CN101717067A - Barium strontium titanate-porous silicon composite material and preparation method thereof - Google Patents
Barium strontium titanate-porous silicon composite material and preparation method thereof Download PDFInfo
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- CN101717067A CN101717067A CN200910114588A CN200910114588A CN101717067A CN 101717067 A CN101717067 A CN 101717067A CN 200910114588 A CN200910114588 A CN 200910114588A CN 200910114588 A CN200910114588 A CN 200910114588A CN 101717067 A CN101717067 A CN 101717067A
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Abstract
The invention discloses a barium strontium titanate-porous silicon composite material and a preparation method thereof. By adopting a spin coating technology, the preparation method compounds the ferroelectric material barium strontium titanate nano crystals to the porous silicon surface, thereby obtaining the barium strontium titanate-porous silicon composite material with adjustable microstructure, which has the advantages of favorable gas sensibility and photoelectric properties. The preparation method of the barium strontium titanate-porous silicon composite material is operated at room temperature and has the advantages of mild preparation conditions, simple technique, and easy and simple operation, and the repetition rate reaches 100%. The composite material has adjustable photoelectric properties and high gas sensibility.
Description
Technical field
The present invention relates to the technology of preparing of composite, specifically is barium strontium titanate and porous silicon composite material and preparation method thereof.
Background technology
The formation that the developing synthetic and the new purposes of material of new material tends to greatly to enrich the field of scientific research and drives new industry.Along with high-speed development of science and technology is intersected infiltration with interdisciplinary, a kind of material of single performance is difficult to satisfy the overall target of various high requests, and the research of functional composite material becomes the research focus in Materials Science and Engineering field.
Barium strontium titanate is owing to have special performances such as high-k, low-dielectric loss, low-leakage current density and high thermal stability, they are in many fields extensive application prospects such as dynamic randon access device, Infrared Detectors, sensor, adjustable microwave devices, but development along with electronic information technology, barium strontium titanate nano-powder material and nano bulk material can not satisfy its requirement aspect integrated technology, and barium strontium titanate is made high-quality film has become the task of top priority.In order to make it compatible mutually, be preferably in fabricate devices on the silicon substrate with integrated technology.Yet monocrystalline silicon is not a desirable backing material, it cause easily ferroelectric material and and silicon substrate between interfacial reaction, want in metal and ferroelectric and semiconductor (MFS) field effect transistor circuitry to obtain very difficulty of good ferroelectric and silicon interface.As everyone knows, lattice mismatch be barium strontium titanate on silicon-based substrate, be difficult to growth good one of reason because the lattice paprmeter of silicon is more much bigger than barium strontium titanate.
Summary of the invention
The objective of the invention is in order to solve barium strontium titanate and silicon heterostructure material lattice constant does not match, the problem of compound back photoelectric characteristic and gas-sensitive property difference, and a kind of porous feature that can either keep traditional porous silicon is provided, on yardstick, have the barium strontium titanate evident layer aggregated(particle) structure, that have high resistance, low substrate loss and the novel porous silicon substrate of low coupling effect and porous silicon composite material and preparation method thereof simultaneously again.
The preparation method of barium strontium titanate of the present invention and porous silicon composite material may further comprise the steps:
(1) preparation backing material porous silicon: the p type single crystal silicon sheet of resistivity 0.015 Ω cm is inserted autoclave, fill by concentration between the hydrofluoric acid (HF) of 8.00～22.00mol/l and the ferric nitrate (Fe (NO of 0.01～0.50mol/l
3)
3) corrosive liquid of solution composition, the liquor capacity compactedness of autoclave is 40～95%, in the corrosion 1 minute～36 hours down of 50～200 ℃ of temperature, promptly prepares the backing material porous silicon;
(2) preparation barium strontium titanate colloidal sol;
(3) barium strontium titanate colloidal sol is spin-coated on the porous silicon substrate of prepared fresh with sol evenning machine,, promptly obtains sensing, luminous and barium strontium titanate and porous silicon composite material that dielectric property is adjustable through annealing under 100～800 ℃ of temperature and the certain protective gas atmosphere.
The raw material of described preparation barium strontium titanate stable sol mainly contains barium acetate, strontium acetate, butyl titanate, acetylacetone,2,4-pentanedione, and its raw material proportioning (mol ratio) is: barium acetate: strontium acetate: butyl titanate: acetylacetone,2,4-pentanedione=0.7: 0.3: 1: 2.
The concentration of described barium strontium titanate colloidal sol is 0.001～1.0mol/L.
Described spin coating condition is: low speed is 400～2000 rev/mins, spin coating 1～20 second; High speed spin coating condition is 2000～6000 rev/mins, spin coating 10 seconds～1 minute.
Described protective gas is oxygen, nitrogen, argon gas, hydrogen or other inert gases.
The porous silicon substrate that the present invention selects for use have compare other silicon substrate structural advantages and the optical characteristics that can not compare: because this substrate belongs to typical micron and nanostructured compound system, its structure plyability is embodied on micron and two yardsticks of nanometer and has formed three clearly demarcated layer of structure; On micro-meter scale, porous silicon by a large amount of uniformly, silicon post fine separation, micron-scale is formed each other, all silicon posts are evenly distributed and formation array structure perpendicular to sample surfaces; On nanoscale, each the silicon post in the array all is cellular, forms the adjustable nano-porous structure in aperture; Hole wall is that the silicon nanocrystal grain of about 4nm is formed by average grain diameter, simultaneously, this substrate has higher luminous efficiency, according to surveying and determination, luminous intensity be anodizing technology preparation porous silicon 2-2.5 doubly, and have in air the not superior characteristics of luminescence such as blue shift of unattenuated, the luminous peak position of long storage time luminous intensity.Because barium strontium titanate is compound to porous silicon surface by even glue spin coating technique in the inventive method, so concentration, the technology of spin coating and the structure that annealing conditions can be regulated and control composite of control colloidal sol.In addition; the existence of barium strontium titanate nanocrystal has not only been carried out further effectively passivation and protection to porous silicon surface; simultaneously since material compound after; the enhancement effect of performance and complementary effect each other; superior sensing capabilities and the photoelectric properties that made this material production are compared backing material as luminous intensity and are strengthened, have ferroelectric properties such as bigger remanent magnetization and coercivity greatly with air-sensitive performance.
Hydro-thermal corrosion that the present invention adopts and the even glue technology of spin coating can at room temperature be operated, the preparation condition gentleness, easy to operation, repetitive rate is 100%, barium strontium titanate that makes and porous silicon composite material have micron, nano double weight structure feature and excellent photoelectric performance, and this material has potential application prospect in technical fields such as the sensor in future and luminescent devices.
Description of drawings
Fig. 1 is the SEM close-up view of Si-NPA;
Fig. 2 is the SEM side enlarged drawing of Si-NPA;
Fig. 3 is the SEM close-up view of Si-NPA and barium strontium titanate composite;
Fig. 4 is the SEM figure of composite substrate and film interface;
Fig. 5 be Si-NPA and composite at 200 ℃ with the fluorescence spectrum figure after the interior annealing;
Fig. 6 is the fluorescence spectrum figure of composite after annealing more than 500 ℃;
Fig. 7 is the gas-sensitive property sensitivity test result curve figure of composite;
Fig. 8 is the gas-sensitive property response time test result curve map of composite;
Fig. 9 is a composite ferroelectric properties test result curve map;
Figure 10 is the SEM close-up view of the Si-NPA of the embodiment of the invention 2;
Figure 11 is the SEM close-up view of the composite of the embodiment of the invention 2;
Figure 12 is the SEM close-up view of the composite of the embodiment of the invention 3.
The specific embodiment
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
(1) be that the monocrystalline silicon piece of P type (111) orientation of 0.015 Ω cm is inserted autoclave with resistivity, filling is the corrosive liquid that the iron nitrate solution of the hydrofluoric acid of 13.00mol/l and 0.04mol/l is formed by concentration, the liquor capacity compactedness of autoclave is 90%, corroded 60 minutes down for 140 ℃ in temperature, prepare backing material porous silicon (feature as shown in Figure 1 and Figure 2);
(2) with barium acetate, strontium acetate, butyl titanate and acetylacetone,2,4-pentanedione are raw material, adopt sol-gel process to prepare barium strontium titanate colloidal sol, its raw material proportioning (mol ratio) is: barium acetate: strontium acetate: butyl titanate: acetylacetone,2,4-pentanedione=0.7: 0.3: 1: 2, the method step for preparing this colloidal sol is as follows: selecting glacial acetic acid and EGME for use is solvent, acetylacetone,2,4-pentanedione is a complexant, during preparation, at first barium acetate and strontium acetate are dissolved in 0.7: 0.3 ratio of mol ratio in 60 ℃ the glacial acetic acid, and add small amount of deionized water to promote course of dissolution, be 1: 2 ratio then in the mol ratio of butyl titanate and acetylacetone,2,4-pentanedione, butyl titanate is gently joined in the acetylacetone,2,4-pentanedione solution, fully stir, make and mix, up to the solution cool to room temperature, to form stable titanium salt complex, then the mixed solution with butyl titanate and acetylacetone,2,4-pentanedione dropwise joins in the mixed solution of barium acetate and strontium acetate, the limit edged stirs, until mixing, the formamide that adds 1ml in the solution is done antimitotic agent, reduce the generation of crackle in the crystallization of thin films, adding EGME at last dilutes solution, concentration up to BST is 0.2mol/L, mixed solution is filtered in bottle,suction, obtain faint yellow transparent barium strontium titanate colloidal sol;
(3) use the desk-top sol evenning machine of KW-4A type (Chinese Academy of Sciences Microelectronics Institute's manufacturing) BST colloidal sol to be spin-coated on the Si-NPA substrate of prepared fresh, the spin coating condition: low-speed conditions are 1200 rev/mins, spin coating 9s; High-speed condition is 4000 rev/mins, spin coating 30s.Each coating at 150 ℃ of baking 10min, evaporates solvent earlier; At 400 ℃ of pyrolysis 30min, burn remaining organic matter again, above process repeats 10 times.At last, with BST and the Si-NPA laminated film 1h that anneals, promptly get product in 700 ℃ of oxygen atmospheres, its product shape characteristic is taken as shown in Figure 3, Figure 4 by the JSM-6700F type emission scan electron microscope of producing with JEOL company;
Ferroelectric-pyroelectricity tester that F-4500 type XRF tester through utilizing Hitachi company to produce, LCR multi-frequency digital electric bridge measuring instrument and U.S. Radiant company produce is tested optics, air-sensitive and the electric property of product, found that, the luminous intensity of material is improved largely than substrate, and can obtain as the ruddiness of Fig. 5 and the blue light material of Fig. 6.The sensitivity and the response time of composite more satisfactory (as Fig. 7, shown in Figure 8) found in the air-sensitive test.Ferroelectric test result shows that composite has bigger remanent polarization and bigger coercivity (as shown in Figure 9).
Embodiment 2:
(1) be that the monocrystalline silicon piece of P type (111) orientation of 0.015 Ω cm is inserted autoclave with resistivity, filling is the corrosive liquid that the iron nitrate solution of the hydrofluoric acid of 15.00mol/l and 0.05mol/l is formed by concentration, the liquor capacity compactedness of autoclave is 90%, corroded 90 minutes down for 160 ℃ in temperature, prepare backing material porous silicon structure (as shown in figure 10);
(2) press the step (2) of embodiment 1 and step (3) preparation barium strontium titanate colloidal sol and laminated film.
BST for preparing and Si-NPA complex thin film structure are as shown in figure 11.
Embodiment 3:
(1) preparation condition of backing material porous silicon is with the step (1) of embodiment 1;
(2) except that the final concentration of BST becomes 0.01mol/L, other condition of preparation colloidal sol is with the step (2) of embodiment 1;
(3) spin coating condition: low-speed conditions are 1000 rev/mins, spin coating 5s; High-speed condition is 6000 rev/mins, spin coating 20s.Each coating at 150 ℃ of baking 10min, evaporates solvent earlier; At 450 ℃ of pyrolysis 30min, burn remaining organic matter again, above process repeats 20 times, and is last, and BST and Si-NPA laminated film are annealed in 750 ℃ of oxygen atmospheres, and its product shape characteristic as shown in figure 12.
Claims (5)
1. the preparation method of barium strontium titanate and porous silicon composite material, it is characterized in that: the preparation method comprises the steps:
(1) preparation backing material porous silicon: the p type single crystal silicon sheet of resistivity 0.015 Ω cm is inserted autoclave, fill by concentration between the hydrofluoric acid (HF) of 8.00～22.00mol/l and the ferric nitrate (Fe (NO of 0.01～0.50mol/l
3)
3) corrosive liquid of solution composition, the liquor capacity compactedness of autoclave is 40～95%, in the corrosion 1 minute～36 hours down of 50～200 ℃ of temperature, promptly prepares the backing material porous silicon;
(2) preparation barium strontium titanate colloidal sol;
(3) barium strontium titanate colloidal sol is spin-coated on the porous silicon substrate of prepared fresh with sol evenning machine,, promptly obtains sensing, luminous and barium strontium titanate and porous silicon composite material that dielectric property is adjustable through annealing under 100～700 ℃ of temperature and the certain protective gas atmosphere.
2. preparation method as claimed in claim 1 is characterized in that: described barium strontium titanate colloidal sol is raw material with barium acetate, strontium acetate, butyl titanate and acetylacetone,2,4-pentanedione, adopts sol-gel process to make, and its preparation method comprises the steps:
(1) barium acetate and strontium acetate are dissolved in 0.7: 0.3 ratio of mol ratio in 600 ℃ the glacial acetic acid, and add small amount of deionized water to promote course of dissolution;
(2) in the mol ratio of butyl titanate and acetylacetone,2,4-pentanedione be 1: 2 ratio, butyl titanate is gently joined in the acetylacetone,2,4-pentanedione solution, fully stir, make to mix, up to the solution cool to room temperature, to form stable titanium salt complex;
(3) according to barium acetate: strontium acetate: butyl titanate: the mol ratio of acetylacetone,2,4-pentanedione=0.7: 0.3: 1: 2 ratio, the mixed solution of above-mentioned butyl titanate and acetylacetone,2,4-pentanedione is dropwise joined in the mixed solution of described barium acetate of step (1) and strontium acetate, the limit edged stirs, until mixing;
(4) formamide that adds 0.1～5mL in the solution is done antimitotic agent, then
(5) adding EGME solution is diluted, is 0.001～1.0mol/L up to the concentration of BST;
(6) mixed solution with step (5) filters in bottle,suction, obtains faint yellow transparent barium strontium titanate colloidal sol.
3. preparation method as claimed in claim 1 is characterized in that: the described spin coating proceeding of step (2) is: low speed spin coating condition is 400～2000 rev/mins, spin coating 1～30 second; High speed spin coating condition is 2000～6000 rev/mins, spin coating 10 seconds～1 minute.
4. preparation method as claimed in claim 1 is characterized in that: described protective gas is oxygen, nitrogen, argon gas, hydrogen or other inert gases.
5. use the barium strontium titanate and the porous silicon composite material of the described preparation method's preparation of claim 1.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346255A (en) * | 2013-06-26 | 2013-10-09 | 济南大学 | Heterojunction, ferroelectric tunnel junction and preparation method and application thereof |
| CN104425213A (en) * | 2013-08-26 | 2015-03-18 | 香港理工大学 | Chemical method for manufacturing barium strontium titanate dielectric thin film on GaAs substrate |
| CN105742060A (en) * | 2016-03-31 | 2016-07-06 | 同济大学 | High-energy-storage-density solid-state thin film integrated circuit capacitor and preparation method therefor |
| CN105869888B (en) * | 2016-03-31 | 2018-08-24 | 同济大学 | Solid film integrated-circuit capacitor with self-repair function and preparation method thereof |
| CN110277248A (en) * | 2019-05-27 | 2019-09-24 | 江苏大学 | A kind of zinc oxide-porous silicon composite material and its preparation method and application |
-
2009
- 2009-11-28 CN CN200910114588A patent/CN101717067A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346255A (en) * | 2013-06-26 | 2013-10-09 | 济南大学 | Heterojunction, ferroelectric tunnel junction and preparation method and application thereof |
| CN103346255B (en) * | 2013-06-26 | 2014-12-10 | 济南大学 | Heterojunction, ferroelectric tunnel junction and preparation method and application thereof |
| CN104425213A (en) * | 2013-08-26 | 2015-03-18 | 香港理工大学 | Chemical method for manufacturing barium strontium titanate dielectric thin film on GaAs substrate |
| CN105742060A (en) * | 2016-03-31 | 2016-07-06 | 同济大学 | High-energy-storage-density solid-state thin film integrated circuit capacitor and preparation method therefor |
| CN105742060B (en) * | 2016-03-31 | 2018-08-24 | 同济大学 | A kind of high energy storage density solid film integrated-circuit capacitor and preparation method thereof |
| CN105869888B (en) * | 2016-03-31 | 2018-08-24 | 同济大学 | Solid film integrated-circuit capacitor with self-repair function and preparation method thereof |
| CN110277248A (en) * | 2019-05-27 | 2019-09-24 | 江苏大学 | A kind of zinc oxide-porous silicon composite material and its preparation method and application |
| CN110277248B (en) * | 2019-05-27 | 2021-04-20 | 江苏大学 | Zinc oxide-porous silicon composite material and preparation method and application thereof |
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Open date: 20100602 |