CN1288981A - Low-electric field inducting control method to orient film prepared through a wet chemical process - Google Patents
Low-electric field inducting control method to orient film prepared through a wet chemical process Download PDFInfo
- Publication number
- CN1288981A CN1288981A CN00112548.6A CN00112548A CN1288981A CN 1288981 A CN1288981 A CN 1288981A CN 00112548 A CN00112548 A CN 00112548A CN 1288981 A CN1288981 A CN 1288981A
- Authority
- CN
- China
- Prior art keywords
- electric field
- film
- low
- wet
- orientation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000007704 wet chemistry method Methods 0.000 title claims description 11
- 230000005684 electric field Effects 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910002115 bismuth titanate Inorganic materials 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 6
- 238000000137 annealing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 27
- 239000010409 thin film Substances 0.000 claims description 18
- 238000007669 thermal treatment Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 7
- 238000000224 chemical solution deposition Methods 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000001149 thermolysis Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000005979 thermal decomposition reaction Methods 0.000 abstract 1
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000002939 deleterious effect Effects 0.000 description 3
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
In the subsequent heat treatment process of film prepared by using wet chemical method the wet film is undergone the process of thermal decomposition and changed into amorphous dry film, and in the subsequent high-temp. annealing crystallization process a D.C. low electric field is introduced to implement orientation control of film. Said invention utilizes low electric field to induce the orientation growth of several different film materials on the several different substrates, and its effect is obvious, in particular, for bismuth titanate film deposited on the silicon substrate with platinum coating or silicon substrate it can induce stronger C shaft orientation.
Description
Method, especially the metatitanic acid salt that the present invention relates to a kind of thin film alignment that adopts the preparation of low-electric field inducting control wet chemistry method is ferroelectric, in the heat treatment process of piezoelectric with the method for low-electric field inducting control thin film alignment.
Wet chemistry method, comprise sol-gel method (Sol-gel), metal-organic decomposition method (Metalorganicdecomposition, MOD) and chemical solution deposition (Chemical solution deposition, CSD), its concrete film-forming process can be realized by lacquering technique (Spin-coating), pickling process (Dipping-coating), spraying method (Spray).The wet-chemical thin films has been the technology of comparative maturity, it is even that it has on substrate microcell component height, stoichiometric ratio is accurate, be easy to mix, be easy to the big area film forming, equipment investment cost is low, technology is simple, being suitable for characteristics such as industrial applications, is to have actual application value among the current thin film preparation method most to have simultaneously one of technology of important scientific research value again, has broad application prospects in microtronics and photoelectronics field.
Yet its weak point is the orientation of difficult control film, and the film that wet chemistry method obtains usually is that random orientation is in the majority.In integrated, the photoelectric device as in surface acoustic wave device, optical waveguides and the infrared eye application at some, ferroelectric, the piezoelectric membrane that need have preferred orientation even extension usually, this requirement have greatly limited the application in practice of wet-chemical thin films.Solve this difficult problem at present and mainly contain two kinds of methods, a kind of is by selecting suitable substrate or introduce adaptive transition layer on substrate, but this method has significant limitation, and another kind of method is by selecting suitable precursor solution, yet this method is pretty troublesome, and not necessarily effective.Chinese patent 96117210 discloses the method and the device of inducing orientation growth of lithium ferrous niobate with electric field, but it is the ferroelectric membranc of vacuum growth.Yet there are no the method for the thin film alignment of low-electric field inducting control wet chemistry method preparation.Especially bismuth be that salt is ferroelectric, in the heat treatment process of piezoelectric with the method for low-electric field inducting control thin film alignment.The wet chemistry method made membrane is a prior art, for example referring to: 1. organometallics decompose deposit growth ferroelectric membranc (Metalorganic decomposition (MOD) processing of ferroelectric and electropotic films:a review "; R.W.Vest; Ferroelctrics; vol.102; 1990; p53-68.2.) 2. ferroelectric membrancs " Ferroelctric thin films ", N.Y.Turova and M.I.Yanovskaya, Gordon andBreach, Amsterdam, 1996, p233-328.
The objective of the invention is: a kind of method that adopts the thin film alignment of low-electric field inducting control wet chemistry method preparation is provided, and the multiple film of preparation band orientation is particularly at commodity platinum coating silicon substrate (Pt/TiO
2/ SiO
2/ sedimentary bismuth titanates (Bi Si) or on the silicon substrate
4Ti
3O
12) film, can induce extremely strong c axle orientation.
The object of the present invention is achieved like this: the present invention adopts a kind of simple and feasible method, by in the subsequent heat treatment technology of wet-chemical thin films (in the rapid thermal treatment process of thermal treatment of conventional tubular diffusion furnace or novelty), promptly thermolysis is transformed into the dry film of unformed shape in follow-up high temperature annealing crystallisation process to wet film, introduce the low electric field of direct current of different directions, different sizes, realize orientation control film.Its growth conditions is, apart from 2-10mm, strength of electric field is 0.01-1kV/cm between top electrode and the lower electrode, and the time of the thermal treatment added electric field of conventional tubular diffusion furnace is 10-120 minute, and the time of added electric field is 10-1200 second in the rapid thermal treatment process.
Characteristics of the present invention are: to the oriented growth of several different thin-film materials of low-electric field inducting at several different substrates, effect is very obvious, particularly to the platinum coating silicon substrate (Pt/TiO in commerce from present
2/ SiO
2/ sedimentary bismuth titanates (Bi Si) or on the silicon substrate
4Ti
3O
12) film, can induce extremely strong c axle orientation, on the ferroelectric field effect tube device, have practicable application prospect.
The invention will be further described below in conjunction with accompanying drawing and by embodiment:
Fig. 1 is to add original position electric field annealing device synoptic diagram in the heat treatment system for apparatus of the present invention.
The X-ray diffraction spectrogram of Fig. 2 bismuth titanate film that rapid thermal process obtains under different strength of electric field.As seen low-electric field inducting goes out intensive C axle oriented growth.Y direction indication diffracted intensity among the figure, directions X is represented angle of diffraction, Pyro represents the green stone phase of deleterious Jiao.
Fig. 3 is SBT film a axle orientation degree, the c axle orientation degree change curve with direction of an electric field, intensity.D: between top electrode and the lower electrode apart from 8mm.
Fig. 4 is the process flow diagram of rapid thermal process of the present invention (RTA) crystalline state multicoating (CMC, following figure) and amorphous multicoating (AMC, top figure) mode.
The enforcement illustration of method is seen Fig. 1
Strength of electric field: forward 0.01-1k V/cm (lower electrode 1 ground connection, top electrode 2 adds positive bias)
Or reverse 0.01-1k V/cm (lower electrode ground connection, top electrode adds negative bias)
Thin-film material 4: bismuth titanates (Bi
4Ti
3O
12, BIT), lanthanium titanate bismuth (Bi
4-xLa
xTi
3O
12, BLT) (X=0-2.8) (chemical solution deposition preparation)
Strontium bismuth tantalate (SrBi
2Ta
2O
9, SBT) (metal-organic decomposition method preparation)
Pb-based lanthanumdoped zirconate titanates (Pb{ZrTi}O
3, PZT), lead titanate (PbTiO
3, PTO), barium titanate (BaTiO
3, BTO) (Prepared by Sol Gel Method), and on substrate material film forming.
Substrate material 3: commercial monocrystalline silicon piece N or P type (100) or (111)
Commercial platinum coating silicon substrate (Pt/TiO
2/ SiO
2/ Si)
And the above-mentioned method for preparing film is prior art, mainly is to adopt suitable precursor solution by appropriate means, forms required wet film, obtaining desired film through follow-up thermal treatment process processing again.
When in Equipment for Heating Processing, heat-treating after the film forming with the electric field induced orientation, Equipment for Heating Processing: conventional tubular diffusion furnace: thermal treatment (Conventional furnace anneal, CFA), the fastest heat-up rate～50 degree/per minutes
Rapid thermal process annealing device: thermal treatment (Rapid thermal anneal, RTA), the fastest heat-up rate～250 thermal treatment process degree/p.s.: amorphous multicoating mode (Amorphous multilayer deposition, AMC): crystalline state multicoating mode (Crystal multilayer deposition, CMC): the film thickness with the growth of above-mentioned technology is: 50 nanometers～3 micron, effect: obtain the preferred orientation film, reduce even removal parafacies or dephasign
For example: 1. bismuth titanates (BIT) film chemical solution-deposition method is deposited on Pt/TiO
2/ SiO
2On/Si the substrate, adopting the distance between 650 (600-700 ℃) rapid thermal process (RTA) crystalline state multicoatings (CMC) and amorphous multicoating (AMC) the mode power-on and power-off pole plate respectively is 2mm, impressed voltage is 100V, and the time of rapid thermal treatment process and added electric field is 180 seconds.
Table one. under the rapid thermal process, low-electric field inducting is to bismuth titanate film orientation and mutually influence
Under the rapid thermal process condition, low-electric field inducting goes out intensive c axle preferrel orientation, and has removed the green stone phase of deleterious Jiao
2. bismuth titanates (BIT) film chemical solution-deposition method is deposited on Si or Pt/TiO
2/ SiO
2On/Si the substrate, adopt conventional tubular diffusion furnace thermal treatment (CFA) crystalline state multicoating (CMC) or amorphous multicoating (AMC) mode; Strength of electric field: forward 0.01-1kV/cm (lower electrode ground connection, top electrode adds positive bias)
Table two. under the prior heat treatment, low-electric field inducting is to bismuth titanate film orientation and mutually influence
Under the prior heat treatment condition, low-electric field inducting goes out tangible c axle preferrel orientation, and reduces even removed the green stone phase of deleterious Jiao
3. strontium bismuth tantalate (SBT) metal-organic decomposition method is deposited on Pt/TiO
2/ SiO
2On/Si the substrate, adopt 750 ℃ of conventional tubular diffusion furnaces thermal treatment (CFA) crystalline state multicoating (CMC) mode, the relation of voltage and c axle orientation is referring to Fig. 3.As seen, under the positive field situation, low-electric field inducting goes out tangible c axle orientation.
4. lead titanate (PTO) sol-gel method is deposited on the Si substrate, adopts 600 ℃ of conventional tubular diffusion furnaces thermal treatment (CFA) amorphous multicoating (AMC) mode
Table three. under the prior heat treatment, low-electric field inducting is to the influence of lead titanate thin film alignment
As seen, low-electric field inducting goes out stronger c axle and a axle orientation.
In the above-described embodiments, heat treated atmosphere and air pressure conditions are as follows: get final product in normal air and atmospheric pressure state, can certainly work under the atmospheric condition of pure oxygen or oxygen enrichment.The time that applies electric field is mainly the most effective in crystallisation process, just at heat treated initial time, and also can stop to apply external voltage in the heat treated later stage.
Claims (3)
1. bismuth system and a lead that adopts low-electric field inducting control wet chemistry method to prepare is the method for thin film alignment, it is characterized in that by in the subsequent heat treatment technology of wet-chemical thin films, thermolysis is transformed into the dry film of unformed shape to wet film, in follow-up high temperature annealing crystallisation process, introduce the low electric field of direct current of different directions, different sizes, realize the orientation control to film, its growth conditions is, apart from 2-10mm, strength of electric field is 0.01-1kV/cm between top electrode and the lower electrode.
2. bismuth system and the lead by the preparation of the described employing low-electric field inducting control of claim 1 wet chemistry method is the method for thin film alignment, the time that it is characterized in that the thermal treatment added electric field of conventional tubular diffusion furnace is 10-120 minute, and the time of added electric field is 10-1200 second in the rapid thermal treatment process.
3. bismuth system and the lead by the preparation of the described employing low-electric field inducting control of claim 1 wet chemistry method is the method for thin film alignment, it is characterized in that bismuth titanates (BIT) film chemical solution-deposition method is deposited on Pt/TiO
2/ SiO
2On/Si the substrate, substrate is selected monocrystalline silicon piece N or P type (100) or (111) for use, commercial platinum coating silicon substrate (Pt/TiO
2/ SiO
2/ Si), adopting 600-700 ℃ of rapid thermal process (RTA) crystalline state multicoating (CMC) and amorphous multicoating (AMC) mode, extra electric field intensity is that strength of electric field is 0.1-0.5kV/cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112548.6A CN1120250C (en) | 2000-09-18 | 2000-09-18 | Low-electric field inducting control method to orient film prepared through a wet chemical process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112548.6A CN1120250C (en) | 2000-09-18 | 2000-09-18 | Low-electric field inducting control method to orient film prepared through a wet chemical process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1288981A true CN1288981A (en) | 2001-03-28 |
| CN1120250C CN1120250C (en) | 2003-09-03 |
Family
ID=4582401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00112548.6A Expired - Fee Related CN1120250C (en) | 2000-09-18 | 2000-09-18 | Low-electric field inducting control method to orient film prepared through a wet chemical process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1120250C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393625C (en) * | 2006-03-06 | 2008-06-11 | 湖北大学 | Neodymium doped bismuth titanate nano line array ferro-electric storage material and its synthetic method |
| CN103952676A (en) * | 2014-05-07 | 2014-07-30 | 武汉理工大学 | Preparation method of b-axis-oriented BaTi2O5 film |
| CN109081609A (en) * | 2018-07-27 | 2018-12-25 | 北京理工大学 | A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation |
-
2000
- 2000-09-18 CN CN00112548.6A patent/CN1120250C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100393625C (en) * | 2006-03-06 | 2008-06-11 | 湖北大学 | Neodymium doped bismuth titanate nano line array ferro-electric storage material and its synthetic method |
| CN103952676A (en) * | 2014-05-07 | 2014-07-30 | 武汉理工大学 | Preparation method of b-axis-oriented BaTi2O5 film |
| CN103952676B (en) * | 2014-05-07 | 2016-01-06 | 武汉理工大学 | A kind of BaTi of b axle orientation 2o 5the preparation method of film |
| CN109081609A (en) * | 2018-07-27 | 2018-12-25 | 北京理工大学 | A kind of ferroelectric thin film and preparation method thereof of strong polarization orientation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120250C (en) | 2003-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Ferroelectric thin films prepared by sol-gel processing | |
| US5650362A (en) | Oriented conductive film and process for preparing the same | |
| JP3436617B2 (en) | Manufacturing method of ferroelectric thin film | |
| US5188902A (en) | Production of PT/PZT/PLZI thin films, powders, and laser `direct write` patterns | |
| EP0687750B1 (en) | Method for manufacturing thin film of composite metal-oxide dielectric | |
| EP0661754A2 (en) | A substrate providing a ferroelectric crystal thin film, its production method and a device using said substrate | |
| KR100442543B1 (en) | Method for manufacturing thin layer of layered superlattice material and electronic device having two thin layer | |
| JPH06119812A (en) | Multi-layer ferroelectric thin film | |
| WO1990013149A1 (en) | SOL GEL PROCESS FOR PREPARING Pb(Zr,Ti)O3 THIN FILMS | |
| JPH08212830A (en) | Orienting ferroelectric thin film element and its manufacture | |
| Xu et al. | Electrical characterizations of polycrystalline and amorphous thin films of Pb (ZrxTi1− x) O3 and BaTiO3 prepared by sol—gel technique | |
| CN1120250C (en) | Low-electric field inducting control method to orient film prepared through a wet chemical process | |
| JPH07330426A (en) | Composite material containing preovskite,its preparation, electronic part and module | |
| Kong et al. | Preparation and characterization of antiferroelectric PLZT2/95/5 thin films via a sol–gel process | |
| KR19990006318A (en) | Deposition of Ferroelectric Films and Ferroelectric Capacitor Devices | |
| WO2004085718A1 (en) | Ferroelectric film | |
| KR0156044B1 (en) | Manufacture for ferroelectric thin film | |
| CN109761605A (en) | One kind having the PZT thin film and preparation method thereof of (100) preferable grain orientation | |
| JP3235279B2 (en) | Manufacturing method of epitaxial ferroelectric thin film device | |
| JPH07300397A (en) | Ferroelectric thin film element and its production | |
| Trtik et al. | A study of laser-deposited PZT, PLZT, PMN and YBCO thin films | |
| CN1779926A (en) | Control of lead zirconate-titanate preferred orientation | |
| Yeh et al. | Formation of the secondary phases in the Pb-containing perovskite films by pulsed laser deposition | |
| JPH07133198A (en) | Production of electric conductive thin film having orientation property | |
| JPH11171590A (en) | Formation of functional ceramic thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |