3Pa; the film growth rate is 120nm/h, and after the growth is finished, 2X 10 is introduced 4 Annealing with Pa oxygen at a cooling rate of 10deg.C/min for 45min to obtain Bi 0.98 Ca 0.02 FeO 3 A film.
Example 4
In this example, x=0.30, and other steps and parameters are the same as in example 1.
Bi prepared in this example 0.70 Ca 0.30 FeO 3 The XRD patterns of the films are shown in FIG. 8, which shows relatively pure patterns.
Bi prepared in this example 0.70 Ca 0.30 FeO 3 The AFM profile of the film is shown in fig. 9, and it can be seen that the film grows flat.
Bi prepared in this example 0.70 Ca 0.30 FeO 3 The I-V graph of the film is shown in fig. 10, and it can be seen that the film has good conductivity.
Bi prepared in this example 0.70 Ca 0.30 FeO 3 The hysteresis loop and butterfly curve of the film are shown in fig. 11, and good hysteresis loop and butterfly curve can be seen.
Example 5
In this example, x=0.05, and other steps and parameters are the same as in example 1.
The implementation isBi prepared in examples 0.95 Ca 0.05 FeO 3 The AFM profile of the film is shown in fig. 12, and it can be seen that the film grows flat.
Bi prepared in this example 0.95 Ca 0.05 FeO 3 The I-V graph of the film is shown in fig. 13, and it can be seen that the film has good conductivity.
Bi prepared in this example 0.95 Ca 0.05 FeO 3 The hysteresis loop and butterfly curve of the film are shown in fig. 14, and good hysteresis loop and butterfly curve can be seen.
Claims (8)
1. The preparation method of the calcium-doped bismuth ferrite film system material is characterized by comprising the following steps of:
(1) Solution preparation
The calcium nitrate tetrahydrate, bismuth nitrate pentahydrate and ferric nitrate nonahydrate are prepared according to Bi 1-x Ca x FeO 3 Weighing the element chemical molar ratio, then weighing citric acid, sequentially dissolving the weighed mixture in a mixed solvent beaker of methanol and ethylene glycol, putting a magnetic stirrer into the beaker, putting the beaker on a constant-temperature magnetic force uniform table, uniformly stirring, controlling the magnetic rotation speed, and obtaining uniform solution after a period of time;
(2) Gel and powder preparation
Moving the solution which is uniform in the step (1) to a heating magnetic force uniform table for stirring and heating for a period of time, placing the beaker in a drying constant temperature oven for fully foaming for a period of time to obtain gel, taking the gel out of the beaker, fully grinding the gel in a pre-cleaned mortar to obtain calcium-doped bismuth ferrite ceramic powder, placing the calcium-doped bismuth ferrite ceramic powder in a box-type furnace for presintering treatment, and controlling the heating rate, the primary sintering time and the sintering temperature to obtain primary calcined powder;
(3) Target preparation
Placing the primary calcined powder in the step (2) into a specific die, performing pressurization treatment to prepare a calcium-doped bismuth ferrite ceramic block, and placing the obtained ceramic block into a box-type furnace for calcination to obtain a calcium-doped bismuth ferrite ceramic target;
(4) Preparation of bottom electrode target material
Dissolving strontium nitrate, lanthanum nitrate and manganese nitrate in deionized water solvent by using a sol-gel method, heating and stirring to form wet gel, and putting into a drying oven for drying; finally grinding the gel, and presintering to obtain nano powder; grinding the nano powder, tabletting, and sintering for the second time to obtain La 0.5 Sr 0.5 MnO 3 A bottom electrode target;
(5) Target and substrate processing
Bi is mixed with 1-x Ca x FeO 3 And La (La) 0.5 Sr 0.5 MnO 3 Polishing target material with sand paper, cleaning with alcohol and dust-free paper, and LaAlO 3 Placing the substrate into a box-type furnace for sintering under normal pressure and air atmosphere; laAlO with silver paste 3 The substrate is fixed at a proper position of the substrate disc, and is heated by an infrared heating lamp, silver paste is dried, and a target material is placed at a proper position of the target;
(6) Thin film growth environment regulation
Vacuumizing the PLD cavity, shielding the cavity by using a baffle when the vacuum degree of the cavity reaches a certain value, setting parameters of a pulse laser, performing pre-sputtering, and starting to heat by using infrared laser after the sputtering is finished;
(7) Film preparation
First grow a layer of La 0.5 Sr 0.5 MnO 3 Bottom electrode, according to the condition of the actual need adjusting bottom electrode growth condition, set up the infrared laser heating temperature of cavity, close the molecular pump, adjust cavity oxygen pressure, film growth rate, after growing bottom electrode, grow Bi 1- x Ca x FeO 3 Setting the infrared laser heating temperature of the cavity, adjusting the oxygen pressure of the cavity and the growth rate of the film, introducing oxygen for annealing after the growth is finished, and controlling the cooling rate and the annealing time to obtain Bi 1-x Ca x FeO 3 A film.
2. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: and (3) in the step (1), x=0.02-0.30, wherein the molar ratio of citric acid to metal cations of calcium-doped bismuth ferrite is 1:1, the volume ratio of methanol to glycol is 5:1-3:1, the stirring time is 30-60 min, and the magnetic rotation speed is 200-400 r/min.
3. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: the heating temperature of the mixed solution in the step (2) is 80-100 ℃, the heating time is 0.5-2 h, the drying temperature of an oven is 50-100 ℃, the drying time is 12-24 h, the grinding time is 0.5-1 h, the heating rate is 2-4 ℃ per minute, the primary sintering temperature is 400-600 ℃, the primary sintering time is 2-4 h, and the sintering conditions are normal pressure and air atmosphere.
4. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: the pressure of the tablet press in the step (3) is 1-2 mpa, the pressurizing time is 20-30 min, the calcining temperature is 700-900 ℃, the heating time is 2-12 h, and the sintering conditions are normal pressure and air atmosphere.
5. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: in the step (4), the secondary calcination temperature is 1200-1450 ℃, the heating time is 2-12 h, and the sintering condition is normal pressure and air atmosphere.
6. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: the sand paper in the step (5) is 500-3000 meshes, laAlO 3 The sintering temperature of the substrate in the box-type furnace is 1000-1450 ℃ and the duration is 0.5-2 h; the heating time of the infrared heating lamp is 3-5 min.
7. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: the vacuum degree of the cavity in the step (6) is 1 multiplied by 10 -4 ~2×10 -4 In Pa, the voltage of the pulse laser is set to be 19-20 kV, the frequency is 3-5 Hz, and the pulse laser canThe amount is 200-350 mJ, and pre-sputtering is carried out for 500-1000 pulses.
8. The method for preparing the calcium-doped bismuth ferrite film system material according to claim 1, which is characterized in that: setting the infrared laser heating temperature of the growth bottom electrode in the step (7) to be 700-750 ℃, closing a molecular pump, adjusting the oxygen pressure of the cavity to be 15-20 Pa, and enabling the film growth rate to be 80-100 nm/h; after growing the bottom electrode, bi is grown 1-x Ca x FeO 3 Setting the infrared laser heating temperature of the cavity to be 600-700 ℃, adjusting the oxygen pressure of the cavity to be 13.3-26.6 Pa, and enabling the film growth rate to be 120-140 nm/h; after the growth is finished, 1 multiplied by 10 is introduced 4 ~2×10 4 Annealing by Pa oxygen at a cooling rate of 10-15 ℃/min for 45-60 min to obtain Bi 1-x Ca x FeO 3 A film.
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