CN101012378A - Method of preparing CdTe quantum dot - Google Patents
Method of preparing CdTe quantum dot Download PDFInfo
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- CN101012378A CN101012378A CN 200710037032 CN200710037032A CN101012378A CN 101012378 A CN101012378 A CN 101012378A CN 200710037032 CN200710037032 CN 200710037032 CN 200710037032 A CN200710037032 A CN 200710037032A CN 101012378 A CN101012378 A CN 101012378A
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Abstract
The invention discloses a making method of CdTe quantum point in the nanometer technical domain, which comprises the following steps: dissolving CdO into oleic acid to form cadmium oleate as Cd ion source; dissolving Te powder into phosphor trioctyl to form tellurium phosphate trioctyl as Te ion source; blending two sources in the liquid paraffine; obtaining the product.
Description
Technical field
That the present invention relates to is a kind of preparation method of field of nanometer technology, particularly a kind of preparation method of CdTe quantum dot.
Background technology
Quantum dot be radius less than or approach the semiconductor nano crystal grain of exciton Bohr radius, can be by the optical excitation of the arbitrary wavelength from the ultraviolet region to the infrared region, send fluorescence, and compare with traditional organic fluorescent dye, have the optical property of a series of excellences such as quantum yield height, stoke shift be big.Therefore the preparation of high-quality semiconductor-quantum-point and use and become the focus that the vast researcher in countries in the world is paid close attention to gradually, and the CdTe quantum dot is one of most widely used II-VI family semiconductor-quantum-point.1993, utilizations such as Bawendi at high temperature made organometallic precursor cracked method synthesize the CdTe quantum dot that has than the hyperfluorescence performance, but this CdTe quantum dot distribution of sizes a wider range (＞15%), and fluorescence efficiency is not high.
Find through literature search prior art, Peng etc. are at " J.Am.Chem.Soc " (American Chemical Society's journal, calendar year 2001s 123 are rolled up the 183-184 page or leaf) delivered the paper that is entitled as " Formation of high-qualityCdTe; CdSe; and CdS nanocrystals using CdO as precursor " (" use CdO is nanocrystalline as presoma synthetic high-quality CdTe, CdSe and CdS "), use CdO, Cd (AC)
2Or CaCO
3As the Cd precursor, stearic acid is as solvent, and adds HPA (hexyl phosphoric acid) or TDPA strong parts such as (tetradecyl phosphoric acid), is that one-step synthesis has gone out high-quality CdTe quantum dot in 90% the oxidation trioctylphosphine phosphorus in purity.Owing to do not adopt organic cadmium as raw material; reaction need not carried out under the condition of anhydrous, the anaerobic of strictness; thereby simplified preparation technology; although because oxidation trioctylphosphine phosphorus has higher boiling point and stronger stability; can stop crystal grain to be assembled by coordination; therefore and be used as the solvent of preparation in the past more than ten years and be extensive use of, but the unusual costliness of its price makes the scale preparation of quantum dot be restricted.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of preparation method of CdTe quantum dot is provided, make it utilize whiteruss to replace oxidation trioctylphosphine phosphorus, synthesizer is simple, cost of material is cheap, can obtain to have good dispersiveness under gentle relatively reaction conditions, the CdTe quantum dot of fluorescence property and stability.
The present invention is achieved through the following technical solutions, the present invention at first selects for use CdO to be dissolved in the oleate of the cadmium that forms in the oleic acid as the Cd ion source, the trioctylphosphine phosphatization tellurium of selecting for use the Te powder to be dissolved in to form in the trioctylphosphine phosphorus is as the Te ion source, then with both in whiteruss, hybrid reaction obtains the CdTe quantum dot.
The present invention includes following concrete steps:
(a) under the condition of 150 ℃ (steady temperatures), CdO is dissolved in the mixing solutions of oleic acid and whiteruss, CdO and oleic mol ratio are 1: 2-1: 5, obtain the oleate solution of cadmium, with the temperature of the oleate solution of cadmium be raised to 200 ℃-260 ℃ standby;
(b) with the Te powder in ultra-sonic oscillation under the nitrogen protection after 10 minutes, again 100 ℃ of heating, make it be dissolved in the trioctylphosphine phosphorus or in the mixing solutions of trioctylphosphine phosphorus and whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 1-1: 10, obtain trioctylphosphine phosphatization tellurium solution;
(c) trioctylphosphine phosphatization tellurium precursor solution is injected in the oleate solution of above-mentioned cadmium, form mixed reaction solution, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter-33.6 mmoles/liter, Cd is 2: 1 with the ratio of the volumetric molar concentration of Te, temperature of reaction is controlled at 200-260 ℃, and logical simultaneously nitrogen protection also accompanies by stirring, react 1 minute-90 minutes after, solution is cooled fast to room temperature, to prevent further growing up of crystal grain;
(d) in step (c), add methyl alcohol in the gained solution of reaction back, leave standstill and make the CdTe quantum dot form flocks, 6000 rev/mins centrifugal, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.
The scope of the fluorescence emission peak of the CdTe quantum dot of the present invention's preparation is 550nm-750nm, the halfwidth of fluorescence emission peak is 30nm-50nm, and fluorescence quantum efficiency is 10%-70%, and crystalline structure is zincblende lattce structure, the particle size range of crystal grain is 3nm-7nm, distribution of sizes＜10%.The inventive method has avoided using oxidation trioctylphosphine phosphorus, HAD expensive, poisonous, inflammable and explosive organic compound such as (cetylamines), the relative conventional high-temperature pyrolytic of required temperature of reaction synthetic method is lower, have only 200 ℃-260 ℃, simple to operate, preparation cost is low, is fit to the synthetic or industrial production of in vitro scale.The present invention can be by the different temperature of reaction of control, the monomeric concentration of Cd monomer and Te, and the mol ratio of Cd and oleic mol ratio, Te and trioctylphosphine phosphorus, parameters such as reaction times obtain the CdTe quantum dot of different size and fluorescent emission wavelength.
Description of drawings
The fluorescence radiation spectrogram that Fig. 1 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 1 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 2 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 2 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 3 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 3 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 4 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 4 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 5 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 5 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 6 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 6 and excitation wavelength.
The fluorescence radiation spectrogram that Fig. 7 obtains during for 400nm for the uv-visible absorption spectra figure of the CdTe quantum dot that makes among the embodiment 7 and excitation wavelength.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment has provided detailed embodiment and process being to implement under the prerequisite with the technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(a) take by weighing 0.026g (0.2mmol) CdO powder and 0.13mL (0.4mmol) oleic acid, the mixed three-necked bottle that places of 20mL whiteruss, making Cd and oleic mol ratio is 1: 2, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 200 ℃ standby;
(b) taking by weighing 0.013gTe (0.1mmol) powder joins in the mixing solutions of 0.05mL (0.1mmol) trioctylphosphine phosphorus and 4mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 1, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes under nitrogen protection, dissolve fully up to Te, obtain trioctylphosphine phosphatization tellurium solution;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 200 ℃, logical simultaneously nitrogen protection also accompanies by powerful the stirring, react after 1 minute, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 1, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 550nm, and fluorescence quantum efficiency is 41%, and particle diameter is 3.1nm, distribution of sizes＜10%.
Embodiment 2
(a) take by weighing 0.026g (0.2mmol) CdO powder and 0.13mL (0.4mmol) oleic acid, the mixed three-necked bottle that places of 20mL whiteruss, making Cd and oleic mol ratio is 1: 2, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 200 ℃ standby;
(b) taking by weighing 0.013gTe (0.1mmol) powder joins in the mixing solutions of 0.25mL (0.5mmol) trioctylphosphine phosphorus and 3.75mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 5, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes under nitrogen protection, dissolve fully up to Te, obtain trioctylphosphine phosphatization tellurium solution;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 200 ℃, logical simultaneously nitrogen protection also accompanies by powerful the stirring, react after 45 minutes, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 2, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 610nm, and crystalline structure is a zincblende lattce structure, and particle diameter is 3.6nm, distribution of sizes＜10%, and fluorescence quantum efficiency is 45%.
Embodiment 3
(a) take by weighing 0.026g (0.2mmol) CdO powder and 0.13mL (0.4mmol) oleic acid, the mixed three-necked bottle that places of 20mL whiteruss, making Cd and oleic mol ratio is 1: 2, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 200 ℃ standby;
(b) taking by weighing 0.013gTe (0.1mmol) powder joins in the mixing solutions of 0.5mL trioctylphosphine phosphorus (1mmol) and 3.5mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 10, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes obtains trioctylphosphine phosphatization tellurium solution under nitrogen protection;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 200 ℃, logical simultaneously nitrogen protection also accompanies by powerful mechanical stirring, react after 1 minute, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 3, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 575nm, and fluorescence quantum efficiency is 42%, and particle diameter is 3.3nm, distribution of sizes＜10%.
Embodiment 4
(a) take by weighing 0.026g (0.2mmol) CdO powder and 0.13mL (0.4mmol) oleic acid, the mixed three-necked bottle that places of 20mL whiteruss, making Cd and oleic mol ratio is 1: 2, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 200 ℃ standby;
(b) taking by weighing 0.013gTe (0.1mmol) powder adds in the mixing solutions of 0.5mL (1mmol) trioctylphosphine phosphorus and 3.5mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 10, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes under nitrogen protection, after Te dissolves fully, obtain trioctylphosphine phosphatization tellurium solution;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 200 ℃, logical simultaneously nitrogen protection also accompanies by powerful mechanical stirring, react after 45 minutes, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 4, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 630nm, and fluorescence quantum efficiency is 63%, and particle diameter is 3.6nm, distribution of sizes＜10%.
Embodiment 5
(a) take by weighing the mixed three-necked bottle that places of 0.11g (0.8mmol) CdO powder and 0.6mL (1.6mmol) oleic acid and 19.4mL whiteruss, making Cd and oleic mol ratio is 1: 2, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 220 ℃ standby;
(b) taking by weighing 0.051g (0.4mmol) Te powder adds in the mixing solutions of 2mL (4mmol) trioctylphosphine phosphorus and 2mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 10, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes under nitrogen protection, after Te dissolves fully, obtain trioctylphosphine phosphatization tellurium solution;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 16.7 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 220 ℃, logical simultaneously nitrogen protection also accompanies by powerful mechanical stirring, react after 90 minutes, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 5, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 670nm, and fluorescence quantum efficiency is 12%, and particle diameter is 4.3nm, distribution of sizes＜10%.
Embodiment 6
(a) take by weighing the mixed three-necked bottle that places of 0.205g (1.6mmol) CdO powder and 1.5mL (4.8mmol) oleic acid and 18.5mL whiteruss, making Cd and oleic mol ratio is 1: 3, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 260 ℃ standby;
(b) taking by weighing 0.102gTe (0.8mmol) powder adds in 4mL (8mmol) the trioctylphosphine phosphorus, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 10, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes after Te dissolves fully, obtains trioctylphosphine phosphatization tellurium solution under nitrogen protection;
(c) the trioctylphosphine phosphatization tellurium solution with preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 33.6 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 260 ℃, logical simultaneously nitrogen protection also accompanies by powerful mechanical stirring, react after 90 minutes, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 6, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 720nm, and fluorescence quantum efficiency is 13%, and particle diameter is 6.5nm, distribution of sizes＜10%.
Embodiment 7
(a) take by weighing the mixed three-necked bottle that places of 0.026g (0.2mmol) CdO powder and 0.3mL (1mmol) oleic acid and 19.7mL whiteruss, making Cd and oleic mol ratio is 1: 5, be heated to 150 ℃, after treating that the CdO powder dissolves fully, obtain the oleate solution of cadmium, with the temperature of solution be raised to 220 ℃ standby;
(b) taking by weighing 0.013g (0.1mmol) Te powder adds in 0.5mL (1mmol) trioctylphosphine phosphorus and the 3.5mL whiteruss, the mol ratio that makes Te and trioctylphosphine phosphorus is 1: 10, ultra-sonic oscillation reheat to 100 ℃ after 10 minutes under nitrogen protection, after Te dissolves fully, obtain trioctylphosphine phosphatization tellurium solution;
(c) storing solution with the Te of preparation in (b) is injected in the oleate solution of cadmium fast, the volumetric molar concentration that makes Te in the mixed reaction solution be 4.2 mmoles/liter, the mol ratio of Cd and Te is 2: 1, temperature of reaction is controlled at 220 ℃, accompany by powerful the stirring simultaneously, react after 1 minute, solution is cooled fast to room temperature;
(d) after above-mentioned reaction, add methyl alcohol in the solution, leave standstill and make the CdTe quantum dot form flocks, with 6000 rev/mins speed centrifugal after, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment with 6000 rev/mins speed after centrifugal once more, obtain being dispersed in the CdTe quantum dot in the normal hexane.As shown in Figure 7, the position of the fluorescence emission peak of the CdTe quantum dot of preparation is 607nm, and fluorescence quantum efficiency is 20%, and particle diameter is 3.6nm, distribution of sizes＜10%.
Claims (10)
1, a kind of preparation method of CdTe quantum dot, it is characterized in that, at first select for use oleate that CdO is dissolved in the cadmium that forms in the oleic acid as the Cd ion source, the trioctylphosphine phosphatization tellurium selecting for use the Te powder to be dissolved in to form in the trioctylphosphine phosphorus is as the Te ion source, with both hybrid reactions in whiteruss, obtain the CdTe quantum dot then.
2, the preparation method of CdTe quantum dot according to claim 1 is characterized in that, concrete steps comprise:
(a) under the steady temperature, CdO is dissolved in the mixing solutions of oleic acid and whiteruss, obtains the oleate solution of cadmium;
(b) with the Te powder after ultra-sonic oscillation under the nitrogen protection, heating makes it be dissolved in the trioctylphosphine phosphorus or in the mixing solutions of trioctylphosphine phosphorus and whiteruss, obtains trioctylphosphine phosphatization tellurium solution;
(c) trioctylphosphine phosphatization tellurium precursor solution is injected in the oleate solution of above-mentioned cadmium, forms mixed reaction solution, logical nitrogen protection also accompanies by stirring, after the reaction, with the solution cool to room temperature;
(d) in step (c), add methyl alcohol in the gained solution of reaction back, leave standstill and make the CdTe quantum dot form flocks, centrifugal, remove behind the supernatant liquid the CdTe resolution of precipitate in normal hexane, remove lower sediment behind the recentrifuge, obtain being dispersed in the CdTe quantum dot in the normal hexane.
3, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the steady temperature described in the step (a) is 150 ℃.
4, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, CdO described in the step (a) and oleic mol ratio are 1: 2-1: 5.
5, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the oleate solution of the cadmium described in the step (a), and its temperature remains on 200 ℃-260 ℃.
6, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the mol ratio of Te powder described in the step (b) and trioctylphosphine phosphorus is 1: 1-1: 10.
7, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the ultra-sonic oscillation described in the step (b), and the time is 10 minutes; Described heating, temperature are 100 ℃.
8, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the mixed reaction solution described in the step (c), wherein the volumetric molar concentration of Te be 4.2 mmoles/liter-33.6 mmoles/liter, Cd is 2: 1 with the ratio of the volumetric molar concentration of Te.
9, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, the reaction described in the step (c), and the time is 1 minute-90 minutes, temperature is 200 ℃-260 ℃.
10, the preparation method of CdTe quantum dot according to claim 2 is characterized in that, centrifugal described in the step (d), and speed is 6000 rev/mins.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245247B (en) * | 2008-03-24 | 2010-06-23 | 湖南大学 | Method for manufacturing fluorescence semiconductor quantum dots containing cadmium |
| CN102134579A (en) * | 2010-12-31 | 2011-07-27 | 杭州师范大学 | Biosynthesizing method of cadmium telluride quantum dots |
| CN101603085B (en) * | 2009-07-07 | 2011-11-09 | 天津工业大学 | Magnetic DNA fluorescent probe and preparation method thereof |
| CN106188874A (en) * | 2016-08-04 | 2016-12-07 | 叶剑 | Composite for packaging polypropylene bottle and preparation method thereof |
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2007
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101245247B (en) * | 2008-03-24 | 2010-06-23 | 湖南大学 | Method for manufacturing fluorescence semiconductor quantum dots containing cadmium |
| CN101603085B (en) * | 2009-07-07 | 2011-11-09 | 天津工业大学 | Magnetic DNA fluorescent probe and preparation method thereof |
| CN102134579A (en) * | 2010-12-31 | 2011-07-27 | 杭州师范大学 | Biosynthesizing method of cadmium telluride quantum dots |
| CN106188874A (en) * | 2016-08-04 | 2016-12-07 | 叶剑 | Composite for packaging polypropylene bottle and preparation method thereof |
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