CN101358378A - Method for rapid depositing barium tungstate micron film at low-temperature - Google Patents
Method for rapid depositing barium tungstate micron film at low-temperature Download PDFInfo
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- CN101358378A CN101358378A CNA2008102226257A CN200810222625A CN101358378A CN 101358378 A CN101358378 A CN 101358378A CN A2008102226257 A CNA2008102226257 A CN A2008102226257A CN 200810222625 A CN200810222625 A CN 200810222625A CN 101358378 A CN101358378 A CN 101358378A
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Abstract
The invention relates to a method for quickly depositing barium tungstate micro film at low temperature, which belongs to the technical field of functional film material preparation. The prior barium tungstate film preparation methods have quite high requirement for the deposition condition, need vacuum, high temperature and other conditions, and restrict the substrates to be conductive. The method takes EDTA-2Na as the complexing agent and prepares the micro barium tungstate film which has pure white tungsten ore structure, small, even and compact grains and is highly crystallized in microwave water bath which is lower than 100 DEG C within 30min. The method has no special requirement for the substrates, i.e. conductive or non-conductive substrates are applicable; adopts a microwave heating method, has simple process, and does not need vacuum, high temperature and other conditions; in addition, the solution is evenly heated, which greatly shortens the deposition time of the film; that EDTA-2Na is adopted as the complexing agent effectively prevents barium ions and wolframate radical ions from being largely nucleated and deposited in the solution.
Description
Technical field
The invention belongs to the film material with function preparing technical field, being specifically related to a kind of is complexing agent in lower temperature with in than the short time with disodium ethylene diamine tetraacetate (EDTA-2Na), and deposition obtains the method for micron order barium wolframate film.
Background technology
Barium wolframate (BaWO
4) crystal is a kind of very promising raman laser crystal, is a kind of important photoelectric functional material, has stimulated Raman scattering performance (SRS).In 1999, T.T.Basiev, A.A.Sobol, people such as P.G.Zverev found BaWO after having measured tungstate and the crystal-like Raman spectrum of other kind
4The crystalline Raman spectrum has bigger raman scattering cross section and Raman scattering intensity, so BaWO
4Crystal all can have bigger Raman gain under nanosecond pulse and picosecond pulse laser effect, and BaWO
4The crystalline transparency range is wide, deliquescence not, therefore, BaWO
4Crystal is a kind of Raman active medium of excellent property, both has been suitable for the frequency inverted of ps pulsed laser and ns pulsed laser, is suitable for the frequency inverted of picosecond pulse laser again.
BaWO
4Be the body-centered teteragonal scheelite-type structure, launch blue light usually.Scheelite crystals is simple in structure, by flat slightly [WO
4] tetrahedron and Ba ion form alternately along the c axle, spacer is I41/a, point group is C
4h
6At present, utilize microemulsion method, Hydrothermal Preparation nanometer, micron-sized BaWO
4The crystal powder technology is very ripe, and has obtained multiple crystal morphology by different experimentations, as nano wire crystal, cylindric crystal, hollow ball-shape crystal, biconical crystal, fiber bundle-like crystal, flower-shaped, shuttle shape crystal etc.And BaWO
4The grain-size of thin-film material is little, and the sidescattering of initiation is less relatively, can make film reach higher resolving power, with respect to powdered material, has better properties.But at present to BaWO
4The preparation research of film less relatively, and existing preparation BaWO
4The method of film only is confined to chemical Vapor deposition process (CVD), vacuum vapour deposition, sputtering method and dipping brushing technique.And above-mentioned technology is had relatively high expectations to mode of deposition, need conditions such as vacuum, high temperature, thereby inevitably destroy original pattern of film, be difficult to accurately control the chemical dosage ratio of the composition of prepared film simultaneously in strict conformity with its molecular formula, and then influence the characteristics of luminescence of film, influence its application.Recently, people such as Yoshimura M. utilizes electrochemical process and hydro-thermal-electrochemical method success to prepare BaWO on the tungsten sheet
4Film, however electrochemical process has selectivity to the substrate of film, is necessary for conductive substrates, thereby influences BaWO
4The further application of film.
Summary of the invention
The objective of the invention is to solve the deficiencies in the prior art, and a kind of method of rapid depositing barium tungstate micron film at low-temperature is provided.The inventive method is to the substrate non-selectivity, and technology is simple, and is with low cost, is suitable for scale operation.
Method provided by the present invention is to be complexing agent with disodium ethylene diamine tetraacetate (EDTA-2Na), in being lower than 100 ℃ microwave water-bath, within 30 minutes, preparation has pure white tungsten ore structure on substrate, the tiny homogeneous densification of crystal grain, and the micron barium wolframate film of highly crystalline, concrete steps are as follows:
1) pre-treatment of substrate: use each ultrasonic cleaning of toluene, acetone and ethanol after 15 minutes successively substrate, deionized water rinsing is immersed in the ethanol standby;
2) complexing agent EDTA-2Na is dissolved in the deionized water, after stirring, the Ba (NO of amount of substances such as adding and EDTA-2Na
3)
26H
2O continues stirred solution, obtains the solution A of clear;
3) in solution A, add NaOH and HNO
3Regulate the pH value to 8-13, obtain solution B;
4) Na of amount of substances such as adding and EDTA-2Na in solution B
2WO
4, and be stirred to and obtain the clear solution C;
5) with pretreated substrate in the step 1) with deionized water rinsing after, put into solution C, make substrate float on solution surface, microwave exposure 10min-30min obtains BaWO
4Film.
Wherein, described substrate is transparent conducting glass (FTO glass) or simple glass.
Compared with prior art, the present invention has following beneficial effect:
1) the inventive method does not have particular requirement to substrate, and conduction and non-conductive substrate all are suitable for; And make substrate float on solution surface, the barium wolframate crystallite that can effectively avoid generating in the liquid phase in the deposition process is adsorbed onto substrate surface.
2) the present invention adopts microwave heating, and technology is simple, conditions such as needing no vacuum and high temperature, and solution is heated evenly, and greatly shortened the thin film deposition time.
3) the present invention adopts disodium ethylene diamine tetraacetate effectively to avoid initial reaction stage barium ion and tungstate ion a large amount of nucleation precipitations in solution as complexing agent.
Description of drawings
X-ray diffraction (XRD) collection of illustrative plates of the barium wolframate film that Fig. 1 the present invention is prepared; Wherein, curve a-d is respectively the XRD figure spectrum of the film for preparing among the embodiment 1-4; FTO is a transparent conducting glass.
The stereoscan photograph of the barium wolframate film of Fig. 2 embodiment 1 preparation.
The stereoscan photograph of the barium wolframate film of Fig. 3 embodiment 2 preparations.
The stereoscan photograph of the barium wolframate film of Fig. 4 embodiment 3 preparations.
The stereoscan photograph of the barium wolframate film of Fig. 5 embodiment 4 preparations.
The invention will be further described below in conjunction with the drawings and specific embodiments.
Embodiment
Adopt the German Bruker Advance D-8X of company ray powder diffraction instrument (Cu K α radiation,
) measure the structure of barium wolframate film; Adopt Hitachi S-3500N determination of electron microscopy microscopic appearance pattern.
Embodiment 1
1) FTO glass was respectively cleaned 15 minutes in ultrasonic cleaning machine with toluene, acetone, ethanol successively, and rinse well, preserve with alcohol immersion with deionized water, standby;
2) 0.03mol complexing agent EDTA-2Na is dissolved in the 60ml deionized water, after the magnetic agitation dissolving, adds and 0.03molBa (NO
3)
26H
2O, lasting stirring obtains the solution A 1 of clear;
3) in solution A 1, add the NaOH solution of 10mol/L and 30% HNO
3Solution, the pH value to 8 of regulator solution A1 obtains solution B 1;
4) to 0.03mol Na
2WO
42H
2Add the 20ml deionized water among the O, be stirred to dissolving fully, then it is added in the solution B 1, add deionized water to 100ml, and stirred 1 minute, obtain clear solution C 1, C1 solution is moved in the wide-necked bottle;
5) the substrate deionized water rinsing that will anticipate, put into solution C 1, and make it float on solution surface, build wide-necked bottle, put it into irradiation 25min in the household microwave oven (2.45GHz, low fiery 120W), after reaction finishes, take out substrate, also at room temperature dry, obtain BaWO with the washed with de-ionized water film surface
4Film a.
By the visible prepared barium wolframate film of Fig. 1 a is pure scheelite-type structure, and crystallinity is fine.Fig. 2 has shown the microscopic appearance of this film: sharp-featured flowers shape crystallite (4-5 μ m), and film is very fine and close, and thickness is about 4 μ m, grain density: 247/1000 μ m
2
Embodiment 2
1) FTO glass was respectively cleaned 15 minutes in ultrasonic cleaning machine with toluene, acetone, ethanol successively, and rinse well, preserve with alcohol immersion with deionized water, standby;
2) 0.02mol complexing agent EDTA-2Na is dissolved in the 60ml deionized water, after the magnetic agitation dissolving, adds and 0.02molBa (NO
3)
26H
2O, lasting stirring obtains the solution A 2 of clear;
3) in solution A 2, add the NaOH solution of 10mol/L and 30% HNO
3Solution, the pH value to 8 of regulator solution A2 obtains solution B 2;
4) to 0.02mol Na
2WO
42H
2Add the 20ml deionized water among the O, be stirred to dissolving fully, then it is added in the solution B 2, add deionized water to 100ml, and stirred 1 minute, obtain clear solution C 2, and C2 solution is moved in the wide-necked bottle;
5) the substrate deionized water rinsing that will anticipate, put into solution C 2, and make it float on solution surface, build wide-necked bottle, put it into irradiation 10min in the household microwave oven (2.45GHz, low fiery 120W), after reaction finishes, take out substrate, also at room temperature dry, obtain BaWO with the washed with de-ionized water film surface
4Film b.
By the visible prepared barium wolframate film of Fig. 1 b is pure scheelite-type structure, and crystallinity is fine.Fig. 3 has shown the microscopic appearance of this film: sharp-featured flowers shape crystallite (4-5 μ m), and film is dense, and thickness is about 4 μ m, grain density: 208/1000 μ m
2
Embodiment 3
1) FTO glass was respectively cleaned 15 minutes in ultrasonic cleaning machine with toluene, acetone, ethanol successively, and rinse well, preserve with alcohol immersion with deionized water, standby;
2) 0.01mol complexing agent EDTA-2Na is dissolved in the 60ml deionized water, after the magnetic agitation dissolving, adds and 0.01molBa (NO
3)
26H
2O, lasting stirring obtains the solution A 3 of clear;
3) in solution A 3, add the NaOH solution of 10mol/L and 30% HNO
3Solution, the pH value to 13 of regulator solution A3 obtains solution B 3;
4) to 0.01mol Na
2WO
42H
2Add the 20ml deionized water among the O, be stirred to dissolving fully, then it is added in the solution B 3, add deionized water to 100ml, and stirred 1 minute, obtain clear solution C 3, solution C3 is moved in the wide-necked bottle;
5) the substrate deionized water rinsing that will anticipate, put into solution C 3, and make it float on solution surface, build wide-necked bottle, put it into irradiation 30min in the household microwave oven (2.45GHz, low fiery 120W), after reaction finishes, take out substrate, also at room temperature dry, obtain BaWO with the washed with de-ionized water film surface
4Film c.
By the visible prepared barium wolframate film of Fig. 1 c is pure scheelite-type structure, and crystallinity is fine.Fig. 4 has shown the microscopic appearance of this film: sharp-featured flowers shape crystallite (2 μ m), film are very fine and close, and thickness is about 2 μ m, grain density: 1164/1000 μ m
2
Embodiment 4
1) common slide glass glass was respectively cleaned 15 minutes in ultrasonic cleaning machine with toluene, acetone, ethanol successively, and rinse well, preserve with alcohol immersion with deionized water, standby;
2) 0.02mol complexing agent EDTA-2Na is dissolved in the 60ml deionized water, after the magnetic agitation dissolving, adds and 0.02molBa (NO
3)
26H
2O, lasting stirring obtains the solution A 4 of clear;
3) in solution A 4, add the NaOH solution of 10mol/L and 30% HNO
3Solution, the pH value to 11 of regulator solution A4 obtains solution B 4;
4) to 0.02mol Na
2WO
42H
2Add the 20ml deionized water among the O, be stirred to dissolving fully, then it is added in the solution B 4, add deionized water to 100ml, and stirred 1 minute, obtain clear solution C 4, C4 solution is moved in the wide-necked bottle;
5) the substrate deionized water rinsing that will anticipate, put into solution C 4, and make it float on solution surface, wide-necked bottle is built, put it into irradiation 20min in the household microwave oven (2.45GHz, low fiery 120W), after reaction finishes, take out substrate, also at room temperature dry, obtain BaWO with the washed with de-ionized water film surface
4Film d.
By the visible prepared barium wolframate film of Fig. 1 d is pure scheelite-type structure, and crystallinity is fine.Fig. 5 has shown the microscopic appearance of this film: sharp-featured flowers shape crystallite (4 μ m), and film is dense, and thickness is about 4 μ m, grain density: 211/1000 μ m
2
Although the present invention has been carried out above-mentioned diagram and description with reference to specific implementations of the present invention, but those skilled in the art are to be understood that, do not breaking away under the situation of the spirit and scope of the present invention that limit by appended claims, can carry out various modifications on form and the details the present invention.
Claims (2)
1, a kind of method of rapid depositing barium tungstate micron film at low-temperature is characterized in that, may further comprise the steps:
1) pre-treatment of substrate: use each ultrasonic cleaning of toluene, acetone and ethanol after 15 minutes successively substrate, deionized water rinsing is immersed in the ethanol standby;
2) complexing agent EDTA-2Na is dissolved in the deionized water, after stirring, the Ba (NO of amount of substances such as adding and EDTA-2Na
3)
26H
2O continues stirred solution, obtains the solution A of clear;
3) in solution A, add NaOH and HNO
3Regulate the pH value to 8-13, obtain solution B;
4) Na of amount of substances such as adding and EDTA-2Na in solution B
2WO
4, and be stirred to and obtain the clear solution C;
5) with pretreated substrate in the step 1) with deionized water rinsing after, put into solution C, make substrate float on solution surface, microwave exposure 10min-30min obtains barium tungstate micron film.
2, method according to claim 1 is characterized in that, described substrate is transparent conducting glass FTO or simple glass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008102226257A CN101358378A (en) | 2008-09-19 | 2008-09-19 | Method for rapid depositing barium tungstate micron film at low-temperature |
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|---|---|---|---|
| CNA2008102226257A CN101358378A (en) | 2008-09-19 | 2008-09-19 | Method for rapid depositing barium tungstate micron film at low-temperature |
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| CN101358378A true CN101358378A (en) | 2009-02-04 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531062A (en) * | 2012-03-02 | 2012-07-04 | 河北联合大学 | Structure-controlling preparation of uniform-thickness ultrathin iron tungstate nanosheet |
| CN104591288A (en) * | 2015-01-19 | 2015-05-06 | 洛阳理工学院 | Preparation method of barium tungstate nanowire |
| CN115770620A (en) * | 2022-11-18 | 2023-03-10 | 北京工业大学 | Heterogeneous single-site preparation method of noble metal substrate |
-
2008
- 2008-09-19 CN CNA2008102226257A patent/CN101358378A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531062A (en) * | 2012-03-02 | 2012-07-04 | 河北联合大学 | Structure-controlling preparation of uniform-thickness ultrathin iron tungstate nanosheet |
| CN104591288A (en) * | 2015-01-19 | 2015-05-06 | 洛阳理工学院 | Preparation method of barium tungstate nanowire |
| CN115770620A (en) * | 2022-11-18 | 2023-03-10 | 北京工业大学 | Heterogeneous single-site preparation method of noble metal substrate |
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