CN105152228A - Controllable preparation method of multielement sulfide semiconductor nano-material - Google Patents
Controllable preparation method of multielement sulfide semiconductor nano-material Download PDFInfo
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- CN105152228A CN105152228A CN201510262386.8A CN201510262386A CN105152228A CN 105152228 A CN105152228 A CN 105152228A CN 201510262386 A CN201510262386 A CN 201510262386A CN 105152228 A CN105152228 A CN 105152228A
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Abstract
The invention relates to a controllable preparation method of a multielement sulfide semiconductor nano-material. The controllable preparation method comprises 1, weighing a metal salt and a high boiling point organic solvent, and carrying out mixing stirring dissolution to obtain a metal salt solution, 2, weighing a solid sulfur source and dissolving the solid sulfur source in the high boiling point organic solvent to obtain a sulfur solution or directly utilizing a liquid sulfur source as a sulfur solution, 3, respectively heating the metal salt solution and the sulfur solution, injecting the sulfur solution into the metal salt solution, heating the mixed solution to a reaction temperature, and carrying out a reaction process, and 4, cooling the reaction liquid, carrying out washing, carrying out centrifugation until the supernatant liquid is clear and transparent, putting the obtained black solids into a drying oven and carrying out drying to obtain the multielement sulfide semiconductor nano-material. Through control of reaction time, a reaction temperature, reaction raw material types and sulfur source types, accurate regulation and control of material morphology, size, phase structure and optical properties are realized. The controllable preparation method of the multielement sulfide semiconductor nano-material has the advantages of low price, simple processes, safety, environmental friendliness and industrial production easiness.
Description
Technical field
The present invention relates to a kind of controllable method for preparing of polynary sulfide semiconductor nano material; Particularly relate to technical field prepared by a kind of binary and quaternary sulfide semiconductor nano material.
Background technology
Along with the aggravation of environmental pollution and the day by day deficient of traditional fossil energy, be that the renewable cleaning new energy of representative is developed rapidly with sun power, and solar cell is as one of the most effective way of Solar use, start to play a role at current new energy field, and constantly affect the energy revolution of a new generation.
Solar cell is based semiconductor material, utilizes " photovoltaic effect ", sun power is directly changed into the device of electric energy.Since mid-term in last century comes out, solar battery technology experienced by three generations, first-generation crystalline silicon (Si) solar cell (silicon single crystal, polysilicon).The s-generation is the thin-film solar cells (cadmium telluride CdTe, the copper-indium-galliun-selenium CuIn that improve and make with inorganic semiconductor
xga
1-xse
2), transformation efficiency all can exceed first-generation battery, crustal elements but needed for battery rare (as indium, gallium etc.), and containing poisonous heavy metal (as cadmium, tellurium, selenium), can not meet the active demand of the mankind to green energy resource and Sustainable development.Third generation novel solar battery mainly comprises quantum dot cell, dye-sensitized cell, organic solar batteries etc., it is higher that they solve first-generation silica-based solar cell cost, the problem that s-generation thin-film solar cells efficiency of conversion is low, there is the advantages such as abundant raw materials, nontoxic, good stability, environmental pollution are little, thus obtain the extensive concern in the whole world, and become important directions and the study hotspot of solar cell development gradually.
Ferrous disulfide (FeS
2, pyrite) there is suitable energy gap (0.95eV), high specific absorbance (is greater than 10 within the scope of hv>1.3eV
5cm
-1), relatively large minority diffusion length (100-1000nm) becomes a kind of proper sun power light absorption layer material.Especially high specific absorbance, allows it only just can absorb the sunlight of more than 90% with the film that 20nm is thick, can greatly reduce battery cost relative to the absorber thickness of silion cell 2 μm.FeS in addition
2fe and the S element comprised has earth rich reserves and the advantage such as nontoxic, and this makes FeS
2there are the potentiality of large-scale application.
Cu
2znSnS
4be called for short CZTS, be also a kind of solar cell material of very promising low cost, its direct band gap is 1.5eV, and match with the best band gap numerical value required by the solar cell that the earth uses, photoabsorption coefficient is up to 10
5cm
-1, and there is the feature such as hypotoxicity and high irradiation stability.CZTS is a kind of semiconductor sulfide of quaternary, has two kinds of crystal formations, and a kind of is the kesterite (kesterite) of tetragonal system, and another kind is the wurtzite-type (wurtzite) of hexagonal system.The element crustal abundance of CZTS composition is high, and the earth reserves of copper, zinc and tin are respectively 630,250 and 5.2 hundred ten thousand tons, and therefore CZTS significantly can reduce the cost of solar cell, is to substitute based on CuIn
xga
1-xse
2the candidate material desirable with the thin-film solar cells of CdTe.
The synthesis of the semiconductor sulfide reported in document mainly contains vapour deposition process, molecular beam epitaxy, spray pyrolysis, thermal decomposition method, hydrothermal method, high temperature vulcanized method etc.Wherein vapour deposition process, molecular beam epitaxy, spray pyrolysis are to equipment requirements and requirement for experiment condition harshness, and prepared material is generally difficult to control in metering component, is unfavorable for prepared by mass-producing.And hydrothermal method and high temperature vulcanized method require all relatively stricter to the pressure and temperature needed for experiment, the material of preparation dimensionally also can be comparatively large, is easy to exceed nano level category.Comparatively speaking, thermal decomposition method is also relatively low to the requirement of experiment condition, and material prepared by this method generally has good distribution of sizes, higher crystal structure degree and dispersed preferably, and is easier to be amplified by equal proportion accomplish scale production.
Summary of the invention
Object of the present invention is for preparing FeS at present
2and the deficiency of the various methods of CZTS nano particle and problem, and the controllable method for preparing of a kind of polynary sulfide semiconductor nano material proposed.
First technical problem to be solved by this invention realizes innovatively having prepared pattern, size, the diversified FeS of phase structure
2and CZTS nano particle.
Second technical problem to be solved by this invention is that the industrial reaction time cycle is short, and the single sintering shortest time is only 1 hours, and repeatability is very good.
3rd technical problem to be solved by this invention is that the technique of invention is simple, low for equipment requirements, compared to hydrothermal method and solvent-thermal method, without the need to using high temperature high pressure device, is applicable to industrialization scale operation.
Technical scheme of the present invention is: a kind of controllable method for preparing of polynary sulfide semiconductor nano material, and its concrete steps are as follows:
1) metal-salt and the dissolving of high boiling organic solvent mix and blend is taken, preparing metal salts solution;
2) take solid sulfur source to be dissolved in high boiling organic solvent and to prepare sulphur solution, or directly use liquid sulfur source as sulphur solution;
3) respectively heating steps 1) in metal salt solution and step 2) in sulphur solution, then by sulphur injection of solution in metal salt solution, then heated solution reacts to temperature of reaction;
4) by the solution cooling after having reacted, to supernatant liquid clear with organic solvent washing, centrifugal (can repeated centrifugation and washing), finally the black solid obtained be put into oven drying and obtain polynary sulfide semiconductor nano material.
Preferably above-mentioned metal-salt is one or more in iron(ic) chloride, iron protochloride, cupric chloride, neutralized verdigris, acetylacetone copper, zinc chloride, zinc acetate, zinc acetylacetonate or tin tetrachloride.
Preferably above-mentioned high boiling organic solvent is one or more in oleyl amine, stearylamine or octadecylene.
Preferably above-mentioned solid sulfur source is sulphur powder; Described liquid sulfur source is n-dodecyl mereaptan.
The temperature of preferred described heating of metal salts solution is 120-250 DEG C; The temperature of described heating sulphur solution is 70-100 DEG C.
Preferably described temperature of reaction is 220-250 DEG C; The described reaction times is 30-180min.
During preparing metal salts solution, preferable alloy salt and organic solvent mass ratio are 1:(10-100); During preparation sulphur solution, preferred solid sulfur source and organic solvent mass ratio are 1:(10-20).
Step 3) in by sulphur injection of solution in metal salt solution, the mass ratio controlling metal-salt and sulfur material is 1:(0.2-5).
The organic solvent being preferred for washing is normal hexane or chloroform.Preferred steps 4) described in centrifugal rotational speed be 6000-8000rpm; Described centrifugation time is 3-5min; Step 4) described in the temperature of drying be 60-80 DEG C; The dry time is 3-6h.
Beneficial effect: due to the unstable of polynary sulfide, cause its synthesis difficulty, especially in material, the ratio of each element is difficult to correct regulation and control especially, causes material to be difficult to reach good effect in final application.The present invention adopts cheap metal-salt and sulfur material to be that raw material reacts in high boiling organic solvent, successfully synthesize the product that stoichiometric ratio is correct, and achieve the accuracy controlling to material morphology, size, phase structure and optical property by control reaction times, temperature of reaction, reaction raw materials kind and sulphur source category.The present invention be the preparation of polynary sulfide semiconductor nano material provide one cheap, technique is simple, and safety and environmental protection, is easy to the method for suitability for industrialized production.
Accompanying drawing explanation
The FeS of Fig. 1 prepared by embodiment 1
2the XRD figure of nano particle;
The FeS of Fig. 2 prepared by embodiment 1
2the SEM figure of nano particle;
The FeS of Fig. 3 prepared by embodiment 2
2the XRD figure of nano particle;
The FeS of Fig. 4 prepared by embodiment 2
2the SEM figure of nano particle;
The FeS of Fig. 5 prepared by embodiment 3
2the XRD figure of nano particle;
The FeS of Fig. 6 prepared by embodiment 3
2the SEM figure of nano particle;
The XRD figure of the CZTS nano particle of Fig. 7 prepared by embodiment 4;
The SEM figure of the CZTS nano particle of Fig. 8 prepared by embodiment 4;
The XRD figure of the CZTS nano particle of Fig. 9 prepared by embodiment 5;
The SEM figure of the CZTS nano particle of Figure 10 prepared by embodiment 5.
Embodiment
Below in conjunction with drawings and Examples, the present invention is described in further detail
FeS
2implementation example prepared by nano particle
Embodiment 1:
1) take 100mg iron protochloride and 10g stearylamine joins in the four-hole boiling flask of 50ml, add rotor stirring and dissolving.
2) take 100mg sulphur powder to be dissolved in 2g stearylamine, be heated to 100 DEG C, stir and make it dissolve.
3) 1 is heated) middle solution to 120 DEG C.By 2) in injection of solution to 1) in solution after continue be heated to 220 DEG C and keep 180min at this temperature.
4) treat that system is cooled to room temperature, with chloroform gained solution and under 6000rpm rotating speed centrifugal 3 minutes.Repeated washing, centrifugal until last centrifugal liquid be clear, the baking oven drying of then black solid obtained being put into 80 DEG C obtained FeS after 6 hours
2nano particle.
X-ray diffractometer is adopted to carry out phase composite qualification to the material prepared by embodiment 1.The 2 θ Angle Position occurred as the peak in Fig. 1, figure are 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 °, 50.5 °, 56.3 °, 59.0 °, correspond respectively to 111,200,210,211,220,221,311,222 crystal faces, are shown as FeS
2(pyrite) crystalline phase.The product described prepared by embodiment 1 is the FeS of pure phase
2.
Scanning electronic microscope (SEM) microtexture to the material prepared by embodiment 1 is adopted to analyze, as shown in Figure 2.As can be seen from the figure, the pattern of material is cubic type, distribution of sizes at 50-200nm, the favorable dispersity of particle.The product described prepared by embodiment 1 has preferable quality.
Embodiment 2:
1) take 278mg iron(ic) chloride and 15g oleyl amine joins in 50ml four-hole boiling flask, add rotor stirring and dissolving.
2) take 192mg sulphur powder to be dissolved in 2g oleyl amine, be heated to 90 DEG C, stirring and dissolving.
3) heat 1) in solution to 220 DEG C, by 2) in injection of solution to 1) in solution, after temperature recovery to 220 DEG C, keep 60min at such a temperature.
4) treat that system is cooled to room temperature, with n-hexane gained solution and under 8000rpm rotating speed centrifugal 5 minutes.Repeated washing, centrifugal until last centrifugal liquid be clear, the baking oven then black solid obtained being put into 80 DEG C must FeS after dry 3 hours
2nano particle.
X-ray diffractometer is adopted to carry out phase composite qualification to the material prepared by embodiment 2.The 2 θ Angle Position occurred as the peak in Fig. 3, figure are 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 °, 50.5 °, 56.3 °, 59.0 °, correspond respectively to 111,200,210,211,220,221,311,222 crystal faces, are shown as FeS
2(pyrite) crystalline phase.The product described prepared by embodiment 2 is the FeS of pure phase
2.
Scanning electronic microscope (SEM) microtexture to the material prepared by embodiment 2 is adopted to analyze, as shown in Figure 4.As can be seen from the figure, the pattern of material is spherical, distribution of sizes at 10-15nm, the favorable dispersity of particle.The product described prepared by embodiment 2 has preferable quality.
Embodiment 3:
1) take 278mg iron(ic) chloride and 10g oleyl amine joins in 50ml four-hole boiling flask, add rotor stirring and dissolving.
2) take 256mg sulphur powder to be dissolved in 4g octadecylene, be heated to 100 DEG C, stirring and dissolving.
3) heat 1) in solution to 220 DEG C, by 2) in injection of solution to 1) in solution, after temperature recovery to 220 DEG C, keep 30min at such a temperature.
4) treat that system is cooled to room temperature, with n-hexane gained solution and under 6000rpm rotating speed centrifugal 3 minutes.Repeated washing, centrifugal until last centrifugal liquid be clear, the baking oven then black solid obtained being put into 70 DEG C must FeS after dry 4 hours
2nano particle.
X-ray diffractometer is adopted to carry out phase composite qualification to the material prepared by embodiment 3.The 2 θ Angle Position occurred as the peak in Fig. 5, figure are 28.5 °, 33.1 °, 37.1 °, 40.8 °, 47.4 °, 50.5 °, 56.3 °, 59.0 °, correspond respectively to 111,200,210,211,220,221,311,222 crystal faces, are shown as FeS
2(pyrite) crystalline phase.The product described prepared by embodiment 3 is the FeS of pure phase
2.
Scanning electronic microscope (SEM) microtexture to the material prepared by embodiment 3 is adopted to analyze, as shown in Figure 6.As can be seen from the figure, the pattern of material is cluster type, distribution of sizes at 50-100nm, the favorable dispersity of particle.The product described prepared by embodiment 3 has preferable quality.
Implementation example prepared by CZTS nano particle
Embodiment 4:
1) take 356mg cupric chloride, 136mg zinc chloride and 701mg tin tetrachloride, add 5g octadecylene and the dissolving of 15g oleyl amine mixed solvent, add rotor stirring and dissolving.
2) take 256mg sulphur powder to be dissolved in 5g oleyl amine, be heated to 70 DEG C, stirring and dissolving.
3) heat 1) in solution to 250 DEG C, by 2) in injection of solution to 1) in solution, after temperature recovery to 250 DEG C, keep 30min.
4) treat that system is cooled to room temperature, with n-hexane gained solution and under 8000rpm rotating speed centrifugal 5 minutes.Repeated washing, centrifugal until last centrifugal liquid be clear, the baking oven then black solid obtained being put into 80 DEG C must CZTS nano particle after dry 3 hours.
With x-ray diffractometer, phase composite qualification is carried out to the material prepared by embodiment 5.The 2 θ Angle Position occurred as the peak in Fig. 7, figure are 28.5 °, 33.0 °, 47.3 °, 56.2 °, 59.0, correspond respectively to 112,200,220,312,224 crystal faces, are shown as CZTS (Emission in Cubic) crystalline phase.The product described prepared by embodiment 5 is pure Emission in Cubic CZTS.
Scanning electronic microscope (SEM) microtexture to the material prepared by embodiment 5 is adopted to analyze, as shown in Figure 8.As can be seen from the figure, the pattern of material is spherical, distribution of sizes at 15-20nm, the favorable dispersity of particle.The product described prepared by embodiment 5 has preferable quality.
Embodiment 5:
1) take 799mg neutralized verdigris, 439mg zinc acetate and 701mg tin tetrachloride, add 10g octadecylene and the dissolving of 10g oleyl amine mixed solvent, add rotor stirring and dissolving.
2) get 9g n-dodecyl mereaptan in four-hole boiling flask, be heated to 100 DEG C
3) heat 1) in solution to 250 DEG C, then by 2) in injection of solution to 1) in solution, after temperature recovery to 250 DEG C, keep 60min at such a temperature.
4) treat that system is cooled to room temperature, with n-hexane gained solution and under 8000rpm rotating speed centrifugal 5 minutes.Repeated washing, centrifugal until last centrifugal liquid be clear, the baking oven then black solid obtained being put into 80 DEG C must CZTS nano particle after dry 3 hours.
X-ray diffractometer is adopted to carry out phase composite qualification to the material prepared by embodiment 6.As Fig. 9, the 2 θ Angle Position that peak in figure occurs are 26.9 °, 28.5 °, 30.5 °, 39.6 °, 47.6 °, 51.8 °, 55.5 °, 56.4 °, 57.6 °, 59.0 °, correspond respectively to 100,002,101,102,110,103,200,112,201,004 crystal face, be shown as CZTS (six side's phases) crystalline phase.The product described prepared by embodiment 6 is six pure side phase CZTS.
Scanning electronic microscope (SEM) microtexture to the material prepared by embodiment 6 is adopted to analyze, as shown in Figure 10.As can be seen from the figure, the pattern of material is spherical, distribution of sizes at 20-30nm, the favorable dispersity of particle.The product described prepared by embodiment 6 has preferable quality.
Claims (10)
1. a controllable method for preparing for polynary sulfide semiconductor nano material, its concrete steps are as follows:
1) metal-salt and the dissolving of high boiling organic solvent mix and blend is taken, preparing metal salts solution;
2) take solid sulfur source to be dissolved in high boiling organic solvent and to prepare sulphur solution, or directly use liquid sulfur source as sulphur solution;
3) respectively heating steps 1) in metal salt solution and step 2) in sulphur solution, then by sulphur injection of solution in metal salt solution, then heated solution reacts to temperature of reaction;
4) by the solution cooling after having reacted, with organic solvent washing, centrifugal to supernatant liquid clear, finally the black solid obtained is put into oven drying and obtain polynary sulfide semiconductor nano material.
2. controllable method for preparing according to claim 1, is characterized in that described metal-salt is one or more in iron(ic) chloride, iron protochloride, cupric chloride, neutralized verdigris, acetylacetone copper, zinc chloride, zinc acetate, zinc acetylacetonate or tin tetrachloride.
3. controllable method for preparing according to claim 1, is characterized in that described high boiling organic solvent is one or more in oleyl amine, stearylamine or octadecylene.
4. controllable method for preparing according to claim 1, is characterized in that described solid sulfur source is sulphur powder; Described liquid sulfur source is n-dodecyl mereaptan.
5. controllable method for preparing according to claim 1, is characterized in that: the temperature of described heating of metal salts solution is 120-250 DEG C; The temperature of described heating sulphur solution is 70-100 DEG C.
6. controllable method for preparing according to claim 1, is characterized in that: described temperature of reaction is 220-250 DEG C; The described reaction times is 30-180min.
7. controllable method for preparing according to claim 1, is characterized in that: metal-salt during preparing metal salts solution and organic solvent mass ratio are 1:(10-100); During preparation sulphur solution, solid sulfur source and organic solvent mass ratio are 1:(10-20).
8. controllable method for preparing according to claim 1, is characterized in that: step 3) in control metal-salt and sulfur material mass ratio be 1:(0.2-5).
9. controllable method for preparing according to claim 1, is characterized in that: the organic solvent for washing is normal hexane or chloroform.
10. controllable method for preparing according to claim 1, is characterized in that: step 4) described in centrifugal rotational speed be 6000-8000rpm; Described centrifugation time is 3-5min; Step 4) described in the temperature of drying be 60-80 DEG C; The dry time is 3-6h.
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| CN105833298A (en) * | 2016-03-24 | 2016-08-10 | 国家纳米科学中心 | Cu3BiS3 nano medicine, preparation method and application thereof |
| CN110240206A (en) * | 2019-05-27 | 2019-09-17 | 深圳大学 | Transient metal sulfide nano particle and preparation method thereof |
| CN110408391A (en) * | 2018-04-27 | 2019-11-05 | 中天科技光纤有限公司 | The preparation method of quantum dot, quantum dot/UV sol solution and quantum dot-doped optical fiber |
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Application publication date: 20151216 |