CN102517003A - Hydro-thermal preparation method for novel near infrared water-soluble copper-indium-sulfur three-element quantum dots - Google Patents
Hydro-thermal preparation method for novel near infrared water-soluble copper-indium-sulfur three-element quantum dots Download PDFInfo
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Abstract
The invention belongs to the technical field of quantum dot preparation, and specifically to a method for preparing copper-indium-sulfur (CuInS2) three-element quantum dots under a hydro-thermal condition. According to the method, common metal salt compounds such as copper chloride and indium chloride, and a sulfhydryl-containing carboxylic acid such as mercaptopropionic acid and mercaptosuccinic acid are adopted to synthesize copper-indium-sulfur (CuInS2) nanoparticles with the particle size of 2-4 nm and emission wavelength in the near infrared region under the hydro-thermal condition. Compared to other organic phase synthesis of the near infrared quantum dots, the method of the present invention has characteristics of less variety of the raw materials, cheap price, simple method, easy operation, good repeatability, and low requirements on equipment. Compared to the traditional quantum dots, the synthesized water-soluble quantum dots of the present invention have the following advantages that: the synthesized water-soluble quantum dots do not contain mercury, cadmium and other toxic metal elements, the emission peak is located in the near infrared region, the synthesized water-soluble quantum dots provide strong penetrabilities for cells and other biological tissues, and the synthesized water-soluble quantum dots can be widely used in immunological assays, nucleic acid hybridizations, gene analysis, cell classification and imaging and other fields.
Description
Technical field
The invention belongs to the quantum dot preparing technical field, be specifically related to a kind of copper indium sulphur (CuInS that under hydrothermal condition, prepares
2) method of ternary quantum dots.
Background technology
Quantum dot is claimed semi-conductor nano particles again, has obtained very big progress in the past in 20 years.Because its unique optical physics and spectrochemical property, quantum dot is widely used in biomolecular labeling, medicine identification, and heavy metal detects and cell imaging.
Compare with GFP with traditional organic dye, quantum dot is having special advantages in many aspects: but narrower and good photochemical stability of the fluorescence of modulation, high quantum yield, the excitation wavelength range of broad, symmetric emission peak and peak width at half etc.Yet the emission wavelength of known most of quantum dot all is in the visible region, because subcutis etc. make fluorescent signal sharply weaken to absorption of visible light and scattering properties.In addition, because the autofluorescence of macromole in some biomass cellss such as collagen protein itself also can produce interference at the signal of visible region to quantum dot, this has just greatly limited the application of quantum dot aspect bio-imaging.In contrast be that the emission wavelength (650nm-900nm) that is positioned near infrared region often has good biological tissue's penetrance and less Rayleigh scattering.This just develops new class bio-imaging material-near-infrared region quantum dot for us and has indicated direction.The near-infrared quantum dots of report mainly is divided three classes at present, and the one, HgTe, II-VI type quantum dots such as CdSe; The 2nd, InP, III-VI type quantum dots such as InAs; The 3rd, copper indium sulphur (CuInS
2) type I-III-VI type quantum dot.Wherein copper indium sulphur quantum dot is because its good photoluminescent property and the hypotoxicity that do not contain heavy metal elements such as Cd and Hg cause increasing concern in recent years.
At present, near infrared copper indium sulphur (CuInS
2) research of the synthetic aspect of quantum dot, be in the starting stage in the world.In a very long time before, through solid phase synthesis, synthetic copper indium sulphur (CuInS such as spraying method
2) compound all is the larger particles more than tens nanometer usually, and do not possess near infrared photoluminescent property.Synthetic copper indium sulphur (CuInS with near-infrared fluorescent characteristic
2) quantum dot method up to the present, substantially can be divided into two kinds, the one, thermolysis precursor process, Stephanie L. Castro (Castro, S.L.; Bailey, S.G.; Banger, K.K.; Hepp, A.F. Chem.Mater., 2003,15,3142-3147.) team with him passes through [(PPh
3)
2Cu (CH
3CN)
2]
+With In (SC2H5)
4 -Special the presoma [(PPh that reaction forms
3)
2CuIn (SC
2H
5)
4] carry out heat, decompose and obtain CuInS being higher than under 250 ℃ the condition presoma
2Nanoparticle.The used presoma compound method of this method is complicated, and raw materials used toxicity is bigger, and temperature drift has very big restriction to equipment.The 2nd, mixed solvent hot preparation method, people such as Peng (Renguo Xie, Michael Rutherford; Xiaogang Peng J.Am.Chem.Soc.; 2009,131 (15), 5691-5697.) make dissolution with solvents Triple Pressed Stearic Acid indium, neutralized verdigris with vaccenic acid; Make the reactive behavior of part balance copper and indium with octadecenic acid and Dodecyl Mercaptan, add the oxidation tri-n-octyl phosphine again and modify CuInS
2The surface, and be aided with the zone heating method and finally make near infrared copper indium sulphur (CuInS
2) quantum dot.The quantum dot emission wavelengths that this method makes is adjustable within the specific limits, but used organic solvent is of a great variety, and cost is higher, and operation steps is complicated, and zone heating is difficult to control.In addition, the quantum dot of these two big class methods gained all carries out in organic solvent, and the quantum dot that obtains all is non-water-soluble, can not directly apply to biomedical sector.Explore and a kind ofly can in the aqueous solution, directly synthesize wetting ability copper indium sulphur (CuInS
2) method of quantum dot, to reducing synthetic cost, increasing bioaffinity and improving its actual application value at biomedical sector has important effect.
Summary of the invention
The present invention is directed to the problem that the sub-point methods of the synthetic copper indium sulfur content of tradition exists, the water that has proposed a kind of novelty prepares copper indium sulphur (CuInS
2) method of quantum dot.This method is simple to operate, plant and instrument required low, raw materials used being simple and easy to, cheapness and toxicity are relatively low.
Its step of the inventive method is following:
1. the compound nantokite and the indium salt compound of solubility of amount of substance such as getting is water-soluble, prepares and contains Cu simultaneously
2+And In
3+The aqueous solution, the concentration range of cupric ion is 9.0mmol/L～36.4mmol/L;
Under the room temperature condition to the above-mentioned Cu that contains simultaneously
2+And In
3+The aqueous solution in, add the carboxylic acid compound contain sulfydryl, wherein cupric ion is 1: 8～1: 30 with the mol ratio that contains the carboxylic acid compound of sulfydryl, stirs and forms yellow small-particle, makes it to be evenly dispersed in the aqueous solution;
3. in above-mentioned system, slowly add NaOH solution, making its pH value is 10～12, stirs 5～20 minutes, and yellow small-particle progressively dissolves in this process, finally obtains light red or colourless transparent solution, shows Cu
2+And In
3+Form with the coordination compound that contains the mercaptan carboxylic acid, and be dispersed in the aqueous solution well;
4. in above-mentioned solution, add thiocarbamide or thioacetamide; The mol ratio of cupric ion and thiocarbamide or thioacetamide is 1: 2～1: 6; Stir and made it to dissolve fully in 10～20 minutes; Gained solution is changed in the reaction kettle, 140 ℃～160 ℃ temperature condition heat after 17～25 hours down, can obtain water miscible copper indium sulphur (CuInS again
2) ternary quantum dots solution, products therefrom is faint yellow transparent solution;
5. the quantum dot solution that the front is obtained adds ethanolic soln by 1: 5～15 volume ratio, makes it centrifugal behind the mixing, removes upper strata liquid, and lower floor's sample can obtained CuInS after the oven dry under 50～70 ℃ of temperature
2The powder of ternary quantum dots.
The compound nantokite of the solubility described in the above-mentioned steps is a kind of in dichloride copper, cupric nitrate or the copper sulfate; The indium salt compound of solubility is a kind of in Indium-111 chloride, indium nitrate or the indium sulfate.The carboxylic acid compound that contains sulfydryl is the 3-thiohydracrylic acid, the 2-dimercaptosuccinic acid, Thiovanic acid, halfcystine, 2 mercaptopropionic acid, sulfydryl butyric acid, sulfydryl valeric acid, mercaptohexanoic acid, sulfydryl enanthic acid, sulfydryl is sad or the sulfydryl n-nonanoic acid in a kind of.
The present invention replaces the copper used in the traditional method and the organic cpds of indium with the water-soluble common inorganic salt of copper and indium, makes water miscible copper indium sulphur (CuInS at aqueous phase
2) ternary quantum dots.The materials safety that the inventive method adopts is easy to get, and is cheap, simple to operate, low to the plant and instrument requirement, and this also is extensive later on synthetic the preparation possibility to be provided.The products therefrom stable homogeneous, low toxicity, and photoluminescent property is good, has excellent photostability.Water miscible CuInS
2Near-infrared quantum dots is because it strongly to the penetrance of subcutis etc. and less scattering signatures, is a kind of good fluorescent marker, and in biological detection, there is the huge applications prospect in fields such as cell, tissue, living imaging.
Embodiment
Embodiment 1:
Water-soluble copper indium sulphur (CuInS
2) preparation of quantum dot is divided into following steps:
A. the dichloride copper (0.02017 gram) of getting 0.15mmol respectively is dissolved in 10.5ml water jointly with four hydration Indium-111 chlorides (0.04397 restrains), stirs the Cu of the amount that obtained out containing same substance in 15 minutes
2+And In
3+The aqueous solution.
B. at ambient temperature in above-mentioned solution, add 156 μ L 3-thiohydracrylic acids, stirred 5 minutes, form yellow small-particle, make it comparatively to be evenly dispersed in the aqueous solution.
C. the NaOH solution that in the above-mentioned system that obtains, slowly adds 2mol/L; Make yellow small-particle all dissolving obtain clear solution, and continue to drip NaOH solution and make pH value of reaction system to 11.2, stirred then 10 minutes; Gained solution is light red or colourless transparent solution, shows Cu
2+And In
3+Form and be dispersed in the aqueous solution well with the coordination compound of 3-thiohydracrylic acid.
D. thiocarbamide (the copper of adding that adds 0.3mmol (0.0228 gram) in the above-mentioned solution; The mol ratio of indium and thiocarbamide is 1: 1: 2) stir and to make it to dissolve fully in 15 minutes; It is changed in the 15mL reaction kettle, 150 ℃ of degrees centigrade of heating can obtain water miscible copper indium sulphur (CuInS after 21 hours again
2) quantum dot, its emission peak positions is 660nm; Products therefrom is faint yellow transparent solution, after dialysis, can directly drop into the application of aspects such as biomass cells mark.
E. the gained quantum dot solution is added ethanolic soln by 1: 10 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining CuInS after 60 ℃ of oven dry of lower floor's sample
2The powder of quantum dot can carry out it sign of X-ray powder diffraction etc.
Accompanying drawing 1 can be known the fluorescence emission peak peak shape symmetry of seeing quantum dot for to press the fluorescence spectrum figure and the uv-absorbing figure of embodiment 1 at D step gained quantum dot solution, and peak width at half is narrower, and peak position is changed to 660nm, and ultraviolet absorption peak is near 570nm.Fig. 2 A and 2B are copper indium sulphur (CuInS
2) the transmission electron microscope photo and the particle size distribution figure of quantum dot, in transmission electron microscope photo, can see comparatively homogeneous of size of particles, roughly be distributed between 2～4nm, this also matches with the structure of Fig. 2 beta particle size distribution plot.Shown in Fig. 2 C, at 28 °, 47 °, there are three obvious characteristics peaks near 55 °, correspond respectively to (112), (204/220) and (116/312) these three lattice plane parameters, and on this X-ray diffraction spectrogram, do not observe other like Cu
2The characteristic peak of S and CuS confirms that thus we have obtained the CuInS of purer yellow copper structure
2Quantum dot.
Through fluorescence spectrum, ultraviolet-visible absorption spectroscopy, transmission electron microscope photo; Particle size distribution figure and X ray diffracting spectrum characterize; The result proves that products therefrom is the single yellow copper structure that has, and particle size distribution is homogeneous comparatively; At near infrared region very strong fluorescent signal being arranged, is high-quality near-infrared quantum dots.
Embodiment 2:
Preparation 2-dimercaptosuccinic acid is the copper indium sulphur (CuInS of stablizer
2) quantum dot.
A. wait the Cu of amount of substance concentration
2+And In
3+The preparation of the aqueous solution, with embodiment 1 steps A.
B. at ambient temperature, in above-mentioned solution, add the 2-dimercaptosuccinic acid powder of 1.8mmol (about 0.2824 gram), stirred 15 minutes, make the dimercaptosuccinic acid powder water-soluble fully.
C. in above-mentioned solution, drip 2mol/LNaOH solution, the pH value is transferred to 11.2, in this process, solution becomes the water white transparency state again again, restir 15 minutes at last earlier by the pale yellow transparent white opacity state that is transformed into gradually.
D. the thiocarbamide that adds 0.3mmol (0.0228 gram) in the above-mentioned C solution stirs and made it to dissolve fully in 15 minutes, it is changed in the 15mL reaction kettle again, and 150 ℃ degrees centigrade are heated after 21 hours, can obtain water miscible copper indium sulphur (CuInS
2) quantum dot, the gained quantum dot solution is slightly yellowy clear solution;
E. the gained quantum dot solution is added ethanolic soln by 1: 5 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining copper indium sulphur (CuInS after 70 ℃ of oven dry of lower floor's sample
2) powder of quantum dot.
Accompanying drawing 3 is that the fluorescence spectrum figure ultraviolet-visible of above-mentioned quantum dot solution absorbs figure.With accompanying drawing 1 ratio, the CuInS that synthesizes with the dimercaptosuccinic acid used as stabilizers
2The fluorescence emission peak of quantum dot; Though but almost constant its emission peak position (655nm) and the ultraviolet absorption peak of strength of signal all shows blue shift to a certain degree; This is because the carboxyl that dimercaptosuccinic acid has more than thiohydracrylic acid; This stablizer and quantum dot surface are more closely combined, its particle diameter is diminished.
Embodiment 3:
The copper indium sulphur (CuInS of preparation higher concentration
2) quantum dot solution.
A.0.40mmol dichloride copper (0.05379 gram) and 0.40mmol (0.1173 gram) four hydration Indium-111 chlorides are dissolved in 10.5ml water, stir and are contained Cu in 15 minutes simultaneously
2+And In
3+The aqueous solution.
B. in above-mentioned solution, add 416 μ L 3-thiohydracrylic acids under the room temperature, stirred 15 minutes, form yellow small-particle, make it comparatively to be evenly dispersed in the aqueous solution.
C. in B step gained solution, add NaOH solution, transferring to the pH value is 11.2, with embodiment 1 step C.
D. in above-mentioned solution, add 0.8mmol (0.0608 gram) thiocarbamide, stir and made it to dissolve fully in 20 minutes, change in the 15mL reaction kettle, 150 ℃ heat get final product after 21 hours water miscible CuInS
2Quantum dot, gained quantum dot solution are yellow transparent solution;
E. the gained quantum dot solution is added ethanolic soln by 1: 15 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining copper indium sulphur (CuInS after 50 ℃ of oven dry of lower floor's sample
2) powder of quantum dot.
Accompanying drawing 4 is the fluorescence spectrum figure and the ultraviolet-visible absorption spectroscopy figure of embodiment 3 synthetic quantum dots; Compare with Fig. 3 with Fig. 1; This routine synthetic quantum dot solution fluorescent signal peak width at half strengthens; Red shift has all appearred in fluorescence emission peak and ultraviolet absorption peak, and this is because under the high density condition when synthetic, CuInS
2Quantum dot is assembled easily, and the size of particles change causes greatly.
Embodiment 4
The copper indium sulphur (CuInS of preparation dilution
2) quantum dot solution.
A.0.10mmol dichloride copper (about 0.01345 gram) and 0.10mmol (about 0.02931 gram) four hydration Indium-111 chlorides are dissolved in 10.5ml water, stir and are contained Cu in 10 minutes simultaneously
2+And In
3+The aqueous solution.
B. in above-mentioned solution, add 104 μ L 3-thiohydracrylic acids under the room temperature, stirred 5 minutes, form yellow small-particle, make it comparatively to be evenly dispersed in the aqueous solution.
C. in B step gained solution, add NaOH solution, transferring to the pH value is 11.2, with embodiment 1 step C.
D. in above-mentioned solution, add 0.2mmol (about 0.0152 gram) thiocarbamide, stir and made it to dissolve fully in 10 minutes, change in the 15mL reaction kettle, 150 ℃ heat get final product after 21 hours water miscible CuInS
2Quantum dot, gained quantum dot solution are shallow yellow transparent solution;
E. the gained quantum dot solution is added ethanolic soln by 1: 10 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining copper indium sulphur (CuInS after 50 ℃ of oven dry of lower floor's sample
2) powder of quantum dot.
Accompanying drawing 5 is the fluorescence spectrum figure and the ultraviolet-visible absorption spectroscopy figure of embodiment 4 synthetic quantum dots; Compare with Fig. 4 with Fig. 1, this routine synthetic quantum dot solution fluorescent signal peak width at half is narrower, and fluorescent emission and ultraviolet are inhaled strength of signal and all reduced; This is because under the low consistency conditions when synthetic, CuInS
2The quantum dot not only quantity in the solution reduces, and particle diameter is less.
Embodiment 5
The copper indium sulphur (CuInS that a small amount of 3-thiohydracrylic acid of preparation coats
2) quantum dot
A. the dichloride copper (about 0.02017 gram) of getting 0.15mmol respectively is dissolved in 10.5ml water jointly with four hydration Indium-111 chlorides (about 0.04397 restrains), stirs the Cu of the amount that obtained out containing same substance in 15 minutes
2+And In
3+The aqueous solution.
B. at ambient temperature in above-mentioned solution, add 104 μ L 3-thiohydracrylic acids, stirred 5 minutes, form yellow small-particle, make it comparatively to be evenly dispersed in the aqueous solution.
C. the NaOH solution that in the above-mentioned system that obtains, slowly adds 2mol/L; Make yellow small-particle all dissolving obtain clear solution, and continue to drip NaOH solution and make pH value of reaction system to 11.2, stirred then 10 minutes; Gained solution is light red or colourless transparent solution, shows Cu
2+And In
3+Form and be dispersed in the aqueous solution well with the coordination compound of 3-thiohydracrylic acid.
D. add the 0.3mmol thiocarbamide of (0.0228 gram) approximately in the above-mentioned solution, stirs and made it to dissolve fully in 15 minutes, it is changed in the 15mL reaction kettle again, 150 ℃ degrees centigrade are heated after 21 hours, can obtain water miscible CuInS
2Quantum dot.
E. the gained quantum dot solution is added ethanolic soln by 1: 5 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining copper indium sulphur (CuInS after 60 ℃ of oven dry of lower floor's sample
2) powder of quantum dot.
Accompanying drawing 6 is the fluorescence spectrum figure and the ultraviolet-visible absorption spectroscopy figure of embodiment 5 synthetic quantum dots; Compare with Fig. 4 with Fig. 1; Institute's synthetic quantum dot fluorescence emission and uv-absorbing intensity all reduce greatly; The 3-thiohydracrylic acid that capacity is described can play the effect of modifying the quantum dot surface improves its photoluminescent property, and this moment, the thiohydracrylic acid add-on was not enough.
Embodiment 6
Prepare excessive 3-thiohydracrylic acid and have the copper indium sulphur (CuInS that coats down
2) quantum dot
A. the dichloride copper (about 0.02017 gram) of getting 0.15mmol respectively is dissolved in 10.5ml water jointly with four hydration Indium-111 chlorides (about 0.04397 restrains), stirs the Cu of the amount that obtained out containing same substance in 15 minutes
2+And In
3+The aqueous solution.
B. at ambient temperature in above-mentioned solution, add 390 μ L 3-thiohydracrylic acids, stirred 5 minutes, form yellow small-particle, make it comparatively to be evenly dispersed in the aqueous solution.
C. the NaOH solution that in the above-mentioned system that obtains, slowly adds 2mol/L; Make yellow small-particle all dissolving obtain clear solution, and continue to drip NaOH solution and make pH value of reaction system to 11.2, stirred then 10 minutes; Gained solution is light red or colourless transparent solution, shows Cu
2+And In
3+Form and be dispersed in the aqueous solution well with the coordination compound of 3-thiohydracrylic acid.
D. the thiocarbamide that adds 0.3mmol (about 0.0228 gram) in the above-mentioned solution stirs and made it to dissolve fully in 15 minutes, it is changed in the 15mL reaction kettle again, and 150 ℃ degrees centigrade are heated after 21 hours, can obtain water miscible CuInS
2Quantum dot.
E. the gained quantum dot solution is added ethanolic soln by 1: 15 volume ratio, make it centrifugal behind the mixing, remove upper strata liquid, obtaining copper indium sulphur (CuInS after 60 ℃ of oven dry of lower floor's sample
2) powder of quantum dot.
Accompanying drawing 7 is the fluorescence spectrum figure and the ultraviolet-visible absorption spectroscopy figure of embodiment 6 synthetic quantum dots, with Fig. 1 and Fig. 4,5; 6 compare; Institute's synthetic quantum dot solution fluorescence emission peak peak width at half obviously broadens, and hangover to a certain degree occurs, and luminous signal intensity also decreases; Stability also descends to some extent, and the adding of this explanation 3-thiohydracrylic acid is excessive not only can be caused fluorescent quenching but also can cause CuInS
2Nanoparticle gathers.
Embodiment 7
Synthetic (CuInS under the different thiocarbamide add-ons
2) quantum dot
Steps A-C is with embodiment 1; Add 0.90mmol thiocarbamide (about 0.0684 gram among the step D; The mol ratio of copper, indium and thiocarbamide is 1: 1: 6), stir and make it dissolving after 20 minutes, all the other steps are all with embodiment 1; The mol ratio of copper and thiocarbamide add-on and copper changed in the scope at 1: 2 to 1: 6 does not almost have influence to the synthetic quantum dot, and quantum dot each item character is all identical with embodiment 1 gained.
Claims (4)
1. new Near water-soluble copper indium sulphur CuInS
2The hydrothermal preparing process of ternary quantum dots, its step is following:
1) it is water-soluble the compound nantokite and the indium salt compound of solubility of amount of substance such as to get, and prepares and contains Cu simultaneously
2+And In
3+The aqueous solution, the concentration range of cupric ion is 9.0mmol/L～36.4mmol/L;
2) under the room temperature condition to the above-mentioned Cu that contains simultaneously
2+And In
3+The aqueous solution in, add the carboxylic acid compound contain sulfydryl, wherein cupric ion is 1: 8～1: 30 with the mol ratio that contains the carboxylic acid compound of sulfydryl, stirs and forms yellow small-particle, makes it to be evenly dispersed in the aqueous solution;
3) in above-mentioned system, slowly add NaOH solution then, making its pH value is 10～12, stirs 5～20 minutes, forms Cu
2+And In
3+Also be dispersed in the aqueous solution well with the coordination compound that contains the mercaptan carboxylic acid;
4) in above-mentioned solution, add thiocarbamide or thioacetamide; The mol ratio of cupric ion and thiocarbamide or thioacetamide is 1: 2～1: 6; Stir and made it to dissolve fully in 10～20 minutes; Gained solution is changed in the reaction kettle, 140 ℃～160 ℃ temperature condition heat after 17～25 hours down, can obtain water miscible copper indium sulphur CuInS again
2Ternary quantum dots solution;
5) quantum dot solution that the front is obtained adds a large amount of ethanolic solns by 1: 5～15 volume ratio, makes it centrifugal behind the mixing, removes upper strata liquid, and lower floor's sample can obtained copper indium sulphur CuInS after the oven dry under 50～70 ℃ of temperature
2The powder of ternary quantum dots.
2. a kind of new Near water-soluble copper indium sulphur CuInS as claimed in claim 1
2The hydrothermal preparing process of ternary quantum dots is characterized in that: the compound nantokite of solubility is a kind of in dichloride copper, cupric nitrate or the copper sulfate.
3. a kind of new Near water-soluble copper indium sulphur CuInS as claimed in claim 1
2The hydrothermal preparing process of ternary quantum dots is characterized in that: the indium salt compound of solubility is a kind of in Indium-111 chloride, indium nitrate or the indium sulfate.
4. a kind of new Near water-soluble copper indium sulphur CuInS as claimed in claim 1
2The hydrothermal preparing process of ternary quantum dots; It is characterized in that: the carboxylic acid compound that contains sulfydryl is the 3-thiohydracrylic acid; The 2-dimercaptosuccinic acid, Thiovanic acid, halfcystine, 2 mercaptopropionic acid, sulfydryl butyric acid, sulfydryl valeric acid, mercaptohexanoic acid, sulfydryl enanthic acid, sulfydryl is sad or the sulfydryl n-nonanoic acid in a kind of.
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| CN107201226A (en) * | 2016-03-17 | 2017-09-26 | 上海科技大学 | CuInS2Quantum dot, CuInS2/ ZnS quantum dot and its preparation and application |
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