CN102701264B - Combining method of Ag2S photoelectric detection material - Google Patents
Combining method of Ag2S photoelectric detection material Download PDFInfo
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- CN102701264B CN102701264B CN201210115223.3A CN201210115223A CN102701264B CN 102701264 B CN102701264 B CN 102701264B CN 201210115223 A CN201210115223 A CN 201210115223A CN 102701264 B CN102701264 B CN 102701264B
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Abstract
The invention relates to a combining method of a Ag2S photoelectric detection material and belongs to the technical field of preparation of inorganic compound semiconductor materials. The method includes mixing sulfocompound and silver nitrate according to the molar ratio of 3-4:1, adding a stabilizer into the mixture, dissolving the mixture into water to prepare mixed solution, conducting reaction for 4-6 hours under the condition of 160-180 DEG C and conducting washing, centrifuging and drying to obtain Ag2S photoelectric detection material powder. The sulfocompound is thiocarbamide or sodium thiosulfate preferably, and the stabilizer is lauryl sodium sulfate or glutathione preferably. The combining method adopts a hydrothermal synthesis method, and is simple in whole operation process, good in repeatability and low in cost. Prepared Ag2S has good photoelectric response characteristics-wide band and high photoelectric response and can be applied to optical detectors.
Description
Technical field
The present invention relates to a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, belongs to technical field prepared by inorganic compound semiconductor material.
Background technology
Along with the development of photoelectric detecting technology, utilize semiconductor light electrical property to carry out the light detecter for semiconductor of response transmission, have efficiently, advantage accurately, is widely used.According to the response interval division of photodetector incident light, can be divided into UV-detector, visible light detector, infrared detector etc.Due to Si good photoelectric properties between visible region, the visible light detector of present stage is the core component using Si material as device still.And the related element of the core material that near infrared and infrared light detector use, mostly be long period element, there is the common material for infrared light detection of report to have the sosoloid HgCdTe being formed by HgTe and CdTe bi-material, InGaAs series material and Ge
xsi
1-xdeng semiconductor material, and the wavelength region that can detect is from 0.8 micron to more than 10 microns, but present reported near infrared and the detectivity of infrared light detector below 800nm are still limited.Ultraviolet light detector utilizes semiconductor material for passing through atmospheric absorption, is in below wavelength 300nm---and the photoelectric response of the UV-light of so-called " day blind area ", is prepared from.As SiC, GaN, AlGaN, ZnO etc., are the ripe semiconductor materials of development preparation.Synthetic convenient, with low cost is also one of UV-detector reason of becoming the swiftest and the most violent light detecter for semiconductor of present stage development.
But the photoelectric response interval of above-mentioned materials is all in single wavelength interval, its response light scope, becomes and limits the further bottleneck of application of these semiconductor materials.If the semiconductor material for photodetector can have photoelectric response ability for all wave band light of infrared-visible-ultraviolet, its using value and range of application all can increase greatly.Therefore, select response interval wide in range, response efficiency is high, preparation method simple and safe semiconductor material become key problem.
Ag
2s is as a kind of narrow bandgap semiconductor material, because it has good chemical stability and light amplitude limit under normal temperature condition, just as a kind of special ionic conductor, can ion and electronics jointly conduct electricity, at photoelectric field, there are the potentiality of application, be applied in photoelectric device and solar cell.Lot of domestic and foreign study group is for Ag
2how the research of S also launches based on this.
For Ag
2the synthesis preparation method of S, ripe reaction mechanism is that react under the modification of stablizer in Yu Yin source, sulphur source.Y.D.Ling, et.al. utilizes stearylamine as stablizer, and S powder is sulphur source, utilizes high-temperature solvent thermal means to prepare Ag
2s nano wire, prepared Ag
2s nano wire has air-sensitive response characteristic for oxygen.But be solid-state under stearylamine normal temperature, and the effect of act as solvents in reaction process, so whole operation need to be located at high temperature to carry out, this is for Preparation equipment, the having relatively high expectations of operation and environment, present stage, its device using value was not high.
L.H.Dong, et.al. mentions and utilizes thiocarbamide for sulphur source, and CTAB is tensio-active agent is prepared cubes pattern Ag through the method for Hydrothermal Synthesis
2s nanostructure.W.S.Chin, et.al. utilizes respectively hexadecylamine (HDA), octylame (OA), quadrol (EDA), the organism stablizers such as Di-Octyl amine (DOA) are prepared Ag
2s nanocrystal.The two is chosen with the selection of reaction conditions for Ag stablizer
2the control of S nanocrystal pattern is explored, but above-mentioned document is in order to pursue Ag
2the pattern of S material, does not propose the easily reaction conditions of realization, in the optimization setting in experimental temperature and reaction times, still needs further improvement.
Summary of the invention
The technical problem to be solved in the present invention is, is with comparatively easy preparation means, optimization experiment temperature and reaction times, prepares the Ag with the strong response of wide band
2s semiconductor crystal material, can be widely used in photodetector it.
Provide a kind of wide wavelength response range, high light electroresponse Ag
2s material preparation method after Silver Nitrate is evenly mixed with the solution of sulfocompound (thiocarbamide or Sulfothiorine) and stablizer, reacts final synthetic have wide band, the Ag of high light electroresponse under the high-temperature and high-pressure conditions of hydro-thermal
2s material.
Technical solution of the present invention is as follows:
A kind of Ag
2the synthetic method of S Photoelectric Detection material, step is as follows:
Take mol ratio 3～4: 1 sulfocompound and Silver Nitrate, as raw material, are added to the water raw material and stablizer, and ultrasonic or magnetic agitation mixes it, obtains precursor solution; Wherein, the consumption of stablizer is 0～0.15 times of Silver Nitrate mole number, and the consumption of water is calculated as 0.03～0.04mol/L by the concentration of Silver Nitrate;
The precursor solution of gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, under 160～180 ℃ of conditions, reacts 4～6 hours, naturally cool to room temperature; Products therefrom alternately washs 4～6 times with redistilled water and ethanol, dry again after centrifugation, obtains Ag
2the powder of S Photoelectric Detection material.
Described sulfocompound is thiocarbamide or Sulfothiorine.
Described stablizer can be the stablizer of prior art use, the one in preferably sodium dodecyl sulfate of the present invention, gsh.
The technical scheme of further optimizing is:
Take 1: 3 Silver Nitrate of mol ratio and Sulfothiorine as raw material, take the sodium lauryl sulphate of 0～0.1 times of Silver Nitrate mole number as stablizer, raw material and stablizer are added to the water, the consumption of water is counted 0.03～0.04mol/L by the consumption of Silver Nitrate, ultrasonic agitation mixes it, obtains precursor solution; Precursor solution is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, and at 160 ℃～180 ℃, isothermal reaction 4～6 hours, naturally cools to room temperature; Centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol, then drying, obtain Ag
2the powder of S Photoelectric Detection material.
The another kind of technical scheme of optimizing is:
Take mol ratio 1: 3～4 Silver Nitrates and thiocarbamide as raw material, take the gsh of 0.15 times of Silver Nitrate mole number as stablizer, raw material and stablizer are added to the water, the consumption of water is counted 0.03～0.04mol/L by the consumption of Silver Nitrate, and ultrasonic agitation mixes it, obtains precursor solution; Precursor solution is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, and at 180 ℃, isothermal reaction 4 hours, naturally cools to room temperature; Centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol, then drying, obtain Ag
2the powder of S Photoelectric Detection material.
The one that the present invention proposes is prepared Ag
2the Ag that the method for S is prepared
2s has good photoelectric response characteristic (wide band, high light electroresponse), and can be applied in photodetector.The method has easy and simple to handle, synthesis condition gentleness, the feature such as speed of response is fast, and cost is low.And character stable homogeneous.
Accompanying drawing explanation
Fig. 1 is the wide wavelength response range of one prepared by embodiment 1, high light electroresponse Ag
2the X ray diffracting spectrum of S Photoelectric Detection material powder;
Fig. 2 is the wide wavelength response range of one prepared by embodiment 1, high light electroresponse Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates;
Fig. 3 is the wide wavelength response range of one prepared by embodiment 1, high light electroresponse Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder.
Fig. 4 is the wide wavelength response range of one prepared by embodiment 2, high light electroresponse Ag
2the X ray diffracting spectrum of S Photoelectric Detection material powder;
Fig. 5 is the wide wavelength response range of one prepared by embodiment 2, high light electroresponse Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates;
Fig. 6 is the wide wavelength response range of one prepared by embodiment 2, high light electroresponse Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder.
Fig. 7 is the wide wavelength response range of one prepared by embodiment 3, high light electroresponse Ag
2the X ray diffracting spectrum of S Photoelectric Detection material powder;
Fig. 8 is the wide wavelength response range of one prepared by embodiment 3, high light electroresponse Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates;
Fig. 9 is the wide wavelength response range of one prepared by embodiment 3, high light electroresponse Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder.
Figure 10 is for certainly building surface photovoltage commercial measurement system architecture schematic diagram.
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to this.
The embodiment of the present invention is raw materials used is commercial analytical pure product, before use, is not further purified.
Wide wavelength response range prepared by the embodiment of the present invention, high light electroresponse Ag
2the thing of S Photoelectric Detection material powder is mutually by X-ray diffraction spectra (XRD) test (XRD, Rigaku Max-2550).
Wide wavelength response range prepared by the embodiment of the present invention, high light electroresponse Ag
2the ultraviolet-visible absorption spectroscopy of S Photoelectric Detection material powder is tested (Shimadzu, UV-3600) by uv-vis spectra scanner.
Wide wavelength response range prepared by the embodiment of the present invention, high light electroresponse Ag
2the surface photovoltage of S Photoelectric Detection material powder is measured by certainly building surface photovoltage commercial measurement system.Installation composition is referring to Figure 10, concrete: light source is a 500W xenon lamp (CHF-XQ500W Global xenon lamp power), by grating monochromator (Omni-5007, No.09010, Zolix), obtains monochromatic ray.For phase-locked photovoltaic technology, use Stanford chopper (Model SR540) modulated monochromatic light, modulating frequency is 20-70Hz, uses Stanford lock-in amplifier (Model SR830-DSP Lock-in Amplifier) to carry out the amplification of photovoltaic signal.The sweep velocity of computer control monochromator, and use lock-in amplifier image data.Spectral resolution is 1nm.
Measuring principle and method are: the monochromatic ray that light-source system provides is radiated at material sample surface, and the light induced electron of generation is separate under the effect of separation mechanism with hole, form photosignal, and signal is gathered by lock-in amplifier.Measured signal is surface photovoltage intensity, and its intensity is relevant with the quantity of photogenerated charge electron-hole pair separation.
Embodiment 1, a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, step is as follows:
Take respectively 1 mmole Silver Nitrate, 3 mmole Sulfothiorine, 0.1 mmole sodium lauryl sulphate, 30 ml waters, ultrasonic agitation mixes it, obtains precursor solution;
By step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, isothermal reaction 4 hours at 180 ℃, naturally cool to after completion of the reaction room temperature, products therefrom is used centrifugation after redistilled water and absolute ethanol washing 4 times at ambient temperature, product after separation obtains Ag after being dried
2the powder of S Photoelectric Detection material.
The Ag that the present embodiment is synthetic
2the X ray diffracting spectrum of S Photoelectric Detection material powder is shown in Fig. 1, synthetic Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates and sees Fig. 2, synthetic Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder is shown in Fig. 3.
Embodiment 2, a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, step is as follows:
Take respectively 1 mmole Silver Nitrate, 3 mmole thiocarbamides, 0.15 mmole gsh, 30 ml waters, ultrasonic agitation mixes it, obtains precursor solution;
By step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, isothermal reaction 4 hours at 180 ℃, naturally cool to after completion of the reaction room temperature, centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol at ambient temperature, product after separation obtains Ag after being dried
2the powder of S Photoelectric Detection material.
The Ag that the present embodiment is synthetic
2the X ray diffracting spectrum of S Photoelectric Detection material powder is shown in Fig. 4, synthetic Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates and sees Fig. 5, synthetic Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder is shown in Fig. 6.
Embodiment 3, a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, step is as follows:
Take respectively 1 mmole Silver Nitrate, 3 mmole Sulfothiorine, 30 ml waters, ultrasonic agitation mixes it, obtains precursor solution;
By step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, isothermal reaction 4 hours at 180 ℃, naturally cool to after completion of the reaction room temperature, centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol at ambient temperature, product after separation obtains Ag after being dried
2the powder of S Photoelectric Detection material.
The Ag that the present embodiment is synthetic
2the X ray diffracting spectrum of S Photoelectric Detection material powder is shown in Fig. 7, synthetic Ag
2the UV, visible light of S Photoelectric Detection material powder absorbs collection of illustrative plates and sees Fig. 8, synthetic Ag
2the surface photovoltage spectrogram of S Photoelectric Detection material powder is shown in Fig. 9.
Embodiment 4, a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, step is as follows:
Take respectively 1 mmole Silver Nitrate, 4 mmole thiocarbamides, 0.15 mmole gsh, 30 ml waters, ultrasonic agitation mixes it, obtains precursor solution;
By step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, isothermal reaction 4 hours at 180 ℃, naturally cool to after completion of the reaction room temperature, centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol at ambient temperature, product after separation obtains Ag after being dried
2the powder of S Photoelectric Detection material.Products therefrom XRD, UV, visible light absorbs and surface photovoltage characterizes substantially the same manner as Example 2.
Embodiment 5, a kind of wide wavelength response range, high light electroresponse Ag
2the hydrothermal synthesis method of S Photoelectric Detection material, step is as follows:
Take respectively 1 mmole Silver Nitrate, 3 mmole Sulfothiorine, 0.1 mmole sodium lauryl sulphate, 30 ml waters, ultrasonic agitation mixes it, obtains precursor solution;
By step 1) the precursor solution of gained is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, isothermal reaction 6 hours at 160 ℃, naturally cool to after completion of the reaction room temperature, centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol at ambient temperature, product after separation obtains Ag after being dried
2the powder of S Photoelectric Detection material.Products therefrom XRD, UV, visible light absorbs and surface photovoltage characterizes substantially the same manner as Example 1.
Claims (4)
1. an Ag
2the synthetic method of S Photoelectric Detection material, step is as follows:
Take mol ratio 3～4: 1 sulfocompound and Silver Nitrate, as raw material, are added to the water raw material and stablizer, and ultrasonic or magnetic agitation mixes it, obtains precursor solution; Described stablizer, is sodium lauryl sulphate or gsh, and the consumption of stablizer is 0.1 or 0.15 times of Silver Nitrate mole number; The consumption of water is calculated as 0.03～0.04mol/L by the concentration of Silver Nitrate;
The precursor solution of gained is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, under 160～180 ℃ of conditions, reacts 4～6 hours, naturally cool to room temperature; Products therefrom alternately washs 4～6 times with redistilled water and ethanol, dry again after centrifugation, obtains Ag
2the powder of S Photoelectric Detection material.
2. a kind of Ag according to claim 1
2the synthetic method of S Photoelectric Detection material, is characterized in that, described sulfocompound is thiocarbamide or Sulfothiorine.
3. a kind of Ag according to claim 1
2the synthetic method of S Photoelectric Detection material, it is characterized in that, take 1: 3 Silver Nitrate of mol ratio and Sulfothiorine as raw material, take the sodium lauryl sulphate of 0.1 times of Silver Nitrate mole number as stablizer, raw material and stablizer are added to the water, the consumption of water is counted 0.03～0.04mol/L by the consumption of Silver Nitrate, and ultrasonic agitation mixes it, obtains precursor solution; Precursor solution is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, and at 160 ℃～180 ℃, isothermal reaction 4～6 hours, naturally cools to room temperature; Centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol, then drying, obtain Ag
2the powder of S Photoelectric Detection material.
4. a kind of Ag according to claim 1
2the synthetic method of S Photoelectric Detection material, it is characterized in that, take mol ratio 1: 3～4 Silver Nitrates and thiocarbamide as raw material, take the gsh of 0.15 times of Silver Nitrate mole number as stablizer, raw material and stablizer are added to the water, the consumption of water is counted 0.03～0.04mol/L by the consumption of Silver Nitrate, ultrasonic agitation mixes it, obtains precursor solution; Precursor solution is transferred in the stainless steel cauldron that liner is tetrafluoroethylene, and at 180 ℃, isothermal reaction 4 hours, naturally cools to room temperature; Centrifugation after products therefrom alternately washs 4 times with redistilled water and dehydrated alcohol, then drying, obtain Ag
2the powder of S Photoelectric Detection material.
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| CN107746070A (en) * | 2017-09-21 | 2018-03-02 | 东华大学 | A kind of preparation method of oil-soluble vulcanization silver nano material |
| CN109054812B (en) * | 2018-08-24 | 2021-06-22 | 南京邮电大学 | Method for preparing near-infrared two-region fluorescent silver sulfide quantum dots in water phase |
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