CN102176355B - Nano Ag particle-(Pb0.4Sr0.6)TiO3 solid solution seepage-type composite ceramic film and preparation method thereof - Google Patents
Nano Ag particle-(Pb0.4Sr0.6)TiO3 solid solution seepage-type composite ceramic film and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000006104 solid solution Substances 0.000 title claims abstract description 14
- 229910010252 TiO3 Inorganic materials 0.000 title abstract 3
- 239000002131 composite material Substances 0.000 title abstract 2
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000003618 dip coating Methods 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 126
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 75
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 42
- 229910052712 strontium Inorganic materials 0.000 claims description 41
- 229910052745 lead Inorganic materials 0.000 claims description 34
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 32
- 239000012046 mixed solvent Substances 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 32
- 239000012298 atmosphere Substances 0.000 claims description 27
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 18
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 238000005352 clarification Methods 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims 1
- KHKWDWDCSNXIBH-UHFFFAOYSA-N [Sr].[Pb] Chemical compound [Sr].[Pb] KHKWDWDCSNXIBH-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 101
- 239000010936 titanium Substances 0.000 description 60
- 239000000463 material Substances 0.000 description 13
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 239000008139 complexing agent Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- ZNTCKLQPLHRPNT-UHFFFAOYSA-N [Ti][Pb][Ag] Chemical class [Ti][Pb][Ag] ZNTCKLQPLHRPNT-UHFFFAOYSA-N 0.000 description 2
- -1 due to Sr 2+ Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- MQALHUDBQYJXKL-UHFFFAOYSA-N C(C(O)C)(=O)O.[O] Chemical compound C(C(O)C)(=O)O.[O] MQALHUDBQYJXKL-UHFFFAOYSA-N 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000005284 basis set Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003437 strontium Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Abstract
The invention discloses a nano Ag particle-(Pb0.4Sr0.6)TiO3 solid solution seepage-type composite ceramic film and a preparation method thereof. The substrate of the ceramic film is polycrystalline perovskite phase ceramics in which nano silver particles scatter. The polycrystalline perovskite phase ceramics is Pb0.4Sr0.6TiO3 and the mol ratio of nano silver to Pb0.4Sr0.6TiO3 is 0.3-0.8:1. The preparation method comprises the following steps: successfully preparing an required sol precursor containing a Ag-Pb-Sr-Ti source; coating on an ITO (indium tin oxide)/glass substrate by a dip-coating method; and sintering in the air to prepare the film. By the method disclosed by the invention, a small-scale nano particle can be prepared by heat treatment in the air and the dispersity of the nano particle in the (Pb0.4Sr0.6)TiO3 film can be ensured, the seepage effect is realized. The permittivity of the film is 2 to 5 times that of apure strontium lead titanate film.
Description
Technical field
The invention belongs to the dielectric film technical field, relate to a kind of seepage flow type solid solution/silver-colored ceramic thin sheet (Pb, Sr) TiO
3-Ag
xThe preparation method.
Background technology
Dielectric film material becomes an important research focus in the fields such as microelectronics, material science and solid state physics gradually in recent years, and thin dielectric film is widely used at microelectronic.
Strontium titanates, lead titanates are two kinds of typical dielectric substances, due to Sr
2+, Pb
2+Radius be more or less the same, be respectively 0.113nm, 0.120nm, strontium titanates and lead titanates can generate continuous solid solution (Pb
1-xSr
x) TiO
3, wherein x represents the wherein molar fraction of strontium.And the different PST that form, character can change regularly with the variation of Pb/Sr, its Curie-point temperature T
cThe linear reduction with the reduction of Pb/Sr, so the Curie temperature of PST, the temperature when being also ferroelectric phase and paraelectric phase generation transformation can be controlled by adjusting the Pb/Sr ratio according to the needs of practical application.(Pb
1-xSr
x) TiO
3Be a kind of typical dielectric material with adjustable, have superior dielectric adjustable.The phenomenon that the dielectric constant that so-called dielectric is adjustable refers to material reduces with the increase of extra electric field, it changes, and greatly dielectric adjustable is better.And when this material is used for tunable microwave device, for fear of the intrinsic dielectric hysteresis of ferroelectric phase with make the loss of material less, common value when all controlling composition is close to paraelectric phase.Also namely when fabricate devices, generally all select Curie temperature close to the ferroelectric material of serviceability temperature.Therefore, utilize (Pb
1-xSr
x) TiO
3Curie temperature can arbitrarily change these characteristics by adjusting Pb/Sr, in conjunction with its superior tunable characteristic, make (Pb
1-xSr
x) TiO
3Huge at numerous areas application potentials such as dynamic random access memory, Nonvolatile ferroelectric memory and tunable microwave devices.In addition, (Pb
1-xSr
x) TiO
3Ferroelectric critical size less, crystallization temperature is low, preparation technology is easily compatible with the Si microelectronic technique, more can satisfy the needs that high-performance Si basis set becomes circuit, develops tool to miniaturization and integrated direction and is of great significance promoting modern device.
In recent years, electronic device is more and more higher to the requirement of miniaturization and high performance, and how obtaining more high performance dielectric film material has become numerous scientific workers target of effort for it.Seep effect is proved to be one of means that effectively improve material dielectric constant.Know, to thin-film material, reach nanoscale and make its content reach percolation threshold by the particle diameter of controlling the Metal Phase in film and could obtain seep effect, also namely obtain the high dielectric constant film material.Based on this thought, utilize the sol-gal process original position to form the method for nanometer metallic silver particle, the big first-class of shutting out has realized seep effect in single lead titanates film, and has applied for Chinese patent ZL200710068236.9.Yet as above-mentioned, the Curie temperature of lead titanates is 485
oC at room temperature, exists with tetragonal phase structure, and temperature will be increased to 485
oThe transformation of Tetragonal-Emission in Cubic just appears in the C left and right.Because this material Curie temperature is very high, obviously will be away from Curie temperature when using under normal room temperature, also namely usually can only be as the materials'use with good ferroelectric phase characteristic, at this moment intrinsic dielectric hysteresis and the dielectric loss of ferroelectric phase all can be apparent in view.Moreover there is not dielectric adjustable substantially in lead titanates film itself yet, has limited this silver-titanium lead plumbate seepage flow type film in the application in the adjustable field of dielectric.And at tuning microwave device field strontium lead titanate solid solution membrane more with potential applications, if select Curie temperature to form at the film of near room temperature, and introduce therein seep effect, further improve performance, improve dielectric constant, will open up dielectric phase/Metal Phase seepage flow type laminated film in the new application in tuning microwave field, greatly expand the range of application of seepage flow type laminated film.
Know, in patent ZL200710068236.9, to use sol-gel process, by introducing complexing agent citric acid and lactic acid in sol system, and after wet film is heat-treated in steam and hydrogen mixing reducing atmosphere, formation contains the seepage flow type silver-titanium lead plumbate laminated film of nano-Ag particles.This relative production cost of technique that nano-Ag particles is incorporated in film is higher, and to deposit coefficient of safety low for hydrogen in the production of reality; Moreover Technology for Heating Processing is loaded down with trivial details, and production efficiency is also relatively low.Therefore the problem of oxidation that is necessary silver in the solution system must just can prepare the difficult problem of Nano Silver by reducing atmosphere to simplify.
Summary of the invention
The object of the present invention is to provide a kind of nanometer Ag particle-(Pb
0.4Sr
0.6) TiO
3Solid solution seepage flow type ceramic thin sheet reaches the method for this film of preparation in air atmosphere.
For achieving the above object, the technical solution used in the present invention is: this nanometer Ag particle-(Pb
0.4Sr
0.6) TiO
3Solid solution seepage flow type ceramic thin sheet is characterized in that: this ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3, described Nano Silver and Pb
0.4Sr
0.6TiO
3Mol ratio be 0.3～0.8:1.
Nanometer Ag particle of the present invention-(Pb
0.4Sr
0.6) TiO
3The preparation method of solid solution seepage flow type ceramic thin sheet comprises the steps:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.5～1:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.3～0.6:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.3～0.8:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.3～0.8:1;
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol;
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, applies altogether more than 4 layers; And after every coating one deck, first with wet film under infrared lamp dry 15 minutes, then in Muffle furnace 520
oC～600
oUnder C and air atmosphere, calcining obtains dry film and at room temperature cooling; At last, with the gained film 520
oC～600
oUnder C and air atmosphere, heat treatment is 2～4 hours, obtains (Pb
0.4Sr
0.6) TiO
3-Ag
xLaminated film, wherein, x=0.3～0.8.
Just must can avoid the difficult problem of silver-colored oxidation in system by reducing atmosphere heat treatment in order to solve, the present invention first uses complexing agent with silver Uniform Dispersion in colloidal sol, and complexing is preserved in the sol-gel conversion process.In the film thermal processing procedure, the oxygen that organic substance decomposing consumption is a large amount of, the reducing environment of formation anoxic in the thin film micro-zone scope make silver by in-situ reducing, and silver-colored grain diameter is controlled.In addition, the dielectric film matrix that the present invention adopts is the dielectric adjustable thin film strontium lead titanate, and composition is more complicated, and will obtain the sol precursor of Ag-PST laminated film, will solve the problem of dissolving each other of the various raw material metals such as lead, strontium, silver, titanium.The present invention adopts EGME and two kinds of solvents of ethylene glycol, the use of solvent pairs solved this strontium, lead, titanium, silver-colored complex system can't be in a system dissolving simultaneously form the difficult problem of even sol system, especially solved strontium, the silver difficult problem of dissolving simultaneously in the system.Further, ZL200710068236.9 compares with patent, another kind and silver ion complexation ability are stronger, when calcining fully, oxygen consumed is the complexing agent of two times of lactic acid oxygen demand by utilizing in the present invention---and the acetylacetone,2,4-pentanedione complexing agent replaces Lactic Acid as Complexing Agent, form reducing environment when film is calcined in the air atmosphere stove like this in the microcell scope, having solved needs to process the difficult problem that could prepare the Nano Silver laminated film under reducing atmosphere; Stronger complexing power has guaranteed that silver ion is not easy to grow up early occuring to reunite simultaneously, thereby the content of Nano Silver in film and particle diameter successfully are under control, successfully at this continuous solid solution (Pb
1-xSr
x) TiO
3Realized seep effect in film.
The nanometer Ag particle PbTiO for preparing under this use solvent pairs of the present invention, two complexing agent and air atmosphere
3-SrTiO
3The method of solid solution complex phase ceramic film, not only its preparation method no longer is subjected to heat treated constraint under strict reducing atmosphere, can successfully control in solid solution membrane in air atmosphere and introduce particle diameter is the metallic silver particles of several nanometers, saved widely cost, improved coefficient of safety and simplified preparation technology; But also the content that can successfully control nano-Ag particles is at continuous solid solution (Pb
1-xSr
x) TiO
3Realize seep effect in film, obtained high-k (Pb
1-xSr
x) TiO
3Film, the application of having opened up the seepage flow type new film.
Compared with prior art, the beneficial effect that has of the present invention is: the present invention has successfully solved the preparation of the required sol precursor of film and controlled a difficult problem that forms a large amount of nanometer metallic silver particles under air atmosphere in film.Solvent pairs EGME and ethylene glycol double solvents have dissolved alkoxide and the inorganic salts of various metals, have solved the difficult problem of Ag-(Pb, Sr)-Ti colloidal sol preparation.And citric acid and acetylacetone,2,4-pentanedione compound complex agent play the effect of two aspects: the one side citric acid is complexing Pb-Ti-O network and Ag well
+Ion makes Ag
+Degree of scatter is very high in colloidal sol, and complexing preserves in sol-gel transforms, and makes Ag evenly distribution in film matrix, has prevented Ag ion quick and extensive reunion and the formation bulky grain in heat treatment process, has controlled well its size; Citric acid and the acetylacetone,2,4-pentanedione more oxygen of relative consumption when thermal decomposition on the other hand, reducing environment in the microcell subrange can be provided when calcining, stop Ag oxidized, therefore can heat-treat in air atmosphere and obtain simple substance silver particle, and obtained particle diameter and only be the silver-colored particle of several nanometers, thereby the standby seepage flow type Pb that obtained
0.4Sr
0.6TiO
3-Ag
xLaminated film.And the Ag/Ti mol ratio is that the dielectric constant of 0.3～0.8 film is all higher than pure (Pb
0.4Sr
0.6) TiO
3Film is 2～5 times of pure PST thin-film material, and the dielectric constant that mol ratio is 0.7 film is single-phase (Pb
0.4Sr
0.6) TiO
3Nearly 5 times of thin-film dielectric constant.In addition, the present invention also provides a kind of new method of introducing evengranular nano-metal particle in thin dielectric film, and thin film technology technique is simple, is convenient to suitability for industrialized production, has good market prospects.
Description of drawings
Fig. 1 is the Pb that embodiment 1 prepares
0.4Sr
0.6TiO
3-Ag
0.6The XRD collection of illustrative plates of ceramic thin sheet;
Fig. 2 is the Pb that embodiment 1 prepares
0.4Sr
0.6TiO
3-Ag
0.6The uv-visible absorption spectra figure of ceramic thin sheet;
Fig. 3 is the Pb that embodiment 1 prepares
0.4Sr
0.6TiO
3-Ag
0.6The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Fig. 4 is the Pb that embodiment 2 prepares
0.4Sr
0.6TiO
3-Ag
0.7The XRD collection of illustrative plates of ceramic thin sheet;
Fig. 5 is the Pb that embodiment 2 prepares
0.4Sr
0.6TiO
3-Ag
0.7The uv-visible absorption spectra figure of ceramic thin sheet;
Fig. 6 is the Pb that embodiment 2 prepares
0.4Sr
0.6TiO
3-Ag
0.7The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Fig. 7 is the Pb that embodiment 3 prepares
0.4Sr
0.6TiO
3-Ag
0.8The XRD collection of illustrative plates of ceramic thin sheet;
Fig. 8 is the Pb that embodiment 3 prepares
0.4Sr
0.6TiO
3-Ag
0.8The uv-visible absorption spectra figure of ceramic thin sheet;
Fig. 9 is the Pb that embodiment 3 prepares
0.4Sr
0.6TiO
3-Ag
0.8The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Figure 10 is the Pb that embodiment 4 prepares
0.4Sr
0.6TiO
3-Ag
0.3The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Figure 11 is the Pb that embodiment 5 prepares
0.4Sr
0.6TiO
3-Ag
0.5The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Figure 12 is the Pb that embodiment 6 prepares
0.4Sr
0.6TiO
3-Ag
0.8The electric capacity of ceramic thin sheet (dielectric constant) is with the frequency change collection of illustrative plates;
Embodiment
In following examples, the dielectric constant of film can adopt the plate condenser model to be calculated as follows:
Wherein,
CBe the capacitance that test obtains, unit is F, ε
0=8.853 * 10
-12F/m, ε
rBe relative dielectric constant, dimensionless is permittivity of vacuum,
SBe the top electrode area,
dThickness for film.Because the thickness of the film for preparing is basic identical, and the area of electrode is also identical, so electric capacity is directly proportional to relative dielectric constant, the variation of electric capacity can show the variation of dielectric constant indirectly, therefore the variation of dielectric constant can replace with capacitance variations.
Embodiment 1:Pb
0.4Sr
0.6TiO
3-Ag
0.6The preparation of laminated film
Concrete preparation is carried out as follows:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.5:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.5:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.5:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.6:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol.
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, applies altogether 4 layers; And after every coating one deck, first that wet film is dry under infrared lamp, then in Muffle furnace 600
oUnder C and air atmosphere, calcining is 10 minutes, obtains dry film and at room temperature cooling; At last, with the gained film 600
oUnder C and air atmosphere, heat treatment is 2 hours, obtains (Pb
0.4Sr
0.6) TiO
3-Ag laminated film.
As shown in Figures 1 and 2, this ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Fig. 3 electric capacity frequency spectrum as seen, in low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably about 10 pF, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.6The electric capacity of laminated film is the 25pF left and right.In whole test spectral range, the purer strontium lead titanate film of film of introducing Nano Silver exceeds more than 2 times.
Embodiment 2:Pb
0.4Sr
0.6TiO
3-Ag
0.7The preparation of laminated film
Concrete preparation is carried out as follows:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.3:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.6:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.6:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.7:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol.
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, and is first that wet film is dry under infrared lamp after every coating one deck, then in Muffle furnace 600
oUnder C and air atmosphere, calcining is 10 minutes; After coating is completed, then with the gained film 600
oUnder C and air atmosphere, heat treatment is 3 hours, obtains (the Pb of four layers
0.4Sr
0.6) TiO
3-Ag
0.7Laminated film.
As Fig. 4 and shown in Figure 5, this ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Fig. 6 electric capacity frequency spectrum as seen, in whole test spectral range, (Pb
0.4Sr
0.6) TiO
3-Ag
07High nearly 2～5 times of the purer strontium lead titanate film of the electric capacity of laminated film.In low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably about 10 pF, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.7The electric capacity of laminated film is the 50pF left and right.And at high band, (Pb
0.4Sr
0.6) TiO
3-Ag
07The electric capacity of film also exceeds pure strontium lead titanate film 3 times of left and right.
Embodiment 3:Pb
0.4Sr
0.6TiO
3-Ag
0.8The preparation of laminated film
Concrete preparation is carried out as follows:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.8:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.4:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.3:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.8:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol.
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, and is first that wet film is dry under infrared lamp after every coating one deck, then in Muffle furnace 600
oUnder C and air atmosphere, calcining is 10 minutes; After coating is completed, then with the gained film 600
oUnder C and air atmosphere, heat treatment is 4 hours, obtains (the Pb of four layers
0.4Sr
0.6) TiO
3-Ag
0.8Laminated film.
As shown in Figures 7 and 8, this ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Fig. 9 electric capacity frequency spectrum as seen, in whole test spectral range, (Pb
0.4Sr
0.6) TiO
3-Ag
08High nearly 2～5 times of the purer strontium lead titanate film of the electric capacity of laminated film.In low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably about 10 pF, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.8The electric capacity of laminated film is higher than 50pF.And at high band, (Pb
0.4Sr
0.6) TiO
3-Ag
07The electric capacity of film also exceeds pure strontium lead titanate film 2～3 times of left and right.
Embodiment 4:Pb
0.4Sr
0.6TiO
3-Ag
0.3The preparation of laminated film
Concrete preparation is carried out as follows:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.3:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.4:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.8:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.3:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol.
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, applies altogether 4 layers; And after every coating one deck, first that wet film is dry under infrared lamp, then in Muffle furnace 560
oUnder C and air atmosphere, calcining is 10 minutes; At last, with the gained film 560
oUnder C and air atmosphere, heat treatment is 3 hours, obtains (Pb
0.4Sr
0.6) TiO
3-Ag
0.3Laminated film.This ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Figure 10 electric capacity frequency spectrum as seen, in low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably about 7 pF, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.3The electric capacity of laminated film is the 16pF left and right.The purer strontium lead titanate film of film of introducing Nano Silver in whole test spectral range exceeds more than 2 times.
Embodiment 5
In experiment, system is Pb
0.4Sr
0.6TiO
3-Ag
0.5, preparation amount of substance concentration is the colloidal sol of 0.2mol/L.
(1) add Pb (CH in the mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 1:1;
First add red fuming nitric acid (RFNA) and citric acid in the mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.3:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.3:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.5:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol;
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, and is first that wet film is dry under infrared lamp after every coating one deck, then in Muffle furnace 520
oUnder the C air atmosphere, calcining is 10 minutes; After coating is completed, then with the gained film 520
oUnder the C air atmosphere, heat treatment is 4 hours, obtains (the Pb of four layers
0.4Sr
0.6) TiO
3-Ag
0.5Laminated film.This ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Figure 11 electric capacity frequency spectrum as seen, in low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably the 6pF left and right, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.5The electric capacity of laminated film is the 18pF left and right.In whole test spectral range, although two kinds of different electric capacity that form film all decrease, the purer strontium lead titanate film of film of introducing Nano Silver still exceeds 3 times of left and right.
Embodiment 6:Pb
0.4Sr
0.6TiO
3-Ag
0.8The preparation of laminated film
Concrete preparation is carried out as follows:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.5:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.4:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.6:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.8:1.
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol.
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor.
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, applies altogether 4 layers; And after every coating one deck, first that wet film is dry under infrared lamp, then in Muffle furnace 520
oUnder C and air atmosphere, calcining is 10 minutes; At last, with the gained film 520
oUnder C and air atmosphere, heat treatment is 3 hours, obtains (Pb
0.4Sr
0.6) TiO
3-Ag.This ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3
By Figure 12 electric capacity frequency spectrum as seen, in low-frequency range, pure (Pb
0.4Sr
0.6) TiO
3The electric capacity of film is probably about 7 pF, and (Pb
0.4Sr
0.6) TiO
3-Ag
0.3The electric capacity of laminated film is the 21pF left and right.The purer strontium lead titanate film of film of introducing Nano Silver in whole test spectral range exceeds more than 2 times.
Claims (2)
1. nanometer Ag particle-(Pb
0.4Sr
0.6) TiO
3Solid solution seepage flow type ceramic thin sheet is characterized in that: this ceramic membrane is dispersed with nano-Ag particles take polycrystalline Perovskite Phase pottery as matrix and in this matrix, and described polycrystalline Perovskite Phase pottery is Pb
0.4Sr
0.6TiO
3, described Nano Silver and Pb
0.4Sr
0.6TiO
3Mol ratio be 0.3～0.8:1.
2. the nanometer Ag particle of a claim 1-(Pb
0.4Sr
0.6) TiO
3The preparation method of solid solution seepage flow type ceramic thin sheet is characterized in that, comprises the steps:
(1) add Pb (CH in the first mixed solvent of EGME and ethylene glycol
3COO)
23H
2O and Sr (NO
3)
2, and after heating for dissolving the cooling Pb-Sr solution that obtains, the volumetric ratio of described EGME and ethylene glycol is 7:3, Pb (CH
3COO)
23H
2O and Sr (NO
3)
2Mol ratio be 0.4:0.6;
First add acetylacetone,2,4-pentanedione in the second mixed solvent of EGME and ethylene glycol, after add again tetra-n-butyl titanate, blended under agitation obtains Ti colloidal sol, the mol ratio of described acetylacetone,2,4-pentanedione and tetra-n-butyl titanate is 0.5～1:1;
First add red fuming nitric acid (RFNA) and citric acid in the 3rd mixed solvent of EGME and ethylene glycol, then add silver nitrate, be stirred to dissolving and obtain Ag colloidal sol, the mol ratio of described red fuming nitric acid (RFNA) and described tetra-n-butyl titanate is 0.3～0.6:1, the mol ratio of described citric acid and described tetra-n-butyl titanate is 0.3～0.8:1, and the mol ratio of described silver nitrate and described tetra-n-butyl titanate is 0.3～0.8:1;
(2) described Ag colloidal sol is slowly joined in Ti colloidal sol mix, and stir and obtain Ag-Ti colloidal sol;
(3) Pb-Sr solution is added in Ag-Ti colloidal sol, stirring obtain orange-yellow transparent, stable, the clarification Ag-(Pb, Sr)-Ti colloidal sol precursor, again to Ag-(Pb, Sr) add the mixed solvent of EGME and ethylene glycol in-Ti colloidal sol precursor until obtain the Ag-(Pb, Sr) that concentration is 0.2mol/L-Ti colloidal sol precursor;
(4) utilize dip-coating method, the Ag-(Pb, Sr) that step (3) is finally obtained-Ti colloidal sol precursor is coated on the ITO/ glass substrate and obtains wet film, applies altogether more than 4 layers; And after every coating one deck, first that wet film is dry under infrared lamp, then in Muffle furnace 520
oC～600
oUnder C and air atmosphere, calcining obtained dry film and at room temperature cooling in 10 minutes; At last, with the gained film 520
oC～600
oUnder C and air atmosphere, annealing in process is 2～4 hours, obtains (Pb
0.4Sr
0.6) TiO
3-Ag
xLaminated film, wherein, x=0.3～0.8.
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| CN1951869A (en) * | 2006-11-14 | 2007-04-25 | 浙江大学 | Preparation method of highly magnesium-doped strontium plumbum titanate high dielectric adjustable film material |
| CN1974461A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Zn doped PST film with adjustable dielectric constant and its prepn process |
| CN101037329A (en) * | 2007-04-26 | 2007-09-19 | 浙江大学 | Seepage type Ag-PbTiO3 composite ceramic film and preparation method therefor |
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| CN1951869A (en) * | 2006-11-14 | 2007-04-25 | 浙江大学 | Preparation method of highly magnesium-doped strontium plumbum titanate high dielectric adjustable film material |
| CN1974461A (en) * | 2006-11-21 | 2007-06-06 | 浙江大学 | Zn doped PST film with adjustable dielectric constant and its prepn process |
| CN101037329A (en) * | 2007-04-26 | 2007-09-19 | 浙江大学 | Seepage type Ag-PbTiO3 composite ceramic film and preparation method therefor |
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