CN103962295B - A kind of simple high efficiency preparation method of zinc sulfide semiconductor film - Google Patents
A kind of simple high efficiency preparation method of zinc sulfide semiconductor film Download PDFInfo
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- CN103962295B CN103962295B CN201410179668.7A CN201410179668A CN103962295B CN 103962295 B CN103962295 B CN 103962295B CN 201410179668 A CN201410179668 A CN 201410179668A CN 103962295 B CN103962295 B CN 103962295B
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Abstract
The invention belongs to semiconductor materials and devices field, particularly a kind of simple high efficiency preparation method of zinc sulfide semiconductor film.(1) xanthic acid zinc list source presoma is synthesized; (2) single source xanthic acid zinc precursor solution is prepared; (3) zinc sulfide film is prepared.Present invention process is simple to operation, and cheaper starting materials is easy to get, and prepared zinc sulfide film crystalline quality is high, and composition is easy to control, continuous in appearance, evenly, fine and close, surfacing light, and with substrate in conjunction with solid and reliable, also can prepare film on complex-shaped substrate; Common multistep complicated technology, process cycle length or high vacuum expensive device etc. can be avoided by above-mentioned technique, cost is low, be applicable to industrialization large-scale production, prepared zinc sulfide film can be applicable in the photoelectric devices such as solar cell, flat-panel monitor and light emitting diode.
Description
Technical field
The invention belongs to field of inorganic materials, particularly a kind of simple high efficiency preparation method of zinc sulfide semiconductor film.
Background technology
Metal sulfide has excellent photoelectromagnetic performance and catalytic performance, becomes the study hotspot in field of inorganic materials.Wherein, zinc sulphide (ZnS) is one of material be widely studied and applied in II-VI compounds of group.ZnS is important II-VI race direct band gap semiconductor material with wide forbidden band, energy gap under room temperature about 3.7 eV, there is higher exciton bind energy (40 meV), have at short wavelength's field of photoelectric devices such as short wavelength semiconductor laser, light emitting diode, UV photodetectors huge potential
Using value.ZnS also can replace poisonous CdS as the important window layer material in CuInGaSe2 (CIGS) film solar battery structure.
The gas phase process preparing zinc sulfide film at present mainly contains chemical vapour deposition technique (such as Surface morphological and photoelectrochemical studies of ZnS thin films developed from single source precursors by aerosol assisted chemical vapour deposition, Thin Solid Films, 2013, 540, 1.), sputtering method (such as Structural and optical properties of ZnS thin films deposited by RF magnetron sputtering. Nanoscale Research Letters 2012, 7, 26.), atomic layer deposition method (such as ALD Growth Characteristics of ZnS Films Deposited from Organozinc and Hydrogen Sulfide Precursors. Langmuir, 2010, 26, 11899.), thermal evaporation (such as Structural and optical properties of thermally evaporated ZnS thin films. The European Physical Journal Applied Physics. 2010, 52, 30301.) etc., liquid phase process mainly contains sol-gel process Sol – gel synthesis of ZnS (O, OH) thin films:Influence of precursor and process temperature on its optoelectronic properties. Journal of Luminescence. 2013, 134, 423.), SILAR method (such as the method for a CN200710045967.1 sinking non crystal ZnS film under room temperature condition), chemical bath deposition method (such as Preparation and characterization of ZnS thin films prepared by chemical bath deposition. Materials Science in Semiconductor Processing. 2013, 16, 1478.) etc.But these methods need expensive instrument, strict experiment condition and/or longer reaction time usually.Therefore, finding a kind of low cost, simple and easy, efficient technology of preparing, is very important and urgent for zinc sulfide film at semiconductor and optoelectronic areas large-scale application.
Single source precursor in situ decomposition method of latest developments, efficiently can prepare nano thin-film fast.Such as, DECTC presoma directly can generate nano metal sulfide structural membrane (such as J. Mater. Chem. 2010 on substrate, 20,6612-6617. Synthesis of metal sulfide nanomaterials via thermal decomposition of single-source precursors).But this method needs to be heated to more than 250 under an inert atmosphere and decomposes presoma.Therefore, find and new the presoma of low-temperature decomposition can prepare zinc sulfide semiconductor film fast and efficiently.
Summary of the invention
The object of the present invention is to provide a kind of can the method for low-temperature decomposition list source precursor power zinc sulfide semiconductor film or stratum granulosum in atmosphere, realize the simple and efficient preparation of semiconductive thin film, be easier to large-scale production and application.
The concrete technical scheme of the present invention is as follows:
(1) single source presoma is synthesized: adopt the precipitation method to synthesize single source xanthic acid zinc precursor;
(2) precursor solution is prepared: single source xanthic acid zinc precursor is dissolved in pyridine or containing in pyridine groups solvent, prepares the xanthic acid zinc precursor solution that uniform concentration is 0.01-2.5g/ml;
(3) prepare zinc sulfide film: be coated on cleaned substrate by xanthic acid zinc precursor solution and form precursor thin-film, then through the annealing of uniform temperature, time and atmosphere, just can obtain zinc sulfide film or stratum granulosum.
Described xanthic acid zinc precursor is the alkyl of different chain length, one or more namely in xanthopone, xanthogen zinc, zinc isopropyl xanthate, zinc butyl xanthate, isobutyl xanthan zinc, tert-butyl group xanthic acid zinc, amyl group xanthic acid zinc, isopentyl xanthic acid zinc and tertiary pentyl xanthic acid zinc.
Xanthic acid zinc precursor can adopt two kinds of method synthesis; One of method is, adopts sodium xanthogenate or potassium xanthate and solvable zinc salt one-step reaction to generate xanthic acid zinc and precipitates, then filtration, lotion, dry must xanthic acid zinc precursor powder; Two of method is, the method of organic synthesis is adopted directly to synthesize required xanthic acid zinc metal organic precursor, the synthesis of such as xanthopone: get 10 mL ethanol, it is entirely molten that 0.40 g NaOH mixes to NaOH, adds 1.4 mL carbon disulfide and stir 2 hours.Then 0.297 g zinc nitrate is dissolved in 50 mL acetone, joins above-mentioned solution stirring reaction 2 hours, leaching filtrate is naturally volatilized in room temperature and is obtained coordination polymer xanthopone precursor powder excessively.
Described annealing temperature is 110-350 DEG C, and annealing time is 5-120 minute, and annealing atmosphere is one or more in air, vacuum, nitrogen, argon gas, hydrogen.
Described painting method is spin coating method, drop-coating, dip coating, spray-on process or ink-jet printing process.
Described substrate is rigid substrate, as sheet glass or silicon chip; Or be flexible substrate, as sheet metal or plastic sheet; Or can be the porous material such as titanium oxide or aluminium oxide of porous, the stratum granulosum of zinc sulphide can be deposited in its space.
The invention has the beneficial effects as follows: present invention process is simple to operation, cheaper starting materials is easy to get, prepared zinc sulfide film crystalline quality is high, composition is easy to control, in appearance continuously, evenly, fine and close, surfacing light, and with substrate in conjunction with solid and reliable, also can prepare film on complex-shaped substrate; Common multistep complicated technology, process cycle length or high vacuum expensive device etc. can be avoided by above-mentioned technique, cost is low, be applicable to industrialization large-scale production, prepared zinc sulfide film can be applicable in the photoelectric devices such as solar cell, flat-panel monitor and light emitting diode.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further illustrated.
Accompanying drawing 1 is the X-ray diffracting spectrum of the zinc sulfide film of embodiment 1;
Accompanying drawing 2 is electron scanning micrographs of the zinc sulfide film of embodiment 2;
Accompanying drawing 3 is transmission electron microscope photos of the zinc sulfide film of embodiment 3;
Accompanying drawing 4 is the absorption spectrum of the zinc sulfide film of embodiment 4.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is further illustrated.
Embodiment 1:
Adopt the aqueous solution one-step reaction of sodium xanthogenate and zinc nitrate to generate xanthic acid zinc to precipitate, then filtration, lotion, dry must xanthic acid zinc precursor powder.Take 0.019 g ethoxy-dithioformic acid zinc powder, dissolve and be dispersed in the solution forming homogeneous transparent in the pyridine of 2 ml, this clear solution is added drop-wise on sheet glass, anneal 120 minutes at the temperature of 110 DEG C and air atmosphere, be cooled to room temperature and take out sheet glass, can find have uniform film to generate on the glass sheet.
Accompanying drawing 1 is the X-ray diffracting spectrum of zinc sulfide film prepared by embodiment 1, can confirm by figure the zinc sulphide that this is cubic structure.
Embodiment 2:
Get 10 mL ethanol, it is entirely molten that 0.40 g NaOH mixes to NaOH, adds 1.4 mL carbon disulfide and stir 2 hours.Then 0.136 g zinc chloride is dissolved in 50 mL acetone, joins above-mentioned solution stirring reaction 2 hours, leaching filtrate is naturally volatilized in room temperature and is obtained coordination polymer xanthopone precursor powder excessively.Take 0.28g ethoxy-dithioformic acid zinc powder, dissolve and be dispersed in the solution forming homogeneous transparent in the 2-picoline of 2ml, by this clear solution rotary coating on silicon chip, anneal 5 minutes at the temperature of 350 DEG C and nitrogen atmosphere, be cooled to room temperature and take out silicon chip, can find on silicon chip, have uniform film to generate.
Accompanying drawing 2 is the electron scanning micrograph of zinc sulfide film prepared by embodiment 2, and zinc sulfide film is evenly distributed on silicon chip surface as seen from the figure.
Embodiment 3:
Adopt the aqueous solution one-step reaction of potassium xanthate and zinc chloride to generate xanthic acid zinc to precipitate, then filtration, lotion, dry must xanthic acid zinc precursor powder.Take 0.45g ethoxy-dithioformic acid zinc powder, dissolve and be dispersed in the solution forming homogeneous transparent in the pyridine of 1 ml, this clear solution is added drop-wise on plastic sheet, anneal 25 minutes at the temperature of 160 DEG C and vacuum, be cooled to room temperature and take out plastic sheet, can find on plastic sheet, have uniform film to generate.
Accompanying drawing 3 is the transmission electron microscope photo of zinc sulfide film prepared by embodiment 3, and zine sulfide nano particles is mostly spherical as seen from the figure, and zine sulfide nano particles diameter is about 2-3 nanometer.
Embodiment 4:
Get 10 mL ethanol, it is entirely molten that 0.40 g NaOH mixes to NaOH, adds 1.4 mL carbon disulfide and stir 2 hours.Then 0.297 g zinc nitrate is dissolved in 50 mL acetone, joins above-mentioned solution stirring reaction 2 hours, leaching filtrate is naturally volatilized in room temperature and is obtained coordination polymer xanthopone precursor powder excessively.Take 0.1 g ethoxy-dithioformic acid zinc powder, dissolve and be dispersed in the solution forming homogeneous transparent in 0.3 ml pyridine, porous oxidation aluminium flake to be immersed in this clear solution after 10 minutes, porous oxidation aluminium flake is taken out from solution, anneal 15 minutes in the temperature of 250 DEG C and air, be cooled to room temperature and take out porous oxidation aluminium flake, can find in the hole of porous oxidation aluminium flake, have uniform film to generate.
Accompanying drawing 4 is the absorption spectrum of zinc sulfide film prepared by embodiment 4.The absworption peak of zinc sulfide film is at about 312 nm as seen from the figure, and the quantum showing zinc sulfide semiconductor falls into territory effect.
Embodiment 5:
Adopt the aqueous solution one-step reaction of sodium xanthogenate and zinc nitrate to generate xanthic acid zinc to precipitate, then filtration, lotion, dry must xanthic acid zinc precursor powder.Take 0.25g ethoxy-dithioformic acid zinc powder, dissolve and be dispersed in the solution forming homogeneous transparent in 0.1ml pyridine, this clear solution is added drop-wise on copper sheet, at the temperature of 150 DEG C and hydrogen annealing 20 minutes, be cooled to room temperature and take out copper sheet, can find on copper sheet, have uniform film to generate.
By reference to the accompanying drawings the specific embodiment of the present invention is described although above-mentioned; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (6)
1. a simple high efficiency preparation method for zinc sulfide semiconductor film, is characterized in that: comprise the steps:
(1) single source presoma is synthesized: adopt the precipitation method to synthesize single source xanthic acid zinc precursor;
(2) precursor solution is prepared: single source xanthic acid zinc precursor is dissolved in pyridine or containing in the solvent of pyridine, prepares the xanthic acid zinc precursor solution that uniform concentration is 0.01-2.5 g/ml;
(3) zinc sulfide film is prepared: be coated on cleaned substrate by single source xanthic acid zinc precursor solution and form precursor thin-film, then through 110-350 DEG C, annealing in 5-120 minute, annealing atmosphere is one or more in air, vacuum, nitrogen, argon gas, hydrogen, just can obtain zinc sulfide film or stratum granulosum.
2. the simple high efficiency preparation method of a kind of zinc sulfide semiconductor film according to claim 1, is characterized in that: described single source xanthic acid zinc precursor is one or more in xanthopone, xanthogen zinc, zinc isopropyl xanthate, zinc butyl xanthate, isobutyl xanthan zinc, tert-butyl group xanthic acid zinc, amyl group xanthic acid zinc, isopentyl xanthic acid zinc and tertiary pentyl xanthic acid zinc.
3. the simple high efficiency preparation method of a kind of zinc sulfide semiconductor film according to claim 1, it is characterized in that: the described precipitation method synthesize single source xanthic acid zinc precursor, reacted by sodium xanthogenate or potassium xanthate and solvable zinc salt to generate xanthic acid zinc and precipitate, filtration, lotion, dry xanthic acid zinc precursor.
4. the simple high efficiency preparation method of a kind of zinc sulfide semiconductor film according to claim 1, is characterized in that: described single source xanthic acid zinc precursor also can adopt methodology of organic synthesis to prepare.
5. the simple high efficiency preparation method of a kind of zinc sulfide semiconductor film according to claim 1, is characterized in that: described painting method is spin coating method, drop-coating, dip coating, spray-on process or ink-jet printing process.
6. the simple high efficiency preparation method of a kind of zinc sulfide semiconductor film according to claim 1, is characterized in that: described substrate is sheet glass, silicon chip, sheet metal, plastic sheet, the titanium oxide of porous or aluminium oxide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793069A (en) * | 1970-08-17 | 1974-02-19 | Tokyo Shibaura Electric Co | Process for preparing a layer of compounds of groups ii and vi |
| CN103400892A (en) * | 2013-07-09 | 2013-11-20 | 山东建筑大学 | Method for preparing zinc sulfide optoelectronic film |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793069A (en) * | 1970-08-17 | 1974-02-19 | Tokyo Shibaura Electric Co | Process for preparing a layer of compounds of groups ii and vi |
| CN103400892A (en) * | 2013-07-09 | 2013-11-20 | 山东建筑大学 | Method for preparing zinc sulfide optoelectronic film |
Non-Patent Citations (2)
| Title |
|---|
| V.G.. Bessergenev,et al.optical and structural proper ties of ZnS and ZnS:Mn films prepared by CVD method.《Metaials Research Bulletin》.1995,第30卷(第11期),第1393-1400页. * |
| 沉淀溶解法制备纳米硫化锌;郝伟等;《无机化学学报》;20070310;第23卷(第3期);第1.2.3节 * |
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