CN102222672B - Bismuth ferrite base film layer stacked structure capacitor and preparation method thereof - Google Patents

Bismuth ferrite base film layer stacked structure capacitor and preparation method thereof Download PDF

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CN102222672B
CN102222672B CN2011101238206A CN201110123820A CN102222672B CN 102222672 B CN102222672 B CN 102222672B CN 2011101238206 A CN2011101238206 A CN 2011101238206A CN 201110123820 A CN201110123820 A CN 201110123820A CN 102222672 B CN102222672 B CN 102222672B
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CN102222672A (en
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杨长红
赵媛媛
吴海涛
胡广达
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University of Jinan
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University of Jinan
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Abstract

The invention discloses a bismuth ferrite base film layer stacked structure capacitor and a preparation method thereof, wherein the capacitor comprises a bottom electrode, a substrate, a buffer layer, a ferroelectric film layer and a metal point electrode in sequence from the bottom to top; the buffer layer is a manganese-doped barium strontium titanate film, the chemical formula is Ba0.6Sr0.4Ti(1-x)MnxO3, x is the mole equivalent of element manganese, and x is equal to 0.005-0.05; and the ferroelectric film layer is a bismuth ferrite base film, the chemical formula is Bi(1-y)LnyFeO3, wherein Ln is one of lanthanide, y is the mole equivalent of lanthanide, and y is equal to 0.01-0.2. The preparation method is simple, and the obtained capacitor is a storage cell of a ferro-electric field effect transistor; and the capacitor overcomes the defects that the bismuth ferrite base film capacitor on ordinary silicon substrate has the defects of poor interface performance and high working voltage, and has good energy storage performance.

Description

A kind of ferrous acid bismuth-based thin films stepped construction capacitor and preparation method thereof
Technical field
The present invention relates to a kind of ferrous acid bismuth-based thin films stepped construction capacitor and preparation method thereof, be specially adapted to non-volatile non-destructive and read high-density storage and integrated ferroelectric device, belong to the microelectronics new material technology field.
Background technology
Metal/ferroelectric thin film/semiconductor (MFS) capacitor is ferro-electric field effect transistor (Ferroelectric field effect transistor, basic unit of storage FFET).Ferro-electric field effect transistor as the gate dielectric layer material, utilizes the polarized state control semiconductor surface electricity of ferroelectric thin film to lead the device of accomplishing memory function with ferroelectric thin film.Write being operating as of data: the plus or minus grid voltage through adding greater than coercive voltage makes ferroelectric thin film be in the plus or minus polarized state, respectively representative " 0 " and " 1 ".Since remove add grid voltage after, still there is residual polarization in ferroelectric thin film, so ferroelectric storage cell does not need keeping of applied voltage, still can keep original stored information, is nonvolatile storage.Being operating as of sense data: through relatively adding the size definite " 0 " and " 1 " of the channel current that source-drain voltage forms, the polarized state of reading ferroelectric thin film in the process of stored information does not change, and reads for nondestructive.That the FFET device has is non-volatile, non-destructive is read, low in energy consumption, simple in structure, integrated level advantages of higher, is considered to a kind of memory device of near ideal, has great application prospect in technical field of information storage.
Mostly the performance of extensive use at present is more superior is the lead base thin-film material, like Pb (Zr, Ti) O 3, Pb (Mg, Nb) O 3Deng, wherein the content of lead oxide is up to 60 ~ 70%.And lead is non-degradable property chemicals, and this will certainly cause serious harm for the mankind and biological environment in the processing procedure after producing, use and discarding.So exploring high-quality lead-free ferroelectric film material has become a big research focus.The beginning of this century, numerous researchers reported ferrous acid bismuth (BiFeO 3) base film has very excellent ferroelectric, piezoelectricity and ferromagnetic property, emerging BiFeO 3Base film is considered to a kind of candidate material that gets a good chance of replacing lead base piezoelectricity ferro and ferromagnetic material.
Metal-the BiFeO that reports at present 3Base film-(resilient coating)-semiconductor structure capacitor, the subject matter of existence is that boundary defect is more, operating voltage is high, thereby causes that interface trap density is big, leakage current big, do not meet the requirement of si-substrate integrated circuit operating voltage.
Summary of the invention
The purpose of this invention is to provide a kind of ferrous acid bismuth-based thin films stepped construction capacitor, this capacitor has advantages such as memory property is good, operating voltage is low, in the ferro-electric field effect transistor memory in future, has a good application prospect.
The present invention also provides the preparation method of this capacitor, and the method is simple to operate, and is easy to implement, capacitor produced function admirable.
The inventor is to existing metal-BiFeO 3The interface trap density that base film-(resilient coating)-semiconductor structure capacitor exists is big, leakage current big, do not meet the shortcomings such as requirement of si-substrate integrated circuit operating voltage; Carried out further exploration and research, attempted through capacitor arrangement, ferroelectric thin film being formed and the variation of the composition of dielectric film overcomes these shortcomings.Through a large amount of related experiment, through selecting lanthanide-doped BiFeO for use 3Film is as ferroelectric layer and the Ba that selects for use the high dielectric manganese element that has lattice match preferably with it to mix 0.6Sr 0.4TiO 3As resilient coating, greatly reduce leakage current.Further, through optimizing resilient coating and BiFeO 3The thickness of base film has reduced the operating voltage of capacitor effectively.Like this, the unleaded BiFeO that obtains 3Based thin film capacitors has the advantage that leakage current is little, memory property is good, operating voltage is low, in the ferro-electric field effect transistor memory in future, has a good application prospect.
Following mask body introduction realizes improved concrete technical scheme:
A kind of ferrous acid bismuth-based thin films stepped construction capacitor comprises hearth electrode, substrate, resilient coating, ferroelectric thin film layer and metal dots electrode from top to bottom successively, and it is characterized in that: said resilient coating is the Mn-doped strontium titanate titanate thin film, and chemical formula is Ba 0.6Sr 0.4Ti (1-x)Mn xO 3, x is the molar equivalent of element manganese, x=0.005-0.05; Said ferroelectric thin film layer is the ferrous acid bismuth-based thin films, and chemical formula is Bi (1-y)Ln yFeO 3, wherein, Ln is a kind of in the lanthanide series, and y is the molar equivalent of lanthanide series, and y=0.01-0.2.
In the above-mentioned capacitor, the thickness of resilient coating is 40～50nm, and the thickness of ferroelectric thin film layer is 200～250nm.
In the above-mentioned capacitor, said backing material is the monocrystalline substrate of p type or n type.
In the above-mentioned capacitor, said hearth electrode and point electrode are Au.
A kind of preparation method of ferrous acid bismuth-based thin films stepped construction capacitor is characterized in that may further comprise the steps:
(1) adopt metal organic decomposition legal system to be equipped with Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The film resilient coating
A. according to Ba 0.6Sr 0.4Ti (1-x)Mn xO 3Stoichiometric proportion, acetate and metatitanic acid four isopropyl esters of choosing barium, strontium, manganese are raw material, choosing glacial acetic acid is solvent, acetylacetone,2,4-pentanedione is a stabilizer, EGME is a viscosity modifier, compound concentration is the precursor solution of 0.02～0.1mol/L;
B. above-mentioned precursor solution is spun on the substrate, then with its on heating plate in 250～300 ℃ of down oven dry, crystallization 5～10 minutes under 700～750 ℃ annealing temperature again;
Spin coating, oven dry, the annealing steps of c, repetition above-mentioned steps b are until Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The thickness of film reaches 40～50nm;
(2) adopt metal organic decomposition legal system to be equipped with Bi (1-y)Ln yFeO 3Film
A. according to Bi (1-y)Ln yFeO 3Stoichiometric proportion, the nitrate of choosing bismuth nitrate, ferric nitrate and certain lanthanide series is raw material, choosing ethylene glycol and glacial acetic acid is solvent, compound concentration is the precursor solution of 0.05～0.3mol/L;
B. above-mentioned precursor solution is spin-coated on the resilient coating, then with its on heating plate in 250～300 ℃ of down oven dry, crystallization 5～10 minutes under 500～550 ℃ annealing temperature again;
C. repeat spin coating, oven dry, the annealing steps of above-mentioned steps b, until Bi (1-y)Ln yFeO 3The thickness of film reaches 200～250nm;
D.Bi (1-y)Ln yFeO 3After film reaches thickness, with the Bi that obtains (1-y)Ln yFeO 3/ Ba 0.6Sr 0.4Ti (1-x)Mn xO 3/ Si annealed 0.5 hour under 550～600 ℃ of temperature, obtained fine and close duplicature;
(3) splash-proofing sputtering metal electrode, the preparation capacitor
Foraminate mask plate is covered on the film; Utilize vacuum sputtering to deposit to the surface of film on metal again; Get metal dots electrode (also can be called top electrode or top electrode); Then metal sputtering is arrived substrate back, obtain hearth electrode, finally obtain ferrous acid bismuth-based thin films stepped construction capacitor of the present invention.
In the said method, deposition is utilized the back side of the cotton swab wiping silicon substrate that dips in dilute hydrofluoric acid during hearth electrode, removes the SiO that substrate is former because of annealing etc. thereby increase 2Layer to guarantee that electrode directly contacts with monocrystalline silicon, utilizes vacuum sputtering with the back side that Au deposits to silicon substrate again, has just obtained testing required hearth electrode.
In the said method, preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During the film resilient coating, 2000～7000 rev/mins of spin coating rotating speeds, 20～40 seconds time; Preparation Bi (1-y)Ln yFeO 3During film, 2000～7000 rev/mins of spin coating rotating speeds, 20～40 seconds time.
In the said method, preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During the film resilient coating, annealing under oxygen atmosphere; Preparation Bi (1-y)Ln yFeO 3During film, annealing under nitrogen atmosphere.
In the said method, preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During film, glacial acetic acid with the ratio of the volumetric usage of EGME is: 1:1～5:1; The volume ratio of acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters is: 1:1.
In the said method, preparation Bi (1-y)Ln yFeO 3During film, the consumption of glacial acetic acid and ethylene glycol is 1:1～10:1.
In the said method, preparation Bi (1-y)Ln yFeO 3During film, the raw material bismuth nitrate adds fashionable excessive 2～5mol%.
Ferrous acid bismuth-based thin films ferroelectric condenser of the present invention is on monocrystalline substrate, to grow as the manganese doping Ba of resilient coating 0.6Sr 0.4TiO 3High dielectric thin film and as the BiFeO of ferroelectric layer 3Base film.Said resilient coating is Ba 0.6Sr 0.4Ti (1-x)Mn xO 3, this film and BiFeO 3Isostructure and have preferably the lattice match relation, have good insulation performance property, have bigger dielectric constant, and crystallization temperature is lower.
Further, BiFeO of the present invention 3The preparation method of based thin film capacitors adopts following steps:
(1) Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The preparation of (0.005 ￡ x ￡ 0.05) film
Adopt metal organic decomposition method, take by weighing the acetate of a certain amount of barium, strontium, manganese respectively, and put into glacial acetic acid solution, stir, when stopping heating after the dissolving fully at 60 ℃ temperature lower magnetic forces; When treating that solution is cooled to room temperature, add an amount of acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters successively, add the proper amount of glycol methyl ether at last and regulate viscosity, fully stir; Concentration range is 0.02～0.1mol/L; The use aperture is to obtain stable Ba after the injecting type filter of 0.2 μ m filters 0.6Sr 0.4Ti (1-x)Mn xO 3Precursor solution.With Ba 0.6Sr 0.4Ti (1-x)Mn xO 3Solution is spun on the monocrystalline substrate with certain rotating speed; Under 250～300 ℃ of temperature, drying on the heating plate; Crystallization 5～10 minutes under 700～750 ℃ of temperature under the quick anneal oven oxygen atmosphere again.Repeat this annealing process layer by layer, make Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The thickness of crystalline film reaches 40～50nm.
(2) Bi (1-y)Ln yFeO 3The preparation of film
Adopt metal organic decomposition method, accurately take by weighing the nitrate of bismuth nitrate, ferric nitrate and certain lanthanide series, it is dissolved in the glacial acetic acid solution, and add ethylene glycol and fully stir by stoichiometric proportion; Concentration range is 0.05～0.3mol/L; The use aperture is to obtain stable [Bi after the injecting type filter of 0.2 μ m filters (1-y)Ln y] FeO 3Precursor solution.With Bi (1-y)Ln yFeO 3Solution is spun on Ba with certain rotating speed 0.6Sr 0.4Ti (1-x)Mn xO 3On/Si the substrate; Under 250～300 ℃ of temperature, drying on the heating plate; Crystallization 5～10 minutes under 500～550 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make [Bi (1-y)Ln y] FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last (1-y)Ln yFeO 3/ Ba 0.6Sr 0.4Ti (1-x)Mn xO 3/ Si annealed 0.5 hour under 550～600 ℃ of temperature under nitrogen atmosphere, obtained dense film;
(4) depositing electrode.
The present invention incites somebody to action high dielectric Ba as thin as a wafer 0.6Sr 0.4Ti (1-x)Mn xO 3Film is as resilient coating.The acceptor doping of Mn ion can make (Ba at a low price ,Sr) TiO 3Fermi level reduce, barrier height increases, insulation property improve, this can effectively stop the injection of electric charge; Ba 0.6Sr 0.4Ti (1-x)Mn xO 3With [Bi (1-y))Ln y] FeO 3Have identical structure, lattice mismatch is merely about 1%, has avoided the generation of boundary defect, and the Ba of crystallization 0.6Sr 0.4Ti (1-x)Mn xO 3Film also can promote [Bi (1-y)Ln y] FeO 3Crystallization, played the effect of Seed Layer.
The present invention adopts the Ba of high dielectric high impedance 0.6Sr 0.4Ti (1-x)Mn xO 3As resilient coating, unleaded strong ferroelectric Bi (1-y)Ln yFeO 3Prepared metal/ferroelectric thin film/insulating barrier/semiconductor structure as ferroelectric layer.The Bi that the present invention is prepared (1-y)Ln yFeO 3/ Ba 0.6Sr 0.4Ti (1-x)Mn xO 3/ Si laminated construction capacitor has advantages such as low-power consumption, good ferroelectric storage property and long-time retentivity, in the high density in future, ferro-electric field effect transistor device that non-destructive is read, has a good application prospect.
The present invention adopts metal organic decomposition thin films, and is simple to operate, is easy to realize, capacitor produced functional.
Description of drawings
Fig. 1 is the sketch map of ferrous acid bismuth-based thin films stepped construction capacitor of the present invention.
Fig. 2 is the X ray diffracting spectrum that the embodiment of the invention 1 obtains film, wherein, (a) is Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3/ Si (b) is Bi 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3/ Si.
The Bi that Fig. 3 obtains for the embodiment of the invention 1 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The cross-section morphology figure of/Si.
The Bi that Fig. 4 obtains for the embodiment of the invention 1 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The capacitance-voltage curve of/Si.
The Bi that Fig. 5 obtains for the embodiment of the invention 1 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The time retention performance curve of/Si.
The X ray diffracting spectrum of the film that Fig. 6 obtains for the embodiment of the invention 2 wherein, (a) is Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3, (b) be Bi 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3/ Si.
The Bi that Fig. 7 obtains for the embodiment of the invention 2 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The cross-section morphology figure of/Si.
The Bi that Fig. 8 obtains for the embodiment of the invention 2 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The capacitance-voltage curve of/Si.
The Bi that Fig. 9 obtains for the embodiment of the invention 2 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The dielectric spectrogram of/Si.
Embodiment
Through accompanying drawing and specific embodiment the present invention is further set forth below, should be understood that, following explanation only is in order to explain the present invention, its content not to be limited.
The used substrate of the present invention is a silicon substrate, and concrete is the monocrystalline substrate of p type or n type.
Embodiment 1
Preparation Au/Bi 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The preparation of film
Take by weighing 0.3096g Ba (CH respectively 3COO) 2, 0.0163g Mn (CH 3COO) 32H 2O, 0.1744g Sr (CH 3COO) 20.5H 2O is dissolved in the 19.41ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 0.59ml acetylacetone,2,4-pentanedione earlier, dropwise adds 0.59ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 19.41ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.05mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.97Mn 0.03O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.97Mn 0.03O 3Solution was coated on the monocrystalline substrate with 2000 rev/mins rotating speed through 30 seconds equably; Heat-treat technology then, be incubated 10 minutes down for 250 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 700 ℃ of following crystallization 5 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The thickness of film reaches 40～50nm.
(2) Bi 0.9La 0.1FeO 3The preparation of film
Take by weighing 1.7992g Bi (NO 3) 35H 2O (excessive 2mol%), 0.1750g La (NO 3) 36H 2O, 1.6406g Fe (NO 3) 39H 2O is dissolved in the 30ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 10ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Bi of the 0.1mol/L of homogeneous transparent 0.9La 0.1FeO 3Solution.With Bi 0.9La 0.1FeO 3Solution was spun on Ba with 3000 rev/mins rotating speed through 30 seconds 0.6Sr 0.4Ti 0.97Mn 0.03O 3On/Si the substrate; Heat-treat technology then, 280 ℃ of temperature are incubated 5 minutes on heating plate earlier; Crystallization 5 minutes under 550 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.9La 0.1FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3/ Si annealed 0.5 hour under 550 ℃ of temperature under nitrogen atmosphere, obtained fine and close bilayer film.
(4) at the upper end sputter Au point electrode of the fine and close bilayer film of step (3) gained, at substrate back sputter Au hearth electrode, capacitor.
Like Fig. 2, prepared Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3And Bi 0.9La 0.1FeO 3Present pure perovskite structure, do not have second dephasign.(110) to the Ba that selects the superior 0.6Sr 0.4Ti 0.97Mn 0.03O 3Resilient coating is as Bi 0.9La 0.1FeO 3The Seed Layer of growth has promoted Bi 0.9La 0.1FeO 3(110) growth of direction.Fig. 3 is the Bi that use emission scan electron microscopic observation arrives 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The cross-section morphology of/Si.Can find out that each interface is more clear, not have diffusion phenomena, film growth is fine and close, and crystallinity is better.Bi 0.9La 0.1FeO 3And Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3The thickness of film respectively is about 44nm and 210nm.The test frequency of capacitance-voltage curve shown in Figure 4 is 1MHz, and sweep speed is 0.5 volt of a per second.The direction of loop line is a clockwise direction, shows that storage mode is the storage of electric polarization type.The memory window has basically no skew, is symmetrical, and size is about 2.2 volts.Resulting capacitance-voltage curve basically identical under different sweep speeds and frequency.As shown in Figure 5, at Bi 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3/ Si is last to be applied+and the voltage of 5V, remove extra electric field 10 3In the time range of second, " opening " attitude electric capacity has reduced by 9.1% under zero electric field.After film Jia Shang – 5V waited for for 10 seconds, " pass " attitude electric capacity had increased by 2.9% under zero electric field.Show Bi 0.9La 0.1FeO 3/ Ba 0.6Sr 0.4Ti 0.97Mn 0.03O 3Film has stable memory property.
Embodiment 2
Preparation Au/Bi 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The preparation of film
Take by weighing 0.2477g Ba (CH respectively 3COO) 2, 0.0195g Mn (CH 3COO) 32H 2O, 0.1395g Sr (CH 3COO) 20.5H 2O is dissolved in the 26.04ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 0.47ml acetylacetone,2,4-pentanedione earlier, dropwise adds 0.47ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 13.02ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.04mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.955Mn 0.045O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.955Mn 0.045O 3Solution was coated on the monocrystalline substrate with 4000 rev/mins rotating speed through 30 seconds equably; Heat-treat technology then, be incubated 9 minutes down for 270 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 710 ℃ of following crystallization 7 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The thickness of film reaches 40～50nm.
(2) Bi 0.95Ce 0.05FeO 3The preparation of film
Take by weighing 2.8487g Bi (NO 3) 35H 2O (excessive 2mol%), 0.1316g Ce (NO 3) 36H 2O, 2.4609g Fe (NO 3) 39H 2O is dissolved in the 32ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 8ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 0.15mol/L Bi of homogeneous transparent 0.95Ce 0.05FeO 3Solution.With Bi 0.95Ce 0.05FeO 3Solution was spun on Ba with 4000 rev/mins rotating speed through 30 seconds 0.6Sr 0.4Ti 0.955Mn 0.045O 3On/Si the substrate; Heat-treat technology then, be incubated 10 minutes under 300 ℃ of temperature on the heating plate earlier; Crystallization 8 minutes under 520 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.95Ce 0.05FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3/ Si annealed 0.5 hour under 580 ℃ of temperature under nitrogen atmosphere, obtained fine and close bilayer film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Like Fig. 6, prepared Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3And Bi 0.95Ce 0.05FeO 3Present pure perovskite structure, no dephasign produces.Fig. 7 is the Bi that use emission scan electron microscopic observation arrives 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The cross-section morphology of/Si.Can find out not have diffusion phenomena between each interface, Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3And Bi 0.95Ce 0.05FeO 3Thickness respectively be about 50nm and 230nm.The test frequency of capacitance-voltage curve shown in Figure 8 is 1MHz, and sweep speed is 0.5 volt of a per second.The direction of loop line is counterclockwise, shows that storage mode is the storage of electric polarization type.The memory window is symmetry shape, and size is about 1.6 volts.Resulting capacitance-voltage curve basically identical under different sweep speeds and frequency.Fig. 9 has shown Bi 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3The relative dielectric constant of/Si structure and dielectric loss factor are with the relation of frequency change, and institute's biasing is 5 volts.The dielectric constant of film and dielectric loss are all more stable in being lower than the frequency range of 100kHz, and when 100kHz, its representative value is respectively 72 and 0.04.Show Bi 0.95Ce 0.05FeO 3/ Ba 0.6Sr 0.4Ti 0.955Mn 0.045O 3/ Si structure has dielectric stability preferably.
Embodiment 3
Preparation Au/Bi 0.85Sm 0.15FeO 3/ Ba 0.6Sr 0.4Ti 0.98Mn 0.02O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.98Mn 0.02O 3The preparation of film
Take by weighing 0.1239g Ba (CH respectively 3COO) 2, 0.0040g Mn (CH 3COO) 32H 2O, 0.0698g Sr (CH 3COO) 20.5H 2O is dissolved in the 23.71ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 0.24ml acetylacetone,2,4-pentanedione earlier, dropwise adds 0.24ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 15.81ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.02mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.98Mn 0.02O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.98Mn 0.02O 3Solution was coated on the monocrystalline substrate with 3000 rev/mins rotating speed through 20 seconds equably; Heat-treat technology then, be incubated 8 minutes down for 250 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 720 ℃ of following crystallization 5 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.98Mn 0.02O 3The thickness of film reaches 40～50nm.
(2) Bi 0.85Sm 0.15FeO 3The preparation of film
Take by weighing 3.4651g Bi (NO 3) 35H 2O (excessive 4mol%), 0.5388g Sm (NO 3) 36H 2O, 3.2812g Fe (NO 3) 39H 2O is dissolved in the 34.3ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 5.7ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Bi of the 0.2mol/L of homogeneous transparent 0.85Sm 0.15FeO 3Solution.With Bi 0.85Sm 0.15FeO 3Solution was spun on Ba with 6000 rev/mins rotating speed through 30 seconds 0.6Sr 0.4Ti 0.98Mn 0.02O 3On/Si the substrate; Heat-treat technology then, be incubated 9 minutes under 280 ℃ of temperature on the heating plate earlier; Crystallization 6 minutes under 540 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.85Sm 0.15FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.85Sm 0.15FeO 3/ Ba 0.6Sr 0.4Ti 0.98Mn 0.02O 3/ Si annealed 0.5 hour under 550 ℃ of temperature under nitrogen atmosphere, obtained fine and close bilayer film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Prepared Au/Bi 0.85Sm 0.15FeO 3/ Ba 0.6Sr 0.4Ti 0.98Mn 0.02O 3/ Si capacitor has good crystallinity, storage property and dielectric stability.
Embodiment 4
Preparation Au/Bi 0.93Pr 0.07FeO 3/ Ba 0.6Sr 0.4Ti 0.96Mn 0.04O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.96Mn 0.04O 3The preparation of film
Take by weighing 0.5573g Ba (CH respectively 3COO) 2, 0.0390g Mn (CH 3COO) 32H 2O, 0.3139g Sr (CH 3COO) 20.5H 2O is dissolved in the 31ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 1.06ml acetylacetone,2,4-pentanedione earlier, dropwise adds 1.06ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 6.88ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.09mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.96Mn 0.04O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.96Mn 0.04O 3Solution was coated on the monocrystalline substrate with 5000 rev/mins rotating speed through 40 seconds equably; Heat-treat technology then, be incubated 7 minutes down for 280 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 740 ℃ of following crystallization 10 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.96Mn 0.04O 3The thickness of film reaches 40～50nm.
(2) Bi 0.93Pr 0.07FeO 3The preparation of film
Take by weighing 2.8161g Bi (NO 3) 35H 2O (excessive 3mol%), 0.1846g Pr (NO 3) 36H 2O, 2.4609g Fe (NO 3) 39H 2O is dissolved in the 33.3ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 6.7ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 0.15mol/L Bi of homogeneous transparent 0.93Pr 0.07FeO 3Solution.With Bi 0.93Pr 0.07FeO 3Solution was spun on Ba with 5000 rev/mins rotating speed through 20 seconds 0.6Sr 0.4Ti 0.96Mn 0.04O 3On/Si the substrate; Heat-treat technology then, be incubated 6 minutes under 290 ℃ of temperature on the heating plate earlier; Crystallization 7 minutes under 500 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.93Pr 0.07FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.93Pr 0.07FeO 3/ Ba 0.6Sr 0.4Ti 0.96Mn 0.04O 3/ Si annealed 0.5 hour under 600 ℃ of temperature under nitrogen atmosphere, obtained fine and close bilayer film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Prepared Au/Bi 0.93Pr 0.07FeO 3/ Ba 0.6Sr 0.4Ti 0.96Mn 0.04O 3/ Si capacitor has good crystallinity, storage property and dielectric stability.
Embodiment 5
Preparation Au/Bi 0.99Eu 0.01FeO 3/ Ba 0.6Sr 0.4Ti 0.95Mn 0.05O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.95Mn 0.05O 3The preparation of film
Take by weighing 0.3716g Ba (CH respectively 3COO) 2, 0.03250g Mn (CH 3COO) 32H 2O, 0.2093g Sr (CH 3COO) 20.5H 2O is dissolved in the 28.95ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 0.70ml acetylacetone,2,4-pentanedione earlier, dropwise adds 0.70ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 9.65ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.06mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.95Mn 0.05O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.95Mn 0.05O 3Solution was coated on the monocrystalline substrate with 5000 rev/mins rotating speed through 30 seconds equably; Heat-treat technology then, be incubated 6 minutes down for 290 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 730 ℃ of following crystallization 9 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.95Mn 0.05O 3The thickness of film reaches 40～50nm.
(2) Bi 0.99Eu 0.01FeO 3The preparation of film
Take by weighing 5.9955g Bi (NO 3) 35H 2O (excessive 3mol%), 0.0541g Eu (NO 3) 36H 2O, 4.9218g Fe (NO 3) 39H 2O is dissolved in the 36.4ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 3.6ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 0.3mol/L Bi of homogeneous transparent 0.99Eu 0.01FeO 3Solution.With Bi 0.99Eu 0.01FeO 3Solution was spun on Ba with 7000 rev/mins rotating speed through 20 seconds 0.6Sr 0.4Ti 0.95Mn 0.05O 3On/Si the substrate; Heat-treat technology then, be incubated 7 minutes under 270 ℃ of temperature on the heating plate earlier; Crystallization 9 minutes under 510 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.99Eu 0.01FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.99Eu 0.01FeO 3/ Ba 0.6Sr 0.4Ti 0.95Mn 0.05O 3/ Si annealed 0.5 hour under 590 ℃ of temperature under nitrogen atmosphere, obtained fine and close bilayer film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Prepared Au/Bi 0.99Eu 0.01FeO 3/ Ba 0.6Sr 0.4Ti 0.95Mn 0.05O 3/ Si capacitor has good crystallinity, storage property and dielectric stability.
Embodiment 6
Preparation Au/Bi 0.82Gd 0.18FeO 3/ Ba 0.6Sr 0.4Ti 0.99Mn 0.01O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.99Mn 0.01O 3The preparation of film
Take by weighing 0.4954g Ba (CH respectively 3COO) 2, 0.0087g Mn (CH 3COO) 32H 2O, 0.2790g Sr (CH 3COO) 20.5H 2O is dissolved in the 30.45ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 0.97ml acetylacetone,2,4-pentanedione earlier, dropwise adds 0.97ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 7.61ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.08mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.99Mn 0.01O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.99Mn 0.01O 3Solution was coated on the monocrystalline substrate with 7000 rev/mins rotating speed through 20 seconds equably; Heat-treat technology then, be incubated 6 minutes down for 260 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 720 ℃ of following crystallization 8 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.99Mn 0.01O 3The thickness of film reaches 40～50nm.
(2) Bi 0.82Gd 0.18FeO 3The preparation of film
Take by weighing 4.2186g Bi (NO 3) 35H 2O (excessive 5mol%), 0.8207g Gd (NO 3) 36H 2O, 4.1015g Fe (NO 3) 39H 2O is dissolved in the 35.6ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 4.4ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 0.25mol/L Bi of homogeneous transparent 0.82Gd 0.18FeO 3Solution.With Bi 0.82Gd 0.18FeO 3Solution was spun on Ba with 6000 rev/mins rotating speed through 40 seconds 0.6Sr 0.4Ti 0.99Mn 0.01O 3On/Si the substrate; Heat-treat technology then, be incubated 8 minutes under 250 ℃ of temperature on the heating plate earlier; Crystallization 10 minutes under 530 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.82Gd 0.18FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.82Gd 0.18FeO 3/ Ba 0.6Sr 0.4Ti 0.99Mn 0.01O 3/ Si annealed 0.5 hour under 560 ℃ of temperature under nitrogen atmosphere, obtained dense film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Prepared Bi 0.82Gd 0.18FeO 3/ Ba 0.6Sr 0.4Ti 0.99Mn 0.01O 3/ Si capacitor has good crystallinity, storage property and dielectric stability.
Embodiment 7
Preparation Au/Bi 0.8Ho 0.2FeO 3/ Ba 0.6Sr 0.4Ti 0.995Mn 0.005O 3/ Si capacitor, step is following:
(1) Ba 0.6Sr 0.4Ti 0.995Mn 0.005O 3The preparation of film
Take by weighing 0.6193g Ba (CH respectively 3COO) 2, 0.0054g Mn (CH 3COO) 32H 2O, 0.3488g Sr (CH 3COO) 20.5H 2O is dissolved in the 31.30ml glacial acetic acid, stirs at 60 ℃ temperature lower magnetic forces, when stopping heating after the dissolving fully; When treating that solution is cooled to room temperature, adding volume ratio respectively in the above-mentioned solution is 1:1 acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters, promptly adds the 1.22ml acetylacetone,2,4-pentanedione earlier, dropwise adds 1.22ml metatitanic acid four isopropyl esters again, continues to be stirred to be evenly distributed; Add the 6.26ml EGME at last, and at room temperature continue to stir 6 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 40ml Ba of the 0.1mol/L of homogeneous transparent 0.6Sr 0.4Ti 0.995Mn 0.005O 3Solution.Utilize sol evenning machine with the above-mentioned Ba for preparing 0.6Sr 0.4Ti 0.995Mn 0.005O 3Solution was coated on the monocrystalline substrate with 6000 rev/mins rotating speed through 40 seconds equably; Heat-treat technology then, be incubated 5 minutes down for 300 ℃ at electric hot plate; Then quick anneal oven oxygen atmosphere and 750 ℃ of following crystallization 6 minutes.Repeat this annealing process layer by layer, until Ba 0.6Sr 0.4Ti 0.995Mn 0.005O 3The thickness of film reaches 40～50nm.
(2) Bi 0.8Ho 0.2FeO 3The preparation of film
Take by weighing 0.8290g Bi (NO 3) 35H 2O (excessive 5mol%), 0.1782g Ho (NO 3) 35H 2O, 0.8203g Fe (NO 3) 39H 2O is dissolved in the 20ml glacial acetic acid, stirs at 80 ℃ temperature lower magnetic forces, is cooled to room temperature after treating to dissolve fully, and in the solution ethylene glycol of adding 20ml.At room temperature fully stirred 10 hours.The use aperture is that the filter of 0.2 μ m is filtered solution into drop bottle, obtains the 0.05mol/L Bi of homogeneous transparent 0.8Ho 0.2FeO 3Solution.With Bi 0.8Ho 0.2FeO 3Solution was spun on Ba with 2000 rev/mins rotating speed through 20 seconds 0.6Sr 0.4Ti 0.995Mn 0.005O 3On/Si the substrate; Heat-treat technology then, be incubated 6 minutes under 260 ℃ of temperature on the heating plate earlier; Crystallization 6 minutes under 520 ℃ of temperature under the quick anneal oven nitrogen atmosphere again.Repeat this annealing process layer by layer, make Bi 0.8Ho 0.2FeO 3The thickness of crystalline film reaches 200～250nm.
(3) Bi the most at last 0.8Ho 0.2FeO 3/ Ba 0.6Sr 0.4Ti 0.995Mn 0.005O 3/ Si annealed 0.5 hour under 570 ℃ of temperature under nitrogen atmosphere, obtained dense film, and top electrode and hearth electrode in the sputter promptly get capacitor.
Prepared Bi 0.8Ho 0.2FeO 3/ Ba 0.6Sr 0.4Ti 0.995Mn 0.005O 3/ Si capacitor has good crystallinity, storage property and dielectric stability.
The present invention is when adopting lanthanide-doped bismuth ferrite thin film, and prepared capacitor all has good memory property and dielectric property, and it is not obvious that character differs.So all lanthanide series all can be used for the ferrite-doping bismuth thin film.

Claims (10)

1. a ferrous acid bismuth-based thin films stepped construction capacitor comprises hearth electrode, substrate, resilient coating, ferroelectric thin film layer and metal dots electrode from top to bottom successively, and it is characterized in that: said resilient coating is the Mn-doped strontium titanate titanate thin film, and chemical formula is Ba 0.6Sr 0.4Ti (1-x)Mn xO 3, x is the molar equivalent of element manganese, x=0.005-0.05; Said ferroelectric thin film layer is the ferrous acid bismuth-based thin films, and chemical formula is Bi (1-y)Ln yFeO 3, wherein, Ln is a kind of in the lanthanide series, y is the molar equivalent of lanthanide series, y=0.01-0.2.
2. capacitor according to claim 1 is characterized in that: the thickness of said resilient coating is 40～50nm, and the thickness of ferroelectric thin film layer is 200～250nm.
3. capacitor according to claim 1 and 2 is characterized in that: said backing material is the monocrystalline substrate of p type or n type.
4. capacitor according to claim 1 and 2 is characterized in that: described hearth electrode and metal dots electrode are Au.
5. the preparation method of the described ferrous acid bismuth-based thin films of claim 1 a stepped construction capacitor is characterized in that may further comprise the steps:
(1) adopt metal organic decomposition legal system to be equipped with Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The film resilient coating
A. according to Ba 0.6Sr 0.4Ti (1-x)Mn xO 3Stoichiometric proportion, acetate and metatitanic acid four isopropyl esters of choosing barium, strontium, manganese are raw material, choosing glacial acetic acid is solvent, acetylacetone,2,4-pentanedione is a stabilizer, EGME is a viscosity modifier, compound concentration is the precursor solution of 0.02～0.1mol/L;
B. above-mentioned precursor solution is spun on the substrate, then with its on heating plate in 250～300 ℃ of down oven dry, crystallization 5～10 minutes under 700～750 ℃ annealing temperature again;
Spin coating, oven dry, the annealing steps of c, repetition above-mentioned steps b are until Ba 0.6Sr 0.4Ti (1-x)Mn xO 3The thickness of film reaches 40～50nm;
(2) adopt metal organic decomposition legal system to be equipped with Bi (1-y)Ln yFeO 3Film
A. according to Bi (1-y)Ln yFeO 3Stoichiometric proportion, the nitrate of choosing bismuth nitrate, ferric nitrate and certain lanthanide series is raw material, choosing ethylene glycol and glacial acetic acid is solvent, compound concentration is the precursor solution of 0.05～0.3mol/L;
B. above-mentioned precursor solution is spin-coated on the resilient coating, then with its on heating plate in 250～300 ℃ of down oven dry, crystallization 5～10 minutes under 500～550 ℃ annealing temperature again;
C. repeat spin coating, oven dry, the annealing steps of above-mentioned steps b, until Bi (1-y)Ln yFeO 3The thickness of film reaches 200～250nm;
D.Bi (1-y)Ln yFeO 3After film reaches thickness, with the Bi that obtains (1-y)Ln yFeO 3/ Ba 0.6Sr 0.4Ti (1-x)Mn xO 3/ Si annealed 0.5 hour under 550～600 ℃ of temperature, obtained fine and close duplicature;
(3) splash-proofing sputtering metal electrode, the preparation capacitor
Foraminate mask plate is covered on the film, with the surface of Metal Deposition, obtain the metal dots electrode again, then metal sputtering is arrived substrate back, obtain hearth electrode, finally obtain ferrous acid bismuth-based thin films stepped construction capacitor of the present invention to film.
6. preparation method according to claim 5 is characterized in that: preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During the film resilient coating, 2000～7000 rev/mins of spin coating rotating speeds, 20～40 seconds time; Preparation Bi (1-y)Ln yFeO 3During film, 2000～7000 rev/mins of spin coating rotating speeds, 20～40 seconds time.
7. preparation method according to claim 5 is characterized in that: preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During the film resilient coating, annealing under oxygen atmosphere; Preparation Bi (1-y)Ln yFeO 3During film, annealing under nitrogen atmosphere.
8. preparation method according to claim 5 is characterized in that: preparation Ba 0.6Sr 0.4Ti (1-x)Mn xO 3During film, glacial acetic acid with the ratio of the volumetric usage of EGME is: 1:1～5:1; The volume ratio of acetylacetone,2,4-pentanedione and metatitanic acid four isopropyl esters is: 1:1.
9. preparation method according to claim 5 is characterized in that: preparation Bi (1-y)Ln yFeO 3During film, the consumption of glacial acetic acid and ethylene glycol is 1:1～10:1.
10. preparation method according to claim 5 is characterized in that: preparation Bi (1-y)Ln yFeO 3During film, the excessive 2～5mol% of raw material bismuth nitrate.
CN2011101238206A 2011-05-13 2011-05-13 Bismuth ferrite base film layer stacked structure capacitor and preparation method thereof Expired - Fee Related CN102222672B (en)

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