CN102208527B - Low-temperature preparation method of barium strontium titanate based functional film - Google Patents

Low-temperature preparation method of barium strontium titanate based functional film Download PDF

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CN102208527B
CN102208527B CN 201110116985 CN201110116985A CN102208527B CN 102208527 B CN102208527 B CN 102208527B CN 201110116985 CN201110116985 CN 201110116985 CN 201110116985 A CN201110116985 A CN 201110116985A CN 102208527 B CN102208527 B CN 102208527B
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strontium titanate
preparation
nitrate
barium
acetate
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CN102208527A (en
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余萍
陈潇洋
朱建国
肖定全
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Sichuan University
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Sichuan University
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Abstract

The invention provides a low-temperature preparation method of a barium strontium titanate based functional film. The method comprises the following steps: (1) dissolving tetrabutyl titanate in a solvent consisting of benzyl alcohol and glycol so as to form a first complex solution; (2) dissolving carbonate or/and nitrate or/and acetate of alkaline earth metal, transition metal or/and nitrate of rare earth metal or/and acetate of transition metal which meet stoichiometric ratio in a molecular formula of the barium strontium titanate based functional film in the solvent consisting of benzyl alcohol and glycol, so as to form a second complex solution; (3) evenly mixing the first and second complex solutions at a volume ratio of 1:1 and standing for at least 40 minutes so as to obtain a barium strontium titanate based precursor solution; (4) leading the precursor solution to form barium strontium titanate based nano crystal, and putting the nano crystal in an ethylene glycol monobutyl ether-acetic acid mixed solution containing a dispersing agent, and evenly mixing so as to form barium strontium titanate based nano crystal sol; and (5) manufacturing the nano crystal sol into a film on a substrate, drying at the temperature of 40-50 DEG C and cooling.

Description

Low-temperature preparation method of barium strontium titanate based functional film
Technical field
The invention belongs to wet chemistry method oxysalt film preparing technology field, particularly a kind of barium-strontium titanate-based thin film technology method.
Background technology
Barium strontium titanate (Ba 1-xSr xTiO 3, being called for short BST) and material has BaTiO concurrently 3High-k, low-dielectric loss and SrTiO 3Constitutionally stable characteristics, and can adjust its Curie temperature by regulating Ba/Sr, so be widely used as non-refrigerated infrared detector material, capacitor material, phase shifter material and dynamic memory material etc., it is a kind of piezoelectricity ferro material with important use.Can say, in all kinds of microelectronics, optoelectronics, photonic propulsion has widely in the new and high technologies such as Integrated ferroelectrics and micro mechanics, important application.
Utilize traditional Czochralski (vertical pulling) method, coprecipitation and solid reaction process successfully to synthesize barium strontium titanate or barium strontium titanate doped monocrystalline or powder, based on existing film preparing technology (as radio frequency sputtering; Laser flash distillation, collosol and gel etc.) barium strontium titanate also obtain very large development.Yet, along with the miniaturization of all kinds of electronic devices and components, integrated and multifunction, requirement can be integrated with silica-based reading circuit based on the electronic devices and components of all kinds of piezoelectricity ferro functional material work, this just require piezoelectric-ferroelectric thin film preparation technology can with the semiconductor planar process compatible.At present, the preparation of piezoelectric-ferroelectric thin film has two kinds of techniques usually: the one, and growth in situ piezoelectric-ferroelectric thin film at a certain temperature, more at high temperature heat-treat; The 2nd, first deposit film at low temperatures, more at high temperature heat-treat.Heat treated purpose is to make film obtain good crystallization.Usually high temperature (more than the 700 ℃) heat treatment process of these two kinds of process conditions, can damage reading circuit (ROIC).In order to make the piezoelectric-ferroelectric thin film device can be integrated with silica-based reading circuit, require the preparation temperature of piezoelectric-ferroelectric thin film below 500 ℃.
Sharma H B etc. disclose adopt the method for improving colloidal sol (Integrated Ferroelectrics, 2011,121:51-57), make the BST crystallization temperature drop to 550 ℃, crystallite dimension is 15nm simultaneously.Yao Xi etc. disclose the colloidal sol that will make, at Pt/Ti/SiO 2Then the upper whirl coating of/Si 400 ℃ of oven dry, then is placed in autoclave, adds the Ba (OH) of appropriate concentration 2And Sr (CH 3COO) 2, at 100～200 ℃ of heating 3～10h.The crystallization temperature of the bst thin film that obtains draws and utilizes hydro thermal method to realize the preparation bst thin film at low temperature, and good preferred orientation is arranged in the scope of～200 ℃, when hydro-thermal, and OH -Play a part when forming film very crucial, film flawless (the Crystal Growth﹠amp that makes; Design, 2006,6 (10): 2197-2199).Although the said film preparation method is obtaining progress aspect the crystallization temperature of barium strontium titanate reducing, but still can't be compatible mutually with the semiconductor planar processing technology of integrated one chip device.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of low-temperature preparation method of barium strontium titanate based functional film is provided, the barium strontium titanate base film that this kind method is prepared is zero defect not only, the well-crystallized, substrate is unrestricted, and compatible with photoetching process in existing semiconductor planar technique, be convenient to realize the integrated of barium-strontium titanate-based function film device and silica-based reading circuit.
Low-temperature preparation method of barium strontium titanate based functional film of the present invention, the molecular formula of its barium-strontium titanate-based function film are (Ba 1-x-y-zSr xA yD z) [Ti The 1-alpha-betaA α' D β'] O 3-δ, in formula, A, A ', D, D ' for the alkali earth metal of doping or/and transition metal or/and thulium, 0.1≤x≤0.4,0≤y≤0.07,0≤z≤0.003,0≤α≤0.005,0≤β≤0.002,0≤δ≤0.005, its processing step is as follows:
(1) preparation the first complex solution
Take butyl titanate as solute, take the mixed liquor of phenmethylol and ethylene glycol as solvent, namely form the first complex solution under room temperature, normal pressure, described solute being dissolved in solvent, described solvent is 1～4: 1 preparation by the volume ratio of phenmethylol and ethylene glycol, the amount of described solute and solvent take the concentration of Ti ion in the first complex solution as 0.1M～0.3M measures;
(2) preparation the second complex solution
Take the carbonate of alkaline-earth metal or/and nitrate or/and acetate, transition metal or/and the nitrate of rare earth metal or/and the acetate of transition metal as solute, take the mixed liquor of phenmethylol and ethylene glycol as solvent, namely form the second complex solution under room temperature, normal pressure, described solute being dissolved in solvent, described solvent is 1～4: 1 preparation by the volume ratio of phenmethylol and ethylene glycol, and the amount of described solute and solvent is to satisfy molecular formula (Ba 1-x-y-zSr xA yD z) [Ti The 1-alpha-betaA α' D β'] O 3-δThe total concentration of other metal ion in the second complex solution except titanium of stoichiometric proportion is (0.1～0.3) [1+2 (alpha+beta)] M metering;
(3) prepare barium-strontium titanate-based precursor solution
With 1: 1 by volume batching of the first complex solution and the second complex solution, mix at least 15 minutes under normal pressure, 0 ℃～40 ℃, then standing at least 40 minutes, namely obtain barium-strontium titanate-based precursor solution;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
the barium-strontium titanate-based precursor solution of step (3) preparation is put into reactor, at normal pressure, 190～220 ℃ of reactions formed the barium strontium titanate base nanometer crystal in 60～72 hours, then with isolated barium strontium titanate base nanometer crystal with putting into the EGME that contains dispersant-acetic acid mixed liquor after ethanol washing, stir and namely form barium-strontium titanate-based nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is 2～4: 1 preparation by the volume ratio of EGME and acetic acid, the concentration of the amount of described barium strontium titanate base nanometer crystal and EGME-acetic acid mixed liquor barium strontium titanate base nanometer crystal in the colloidal sol is the 0.05M metering, described dispersant is TGA, the mol ratio of TGA and barium strontium titanate base nanometer crystal is 1～4: 1,
(5) film forming is with dry
Adopt spin coating technique that the barium-strontium titanate-based nanocrystalline colloidal sol of step (4) preparation is made film on conduction or nonconducting, crystalline state or amorphous substrate, in normal pressure, 40 ℃～50 ℃ oven dry, namely obtain barium-strontium titanate-based function film after cooling.
In said method, doped metallic elements A is Ag or Ca, doped metallic elements A ' be Mg, Mn, Ni, Co, Fe, at least a, doped metallic elements D is Nd or Pr, doped metallic elements D ' is Yb, Dy, Y, Sc, at least a in In.
In said method, the carbonate of described alkaline-earth metal is the carbonate of Sr, and the nitrate of described alkaline-earth metal is the nitrate of Mg or the nitrate of Sr, and the acetate of described alkaline-earth metal is at least a in the acetate of acetate, Sr of acetate, the Ba of Ca; The nitrate of described transition metal is at least a in the nitrate of nitrate, Y of nitrate, the Sc of nitrate, the Ag of nitrate, the In of nitrate, the Mn of Fe, and the acetate of described transition metal is at least a in the acetate of acetate, Ni of acetate, the Co of Mn; The nitrate of described rare earth metal is at least a in the nitrate of nitrate, Yb of nitrate, the Pr of nitrate, the Dy of Nd.
The barium-strontium titanate-based function film of the method for the invention preparation, grain size scope 10nm～500nm, thickness 100nm～3000nm, heat treatment temperature is lower than 500 ℃.
The present invention has following beneficial effect:
1, adopt the method for the invention to prepare the barium-strontium titanate-based function film of multiple doping, dry in normal pressure, 40～50 ℃ of air atmospheres, namely obtain barium-strontium titanate-based polycrystal film after cooling, when film pattern, be not subjected to photoresist remove photoresist dissolving or the corrosion of liquid, can carry out again further heat treatment after removing photoresist under 500 ℃, obtain the film of perfect crystalline densification, thereby can realize with the semiconductor planar processing technology in the compatibility of photoetching process, be applicable to prepare the barium-strontium titanate-based integrated functionality device of one chip of film-type.
2, the barium-strontium titanate-based function film prepared of the method for the invention is compared with the film that traditional preparation method obtains, the advantages of good crystallization of film, zero defect, thereby guaranteed the serviceability of film.
Description of drawings
Fig. 1 is the Ba with the method for the invention preparation 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995The X-ray diffractogram of film;
Fig. 2 is the Ba with the method for the invention preparation 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline transmission electron microscope picture;
Fig. 3 is the Ba with the method for the invention preparation 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995The flying-spot microscope photo figure of film;
Fig. 4 is the Ba with the method for the invention preparation 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Stereoscan photograph;
Fig. 5 is the Ba with the method for the invention preparation 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998The X-ray diffractogram of film;
Fig. 6 is the Ba with the method for the invention preparation 0.8Sr 0.2TiO 3The X-ray diffractogram of film;
Fig. 7 is the Ba with the method for the invention preparation 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997The X-ray diffractogram of film.
Embodiment
Embodiment 1: preparation Ba 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.2M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995The nitrate of the acetate of the Ba of stoichiometric proportion, the carbonate of Sr, Mg and In is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Sr, Mg, In is the complex solution of 0.2024M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 45 minutes under normal pressure, 0 ℃ standing 50 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Mg, In;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 200 ℃ of reactions 72 hours, obtain the Ba that particle diameter is 3～6nm 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Nanocrystalline, as then centrifugation to be gone out Ba 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 3: 1 by the volume ratio of EGME and acetic acid, described Ba 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 4: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995Nanocrystalline colloidal sol is made film on silicon chip substrate, described film is put into baking oven, oven dry under normal pressure, 40 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba of the present embodiment preparation 0.7Sr 0.3Ti 0.993Mg 0.004In 0.002O 2.995The XRD of film the results are shown in Figure 1, Fig. 1 and shows, it is the crystalline state film, and grain size is 32nm as calculated.
Embodiment 2: preparation Ba 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.1M, and described solvent is preparation in 3: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997The acetate of the Ba of stoichiometric proportion, Sr, Ca, Ni and the nitrate of Sc are dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Sr, Ca, Ni, Sc is the complex solution of 0.1008M, and described solvent is preparation in 3: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 30 minutes under normal pressure, 10 ℃ standing 40 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Ca, Ni, Sc;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 192 ℃ of reactions 72 hours, obtain the Ba that particle diameter is 3～9nm 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline, as then centrifugation to be gone out Ba 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 2: 1 by the volume ratio of EGME and acetic acid, described Ba 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 3: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline colloidal sol is made film on silicon chip substrate, described film is put into baking oven, oven dry under normal pressure, 40 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.6Sr 0.33Ca 0.07Ti 0.996Ni 0.002Sc 0.002O 2.997Nanocrystalline TEM (transmission electron microscope) analysis the results are shown in Figure 2, Fig. 2 and shows, nanocrystalline particle diameter is the 5nm left and right.
Embodiment 3: preparation Ba 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.3M, and described solvent is preparation in 1: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995The nitrate of the acetate of the Ba of stoichiometric proportion, Sr, Co, Ag and Pr is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Sr, Co, Ag, Pr is the complex solution of 0.3012M, and described solvent is preparation in 1: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 15 minutes under normal pressure, 40 ℃ standing 45 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Ag, Pr, Co;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 195 ℃ of reactions 60 hours, obtain the Ba that particle diameter is 3～6nm 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Nanocrystalline, as then centrifugation to be gone out Ba 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 4: 1 by the volume ratio of EGME and acetic acid, described Ba 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 1: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995Nanocrystalline colloidal sol is made film on glass substrate, described film is put into baking oven, oven dry under normal pressure, 50 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.599Sr 0.4Ag 0.01Pr 0.001Ti 0.998Co 0.002O 2.995The scanning electron microscope analysis of film the results are shown in Figure 3, Fig. 3 and shows, thin film crystallization is good, and size of microcrystal is approximately and is about 50nm.
Embodiment 4: preparation Ba 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.2M, and described solvent is preparation in 1: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985The nitrate of carbonate, Ag, Nd and the Dy of the Ba of stoichiometric proportion, the acetate of Mn, Sr is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Mn, Sr, Ag, Nd, Dy is the complex solution of 0.2028M, and described solvent is preparation in 1: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 25 minutes under normal pressure, 20 ℃ standing 40 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Ag, Nd, Mn, Dy;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 200 ℃ of reactions 68 hours, obtain the approximately Ba of 6nm of particle diameter 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Nanocrystalline, as then centrifugation to be gone out Ba 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 3: 1 by the volume ratio of EGME and acetic acid, described Ba 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 4: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985Nanocrystalline colloidal sol is made film on the LNO/ glass substrate, described film is put into baking oven, oven dry under normal pressure, 45 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.657Sr 0.33Ag 0.01Nd 0.003Ti 0.996Mn 0.005Dy 0.002O 2.9985The scanning electron microscope analysis of film the results are shown in Figure 4, Fig. 4 and shows, it is the crystalline state film, and thin film crystallization is good, and size of microcrystal is approximately and is about 300nm.
Embodiment 5: preparation Ba 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.2M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998The nitrate of the acetate of the Ba of stoichiometric proportion, the carbonate of Sr, Fe and Yb is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Sr, Fe, Yb is the complex solution of 0.2012M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 20 minutes under normal pressure, 30 ℃ standing 50 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Fe, Yb;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 220 ℃ of reactions 72 hours, obtain particle diameter and be the approximately Ba of 5～10nm 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Nanocrystalline, as then centrifugation to be gone out Ba 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 2: 1 by the volume ratio of EGME and acetic acid, described Ba 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 4: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998Nanocrystalline colloidal sol is made film on silicon chip substrate, described film is put into baking oven, oven dry under normal pressure, 40 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.9Sr 0.1Ti 0.997Fe 0.002Yb 0.001O 2.998The XRD analysis of film the results are shown in Figure 5, Fig. 5 and shows, it is the crystalline state film.
Embodiment 6: preparation Ba 0.8Sr 0.2TiO 3Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.2M, and described solvent is preparation in 4: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.8Sr 0.2TiO 3The acetate of the Ba of stoichiometric proportion, the carbonate of Sr are dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, and the total concentration of preparation Ba, Sr is the complex solution of 0.2M, and described solvent is preparation in 4: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 35 minutes under normal pressure, 10 ℃ standing 50 minutes, obtain the barium strontium titanate precursor solution;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 190 ℃ of reactions 72 hours, obtain particle diameter and be the approximately Ba of 5～10nm 0.8Sr 0.2TiO 3Nanocrystalline, as then centrifugation to be gone out Ba 0.8Sr 0.2TiO 3Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.8Sr 0.2TiO 3Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 4: 1 by the volume ratio of EGME and acetic acid, described Ba 0.8Sr 0.2TiO 3The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.8Sr 0.2TiO 3Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 3: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.8Sr 0.2TiO 3Nanocrystalline colloidal sol is put into baking oven at the LNO/ film of making on glass with described film, oven dry under normal pressure, 50 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.8Sr 0.2TiO 3The XRD of film the results are shown in Figure 6, Fig. 6 and shows, it is the crystalline state film.
Embodiment 7: preparation Ba 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Film
(1) preparation the first complex solution
Under room temperature, normal pressure, butyl titanate is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, preparation Ti ion concentration is the first complex solution of 0.2M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(2) preparation the second complex solution
To satisfy molecular formula Ba under room temperature, normal pressure 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997The nitrate of the acetate of the Ba of stoichiometric proportion, Sr, Mn and Y is dissolved in the solvent of 15ml phenmethylol and ethylene glycol composition, the total concentration of preparation Ba, Sr, Mn, Y is the complex solution of 0.2012M, and described solvent is preparation in 2: 1 by the volume ratio of phenmethylol and ethylene glycol;
(3) prepare barium-strontium titanate-based precursor solution
With the second complex solution of the first complex solution of step (1) preparation and step (2) preparation after mixing 20 minutes under normal pressure, 25 ℃ standing 40 minutes, obtain the barium-strontium titanate-based precursor solution of mixing Mn, Y;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
The barium strontium titanate doped basic precursor solution of step (3) preparation is put into reactor, normal pressure, 190 ℃ of reactions 72 hours, obtain particle diameter and be the approximately Ba of 5～10nm 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Nanocrystalline, as then centrifugation to be gone out Ba 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Nanocrystallinely stir with putting into the EGME that contains the dispersant TGA-acetic acid mixed liquor after ethanol washing, namely form Ba 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is preparation in 3: 1 by the volume ratio of EGME and acetic acid, described Ba 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997The amount of nanocrystalline and EGME-acetic acid mixed liquor is with Ba in colloidal sol 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Nanocrystalline concentration is the 0.05M metering, and described dispersant TGA and described nanocrystalline mol ratio are 2: 1;
(5) film forming is with dry
Under normal pressure, room temperature, adopt spin coating technique with the Ba of step (4) preparation 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997Nanocrystalline colloidal sol is made film on silicon chip substrate, described film is put into baking oven, oven dry under normal pressure, 45 ℃, and then powered-down is cooled to room temperature with baking oven.
The Ba that the present embodiment is prepared 0.65Sr 0.35Ti 0.997Mn 0.002Y 0.001O 2.997The XRD of film the results are shown in Figure 7, Fig. 7 and shows, it is the crystalline state film.

Claims (3)

1. low-temperature preparation method of barium strontium titanate based functional film, the molecular formula of described barium-strontium titanate-based function film is (Ba 1-x-y-zSr xA yD z) [Ti The 1-alpha-betaA α' D β'] O 3-δ, in formula, A is alkali earth metal or the transition metal of doping, A ' for the doping alkali earth metal or/and transition metal, D is the thulium of doping, D ' for the thulium of doping or/and transition metal, 0.1≤x≤0.4,0≤y≤0.07,0≤z≤0.003,0≤α≤0.005,0≤β≤0.002,0≤δ≤0.005, its processing step is as follows:
(1) preparation the first complex solution
Take butyl titanate as solute, take the mixed liquor of phenmethylol and ethylene glycol as solvent, namely form the first complex solution under room temperature, normal pressure, described solute being dissolved in solvent, described solvent is 1～4: 1 preparation by the volume ratio of phenmethylol and ethylene glycol, the amount of described solute and solvent take the concentration of Ti ion in the first complex solution as 0.1M～0.3M measures;
(2) preparation the second complex solution
Acetate with the carbonate of Sr or nitrate or acetate, Ba, and the nitrate of alkaline-earth metal of doping or acetate or/and transition metal or/and the nitrate of rare earth metal or/and the acetate of transition metal is solute, take the mixed liquor of phenmethylol and ethylene glycol as solvent, namely form the second complex solution under room temperature, normal pressure, described solute being dissolved in solvent, described solvent is 1～4: 1 preparation by the volume ratio of phenmethylol and ethylene glycol, and the amount of described solute and solvent is to satisfy molecular formula (Ba 1-x-y-zSr xA yD z) [Ti The 1-alpha-betaA α' D β'] O 3-δThe total concentration of other metal ion in the second complex solution except titanium of stoichiometric proportion is (0.1～0.3) [1+2 (alpha+beta)] M metering;
(3) prepare barium-strontium titanate-based precursor solution
With 1: 1 by volume batching of the first complex solution and the second complex solution, mix at least 15 minutes under normal pressure, 0 ℃～40 ℃, then standing at least 40 minutes, namely obtain barium-strontium titanate-based precursor solution;
(4) prepare barium-strontium titanate-based nanocrystalline colloidal sol
the barium-strontium titanate-based precursor solution of step (3) preparation is put into reactor, at normal pressure, 190～220 ℃ of reactions formed the barium strontium titanate base nanometer crystal in 60～72 hours, then with isolated barium strontium titanate base nanometer crystal with putting into the EGME that contains dispersant-acetic acid mixed liquor after ethanol washing, stir and namely form barium-strontium titanate-based nanocrystalline colloidal sol, described EGME-acetic acid mixed liquor is 2～4: 1 preparation by the volume ratio of EGME and acetic acid, the concentration of the amount of described barium strontium titanate base nanometer crystal and EGME-acetic acid mixed liquor barium strontium titanate base nanometer crystal in the colloidal sol is the 0.05M metering, described dispersant is TGA, the mol ratio of TGA and barium strontium titanate base nanometer crystal is 1～4: 1,
(5) film forming is with dry
Adopt spin coating technique that the barium-strontium titanate-based nanocrystalline colloidal sol of step (4) preparation is made film on conduction or nonconducting, crystalline state or amorphous substrate, in normal pressure, 40 ℃～50 ℃ oven dry, namely obtain barium-strontium titanate-based function film after cooling.
2. low-temperature preparation method of barium strontium titanate based functional film according to claim 1, it is characterized in that doped metallic elements A is Ag or Ca, doped metallic elements A ' is at least a in Mg, Mn, Ni, Co, Fe, doped metallic elements D is Nd or Pr, doped metallic elements D ' is Yb, Dy, Y, Sc, at least a in In.
3. low-temperature preparation method of barium strontium titanate based functional film according to claim 1 and 2, when it is characterized in that preparing the second complex solution, the nitrate of the alkaline-earth metal of described doping is the nitrate of Mg, and the acetate of the alkaline-earth metal of described doping is the acetate of Ca;
The nitrate of the transition metal of described doping is at least a in the nitrate of nitrate, Y of nitrate, the Sc of nitrate, the Ag of nitrate, the In of nitrate, the Mn of Fe, and the acetate of the transition metal of described doping is at least a in the acetate of acetate, Ni of acetate, the Co of Mn;
The nitrate of the rare earth metal of described doping is at least a in the nitrate of nitrate, Yb of nitrate, the Pr of nitrate, the Dy of Nd.
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