CN101407377B - Method of preparing nano Bi2S3 film - Google Patents

Abstract

The invention discloses a preparation method of a nano Bi2S3 thin film, which comprises the following steps of: adding the Bi(NO3)3.5H2O of analytically pure into distilled water for preparing an A solution; then adding the Na2S2O3 of the analytically pure and trisodium citrate into the A solution and regulating pH value to be 4.3-6.5 under stirring for preparing a B solution; placing the B solution in an electrodepositing device, ultrasonic washing an ITO glass substrate in ethanol, taking the ITO glass substrate as a cathode and graphite as an anode, and preparing the Bi2S3 thin film on the ITO glass substrate by using a mode of cathode constant voltage depositing; after finishing depositing, airing the prepared thin film in air and then obtaining the final product of the Bi2S3 thin film. The method adopts the electrodepositing method for preparing the Bi2S3 thin film with compact and even composition and oriented growth along (240) crystal face. Ultrasonic wave is adopted for assisting dissolving the Bi(NO3)3.5H2O, therefore nitric acid is not needed for dissolving so as to improve the stability of reaction solution, the pH value can be regulated in a large range, technical equipment is simple, in addition the method can prepare the Bi2S3 thin film high effectively with large area.

Description

A kind of nanometer Bi 2S 3The thin film technology method

Technical field

The present invention relates to a kind of nanometer Bi ₂S ₃The material preparation method is specifically related to a kind of nanometer Bi ₂S ₃The thin film technology method.

Background technology

Bi ₂S ₃Belong to quadrature (tiltedly side) crystallographic system, crystal is long column shape or needle-like, is that (directly forbidden band Eg=1.2～1.7ev) has a lot of potential application such as photodiode or photocell, photochemical catalyst, biomarker, electrochemical cell etc. to a kind of important semi-conducting material.At present, the research of relevant bismuth sulfide has received very big concern.Along with Bi ₂S ₃Nanometer, can not only cause absorbing wavelength and fluorescent emission generation blue shift, can also produce nonlinear optical response, and the redox ability of enhancing nano particle, have more excellent photocatalytic activity, have a wide range of applications at aspects such as luminescent material, nonlinear optical material, catalysis materials.

Up to now, many researchers use the methods such as ionic liquid method, hot solvent method, hydro-thermal method, microwave-hydrothermal method successfully to synthesize the Bi of different structure ₂S ₃The people such as nano material such as Zhao Rongxiang, Xu Zhude, Li He and Xu Huili [Zhao Rongxiang, Xu Zhude, Li He etc. Chinese Journal of Inorganic Chemistry, 2007,5 (23): 839-843.] adopting bismuth nitrate and thiocarbamide is pioneer's raw material, take ionic liquid as reaction medium, has synthesized the bismuth sulfide monocrystal nano rod; Ancient country China, Wang Wei, Lv Weili, the people such as Hu Zhengshui [ancient country China, Wang Wei, Lv Weili, Hu Zhengshui. Rare Metals Materials and engineering, 2007,36 (8): 108-111.] utilize the hot solvent legal system for rose-shaped Bi ₂S ₃Nano material; Sheng-Cong Liufu, Li-Dong Chen, [Sheng-Cong Liufu, Li-Dong Chen, Qun Wang, the and Qin Yao.CrystalGrowth﹠amp such as Qun Wang; Design.2007,7 (4): 639-643.] utilize the hydrothermal treatment consists method to make perfect crystalline, uniform nanometer Bi at lower temperature ₂S ₃Film, the bismuth sulfide crystal that obtains is monocrystalline, along the growth of (001) crystal face; Wen-hui Li[Wen-hui Li.Materials Letters.2008 (62): 243-245] synthesized Bi by microwave-hydrothermal method ₂S ₃Nano wire.As seen, Bi ₂S ₃Nano material has a lot of potential application, and a lot of researchers are devoted to prepare nanometer Bi by the whole bag of tricks ₂S ₃Material.But up to the present, electrodeposition process prepares nanometer Bi ₂S ₃Thin film technology yet there are no report.But carry out under the galvanic deposit thin films normal temperature, be easy to carry out composition and the thickness that big area deposits, is easy to film, simple to operate, safety has very big development prospect.

Summary of the invention

It is low to the objective of the invention is to propose a kind of not only preparation cost, and nanometer Bi simple to operate, that reaction time is short ₂S ₃The thin film technology method.

For achieving the above object, the technical solution used in the present invention is:

1) at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultra-sonic dispersion in the ultrasonic generator, is mixed with Bi ³⁺Concentration is the clear solution of 0.01mol/L～0.5mol/L, and gained solution is designated as A;

2) then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:4～7:1, stirring the lower pH of adjusting value is 4.3～6.5, forms precursor solution, gained solution is designated as B;

3) B solution is placed electric deposition device, ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 0.5～10V, and sedimentation time is 10～30min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

The present invention adopts electrodeposition process, prepares film and forms even compact, along the Bi of (240) high preferred orientation growth ₂S ₃Film.Adopt ultrasonic wave assist in dissolving Bi (NO ₃) ₃5H ₂O need not to use nitric acid dissolve can improve the stability of reaction solution, and the pH value is adjustable on a large scale, and process equipment is simple, but large tracts of land prepares Bi efficiently ₂S ₃Film.

Description of drawings

Fig. 1 is the nanometer Bi of the present invention's preparation ₂S ₃The X-ray diffraction of film (XRD) collection of illustrative plates, wherein abscissa is the angle of diffraction 2 θ, unit is °; Ordinate is diffraction peak intensity, and unit is cps.

Fig. 2 is the nanometer Bi of the present invention's preparation ₂S ₃The AFM of film (AFM) photo.

Embodiment

Below in conjunction with drawings and Examples the present invention is described in further detail.

Embodiment 1: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.0125mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:5:1, stirring the lower pH of adjusting value is 4.5, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 1V, and sedimentation time is 20min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Bi with gained ₂S ₃Film finds that with Rigaku D/max2000PC x-ray diffractometer analytic sample product is the rhombic system Bi that JCPDS is numbered 17-0320 ₂S ₃The oriented growth characteristic that (Fig. 1) has (240) crystal face.This sample is observed the Surface Microstructure (Fig. 2) of film with SPA400-SPI3800N type AFM, can be found out that from photo prepared film surface presents long column shape Bi ₂S ₃Crystal grain has obvious oriented growth feature.

Embodiment 2: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.2mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:7:1, stirring the lower pH of adjusting value is 5.5, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 3V, and sedimentation time is 17min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Embodiment 3: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.3mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:4:1, stirring the lower pH of adjusting value is 4.3, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 8V, and sedimentation time is 13min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Embodiment 4: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.5mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:6:1, stirring the lower pH of adjusting value is 6.0, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 5V, and sedimentation time is 22min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Embodiment 5: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.01mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:5.5:1, stirring the lower pH of adjusting value is 5.0, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 10V, and sedimentation time is 10min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Embodiment 6: at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultrasonic dispersion in the supersonic generator that power is 100W, is mixed with Bi ³⁺Concentration is the clear solution of 0.4mol/L, and gained solution is designated as A; Then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:6.7:1, stirring the lower pH of adjusting value is 6.5, forms precursor solution, gained solution is designated as B; B solution is placed electric deposition device, and ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 0.5V, and sedimentation time is 30min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

Claims (1)

1. nanometer Bi ₂S ₃The thin film technology method is characterized in that:

1) at first with analytically pure Bi (NO ₃) ₃5H ₂O adds in the distilled water, and is placed on ultra-sonic dispersion in the ultrasonic generator, is mixed with Bi ³⁺Concentration is the clear solution of 0.01mol/L～0.5mol/L, and gained solution is designated as A;

2) then, in A solution, add analytically pure Na ₂S ₂O ₃And trisodium citrate, so that [Bi in the mixed solution ³⁺]: [S ₂O ₃ ^2-]: [C ₆H ₅O ₇ ^3-The mol ratio of]=1:4～7:1, stirring the lower pH of adjusting value is 4.3～6.5, forms precursor solution, gained solution is designated as B;

3) B solution is placed electric deposition device, ultrasonic cleaning is as negative electrode in ethanol with ito glass substrate, and employing graphite is anode, and the mode that deposits with the negative electrode constant voltage prepares Bi at ito glass substrate ₂S ₃Film; Deposition voltage is 0.5～10V, and sedimentation time is 10～30min, and deposition is dried prepared film in air after finishing naturally, namely gets end product Bi ₂S ₃Film.

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