CN102241975B - Quantum dot with core shell structure and preparation method of quantum dot - Google Patents
Quantum dot with core shell structure and preparation method of quantum dot Download PDFInfo
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Abstract
本发明公开了一种具有核壳结构的量子点，同时还公开了一种量子点的制备方法。该具有核壳结构的量子点具有以硫化镉材料为核，以亚硫酸镉材料为壳的核壳结构，通过水热合成法制得。本发明提供的具有核壳结构的量子点其核的尺寸为3～6nm，壳层的厚度为0.1～0.5nm，结晶完美，具有稳定性高、荧光发射峰形好、最大发射峰位稳定等优点。本发明提供的具有核壳结构的量子点的制备方法采用水热合成法，不仅克服了目前水法制备所得量子点结构缺陷多、化学稳定欠佳、荧光发射性能不好等缺点，同时也避免了金属有机法的毒性与高成本，且制备方法简单、易操作、成本低，并且利用本发明的水热合成法，可制备出粒度可调控的具有核壳结构的量子点。
The invention discloses a quantum dot with a core-shell structure, and also discloses a preparation method of the quantum dot. The quantum dot with a core-shell structure has a core-shell structure with cadmium sulfide material as the core and cadmium sulfite material as the shell, and is prepared through a hydrothermal synthesis method. The quantum dots with a core-shell structure provided by the invention have a core size of 3-6 nm, a shell thickness of 0.1-0.5 nm, perfect crystallization, high stability, good fluorescence emission peak shape, stable maximum emission peak position, etc. advantage. The preparation method of quantum dots with a core-shell structure provided by the present invention adopts the hydrothermal synthesis method, which not only overcomes the shortcomings of the quantum dots prepared by the current water method, such as many structural defects, poor chemical stability, and poor fluorescence emission performance, but also avoids The toxicity and high cost of the metal-organic method are avoided, and the preparation method is simple, easy to operate, and low in cost, and the hydrothermal synthesis method of the present invention can be used to prepare quantum dots with a core-shell structure with an adjustable particle size.
Description
Technical field
The present invention relates to the photovoltaic cell technical field of nano material, be specifically related to a kind of quantum dot with nucleocapsid structure and preparation method thereof.
Background technology
The sun offers our utilizable energy and is approximately 100,000 terawatts, and these data are about 10,000 times of present earth energy spending rate.Photovoltaic cell is used to develop these huge Energy resources just more and more, and will bring into play crucial effect in following sustainable energy system.But owing to by photovoltaic cell, sun power directly being converted at present the high cost of electric power, for example its cost is 5～10 times of nuclear energy, be 25～50 times of elementary fossil energy, so this problem of high cost unanimously hamper the fast development of photovoltaic cell industry.
Recently there is test to show, can significantly improves the photoelectric transformation efficiency of photovoltaic cell based on the quantum dot new technology of nanotechnology, therefore can effectively reduce by photovoltaic cell, sun power directly is converted to the cost of electric power, promote the competitive power of solar energy generation technology.The senior researcher Nozik in American National renewable energy resources laboratory, A.J. think, the photovoltaic solar cell photoelectric transformation efficiency of technology of quantum dots can reach 42%, far above present silica-based solar cell (approximately 18%).The scientist of USDOE National Laboratory finds, the semiconductor-quantum-point material has superior photoelectric characteristic, quanta point material discharges electronics when clashed into by high-energy photon quantity is more than 2 times of silicon semiconductor material, reach as high as 7 times, this means that electricity conversion can be greatly enhanced, reduce the cost of electricity-generating of solar cell.Moreover, because quanta point material can obtain by simple chemical reaction, its material price will be very cheap.
Quantum dot can be described as again nanocrystallinely, is the semiconductor nano material new technology that scientist concentrated on studies since the nineties in last century always.Generally, quantum dot is exactly metal or the semiconductor nanoparticle materials with quantum confined effect.The research of quantum dot Application Areas mainly concentrates on biological field, be that quantum dot is in the research of cell, imaging of tissue and immunoassay context of detection, recently begin the Exploration of Quantum point in the application of area of solar cell, be exactly mainly the photoelectric transformation efficiency that improves solar cell, to reduce cost of electricity-generating.
Photovoltaic cell has proposed following requirement to quantum dot: the quantum dot that (1) is selected has superpower absorption in UV-light～visible-range, then transforms and launches the light wave (blue green light) of the strong absorption region of silica-based solar cell or directly launch a plurality of electronics; (2) quantum dot light physics and spectrochemical property are stable, and the life-span is long.Present quantum dot is little due to size, specific surface area is huge, and therefore easily oxidized and other reason goes bad, maximum half a year in life-span.
Physical vapor deposition (PVD) and the chemical vapor deposition (CVD) methods of adopting prepare photovoltaic cell modification quantum dot nano thin-film coating more now in the world, and mostly are the silicon nanocrystal quantum dot.This technical sophistication relatively rely on equipment, and cost is expensive.
It is very fast that domestic employing technology of quantum dots is carried out Recent Advances In Modification to photovoltaic cell, but mainly still simulate the brilliant quantum dot syntheti c route of USDOE silicon-based nano, the chemical Vapor deposition process (CVD mostly is PECVD) that adopts inclined to one side physics and rely on plant and instrument for counsel obtains the silicon-based nano crystalline substance.In recent years, in the project that has also occurred in state natural sciences fund as the Cui Can of Institutes Of Technology Of Zhejiang etc. " preparation of array semiconductor-quantum-point and in the application in solar cell ", carried out the research that Physical or chemical Vapor deposition process prepare quantum dot and be used for silicon solar cell modification aspect.In addition, chemical method synthesizing nanocrystalline quantum dot (general quantum dot, non-nucleocapsid structure) also has been seen in report for the research of sensitization solar battery.But the pure chemistry synthesis method is synthesized nano-crystal with core-shell structure, and directly uses it for the research that improves the silicon solar cell photoelectric transformation efficiency and there is not yet report.
The photovoltaic solar cell electricity conversion there are the potentiality of huge raising based on the nanocrystalline quantum dot of type material, the quantum dot with good photoelectric properties and long service life of development of new, and the development of using it for nanocrystalline quantum dot silica-based solar cell not only has certain fundamental research meaning, and has important practical value to developing the high-photoelectric transformation efficiency quantum dot solar cell in the future.
Summary of the invention
The object of the present invention is to provide that a kind of photoelectric properties are good, the quantum dot with nucleocapsid structure of long service life.
The present invention also aims to provide a kind of preparation method of quantum dot.
In order to realize above purpose, the technical solution adopted in the present invention is: a kind of quantum dot with nucleocapsid structure, this quantum dot have take the Cadmium Sulfide material as core, the nucleocapsid structure take the cadmium sulfite material as shell.The particle diameter of the core of described quantum dot is 3～6nm, and the thickness of shell is 0.1～0.5nm.The fluorescence excitation peak λ of described quantum dot
Ex.maxBe positioned at 355～362nm, emission peak λ
Em.maxBe positioned at 462～472nm.
Find two cover crystal parameters in X ray powder crystal diffraction (XRD) collection of illustrative plates of the quantum dot with nucleocapsid structure provided by the invention: an XRD for the greenockite of hexagonal structure (Greenockite) composes, another is the cadmium sulfite XRD spectrum of monocline primitive lattice, the corresponding core of difference and shell material, Cadmium Sulfide is core, and cadmium sulfite is peripheral shell.Character with quantum dot of nucleocapsid structure provided by the invention is better than simple naked cadmiumsulfide quantum dot, the surface of naked cadmiumsulfide quantum dot directly is subject to the external environment impact, such as oxygenizement, make its every character unstable, comprise the character of chemical stability and emitting fluorescence.Nuclear shell structure quantum point can effectively be protected core due to the existence of shell, the various effects that sealing is extraneous; make its stable in properties, stability greatly strengthens, and inner core surface tissue defective is few; stable to absorption and stimulation of light, long service life is for its use has brought facility.And because Shell Materials is cadmium sulfite, have strong resistance of oxidation, therefore the life-span in life-span of quantum dot provided by the invention obviously extends.
a kind of preparation method with quantum dot of nucleocapsid structure, take cadmium acetate and sulphur source as raw material, with the raw material reaction soln that is mixed with soluble in water, wherein the concentration of cadmium acetate in reaction soln is 5～54.5mmol/L, the concentration of sulphur source in reaction soln is 4.5～56.5mmol/L, pH value with reaction soln is adjusted to 9～13 afterwards, then begin to react in autoclave, temperature of reaction is controlled to be 110～150 ℃, reaction pressure is controlled to be 1～3 normal atmosphere, reaction times is 3～5 hours, reaction gained precipitation is the quantum dot with nucleocapsid structure, this is precipitated as yellow mercury oxide.
In described raw material, the mol ratio of Cd/S is 0.77≤Cd/S＜1.0.
Described sulphur source is Cys, thiocarbamide or 3-thiohydracrylic acid.
Preparation method with quantum dot of nucleocapsid structure provided by the invention is by the dynamic conditions of High Temperature High Pressure is provided, and controls the relative size of Cadmium Sulfide/cadmium sulfite crystal nucleation speed and growth velocity and obtains the controlled Cadmium Sulfide with nucleocapsid structure of size/cadmium sulfite quantum dot.Find in research process, the factor of regulation and control Cadmium Sulfide/cadmium sulfite quantum dot size mainly contains: the pH value of raw material type, proportioning raw materials, reactant concn, reaction mixture.The factor that affects the fluorescent emission performance of the quantum dot product with nucleocapsid structure mainly contains: the pH value of reaction mixture, the crystal formation of quantum dot, the High Temperature High Pressure residence time.Affect the factor of product stability except keeping in Dark Place, main relevant with the gauge of shell.In preparation method provided by the invention, when the mol ratio Cd/S of Cd/S in raw material＜0.77, the cadmium sulfite shell of formation is too thick, greater than 0.5nm, although the chemical stability of the quantum dot of generation is very high, and its fluorescent emission degradation; When the mol ratio Cd/S of Cd/S in raw material 〉=1.0, can not get the cadmium sulfite shell, the core Cadmium Sulfide can not be effectively protected, the poor stability of the quantum dot that makes.Provided by the invention have the quantum dot of nucleocapsid structure by process primary first-order equation generation in autoclave of first nucleation, rear involucrum.
Particularly, the raw material type that the present invention selects is: cadmium source employing cadmium acetate, sulphur source employing Cys, thiocarbamide or 3-thiohydracrylic acid.The preferred Cys in sulphur source, the viscosity of using Cys to be beneficial to very much to control reaction soln and sulphur source have a form, and then be convenient to control the quantum dot size that makes.Most preferably cadmium acetate and Cys be as reaction raw materials, further processes because need not washing etc., and the quantum dot that makes has fluorescent emission performance preferably.
Proportioning raw materials is one of main factor that affects quantum dot size, and it is comparatively suitable that the Cd/S mol ratio is controlled to be 0.77≤Cd/S＜1.0.
The concentration of reactant in reaction soln is also very obvious on the impact of quantum dot size.The increase of reactant concn is conducive to the rising of system viscosity, quantum dot size is diminished, but excessive concentration, concentration as cadmium acetate in reaction soln surpasses 54.5mmol/L, the concentration of sulphur source in reaction system surpasses 56.5mmol/L, the quantum dot agglomeration that generates is obvious, and the quantum dot product that makes also needs further to separate; On the contrary, if concentration is too low, the concentration as cadmium acetate in reaction soln is lower than 5mmol/L, and the concentration of sulphur source in reaction soln obtains oarse-grained product (greater than 10nm), and can not get quantum dot lower than 4.5mmol/L.
The pH value of reaction soln is to realize by the viscosity that changes system on the impact of product quantum dot granularity, and more suitable pH value general control is between 9-13.
Preparation method with quantum dot of nucleocapsid structure of the present invention adopts hydrothermal synthesis method, is to be forced into 1～3 normal atmosphere in autoclave, is warming up to 110～150 ℃, holds time 3-5 hour.Because the temperature height has Different Effects to crystal nucleation and crystal growth, namely lower temperature is conducive to nucleation relatively, and higher temperatures is conducive to crystal and grows up.When system temperature was elevated to 150 ℃ from 110 ℃, the nanocrystalline size that obtains was always in continuous increase, therefore can obtain the quantum dot of different-grain diameter from small to large.Temperature is not very direct to the quantum dot fluorescence emitting performance, and it is realized by changing quantum dot size and then changing its fluorescent emission wavelength.Equally, also by changing quantum dot product size and then impact, the prolongation of low-temperature zone time tends to make the quantum dot size that makes to reduce to temperature, stability decreases on the stability of quantum dot.Preparation method with quantum dot of nucleocapsid structure provided by the invention adopts hydrothermal synthesis method, with one of maximum differential of existing water law (being general colloid method) be exactly temperature of reaction, temperature of reaction of the present invention will be far away higher than the boiling point of water under standard atmosphere pressure.
The particle diameter of the core of the quantum dot with nucleocapsid structure provided by the invention is 3～6nm, and the thickness of shell is 0.1～0.5nm, and crystallization is perfect, has the advantages such as chemical stability is high, the fluorescent emission peak shape is good, the emission maximum peak position is stable.Quantum dot with nucleocapsid structure provided by the invention can be used for being intended to improving the modification of the silicon solar cell of photoelectric transformation efficiency, have high oxidation-resistance and compare more stable fluorescent emission performance with naked cadmiumsulfide quantum dot, that is corresponding stable photochemical properties and use properties.
Preparation method with quantum dot of nucleocapsid structure provided by the invention adopts hydrothermal synthesis method, not only overcome present water law and prepared the shortcomings such as gained quantum-dot structure defective is many, chemically stable is not good enough, the fluorescent emission performance is bad, also avoided simultaneously the toxicity of the organic method of metal and expensive, and the inventive method is simple, easy to operate, cost is low, and utilize hydrothermal synthesis method of the present invention, can prepare the regulatable quantum dot with nucleocapsid structure of granularity.
Description of drawings
Fig. 1 is the XRD figure spectrum of the quantum dot of the embodiment of the present invention 1;
Fig. 2 is the high-resolution-ration transmission electric-lens collection of illustrative plates of the quantum dot of the embodiment of the present invention 1, and the scale of wherein scheming A is 30nm, and the scale of figure B is 7nm;
Fig. 3 is that the quantum dot of the embodiment of the present invention 1 is being placed the fluorescence excitation and emission collection of illustrative plates of measuring afterwards in 1 year;
Fig. 4 is the fluorescent emission graphic representation of quantum dot under different excitation wavelengths of the embodiment of the present invention 1.
Embodiment
Embodiment 1
The quantum dot with nucleocapsid structure of the present embodiment, this quantum dot have take the Cadmium Sulfide material as core, and the nucleocapsid structure take the cadmium sulfite material as shell, the particle diameter of core are 3～6nm, and the thickness of shell is 0.1～0.5nm.The fluorescence excitation peak λ of this quantum dot
Ex.maxBe positioned at 358nm, emission peak λ
Em.maxBe positioned at 470nm.
the preparation method of the quantum dot with nucleocapsid structure of the present embodiment, take cadmium acetate and Cys as raw material, measure the cadmium acetate aqueous solution 100ml of 0.1mol/L and the Cys aqueous solution 110mL of 0.1mol/L, put into afterwards Erlenmeyer flask and be hybridly prepared into reaction soln, wherein the mol ratio of Cd/S is 0.91, wherein the concentration of cadmium acetate in reaction soln is 47.6mmol/L, the concentration of Cys in reaction soln is 52.4 mmol/L, regulate pH value to 10 with potassium hydroxide afterwards, again above-mentioned reaction soln through overregulating the pH value is changed in the autoclave inner bag afterwards, airtight and the symmetrical airtight nut that tightens autoclave of gradation with autoclave, energising is heated to 125 ℃, be up to 130 ℃, reaction pressure is 2 normal atmosphere, pyroreaction 3 hours.After dropping to normal pressure, the autoclave internal pressure opens kettle cover when naturally cooling to room temperature in autoclave and guaranteeing, product yellow mercury oxide in reactor is transferred in a port grinding bottle, this yellow mercury oxide is to have take the Cadmium Sulfide material as core, the quantum dot of the nucleocapsid structure take the cadmium sulfite material as shell.
Embodiment 2
The quantum dot with nucleocapsid structure of the present embodiment, this quantum dot have take the Cadmium Sulfide material as core, the nucleocapsid structure take the cadmium sulfite material as shell.
the preparation method of the quantum dot with nucleocapsid structure of the present embodiment, take cadmium acetate and thiocarbamide as raw material, measure the cadmium acetate aqueous solution 85ml of 0.1mol/L and the thiourea solution 110mL of 0.1mol/L, put into afterwards Erlenmeyer flask and be hybridly prepared into reaction soln, wherein the mol ratio of Cd/S is 0.77, wherein the concentration of cadmium acetate in reaction soln is 43.6mmol/L, the concentration of thiocarbamide in reaction soln is 56.4 mmol/L, regulate pH value to 9 with potassium hydroxide afterwards, again above-mentioned reaction soln through overregulating the pH value is changed in the autoclave inner bag afterwards, airtight and the symmetrical airtight nut that tightens autoclave of gradation with autoclave, energising is heated to 125 ℃, be up to 150 ℃, reaction pressure is 1 normal atmosphere, pyroreaction 3 hours.After dropping to normal pressure, the autoclave internal pressure opens kettle cover when naturally cooling to room temperature in autoclave and guaranteeing, product yellow mercury oxide in reactor is transferred in a port grinding bottle, this yellow mercury oxide is to have take the Cadmium Sulfide material as core, the quantum dot of the nucleocapsid structure take the cadmium sulfite material as shell.
Embodiment 3
The quantum dot with nucleocapsid structure of the present embodiment, this quantum dot have take the Cadmium Sulfide material as core, the nucleocapsid structure take the cadmium sulfite material as shell.
the preparation method of the quantum dot with nucleocapsid structure of the present embodiment, take cadmium acetate and thiocarbamide as raw material, measure the cadmium acetate aqueous solution 108ml of 0.1mol/L and the thiourea solution 110mL of 0.1mol/L, put into afterwards Erlenmeyer flask and be hybridly prepared into reaction soln, wherein the mol ratio of Cd/S is 0.98, wherein the concentration of cadmium acetate in reaction soln is 49.5mmol/L, the concentration of thiocarbamide in reaction soln is 50.5 mmol/L, regulate pH value to 13 with potassium hydroxide afterwards, again above-mentioned reaction soln through overregulating the pH value is changed in the autoclave inner bag afterwards, airtight and the symmetrical airtight nut that tightens autoclave of gradation with autoclave, energising is heated to 110 ℃, be up to 130 ℃, reaction pressure is 3 normal atmosphere, pyroreaction 5 hours.After dropping to normal pressure, the autoclave internal pressure opens kettle cover when naturally cooling to room temperature in autoclave and guaranteeing, product yellow mercury oxide in reactor is transferred in a port grinding bottle, this yellow mercury oxide is to have take the Cadmium Sulfide material as core, the quantum dot of the nucleocapsid structure take the cadmium sulfite material as shell.
Embodiment 4
The quantum dot with nucleocapsid structure of the present embodiment, this quantum dot have take the Cadmium Sulfide material as core, the nucleocapsid structure take the cadmium sulfite material as shell.
the preparation method of the quantum dot with nucleocapsid structure of the present embodiment, take cadmium acetate and 3-thiohydracrylic acid as raw material, measure the cadmium acetate aqueous solution 100ml of 0.011mol/L and the 3-thiohydracrylic acid aqueous solution 120mL of 0.0099mol/L, put into afterwards Erlenmeyer flask and be hybridly prepared into reaction soln, wherein the mol ratio of Cd/S is 0.93, wherein the concentration of cadmium acetate in reaction soln is 5mmol/L, the concentration of 3-thiohydracrylic acid in reaction soln is 4.5mmol/L, regulate pH value to 13 with potassium hydroxide afterwards, again above-mentioned reaction soln through overregulating the pH value is changed in the autoclave inner bag afterwards, airtight and the symmetrical airtight nut that tightens autoclave of gradation with autoclave, energising is heated to 110 ℃, be up to 130 ℃, reaction pressure is 3 normal atmosphere, pyroreaction 5 hours.After dropping to normal pressure, the autoclave internal pressure opens kettle cover when naturally cooling to room temperature in autoclave and guaranteeing, product yellow mercury oxide in reactor is transferred in a port grinding bottle, this yellow mercury oxide is to have take the Cadmium Sulfide material as core, the quantum dot of the nucleocapsid structure take the cadmium sulfite material as shell.
The quantum dot that embodiment 1 is made has carried out sign and performance test, its XRD figure spectrum as shown in Figure 1, the high-resolution-ration transmission electric-lens collection of illustrative plates as shown in Figure 2, quantum dot is being placed the fluorescence excitation of measuring afterwards in 1 year and is launching collection of illustrative plates as shown in Figure 3, and the fluorescent emission graphic representation of quantum dot under different excitation wavelengths as shown in Figure 4.
In Fig. 1, the broadening feature of spectral line is that nano material is peculiar, two cover crystal parameters are arranged in spectrogram shown in Figure 1: an XRD for the greenockite of hexagonal structure (Greenockite) composes (with the part of square frame, 41-1049), another is that the cadmium sulfite XRD spectrum of monocline primitive lattice is not (with the part of square frame, 37-0001), the corresponding core of difference and shell matter.Can be concluded by Fig. 1, the quantum dot with nucleocapsid structure of embodiment 1 is to have take the Cadmium Sulfide material as core, the quantum dot of the nucleocapsid structure take the cadmium sulfite material as shell.
In Fig. 2, the scale of figure A is 30nm, and the scale of figure B is 7nm, shows in figure that the particle diameter of the core of most of quantum dot is 3～6nm, and the thickness of shell is 0.1～0.5nm, and size is even, the well-crystallized.
Fig. 3 is that embodiment 1 quantum dot is being placed the fluorescence excitation and emission collection of illustrative plates of measuring afterwards in 1 year, and the maximum excitation peak position is in 358nm, and the maximum fluorescence emission peak position is in 470nm.Because being places at the quantum dot that embodiment 1 makes to test afterwards in 1 year, therefore can illustrate that it has the high characteristics of chemical stability.
In Fig. 4, the fluorescent emission curve of embodiment 1 quantum dot that 4 curves from bottom to top obtain when corresponding excitation wavelength is 340nm, 350nm, 360nm, 370nm respectively, fluorescent emission curve peak-peak corresponding wavelength marks in Fig. 4, be respectively 462nm, 463nm, 468nm, 470nm, the position excursion at peak is very little, can think that embodiment 1 quantum dot fluorescence emitting performance is stable.Wherein the fluorescent emission stable performance refers to that excitation wavelength changes, the character that emission wavelength is substantially constant.
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