CN109825872A - One-dimensional high-performance BaTiO3/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between - Google Patents
One-dimensional high-performance BaTiO3/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between Download PDFInfo
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Abstract
The present invention relates to a kind of controllable preparation high-performance one-dimensional BaTiO3/SrTiO3The nano combined method for seeing crystal that is situated between.For this method using four metatitanic acids as template, alkaline earth oxide, hydroxide are raw material, obtain the BaTiO of different ratio using two step hydrothermal method controllable preparations3/SrTiO3Nano combined Jie sees crystal.Preparation process has high controllability, can demand depending on the application, prepare the nano complex of different ratio.The BaTiO being prepared by this method3/SrTiO3For 1-dimention nano, compound Jie sees crystal, has regular Rod-like shape, the more one-dimensional BaTiO of maximum piezoelectric property3Monomer is higher by 253 times.In addition, template used in preparation process and reactant and the waste liquid for preparing product generation do not generate harm to environment and human body, can be applied to layer capacitor, thermistor, optoelectronic device, electromechanical equipment, sensor, dynamic RAM and field effect transistor and other microdevices etc..
Description
Technical field
The invention belongs to nanocomposite technical fields, in particular to a kind of controllable preparation high-performance one-dimensional
BaTiO3/SrTiO3The nano combined method for seeing crystal that is situated between.
Background technique
Important component of the piezoelectric material as microelectronic field, plays an important role in modern industry.In order to
Meet the needs of modern industry, piezoelectric material just towards miniaturization, develop by integrated and unleaded direction.Therefore, unleaded
Piezoelectric material has become the material that can satisfy environmental protection requirement and piezoelectric property.Perovskite structure, blue steel structure and
The bismuth laminated primary structure for having become combination lead-free piezoelectric material.However, such as BaTiO3(BT), Sr1-xBaxNb2O6With
Bi4Ti3O12Piezoelectric material powder Deng the one-component by these structure compositions has relatively low piezoelectric property, is unable to satisfy
Substitution is with the requirement of PbO mainstream lead-containing materials as main component.For the above reason, in actual production often through mixing
Miscellaneous, compound or any other method promotes the performance of lead-free piezoelectric material powder, so that it obtains good piezoelectric property.It mixes
Miscellaneous method is mainly by improving pure phase piezoresistive material in A or B addition rare earth elements of piezoelectric material or yttrium
The performance of material improves the characteristic of piezoelectric material using strain engineering.Complex method is mainly by the piezoelectric material of pure phase and second
It is compound mutually to carry out macroscopic view, utilizes and is orientated the electromechanical performance that engineering improves material.Currently, using the building of existing complex method
The compound systems such as BT/PVDF, BT/PDMS show higher piezoelectric response, however the leadless piezoelectric material that above method obtains
There is the disadvantages of big product dimension, complex process in material or device.At the same time, the above method just thinks of performance in a certain respect
Promotion, the collective effect of orientation engineering, strain engineering, farmland engineering cannot be taken into account to promote the piezoelectricity of lead-free piezoelectric material
Energy.
Titanate piezoelectric material Jie obtained by predecessor using hydro-thermal method is seen crystal and can make full use of orientation engineering
With farmland engineering, being formed on 1D or 2D scale, there is the titanate polycrystalline of common orientation effectively to be mentioned due to identical orientation
The high piezoelectric property of material.The present inventor is once by using H1.07Ti1.73O4It is prepared as predecessor using one step hydro thermal method
BaTiO3、BaxSr1-xTiO3、NaxBi1-xTiO3Good electromechanical is shown on the ceramic block of its sintering
Energy.On this basis, it is effectively constructed on the basis of topochemical reaction using multi-section hydro-thermal method/solvent thermal reaction different
Matter epitaxial interface.The BaTiO obtained by compatible orientation engineering, farmland engineering and strain engineering3/SrTiO3、 BaTiO3/
CaTiO3、BaTiO3/NaxBi1-xTiO3、BaTiO3/Bax(Na,Bi)1-xTiO3Crystal is seen etc. a series of nano combined Jie,
It is demonstrated by good piezoelectric property.However, the performance of titanate series lead-free piezoelectric material still needs further to be broken through.
Summary of the invention
In view of the deficiencies in the prior art, the purpose of the present invention is to provide a kind of one-dimensional high-performance BaTiO of controllable preparation3/
SrTiO3The method that nano complex Jie sees crystal, to utilize BaTiO3/SrTiO3Nano complex, which is situated between, sees crystal promotion
BaTiO3The performance of base leadless piezoelectricity material.
In order to realize above-mentioned technical purpose of the invention, inventor is finally adopted by a large number of experiments research and persistent exploration
Pass through change first step reaction process Ti's and Ba using one-dimensional four metatitanic acid as reaction template with two step hydro-thermal softening methods
Molar ratio, reaction temperature and second step reaction process strontium hydroxide concentration of aqueous solution and the step reaction temperature, controllable preparation are one-dimensional
BaTiO3/SrTiO3Nano complex, which is situated between, sees crystal percentage, effectively increases BaTiO3The performance of base leadless piezoelectricity material.
Specifically, technical solution of the present invention includes the following: a kind of one-dimensional BaTiO3/SrTiO3Nano combined Jie sees crystal
Controllable method for preparing, include the following steps:
(1) preparation of HTO/BT complex: metatitanic acid monocrystalline H is weighed2Ti4O9, according to Ti:Ba molar ratio 1:(0.6-0.8)
Barium hydroxide is weighed, is separately added into reaction kettle, water is then added, after mixing in 120-200 DEG C of reaction 8-16h, reaction
After, product is filtered, 18-30h is impregnated with 0.3-0.6mol/L acetum, filters and be washed with water, it is dry, it obtains
HTO/BT complex；
(2)BaTiO3/SrTiO3The controllable preparation of the nano combined sight crystal that is situated between: take HTO/BT complex that reaction kettle is added
Interior, according to Ti:Sr molar ratio 1:(6-30) strontium hydroxide aqueous solution is added and is uniformly mixed, in 120-200 DEG C of reaction 8-16h,
After completion of the reaction, product is filtered, impregnates 18-30h with 0.3-0.6mol/L acetum, filters and be washed with water, it is dry,
Obtain BaTiO3/SrTiO3Nano combined Jie sees crystal.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein reaction kettle described in step (1) and step (2) is ptfe autoclave.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein operating procedure dry in step (1) and step (2) are as follows: in 45-53 DEG C of drying of air dry oven.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein reaction temperature is preferably 150-200 DEG C in step (1), and the reaction time is preferably 11-13h.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein according to Ti:Sr molar ratio 1:(6-12 in step (2)) strontium hydroxide aqueous solution is added and reacts after mixing.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein reaction temperature is preferably 150-200 DEG C in step (2), and the reaction time is preferably 11-13h.
It is further preferred that one-dimensional BaTiO as described above3/SrTiO3The controllable preparation side of the nano combined sight crystal that is situated between
Method, wherein the concentration of strontium hydroxide aqueous solution described in step (2) is 0.1-0.6mol/L.
Compared with prior art, one-dimensional BaTiO provided by the invention3/SrTiO3The controllable preparation of the nano combined sight crystal that is situated between
Method, using four metatitanic acids as template, using alkaline earth oxide, hydroxide as raw material, using two step hydrothermal method controllable preparations
Obtain the BaTiO of different ratio3/SrTiO3Nano combined Jie sees crystal, has the following advantages that and significant progress:
(1) by carrying out BaTiO using HTO3/SrTiO3The nano combined preparation for being situated between sight crystal can be obtained with larger
The Rod-like shape of aspect ratio can generate the performance of this compound body piezoelectric by improving hetero-epitaxy interphase density
Great breakthrough, maximum piezoelectric property can achieve 866.79pm/V, more one-dimensional BaTiO3Monomer is higher by 253 times.
(2) reach control BaTiO by regulating and controlling reaction process Ba, Sr constituent content3/SrTiO3Nano combined Jie sees crystal
Middle BaTiO3、SrTiO3The purpose of ratio completes the preparation that target Jie sees crystal according to different piezoelectric property demands, entire to prepare
Process has high controllability.
(3) BaTiO being prepared by this method3/SrTiO3For 1-dimention nano, compound Jie sees crystal, has regular
Rod-like shape, average-size are width x thickness × length=600 × 400 × Lnm, which is by BaTiO3And SrTiO3It receives
The diffraction pattern of monocrystalline is presented in the polycrystalline of meter Jing Ti dense arrangement composition, selective electron diffraction style.
(4) template used in preparation process and reactant and the waste liquid of product generation is prepared not to environment and human body
Harm is generated, has the characteristics that nontoxic, cheap, strong adsorption force, can be applied to layer capacitor, thermistor, photoelectricity and set
Standby, electromechanical equipment, sensor, dynamic RAM and field effect transistor and other microdevices etc..
Detailed description of the invention
Fig. 1 is that the present invention prepares one-dimensional BaTiO3/SrTiO3Complex, which is situated between, sees the reaction mechanism schematic diagram of crystal.
Fig. 2 is H2Ti4O9With Ba (OH)2According to molar ratio Ti:Ba=1:0.6 100 DEG C of (b), (c) 120 DEG C, (d) 150
DEG C, (e) 200 DEG C of material phase analysis figures carried out after the soft chemical reaction 12h of first step hydro-thermal.
Fig. 3 is HTO/BaTiO3Complex and 0.1mol/L Sr (OH)2BaTiO after reactant aqueous solution 12h3/SrTiO3It receives
Meter Fu He, which is situated between, sees the XRD spectrum of crystal, in which: (a) 0.6BT-0.1ST-120-150, (b) 0.6BT-0.1ST-120-200,
(c) 0.6BT-0.1ST-150-150, (d) 0.6BT-0.1ST-150-200, (e) 0.6BT-0.1ST-200-150, (f)
0.6BT-0.1ST-200-180, (g) 0.6BT-0.1ST-200-200, (h) 0.7BT-0.1ST-200-200, (i) 0.8BT-
0.1ST-200-200。
Fig. 4 is BaTiO3/SrTiO3The SEM photograph of the nano combined sight crystal that is situated between, in which: (a) 0.6BT-0.1ST-120-
150, (b) 0.6BT-0.1ST-120-200, (c) 0.6BT-0.1ST-150-150, (d) 0.6BT-0.1ST-150-200, (e)
0.6BT-0.1ST-200-150, (f) 0.6BT-0.1ST-200-200.
Fig. 5 is BaTiO3/SrTiO3The SEM photograph of the nano combined sight crystal that is situated between, wherein (a) 0.6BT-0.1ST-200-
150, (b) 0.6BT-0.1ST-200-200, (c, d) 0.7BT-0.1ST-200-200, (e, f) 0.8BT-0.1ST-200-
200, (d) and (f) be respectively (c) and (e) partial enlargement photo.
Fig. 6 is (a-d) H2Ti4O9, (e-h) 0.6BT-100, and (i-l) 0.6BT-150 TEM photo (a, e, i) and
HRTEM photo (b, c, f, g, j, k) and SAED style (d, h, l).
Fig. 7 is (a-d) 0.6BT-0.1ST-150-200, (e-h) 0.6BT-0.1ST-200-150, (i-l) 0.6BT-
TEM photo (a, e, i), HRTEM photo (b, c, f, g, j, k) and the SAED style (d, h, l) of 0.1ST- 200-200.
Fig. 8 is BaTiO3/SrTiO3The TEM photo (a) of the nano combined sight crystal 0.8BT-0.1ST-200-200 that is situated between,
HRTEM photo (b, c), SAED style (d) and (e) power spectrum Surface scan result figure.
Fig. 9 is BaTiO3/SrTiO3Nano combined Jie sees crystal (a-c) 0.6BT-0.1ST-200-150, (d-f) 0.6BT-
0.1ST-200-200, (g-i) 0.7BT-0.1ST-200-200, the AFM altitude signal of (j-l) 0.8BT-0.1ST-200-200
Image (a, d, g, j), 3DAFM image (b, e, h, k) and PFM piezoelectric forces response curve (c, f, i, l).
Specific embodiment
Below by specific embodiment, invention is further described in detail.It will be apparent, however, to one skilled in the art, that
The following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.In addition, tool is not specified in embodiment
Body technique operating procedure or condition person described technology or conditions or say according to product according to the literature in the art
Bright book carries out.Reagents or instruments used without specified manufacturer, being can be with conventional products that are commercially available.
Embodiment 1: one-dimensional BaTiO3/SrTiO3Complex, which is situated between, sees the reaction condition development test of crystal
Weigh 0.25g metatitanic acid monocrystalline (H2Ti4O9), it is that 1:0.6 weighs barium hydroxide (Ba according to Ti:Ba molar ratio
(OH)2·8H2O) 0.5316g is added in 50mL ptfe autoclave, and 30mL water is added, after mixing in being contrary
It answers in device respectively in 100,120,150,200 DEG C of reaction 12h.H before reacting2Ti4O9Object phase composition such as Fig. 2 a, when reaction exist
When carrying out at 100 DEG C, the XRD spectrum of product shows the form (Fig. 2 b) of amorphous, when reaction at 120,150,200 DEG C into
When row reaction, the object phase composition of product both includes H2Ti4O9Phase also includes BaTiO3Phase (Fig. 2 c-e).Therefore selection 120,
150, the product obtained under the conditions of 200 carries out next step reaction as intermediate product, is denoted as 0.6BT-120,0.6BT- respectively
150,0.6BT-200.In order to obtain more high proportion BaTiO3H2Ti4O9/BaTiO3Complex, according to above-mentioned H2Ti4O9Quality
It is respectively that 1:0.7,1:0.8 weigh barium hydroxide (Ba (OH) according to Ti:Ba molar ratio2·8H2O it) is carried out at 200 DEG C anti-
Intermediate product should be obtained, is denoted as 0.7BT-200,0.8BT-200 respectively.By above-mentioned intermediate product and 30mL 0.1mol/L Sr
(OH)2Solution carries out second step hydro-thermal reaction.When 0.6BT-120 is after 150 DEG C of progress second step hydro-thermal reactions, the object of product
Phase composition both includes H2Ti4O9Also include mutually BT phase and ST phase (Fig. 3 a), illustrates that reaction at this time is incomplete.It is this endless
The phenomenon that full response the second step hydro-thermal reaction (Fig. 3 b) in 0.6BT-120 at 200 DEG C, 0.6BT-150 is at 150 DEG C
Second step hydro-thermal reaction (Fig. 3 c), 0.6BT-150 can have found in the second step hydro-thermal reaction (Fig. 3 d) at 200 DEG C.When
0.6BT-200 carry out second step reaction when, whether 150 DEG C (Fig. 3 e) or 200 DEG C (Fig. 3 g) can obtain only have BT phase with
Object phase composition existing for ST phase, the appearance at this point, BT phase and ST accompany.Illustrate when 0.6BT-200 is as intermediate product, BT/
ST complex is obtained, but may determine that by the diffraction peak intensity of BT phase and ST phase, the BT/ST obtained under the conditions of the two
The BT phase of complex and the accounting of ST phase are different.When 0.6BT-200 carries out second step reaction at 180 DEG C, H2Ti4O9
It disappears, but while BT phase ST phase generates, transition state TiO2Mutually also supervene (Fig. 3 f).It is possible thereby to illustrate, at certain
When carrying out second step hydro-thermal reaction under a little specific temperatures, H2Ti4O9Matrix can not only generate BT/ST complex, can also generate
Decomposition product TiO2.When 0.7BT-200 is in 200 DEG C of progress second step reactions, it has been similarly formed BT/ST complex, it is multiple at this time
The ratio of BT and ST is further to (Fig. 3 h) in zoarium.Until 0.8BT-200 acquisition when carrying out hydro-thermal reaction for 200 DEG C
The ratio of BT and ST reaches unanimity (Fig. 3 i) in BT/ST.It is similar to result above, when intermediate product and 0.2,0.5mol/L Sr
(OH)2Solution, which carries out second step hydro-thermal reaction, can also obtain BT/ST complex.In conjunction with obtain BT/ST complex condition and
The integral area of BT phase, ST phase, can be tabulated below by the condition of controllable preparation BT/ST complex.Wherein, the name of sample
Mode are as follows: (Bi:Ti) BT- (Sr (OH) in second step hydro-thermal reaction2Concentration) ST- first step hydrothermal temperature-second step water
Thermal response temperature.The BT/ST complex by BT phase and ST phase composition, complex can be obtained in table under the conditions of serial number 1-11
Controlled range is BT0.71-0.06；What is obtained under the conditions of serial number 12-16 is the BT/ST complex not reacted completely, object phase
In still have H2Ti4O9Mutually exist, when calculating BT/ST ratio, does not calculate the accounting of HTO phase；Under conditions of serial number 16-25
When obtaining BT/ST complex, it is accompanied by decomposition product TiO2It generates, when calculating BT/ST component ratio, also without by TIO2Phase
It counts.
In conjunction with the microscopic appearance for obtaining product, it can be found that 0.6BT-200 and 30mL 0.1mol/L Sr (OH)2Solution into
The BT/ST complex pattern and H obtained after row second step hydro-thermal reaction2Ti4O9Matrix maintains identical Rod-like shape (figure
4a-f).It chooses 0.6BT-0.1ST-200-150 (Fig. 5 a), 0.6BT-0.1ST-200-200 (Fig. 5 b), 0.7BT-0.1ST-
200-200 (Fig. 5 c), 0.8BT-0.1ST-200-200 (Fig. 5 e) are observed it can be found that the BT/ST of Rod-like shape is compound
The powder of body is long to be greater than 1 μm having a size of wide 300nm.Pass through 0.7BT-0.1ST-200-200 (Fig. 5 d), 0.8BT-0.1ST-
The partial enlarged view of 200-200 (Fig. 5 f) can also know, the BT/ST complex of formation be by tiny nanocrystal orderly,
What close arrangement was formed.
It is analyzed by product of the crystallographic analysis to acquisition it can be found that H2Ti4O9TEM image still display bar
Shape pattern (Fig. 6 a), HRTEM image, which is observed that, belongs to H2Ti4O9(003) lattice fringe (Fig. 6 b, c) of crystal face, from
H2Ti4O9(Fig. 6 d) can summarize H in the selective electron diffraction style of monocrystalline2Ti4O9[001] direction along nanorod length
Direction growth, H2Ti4O9[010] direction along nanometer rods width direction grow.Form H2Ti4O9/BaTiO3After complex,
The nanorod surfaces of 0.6BT-100 are no longer smooth (Fig. 6 e), and H can not only be found on HRTEM image2Ti4O9Lattice item
Line, also it can be found that BaTiO3(110) lattice fringe (Fig. 6 f, g) of crystal face.In conjunction with selective electron diffraction style (figure at this time
Can 6h) it know, the H at 100 DEG C2Ti4O9/BaTiO3Complex has been formed, and BaTiO3[100], [010] direction is distinguished
With H2Ti4O9[001], [010] direction is consistent.When obtaining 0.6BT-150, H2Ti4O9More coarse (the figure in the surface of matrix
6i), one group of H can only be found on HRTEM image2Ti4O9Lattice fringe (Fig. 6 j, k), in diffraction pattern (Fig. 6 l),
BaTiO3With H2Ti4O9It maintains and the consistent relationship of 0.6BT-100.It is possible thereby to learn, H2Ti4O9/BaTiO3Complex exists
In forming process, H2Ti4O9/BaTiO3Complex and H2Ti4O9Maintain certain topological relation.H2Ti4O9/BaTiO3It is compound
The formation of body follows topology Jie and sees transition mechanisms.As 0.6BT-150 and 0.1mol/L Sr (OH)2Second is carried out at 200 DEG C
After walking hydro-thermal reaction, dentation crystal grain is arranged in matrix (Fig. 7 a).In the HRTEM image of 0.6BT-0.1ST-150-200
In, the lattice fringe of BT and ST respectively appear in the two sides of crystal boundary, crystal boundary can be used as between two-phase boundary line (Fig. 7 b,
c).In addition to this, it can be found that the lattice fringe that spacing is 3.58 corresponds to H2Ti4O9(011) crystal face (Fig. 7 b).BT/ST and
H2Ti4O9Coexist it is existing to (Fig. 6 d) consistent with the XRD spectrum of 0.6BT-0.1ST-150-200.Belong to H2Ti4O9Diffraction
Spot is equally also difficult to find in corresponding favored area electron diffraction pattern, only occurs a small amount of H on style2Ti4O9004 spreads out
Penetrate spot.Other reciprocal points in the style are then respectively belonging to BT and ST (Fig. 7 d).The phase isomorphous having due to cubic phase ST
Lattice constantTherefore the length direction in the plane along rod-type matrices is defined as ST [100], separately
One direction definition is ST [010] to further discriminate between the relationship between ST the and BT direction of growth.That is, 0.6BT-
ST crystal growth direction in 0.1ST-150-200 is identical as the direction of BT.Since two groups of crystal zone axis are BT [001] and ST
[001], [100] direction ST is close to BT [100] direction, and [010] direction ST is close to BT [010] direction.Meanwhile BT structure cell is always
With ST structure cell at 4 ° of angles (Fig. 7 d).When the raw material that 0.6BT-200 is used as second step hydro-thermal reaction is nano combined to synthesize BT/ST
When material, the presence of H2TI4O9 phase is no longer found in BT/ST nano complex.In figure 7e, 0.6BT-0.1ST-200-150
The significant crystallite dimension less than in 0.6BT-0.1ST-150-200 of crystallite dimension.The complex obtained at this time, in its correspondence
HRTEM image in can not find the lattice fringe for belonging to H2TI4O9.From HRETM it can be observed that BT (200), BT
(110), (200) ST, ST (110), the spacing of lattice of ST (100) are respectively 2.01,2.82-2.89,1.94,2.75-2.77,(Fig. 7 f, g).Crystal boundary equally as the boundary distinguished between BT and ST, separates the lattice fringe of two kinds of crystal.Crystal
Growth causes the thickness of matrix stick to increase, prevent electron beam is when carrying out electronic diffraction from providing gem-pure point diffraction
Feedback.However, diffraction pattern provides the point diffraction for being enough to feed back the growth relationship between BT and ST crystal.0.6BT-0.1ST-
The SAED style of 200-150 will BT [001] and ST [001] be assigned as its crystal zone axis (Fig. 7 h).Belong to BT and the ST not isomorphous
The reciprocal point in face is determined separately.[100] direction ST is in 4 ° of angles close to BT [100] direction, and ST [010] direction is close to BT
[010] direction is equally in 4 ° of angles.Therefore, 0.6BT-0.1ST-200-150 and 0.6BT-0.1ST-150-200 maintains phase
Same growth relationship.Occur being received by the rodlike BT/ST that more fine grain forms on the TEM photo of 0.6BT-0.1ST-200-200
Rice complex (Fig. 7 i).Clearer crystal boundary serves as interval to distinguish BT and ST crystal.The lattice fringe of both crystal can be with
It is found in HRTEM image j and k.Similarly the growth rhythm of BT and ST also (scheme in 0.6BT-0.1ST-200-200 by discovery
7l).In conjunction with the diffraction flower of 0.6BT-0.1ST-150-200,0.6BT-0.1ST-200-150 and 0.6BT-0.1ST-200-200
The growth pattern of BT/ST nano complex (Fig. 7 d, h and can l) be summarized as follows by sample.BT/ST is by BT polycrystalline and ST polycrystalline
The nano complex of composition.This nano complex being made of polycrystalline has monocrystalline style on selective electron diffraction style
Pattern.Show BT polycrystal with identical oriented growth, and ST polycrystal is also according to their oriented growth.Show BT/
ST is a kind of nano combined Jie's sight crystal.It is interesting that not only being maintained consistent with matrix with the growth of BT and ST crystal
Form, and BT and ST crystal growth also have certain regularity.ST [100] direction is always to maintain and BT [100] side
It is grown up to 4 ° of side, and ST [010] direction also keeps growing up with the side in 4 ° of BT [010] direction.This 4 ° of angles are
Caused by the lattice mismatch due to caused by BT and ST different cell parameters.The growth mechanism of BT and ST can be summarized briefly
Are as follows: BT and ST is grown on identical a axis, b axis and c-axis.Using the c-axis of BT and ST as crystal zone axis, a axis is always along stick base
The length of matter, and b axis is always along H2Ti4O9The width of matrix.In conjunction with from H2Ti4O9To H2Ti4O9Nano combined Jie of/BT sees
The Forming Mechanism of crystal, from H2Ti4O9It is that one kind is opened up that monocrystalline, which sees two step hydrothermal reaction process of crystal to nano combined Jie of BT/ST,
It flutters chemistry Jie's sight and shifts to new management mechanisms (Fig. 1).
In 0.8BT-0.1ST-200-200, the surface (Fig. 8 a) of finer and close crystal covering matrix leads to only BT
(110) lattice fringe of the lattice fringe of crystal face and ST (110) crystal face can be found (Fig. 8 b, c) on its HRTEM image.It sees
Two groups of point diffractions in [001] direction BT and ST [001] direction are examined as crystal zone axis, BT (400), BT (1-10), ST (400) and ST
The reciprocal point of (1-10) appears on SAED style (Fig. 8 d).[100] direction BT and the direction [1-10] BT and corresponding ST crystal
Orientation keeps 4 ° of angle.This phenomenon is consistent with BT/ST Forming Mechanism.BT and ST based on 0.6BT-0.1ST-200-200
The very close reason of phase component content, randomly chooses one of rod-like polycrystal to analyze its Elemental redistribution.Unfortunately,
Due to the bombardment of electron beam, the bar-like polycrystal by energy affect is destroyed (Fig. 8 e) in the lower left corner by proximal end.So
And can visually see from its EDS Surface scan result, the element of Ba present in BT/ST, Sr, Ti and O are evenly distributed
In the different location of stick.Should the result shows that, the BT and ST of crystalline substance BT/ST nanocomposite are evenly distributed on entire stick in composition
On, rather than BT and ST concentrate on some position of matrix.It further illustrates different by two step hydro-thermal reactions building BT and ST
The strategy of matter epitaxial interface is feasible.Also illustrate at the same time, cited scheme is equally applicable to BT/ST nanometers in table
The controllable preparation of the compound sight crystal that is situated between.
Embodiment 2:BaTiO3/SrTiO3The preparation of the nano combined sight crystal 0.8BT-0.1ST-200-200 that is situated between
Weigh 0.0500g metatitanic acid monocrystalline (H2Ti4O9), barium hydroxide (Ba is weighed according to Ti:Ba molar ratio 1:0.8
(OH)2·8H2O) 0.1236g is added in 50mL ptfe autoclave, and 30mL water is added, after mixing in being contrary
Answer 200 DEG C of reaction 12h in device.After completion of the reaction, product is filtered, is impregnated for 24 hours, is filtered with 0.5mol/L acetic acid (HAc) solution
And washed with massive laundering, in 50 DEG C of dryings of air dry oven.Above-mentioned dry products 0.05g is weighed, 50mL polytetrafluoroethylene (PTFE) is added
In reaction kettle, 30mL 0.1mol/L strontium hydroxide aqueous solution is added and is uniformly mixed, in 200 DEG C of reactions in homogeneous reactor
12h.After completion of the reaction, product is filtered, is impregnated for 24 hours with 0.5mol/L acetic acid (HAc) solution, filters and washed with massive laundering,
In 50 DEG C of dryings of air dry oven.
Interpretation of result: the product X RD map such as Fig. 3 (i) synthesized under above-mentioned condition, appearance is obvious in figure, position difference
With BaTiO3(ICDD NO.31-0174)、SrTiO3(ICDD NO.74-1296) is corresponding, and whole XRD spectrum is without other peaks,
The substance for illustrating synthesis is BaTiO3、SrTiO3.By comparing the integral area of appearance, it can be deduced that BaTiO3Phase and SrTiO3
Phase integral area ratio is 0.45:0.55.The example is prepared shown in sample topography such as Fig. 5 (e), and sample still maintains one-dimensional rod-like
Pattern, surface microstructure are neatly arranged.By transmission electron microscope (Fig. 8 (a)) to the product and high-resolution-ration transmission electric-lens (Fig. 8 (b),
(c)) it is analyzed, it is obvious that being respectively present on the same one-dimensional ribbon samples surface with a crystal boundary two sides
BaTiO3(110) crystal face and SrTiO3(110) crystal face.The analysis of power spectrum Surface scan, Ba element and Sr element have been carried out to the sample
It is evenly distributed on the one-dimensional ribbon samples of Fig. 8 (e) presentation.The above result shows that prepared sample is one-dimensional BaTiO3/SrTiO3
Complex, which is situated between, sees crystal.
Embodiment 3:BaTiO3/SrTiO3The preparation of the nano combined sight crystal 0.6BT-0.1ST-200-150 that is situated between
Weigh 0.0500g metatitanic acid monocrystalline (H2Ti4O9), barium hydroxide (Ba is weighed according to Ti:Ba molar ratio 1:0.6 respectively
(OH)2·8H2O) 0.1063g is added in 50mL ptfe autoclave, and 30mL water is added, after mixing in being contrary
Answer 200 DEG C of reaction 12h in device.After completion of the reaction, product is filtered, is impregnated for 24 hours, is filtered with 0.5mol/L acetic acid (HAc) solution
And washed with massive laundering, in 50 DEG C of dryings of air dry oven.Above-mentioned dry products 0.05g is weighed, 50mL polytetrafluoroethylene (PTFE) is added
In reaction kettle, 30mL 0.1mol/L strontium hydroxide aqueous solution is added and is uniformly mixed, in 150 DEG C of reactions in homogeneous reactor
12h.After completion of the reaction, product is filtered, is impregnated for 24 hours with 0.5mol/L acetic acid (HAc) solution, filters and washed with massive laundering,
In 50 DEG C of dryings of air dry oven.
Interpretation of result: the product X RD map such as Fig. 3 (f) synthesized under above-mentioned condition, appearance is sharply obvious in figure, position
And appearance situation is same as Example 2, respectively with BaTiO3(ICDD NO.31-0174)、SrTiO3(ICDD NO. 74-
1296) corresponding, and whole XRD spectrum illustrates that the substance of synthesis is BaTiO without other peaks3、SrTiO3.By comparing appearance
Integral area, it can be deduced that BaTiO3Phase and SrTiO3Phase integral area ratio is 0.65:0.35.The example prepares sample topography such as
Shown in Fig. 4 (e), sample still maintains one-dimensional rod-like pattern, and surface microstructure is neatly arranged.The above result shows that prepared sample
For one-dimensional Ba0.6TiO3/Sr0.4TiO3Complex, which is situated between, sees crystal.
Embodiment 4:BaTiO3/SrTiO3The performance test of the nano combined sight crystal that is situated between
0.6BT-0.1ST-200-150,0.6BT-0.1ST-200-200,0.7BT-0.1ST-200- 200 and 0.8BT-
0.1ST-200-200 is tested under contact mode using SPM, they AFM still it is lower keep rod-like morphology (Fig. 9 a, d,
G, j).However, nano combined Jie of the BT/ST with piezoelectric effect probed into sees crystal reflection under the influence of needle point effect
Big morphology and size.0.6BT-0.1ST-200-150 shows three rod-like samples presented side by side, and afm image is shown
Its single stick width is 450nm and thickness is 818.8nm (Fig. 9 a, b).But it is only 300nm (figure that SEM image, which feeds back the Sample Width,
5a).In its 3D afm image (Fig. 9 b), show that the sample is made of the nanocrystal of ordered arrangement again.Pass through PFM
The piezoelectricity curve (Fig. 9 c) for obtaining 0.6BT-0.1ST-200-150, unlike standard butterfly curve, the piezoelectricity of the sample
Force-responsive curve actually shows broader butterfly's wing.The reason of generating this phenomenon is somebody's turn to do when obtaining piezoelectric signal
Under the conditions of the BT/ST that obtains it is nano combined be situated between to see crystal and generated by the bias that probe applies resonate, due to being dispersed in golden plate
Powder keep lightweight and small contact area, therefore caused by they are not easy to be fixed in golden plate.The result shows that
0.6BT-0.1ST-200-150 shows d on its butterfly curve33*=629.69pm/V signal strength.0.6BT-
The thickness of 0.1ST-200-200 about 1.45 μm of display in AFM altitude signal image (Fig. 9 d), in 3D afm image (Fig. 9 e)
The width of middle about 1.5 μm of display, its width is only 500nm (Fig. 5 b) in SEM image.Similarly, 0.6BT-0.1ST-200-
200 piezoelectricity curve keeps shape similar with the curve in 0.6BT-0.1ST-200-150.Curve explanation by apply ±
It is d that the 0.6BT-0.1ST-200-200 that the bias of 8V completes circulation, which provides its piezoelectric response result,33*=623.95pm/V
(Fig. 9 f).0.7BT-0.1ST-200-200 shows biggish landform dimensional discrepancy on afm image.AFM height sensor figure
As (Fig. 9 g) and 3D afm image (Fig. 9 h) show that its thickness and width respectively may be about 1.68 μm and 2.68 μm, but SEM figure
It is only about 400nm (Fig. 5 c) as characterizing its width, and as can be seen that the Sample Width and thickness are almost from its SEM image
Uniformly (Fig. 5 d).Piezoelectric forces response signal shows biggish improvement on 0.7BT-0.1ST-200-200 curve, catches
D is obtained33*=772.14pm/V result (Fig. 9 i).Maximum pressure is had found on the sample of 0.8BT-0.1ST-200-200
Electroresponse and sample size difference.It shows 1.4 μm of thickness (Fig. 9 j) and 2.9 μm of width (Fig. 9 k), in SEM
It can be found that the width (Fig. 5 e) of about 400nm in image.It shows d under the bias of application ± 10V33*=866.79pm/V
(Fig. 9 l), this is also the highest d reported so far33* the BT/ST nanocomposite being worth.
Claims (7)
1. a kind of one-dimensional BaTiO3/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, which is characterized in that including as follows
Step:
(1) preparation of HTO/BT complex: metatitanic acid monocrystalline H is weighed2Ti4O9, according to Ti:Ba molar ratio 1:(0.6-0.8) and weigh hydrogen
Barium monoxide is separately added into reaction kettle, and water is then added, after mixing in 120-200 DEG C of reaction 8-16h, after completion of the reaction,
Product is filtered, 18-30h is impregnated with 0.3-0.6mol/L acetum, filters and be washed with water, it is dry, it is compound to obtain HTO/BT
Body；
(2)BaTiO3/SrTiO3The controllable preparation of the nano combined sight crystal that is situated between: taking HTO/BT complex to be added in reaction kettle, according to
Ti:Sr molar ratio 1:(6-30) strontium hydroxide aqueous solution is added and is uniformly mixed, in 120-200 DEG C of reaction 8-16h, end of reaction
Afterwards, product is filtered, impregnates 18-30h with 0.3-0.6mol/L acetum, filters and be washed with water, it is dry, obtain BaTiO3/
SrTiO3Nano combined Jie sees crystal.
2. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is that reaction kettle described in step (1) and step (2) is ptfe autoclave.
3. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is, dry operating procedure in step (1) and step (2) are as follows: in 45-53 DEG C of drying of air dry oven.
4. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is that reaction temperature is 150-200 DEG C in step (1), and the reaction time is preferably 11-13h.
5. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is, according to Ti:Sr molar ratio 1:(6-12 in step (2)) strontium hydroxide aqueous solution is added and reacts after mixing.
6. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is that reaction temperature is 150-200 DEG C in step (2), reaction time 11-13h.
7. one-dimensional BaTiO according to claim 13/SrTiO3The controllable method for preparing of the nano combined sight crystal that is situated between, it is special
Sign is that strontium hydroxide concentration of aqueous solution described in step (2) is 0.1-0.6mol/L.
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