CN1693206A

CN1693206A - Process for preparing water soluble cadmium telluride quantum point with program controlling microwave

Info

Publication number: CN1693206A
Application number: CN 200510025504
Authority: CN
Inventors: 黄维; 汪联辉; 范曲立; 何耀; 陆昊婷
Original assignee: Fudan University
Current assignee: Fudan University
Priority date: 2005-04-28
Filing date: 2005-04-28
Publication date: 2005-11-09

Abstract

A program controlled microwave processes for preparing the quantum point of water-soluble CdTe includes such steps as mixing Cd salt (or oxide) with water-soluble mercapto compound in water phase, adding sodium (or potassium) tellurohydride to obtain the precursor solution, filling it in glass tube, and program controlled microwave irradiating in microwave reactor.

Description

The program controlling microwave preparation method of water soluble cadmium telluride quantum point

Technical field

The invention belongs to nano material and bioanalysis detection technique field, be specifically related to a kind of program controlling microwave preparation method of water soluble cadmium telluride quantum point.Be to be raw material, utilize the program controlling microwave technology to prepare the CdTe quantum dot with cadmium salt (or its oxide compound, oxyhydroxide) and sodium hydrogen telluride (or hydrogen telluride potassium, tellurium powder).

Technical background

Quantum dot is a class by the elementary composition radius of II-VI family or III-V family less than or near the semiconductor nano crystal grain of exciton Bohr radius.Semiconductor nano has quantum size effect, and its optical property changes with size of particles and changes, and its luminous efficiency is compared also with body phase material and improved a lot simultaneously.Alivisatos in 1998 and Nie SM etc. respectively reported first utilize semiconductor nano to substitute organic fluorescent dye as the biomolecular labeling thing, successfully mark (Alivisatos.et, Science, 1998 such as iron transfer protein and immunoglobulin (Ig), 281,2013-2016; Nie SM.et, Science, 1998,281,2016-2018), indicated nanocrystalline huge applications potentiality in biological markers detection.The traditional biological fluorescence dye is commonly used the second of smelling ingot, rhodamine etc., can only carry out monochromatic mark, and its poor stability, and sensitivity is also restricted; And the fluorescence semiconductor nano material is compared with the bioluminescence dyestuff as fluorescent marker, has that fluorescent line is narrow, luminous efficiency is high, glow color is adjustable, can carry out series of advantages such as multi-color marking, and good light stability.

The semiconductor nano that needs in the practical application must have good luminescent properties (luminous efficiency height, fluorescence spectrum half-peak width, good stability), semiconductor nano is applied to biomarker, also requires it to have excellent biological compatibility.Therefore, the good water-soluble quantum dot of preparation luminescent properties becomes hot research in recent years.The preparation of the water-soluble quantum dot of report at present mainly contains common aqueous solution heating means (Rogach A.L, et.J.Phys.Chem.B, 2002,106,7177-7185; Rogach A.L, et.Adv.Mater, 2001,13,1684-1687), but this method prepares quantum dot requirement temperature low (≤100 ℃), reaction times grows (several hours～tens hours), makes that forming the quantum dot surface imperfection increases, thereby has caused that quantum dot light emitting efficient is low, the fluorescence spectrum peak width at half height is too wide.People such as Bai Yang have proposed to adopt the pyritous hydrothermal method to prepare the higher water soluble cadmium telluride quantum point of fluorescence quantum efficiency in 2003, and successfully be used for small white mouse L929 cell marking (Bai Yang, et.Adv.Mater, 2003,15,1712-1715).People such as Ren JC have reported that 2005 the method that adopts direct microwave radiation prepares the aqueous fusion cadmium telluride quantum dot, make fluorescence quantum efficiency be further enhanced (RenJC, et.Chem Comm, 2005,528-530).

Summary of the invention

The objective of the invention is at problem recited above, a kind of operational safety, fast and convenient water soluble cadmium telluride quantum point program controlling microwave preparation method are provided.

The program controlling microwave preparation method of water soluble cadmium telluride quantum point provided by the invention, concrete steps are as follows:

1, preparation is as the sodium hydrogen telluride NaHTe or the hydrogen telluride potassium KHTe solution in tellurium source: with mol ratio be 1.5: 1 to 5: the sodium borohydride NaBH of l ₄Or POTASSIUM BOROHYDRIDE KBH ₄Te places water with the tellurium powder, 0～30 degree centigrade of following standing and reacting 7～30 hours, obtains NaHTe or hydrogen telluride potassium KHTe solution;

2, preparation is as the 0.0005～0.1mol/L cadmium salt in cadmium source or oxide compound, oxyhydroxide and the water-soluble sulfhydryl compound solution of cadmium, and NaHTe or KHTe solution are injected in pH value to 7～13 of regulator solution, deposit under the nitrogen protection.Cadmium source, sulfhydryl compound, tellurium source consumption are Cd in molar ratio ²⁺: sulfhydryl compound: HTe ^-=1: (1.5～5): (0.3～0.7);

3, the CdTe precursor solution is carried out microwave procedure and add thermal control, the reaction times of control distinct program and the water-soluble CdTe semiconductor nano (being the CdTe quantum dot) that temperature of reaction can obtain different emission wavelengths.Microwave heating condition is: microwave power 15W～1000W, and first programmed heating times 5 second～60 minute, 50～90 degrees centigrade of Heating temperatures, the second programmed heating time was 30 second～5 hour, 90～160 degrees centigrade of Heating temperatures.

Oxide compound, the oxyhydroxide of cadmium salt described in the present invention or cadmium comprise: Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate etc., described water miscible sulfhydryl compound comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol etc.

The present invention carries out at aqueous phase fully, and operational safety is fast and convenient, and toxicity is little, and materials safety is easy to get.The water soluble cadmium telluride quantum point of gained has good monodispersity, photoluminescent property and quantum yield height, and good stability has good water-solubility, can be used as fluorescent marker and is widely used in biological detection and analysis.

Description of drawings

Fig. 1 is the ultraviolet-fluorescence spectrum of the CdTe quantum dot for preparing with the present invention.

Fig. 2 is the TEM and the HRTEM result of the CdTe quantum dot for preparing with the present invention.

Embodiment

In order to understand the content of patent of the present invention better, further specify the present invention below in conjunction with specific embodiment and legend.

Embodiment 1

(1). the sodium hydrogen telluride preparation:

With 80 milligrams of NaBH ₄Solid and 91.2 milligrams of Te powder are put in the little flask, add 2 ml waters, can obtain the NaHTe solution for standby in reaction under 10 degrees centigrade after 10 hours;

(2) CdTe precursor solution preparation

With 21.9 milligrams of CdCl ₂Be dissolved in 100 ml waters, add 0.03 milliliter of Thiovanic acid, regulate pH=10, inject 0.2 milliliter of NaHTe solution, as the CdTe precursor solution with the NaOH solution of 0.5 mol;

(3) the program controlling microwave radiation prepares the CdTe quantum dot

Resulting CdTe precursor solution is carried out the program controlling microwave radiation, can obtain the CdTe quantum dot.The time variable control condition is as follows:

First program microwave power: the 50W; First program temperature: 70 ℃; First program time: 30s;

Second program microwave power: the 100W; Second program temperature: 120 ℃; Second program time: 1min.

Embodiment 2

(1). the sodium hydrogen telluride preparation

With 92.7 milligrams of NaBH ₄Solid and 127.6 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain the NaHTe solution for standby in reaction under 15 degrees centigrade after 7 hours;

(2) CdTe precursor solution preparation

With 30 milligrams of CdCl ₂Be dissolved in 100 ml waters, add 0.03 milliliter of Thiovanic acid, regulate pH=9, inject 0.3 milliliter of NaHTe solution, as the CdTe precursor solution with the NaOH solution of 0.5 mol;

(3) the program controlling microwave radiation prepares the CdTe quantum dot

First program microwave power: the 70W; First program temperature: 80 ℃; First program time: 60s;

Second program microwave power: the 300W; Second program temperature: 110 ℃; Second program time: 5min.

Embodiment 3

(1). the preparation of hydrogen telluride potassium:

With 110.5 milligrams of KBH ₄Solid and 91.6 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain KHTe solution in reaction under 0 degree centigrade after 20 hours, and are standby;

(2) CdTe precursor solution preparation

With 36.8 milligrams of CdCl ₂Be dissolved in 100 ml waters, add 0.05 milliliter of Thiovanic acid, regulate pH=11.0, inject 0.30 milliliter of KHTe solution, as the CdTe precursor solution with the NaOH solution of 0.5 mol;

(3) the program controlling microwave radiation prepares the CdTe quantum dot

First program microwave power: the 70W; First program temperature: 90 ℃; First program time: 30s;

Second program microwave power: the 500W; Second program temperature: 100 ℃; Second program time: 10min.

Embodiment 4

(1). the sodium hydrogen telluride preparation

With 92.7 milligrams of NaBH ₄Solid and 127.6 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain the NaHTe solution for standby in reaction under 20 degrees centigrade after 8 hours;

(2) CdTe precursor solution preparation

With 22.9 milligrams of CdCl ₂Be dissolved in 100 ml waters, add 0.03 milliliter of Thiovanic acid, regulate pH=9.5, inject 0.3 milliliter of NaHTe solution, as the CdTe precursor solution with the NaOH solution of 0.5 mol;

(3) the program controlling microwave radiation prepares the CdTe quantum dot

First program microwave power: the 50W; First program temperature: 65 ℃; First program time: 3min;

Second program microwave power: the 150W; Second program temperature: 110 ℃; Second program time: 10min.

Embodiment 5

(1). the preparation of hydrogen telluride potassium:

With 95.5 milligrams of KBH ₄Solid and 82.5 milligrams of Te powder are put in the little flask, add 3 ml waters, can obtain KHTe solution in reaction under 5 degrees centigrade after 15 hours, and are standby;

(2) CdTe precursor solution preparation

With 19 milligrams of CdCl ₂Be dissolved in 100 ml waters, add 0.02 milliliter of Thiovanic acid, regulate pH=8.5, inject 0.30 milliliter of KHTe solution, as the CdTe precursor solution with the NaOH solution of 0.5 mol;

(3) the program controlling microwave radiation prepares the CdTe quantum dot

First program microwave power: the 50W; First program temperature: 80 ℃; First program time: 2min;

Second program microwave power: the 200W; Second program temperature: 100 ℃; Second program time: 15min.

By the method for the invention, can prepare the water soluble cadmium telluride quantum point of other type-stable agent.

Claims

1, a kind of program controlling microwave preparation method of water soluble cadmium telluride quantum point, its feature concrete steps are as follows:

(a) preparation is as the sodium hydrogen telluride NaHTe or the hydrogen telluride potassium KHTe solution in tellurium source: the sodium borohydride NaBH that with mol ratio is 1.5: 1 to 5: 1 ₄Or POTASSIUM BOROHYDRIDE KBH ₄Te places water with the tellurium powder, 0～30 degree centigrade of following standing and reacting 7～30 hours, obtains NaHTe or hydrogen telluride potassium KHTe solution;

(b) preparation is oxide compound, oxyhydroxide and the water-soluble sulfhydryl compound solution of 0.0005～0.1mol/L cadmium salt or cadmium as the concentration in cadmium source, pH value to 7～13 of regulator solution, inject NaHTe or KHTe solution, obtain the CdTe precursor solution, deposit under the nitrogen protection;

(c) the CdTe precursor solution is carried out the program controlling microwave heating, obtain the water-soluble CdTe quantum dots of different emission wavelengths, wherein microwave heating condition is: microwave power 15W～1000W, the first programmed heating time was 10 second～60 minute, 50～90 degrees centigrade of Heating temperatures, the second programmed heating time was 30 second～5 hour, 90～160 degrees centigrade of Heating temperatures.

2, preparation method according to claim 1, it is characterized in that in the step (b): raw material cadmium source, sulfhydryl compound, tellurium source are Cd in molar ratio ²⁺: sulfhydryl compound: HTe-=1: (1.5～5): (0.3～0.7).

3, described preparation method as claimed in claim 1, the oxide compound, the oxyhydroxide that it is characterized in that described cadmium salt or cadmium comprise: Cadmium chloride fine powder, cadmium iodide, cadmium bromide, cadmium nitrate, Cadmium oxide, cadmium perchlorate, cadmium chlorate, cadmium iodate, Cadmium Sulphate, cadmium hydroxide or cadmium carbonate, described water miscible sulfhydryl compound comprises Thiovanic acid, thiohydracrylic acid, sulfydryl butyric acid, thioglycolate salt, mercapto propionate, halfcystine, Gelucystine, mercaptoethanol or mercaprol.