CN103131420A - Preparation method and application of CdHgTe quantum dot solution, CdHgTe quantum dot and bimodal semiconductor nanometer material - Google Patents
Preparation method and application of CdHgTe quantum dot solution, CdHgTe quantum dot and bimodal semiconductor nanometer material Download PDFInfo
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Abstract
The invention provides a preparation method of CdHgTe quantum dot solution, CdHgTe quantum dot, bimodal semiconductor nanometer material and bimodal semiconductor nanometer material. The preparation method of the CdHgTe quantum dot comprises the following steps: dissolving tellurium in organic phosphine to obtain tellurium precursor; adding mercuric acetate into carbinol containing potassium hydroxide and 1-dodecanethiol to react to obtain sedimentation,and drying and washing the sedimentation and dissolving the sedimentation in chloroform to obtain mercury precursor; under protection of nitrogen, heating mixed cadmium oxide, oleylamine, myristyl phosphoric acid and octadecene to 280-310 DEG C, adding the tellurium precursor, cooling to 240-260 DEG C to react to obtain reaction liquid; and conducting centrifugal separation after mixing the reaction liquid and acetone, dissolving a sedimentation obtained through centrifuging in the chloroform, adding the mercury precursor to react for two hours, adding mixing liquid of normal hexane and the carbinol, centrifuging the mixed liquid and obtaining the CdHgTe quantum dot solution. The preparation method of the CdHgTe quantum dot solution is easy to operate.
Description
Technical field
The present invention relates to a kind of preparation method of CdHgTe quantum dot solution, the preparation method of CdHgTe quantum dot, preparation method and the bimodal semiconductor nano material of bimodal semiconductor nano material.
Background technology
Semiconductor nano material (quantum dot) has electricity and the optical property of Size dependence by the nanoparticle with certain crystallographic structure that inorganic semiconductor material forms, and is widely used in biological detection, catalysis, the fields such as photovoltaic energy conversion.Since 1998 were used to biological fluorescent labelling, quantum dot was widely used in the subjects such as molecular biology, medical diagnosis as bioprobe.The Another application field of quantum dot is the research for biomedical living imaging, visible region (400 ~ 650nm) imaging meetings be subject to biological tissue in the impact of ABSORPTION AND SCATTERING of endogenous material (melanochrome, aerobic/anaerobic oxyphorase, bilirubin and water etc.).And near infrared region (650 ~ 900nm) energy is difficult for being absorbed by endogenous material in biological tissue, therefore adopts the near-infrared quantum dots imaging to have penetration power strong, the advantages such as sensitivity height.But itself still has certain limitation the image technology of this single mode, therefore integrate the advantage of various image technologies, develop non-single mode molecular image means (sound, light, thermal and magnetic, core etc.), the defective that makes up the single mode image technology becomes the trend of nano-probe future development.
Summary of the invention
Based on this, the bimodal semiconductor nano material of the preparation method's preparation that is necessary the preparation method of a kind of CdHgTe quantum dot solution, CdHgTe quantum dot, bimodal semiconductor nano material to be provided and to adopt this bimodal semiconductor nano material makes this bimodal semiconductor nano material possess near-infrared fluorescence imaging and nuclear magnetic resonance function.
A kind of preparation method of CdHgTe quantum dot comprises the steps:
Tellurium is dissolved in obtains the tellurium precursor in organic phosphine, wherein, described organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine, and the mass ratio of described tellurium and described organic phosphine is (0.0128 ~ 0.128): (0.1 ~ 1);
Mercuric acetate is joined react in the methyl alcohol that contains potassium hydroxide and Dodecyl Mercaptan and be precipitated in 20 minutes ~ 40 minutes, obtain the mercury precursor in chloroform with being dissolved in after the dry washing of described precipitation, wherein, the mol ratio of described mercuric acetate and described Dodecyl Mercaptan is (1 ~ 5): (3 ~ 15);
under the protection of nitrogen, with Cadmium oxide, oleyl amine, tetradecyl phosphoric acid and octadecylene mixing post-heating to 280 ℃ ~ 310 ℃, add the tellurium precursor, be cooled to 240 ℃ ~ 260 ℃ reaction 15s ~ 10min and obtain reaction solution, wherein, described Cadmium oxide, the mass ratio of described oleyl amine and described tetradecyl phosphoric acid is (0.0257 ~ 0.257): (1 ~ 10): (0.122 ~ 1.22), the solid-to-liquid ratio of described Cadmium oxide and octadecylene is (0.0257g ~ 0.257g): (8ml ~ 40ml), tellurium in described tellurium precursor and the mass ratio of described Cadmium oxide are (0.01276 ~ 0.1276): (0.0257 ~ 0.257), and
Centrifugation after described reaction solution is mixed with acetone is dissolved in the centrifugal throw out that obtains in chloroform, adds the mercury precursors reaction two hours, adds the mixed solution of normal hexane and methyl alcohol, and the upper solution that obtains after centrifugal is the CdHgTe quantum dot solution.
In embodiment, make described tellurium be dissolved in described organic phosphine by ultrasonic under 80 ℃ ~ 100 ℃ therein.
Therein in embodiment, in the described methyl alcohol that contains potassium hydroxide and Dodecyl Mercaptan, the mass ratio of described potassium hydroxide and described Dodecyl Mercaptan is 1:2 ~ 1:3, and the concentration of described Dodecyl Mercaptan is 0.1g/mL ~ 0.2g/mL.
In embodiment, after described reaction solution is mixed with acetone, in the step of centrifugation, the rotating speed of centrifugation is 4000 rev/mins ~ 10000 rev/mins therein, and the time of centrifugation is 5 minutes ~ 10 minutes.
In embodiment, the volume ratio of normal hexane and described methyl alcohol described in the mixed solution of described normal hexane and methyl alcohol is 1:1 ~ 1:2 therein.
A kind of preparation method of CdHgTe quantum dot comprises the following steps:
Adopt the preparation method of above-mentioned CdHgTe quantum dot solution to prepare the CdHgTe quantum dot solution; And
Add excessive methanol in described quantum dot solution, then centrifugation, the rotating speed of centrifugation is 4000 rev/mins ~ 10000 rev/mins, the time of centrifugation is 5 minutes ~ 10 minutes, obtains the CdHgTe quantum dot.
A kind of preparation method of bimodal semiconductor nano material is characterized in that, comprises the following steps:
Adopt the preparation method of the described CdHgTe quantum dot solution of claim 1 ~ 5 any one to prepare the CdHgTe quantum dot solution;
Be (0.07 ~ 0.7) with mass ratio: (0.8 ~ 8): after the zinc diethyldithiocarbamate of (0.8 ~ 8), octadecylene and organic phosphine mix, ultrasonic dissolution obtains zinc diethyldithiocarbamate solution, and described organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine;
Trioctylphosphine oxygen phosphorus, oleyl amine and octadecylene are added described CdHgTe quantum dot solution, vacuumize 30 ~ 60 minutes under 30 ℃ ~ 80 ℃, be warming up to 80 ℃ ~ 130 ℃, add described zinc diethyldithiocarbamate solution, react and be warming up to 150 ℃ ~ 180 ℃ reactions 0.5 hour ~ 4 hours after 10 minutes ~ 60 minutes, add the ethanol precipitating after being cooled to room temperature, obtain CdHgTe@ZnS quantum dot after centrifugation, wherein@represents to coat;
Be (20 ~ 200) with mass ratio: the Thioctic Acid of (6 ~ 60) and polyethyleneglycol modified Thioctic Acid add in ultrapure water, add sodium borohydride reaction 1 ~ 2 hour, regulating the pH value with sodium hydroxide is 9 ~ 11 to obtain Thioctic Acid solution, and the mass ratio of wherein said Thioctic Acid and described sodium borohydride is (20 ~ 200): (30 ~ 300);
Described CdHgTe@ZnS quantum dot is added in chloroform dissolve, add Thioctic Acid solution, centrifugal after concussion, get supernatant liquid, after ultrafiltration, filter residue is used the dissolving of neutral buffered liquid, add the solution that contains gadolinium ion, remove filtrate after ultrafiltration and obtain the bimodal semiconductor nano material.
Therein in embodiment, in the described solution that contains gadolinium ion, the concentration of gadolinium ion is 0.1 ~ 5mg/mL.
Therein in embodiment, the solid-to-liquid ratio of described CdHgTe@ZnS quantum dot and described chloroform is (10mg ~ 100mg): (0.5ml ~ 5ml).
A kind of bimodal semiconductor nano material is by preparation method's preparation of above-mentioned bimodal semiconductor nano material.
above-mentioned CdHgTe quantum dot solution, the CdHgTe quantum dot, the preparation method of bimodal semiconductor nano material, by preparation CdHgTe quantum dot solution, adopt again zinc diethyldithiocarbamate zinc diethyldithiocarbamate solution involucrum to improve output, by by Thioctic Acid and polyethyleneglycol modified Thioctic Acid, synthetic quantum dot being carried out aquation, then by surperficial carboxyl and the synthetic bimodal semiconductor nano material with near infrared and nuclear magnetic resonance of gadolinium positively charged ion coordination, the bimodal semiconductor nano material possesses near-infrared fluorescence imaging and nuclear magnetic resonance function and has a NMR response strong, light stability is strong, size is little, prepare the advantages such as simple and good dispersity, the emission wavelength of the cations controllable adjustment CdHgTe@ZnS quantum dot of replacing by change by cation exchange reaction.
Description of drawings
Fig. 1 is preparation method's the schema of the CdHgTe quantum dot solution of an embodiment;
Fig. 2 is preparation method's the schema of the CdHgTe quantum dot of an embodiment;
Fig. 3 is preparation method's the schema of the bimodal semiconductor nano material of an embodiment;
Fig. 4 is the graphic representation of Gd concentration and magnetic resonance imaging signal intensity relative intensity in the bimodal semiconductor nano material of embodiment 10;
Fig. 5 is the fluorescence emission spectrogram of the CdHgTe quantum dot solution of preparation in embodiment 3,4,7 ~ 9.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can be in the situation that do similar improvement without prejudice to intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
See also Fig. 1, the preparation method of the CdHgTe quantum dot solution of an embodiment comprises the steps:
Step S110, tellurium (Te) is dissolved in obtains the tellurium precursor in organic phosphine.
Wherein, organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine, and the mass ratio of tellurium and organic phosphine is (0.0128 ~ 0.128): (0.1 ~ 1).
Preferably, tellurium is the tellurium powder.
Preferably, be dissolved in organic phosphine by the ultrasonic tellurium powder that makes under 80 ℃ ~ 100 ℃.Further, in glove box, tellurium (Te) powder is added in vial, then adds organic phosphine, take out from glove box after cover lid carry out again ultrasonic.
Step S120, mercuric acetate is joined in the methyl alcohol that contains potassium hydroxide and Dodecyl Mercaptan reaction and be precipitated in 20 minutes ~ 40 minutes, will precipitate to be dissolved in after dry the washing and obtain mercury (Hg) precursor in chloroform.
Wherein, the mol ratio of mercuric acetate and Dodecyl Mercaptan is (1 ~ 5): (3 ~ 15).
In this step, mercuric acetate and Dodecyl Mercaptan reaction generate Dodecyl Mercaptan mercury (Hg[CH
3(CH
2)
11S]
2).
Preferably, contain in the methyl alcohol of potassium hydroxide and Dodecyl Mercaptan, the mass ratio of potassium hydroxide and Dodecyl Mercaptan is 1:2 ~ 1:3, and the concentration of Dodecyl Mercaptan is 0.1g/ml ~ 0.2g/ml.
Preferably, precipitation is used methyl alcohol and each washing of ether once.
Preferably, precipitation is (0.0245g ~ 0.245g): (0.5ml ~ 5ml) with the solid-to-liquid ratio of chloroform.
Step S130, under the protection of nitrogen, with Cadmium oxide (CdO), oleyl amine, tetradecyl phosphoric acid and octadecylene mixing post-heating to 280 ℃ ~ 310 ℃, add the tellurium precursor, be cooled to 240 ℃ ~ 260 ℃ reaction 15s ~ 600s and obtain reaction solution.
Wherein, the mass ratio of Cadmium oxide, oleyl amine and tetradecyl phosphoric acid is (0.0257 ~ 0.257): (1 ~ 10): (0.122 ~ 1.22), the solid-to-liquid ratio of Cadmium oxide and octadecylene is that (0.0257g ~ 0.257g): (8ml ~ 40ml), the tellurium in the tellurium precursor and the mass ratio of Cadmium oxide are (0.01276 ~ 0.1276): (0.0257 ~ 0.257).
Preferably, the tellurium precursor adds by injection.
Preferably, the molar ratio of the Te in the Cd in Cadmium oxide and tellurium precursor is 0.5:1 ~ 5:1.
Step S140, reaction solution is mixed with acetone after centrifugation, the centrifugal throw out that obtains is dissolved in chloroform, added the mercury precursors reaction two hours, add the mixed solution of normal hexane and methyl alcohol, the upper solution that obtains after centrifugal is the CdHgTe quantum dot solution.
In this step, throw out is the CdTe quantum dot.
Preferably, the mol ratio of the Dodecyl Mercaptan mercury in throw out and mercury precursor is 10:1 ~ 2:1.
Preferably, in the CdHgTe quantum dot in the CdHgTe quantum dot solution, the amount of substance sum of Cd+Hg is 1:1 with the ratio of the amount of substance of Te, and the molar ratio of Hg and Cd+Hg is 0.05:1 ~ 0.6:1.
Preferably, the rotating speed of centrifugation is 4000 rev/mins ~ 10000 rev/mins, and the time of centrifugation is 5 minutes.
Preferably, the mass ratio of throw out and chloroform is 0.01:1 ~ 0.0002:1.
Preferably, in the mixed solution of normal hexane and methyl alcohol, the volume ratio of normal hexane and methyl alcohol is 1: 1 ~ 1:2.
The preparation method of above-mentioned CdHgTe quantum dot solution, preparation method are comparatively simple, and condition relatively relaxes.
Need to prove, preparation process in the preparation method of above-mentioned CdHgTe quantum dot solution might not be carried out according to the order of listing, such as step S110 can change or synchronize execution with the order of step S120, step S120 can carry out after step S130 or synchronous the execution.
See also Fig. 2, the preparation method of the CdHgTe quantum dot of an embodiment comprises the following steps:
The preparation method of step S210, the above-mentioned CdHgTe quantum dot solution of employing prepares the CdHgTe quantum dot solution.
Step S220, to add excessive methanol, then centrifugation, the rotating speed of centrifugation in quantum dot solution be 4000 rev/mins ~ 10000 rev/mins, and the time of centrifugation is 5 minutes ~ 10 minutes, obtains the CdHgTe quantum dot.
Preferably, the volume ratio of quantum dot solution and described methyl alcohol is 3:1 ~ 5:1.
Above-mentioned CdHgTe quantum dot the preparation method, the preparation method is comparatively simple, condition relatively relaxes.
See also the preparation method of the bimodal semiconductor nano material of Fig. 3, an embodiment, comprise the steps:
The preparation method of step S310, the above-mentioned CdHgTe quantum dot solution of employing prepares the CdHgTe quantum dot solution.
Step S320, be (0.07 ~ 0.7) with mass ratio: (0.8 ~ 8): after the zinc diethyldithiocarbamate of (0.8 ~ 8), octadecylene and organic phosphine mix, ultrasonic dissolution obtains zinc diethyldithiocarbamate solution.
Wherein, organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine.
Preferably, in glove box, zinc diethyldithiocarbamate, octadecylene and tri octyl phosphine are added in vial, take out from glove box after cover lid carry out ultrasonic.
Step S330, trioctylphosphine oxygen phosphorus, oleyl amine and octadecylene are added the CdHgTe quantum dot solution, vacuumize 30 ~ 60 minutes under 30 ℃ ~ 80 ℃, be warming up to 80 ℃ ~ 130 ℃, add zinc diethyldithiocarbamate solution, react and be warming up to 150 ℃ ~ 180 ℃ reactions 0.5 hour ~ 4 hours after 10 minutes ~ 60 minutes, add the ethanol precipitating after being cooled to room temperature, obtain CdHgTe@ZnS quantum dot after centrifugation, wherein@represents to coat.
Preferably, the mass ratio of trioctylphosphine oxygen phosphorus, oleyl amine and octadecylene is 1:2:5 ~ 1:4:8, and the mass ratio of trioctylphosphine oxygen phosphorus and CdHgTe quantum dot solution is (1g ~ 5g): (2.5g ~ 10g).
Preferably, the ratio of the amount of substance of the zinc diethyldithiocarbamate in the CdHgTe quantum dot in the CdHgTe quantum dot solution and zinc diethyldithiocarbamate solution is 5000:1 ~ 10000:1.
Step S340, be (20 ~ 200) with mass ratio: the Thioctic Acid of (6 ~ 60) and polyethyleneglycol modified Thioctic Acid add in ultrapure water, add sodium borohydride reaction 2 hours, regulating the pH value with sodium hydroxide is 9 ~ 11 to obtain Thioctic Acid solution, and wherein the mass ratio of Thioctic Acid and sodium borohydride is (20 ~ 200): (30 ~ 300).
Preferably, the solid-to-liquid ratio of Thioctic Acid and ultrapure water is (20mg ~ 200mg): (2ml ~ 10ml).
Step S350, CdHgTe@ZnS quantum dot is added in chloroform dissolve, add Thioctic Acid solution, centrifugal after concussion, get supernatant liquid, after ultrafiltration, filter residue is used the dissolving of neutral buffered liquid, add the solution that contains gadolinium ion, remove filtrate after ultrafiltration and obtain the bimodal semiconductor nano material.
Preferably, the molar ratio of the Thioctic Acid in the Thioctacid zinc solution and CdHgTe@ZnS quantum dot is 1000:1 ~ 10000:1.In the present invention, the amount of substance of CdHgTe@ZnS quantum dot calculates according to the CdTe quantum dot that begins to synthesize most, by measuring the uv-absorbing numerical value of CdTe quantum dot, then calculates according to the experimental formula in document.
Preferably, neutral buffered liquid is phosphoric acid buffer or borate buffer.
Preferably, the concentration that contains gadolinium ion in the solution of gadolinium ion is 0.1 ~ 5mg/mL.The molar ratio of gadolinium ion and CdHgTe@ZnS quantum dot is 1:1 ~ 4:1.Contain negatively charged ion in the solution of gadolinium ion and be selected from least a in chlorion and nitrate ion.
Preferably, the solid-to-liquid ratio of CdHgTe@ZnS quantum dot and chloroform is (10mg ~ 100mg): (0.5ml ~ 5ml).
Preparation method's operation steps of above-mentioned bimodal semiconductor nano material is not necessarily carried out according to the order of listing, and also can change as required, and perhaps two steps are carried out simultaneously.
the preparation method of above-mentioned bimodal semiconductor nano material is comparatively simple, by preparation CdHgTe quantum dot solution, adopt again zinc diethyldithiocarbamate zinc diethyldithiocarbamate solution involucrum to improve output, by by Thioctic Acid and polyethyleneglycol modified Thioctic Acid, synthetic quantum dot being carried out aquation, then by surperficial carboxyl and the synthetic bimodal semiconductor nano material with near infrared and nuclear magnetic resonance of gadolinium positively charged ion coordination, the bimodal semiconductor nano material possesses near-infrared fluorescence imaging and nuclear magnetic resonance function and has a NMR response strong, light stability is strong, size is little, prepare the advantages such as simple and good dispersity, the emission wavelength of the cations controllable adjustment CdHgTe@ZnS quantum dot of replacing by change by cation exchange reaction, regulate emission wavelength by changing Hg content, bimodal semiconductor nano material particle diameter is little, and penetrating power is strong, near infrared emission, and the fluorescence imaging background is low, and good light stability is difficult for by photobleaching.
Further illustrate below in conjunction with specific embodiment.
Embodiment 1
1, the preparation of Te precursor: in glove box, the 0.0128Te powder is added in the 20mL vial, then add the 0.1g tri octyl phosphine.Cover lid also takes out from glove box, is heated to 100 ° of C until Te dissolves fully.
2, Hg precursor: under room temperature condition, mercuric acetate 1mmol is added dropwise in the methanol solution that contains potassium hydroxide of Dodecyl Mercaptan 3mmol, and reaction 20min then with sedimentation and filtration, and respectively washes once vacuum-drying with methyl alcohol and ether.Get 0.0245g and add in the 0.5ml chloroform, stand-by.
3, zinc diethyldithiocarbamate solution: just 0.07g zinc diethyldithiocarbamate, 0.8g octadecylene and 0.8g tri octyl phosphine add in the 20mL vial in glove box, and cover lid also takes out from glove box, and be ultrasonic until dissolving fully.
4,0.0257gCdO, 8ml octadecylene, 1g oleyl amine and 0.122g tetradecyl phosphoric acid are joined in three mouthfuls of round-bottomed flasks of 100mL logical N
2And be heated to 300 ° of C.Te precursor solution 0.1mmol is expelled in reactor.Cooling to 250 ° of C increases quantum dot.
5, etc. after reaction product is cooled to room temperature, add the centrifugal precipitation that makes it of acetone, 10000 rev/mins of centrifugation 5min discard supernatant liquid, and throw out is taken out, and add the dissolving of 5ml chloroform.
6. get above-mentioned quantum dot solution 2ml, add the 0.05mlHg precursor solution, reaction 2h adds volume ratio to be normal hexane and the methanol solution of 1:2, and centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution.
7. get 2g trioctylphosphine oxygen phosphorus, 1g oleyl amine and 2ml octadecylene join above-mentioned quantum dot solution, at 60 ° of C, vacuumize 30min, then be warmed up to 130 ° of C, drip 0.3mL zinc diethyldithiocarbamate solution in reactor, be warmed up to 180 ° of C reaction 2h after 30min.After reaction product is cooled to room temperature, add the ethanol precipitation, centrifugation gets the CdHgTe/ZnS quantum dot.
8, take the polyethyleneglycol modified Thioctic Acid of 20mg Thioctic Acid and 6mg and join in the 2mL ultrapure water, add the 30mg sodium borohydride, reaction 2h transfers to 9 with sodium hydroxide with pH value of solution.
9. getting 10mgCdHgTe@ZnS quantum dot joins in the 0.5mL chloroform and dissolves, add 1ml Thioctic Acid solution, concussion, the centrifuging and taking supernatant liquor, filtrate is removed in ultrafiltration, be that 7.4 borate buffer dissolves medium with pH, adding gadolinium ion concentration is the gadolinium ion solution of 0.1mg/mL, and filtrate is removed in ultrafiltration, obtains possessing the semiconductor nano material of near infrared imaging and nuclear magnetic resonance function.
1, the preparation of Te precursor: in glove box, 0.064g Te powder is added in the 20mL vial, then add the 0.5g tributylphosphine, cover lid also takes out from glove box, ultrasonic (can be heated to 100 ° of C) until Te dissolve fully.
2, Hg precursor: under room temperature condition, mercuric acetate 1mmol is added dropwise in the methanol solution that contains potassium hydroxide of Dodecyl Mercaptan 3mmol, and reaction 20min then with sedimentation and filtration, and respectively washes once vacuum-drying with methyl alcohol and ether.Get 0.0245g and add in the 0.5ml chloroform, stand-by.
3, zinc diethyldithiocarbamate solution: in glove box, 0.14g zinc diethyldithiocarbamate, 1.6g octadecylene and 1.6g tributylphosphine are added in the 20mL vial, cover lid also takes out from glove box, and is ultrasonic until dissolving fully.
4,0.0257gCdO, 8ml octadecylene, 1g oleyl amine and 0.122g tetradecyl phosphoric acid are joined in three mouthfuls of round-bottomed flasks of 100mL logical N
2And be heated to 300 ° of C.Te precursor solution 0.1mmol is expelled in reactor.Cooling to 250 ° of C increases quantum dot.
5, etc. after reaction product is cooled to room temperature, add the centrifugal precipitation that makes it of acetone, 10000 rev/mins of centrifugation 5min discard supernatant liquid, and throw out is taken out, and add the dissolving of 5ml chloroform to obtain quantum dot solution.
6. get above-mentioned quantum dot solution 2ml, add the 0.05mlHg precursor solution, reaction 2h adds volume ratio to be normal hexane and the methanol solution of 1:2, and centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution.
7. get 2g trioctylphosphine oxygen phosphorus, 1g oleyl amine and 2ml octadecylene join above-mentioned quantum dot solution, at 60 ° of C, vacuumize 30min, then be warmed up to 130 ° of C, drip 0.3mL zinc diethyldithiocarbamate solution in reactor, be warmed up to 180 ° of C reaction 2h after 30min.After reaction product is cooled to room temperature, add the ethanol precipitation, centrifugation gets the CdHgTe/ZnS quantum dot.
8, take the polyethyleneglycol modified Thioctic Acid of 20mg Thioctic Acid and 6mg and join in the 2mL ultrapure water, add the 30mg sodium borohydride, reaction 2h transfers to 9 with sodium hydroxide with pH value of solution.
9. getting the 10mg quantum dot joins in the 0.5mL chloroform and dissolves, add 1ml Thioctic Acid solution, concussion, the centrifuging and taking supernatant liquor, filtrate is removed in ultrafiltration, be that 7.4 borate buffer dissolves medium with pH, the gadolinium ion that adds 0.1mg/mL, filtrate is removed in ultrafiltration, obtains possessing the semiconductor nano material of near infrared imaging and nuclear magnetic resonance function.
1, the preparation of Te precursor: in glove box, 0.128g Te powder is added in the 20mL vial, then add the 1g tributylphosphine, cover lid also takes out from glove box, ultrasonic (can be heated to 100 ° of C) until Te dissolve fully.
2, Hg precursor: under room temperature condition, mercuric acetate 5mmol is added dropwise in the 15ml methanol solution that contains 4.5g potassium hydroxide of Dodecyl Mercaptan 15mmol, and reaction 40min then with sedimentation and filtration, and respectively washes once vacuum-drying with methyl alcohol and ether.Get 0.0245g and add in the 0.5ml chloroform, stand-by
3, single precursor: in glove box, 0.7g zinc diethyldithiocarbamate, 8g octadecylene and 8g tributylphosphine are added in the 20mL vial, cover lid also takes out from glove box, and is ultrasonic until dissolving fully.
4,0.257gCdO, 32g octadecylene, 10g oleyl amine and 1.22g tetradecyl phosphoric acid are joined in three mouthfuls of round-bottomed flasks of 100mL logical N
2And be heated to 280 ° of C.Te precursor solution 2mmol is expelled in reactor.Cooling to 260 ° of C increases quantum dot.
5, etc. after reaction product is cooled to room temperature, add the centrifugal precipitation that makes it of acetone, 4000 rev/mins of centrifugation 5min discard supernatant liquid, and throw out is taken out, and add the dissolving of 50ml chloroform.
6. get above-mentioned quantum dot solution 2ml, add the 0.05mlHg precursor solution, reaction 2h, adding volume ratio is normal hexane and the methanol solution of 1:2, centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution, in the CdHgTe quantum dot solution, mercury content is that the ratio of amount of substance of amount of substance and (mercury+cadmium) of mercury is 0.22:1.
7. get 2g trioctylphosphine oxygen phosphorus, 8g oleyl amine and 16g octadecylene join above-mentioned quantum dot solution, at 60 ° of C, vacuumize 30min, then are warmed up to 130 ° of C, drip the 0.6mL single precursor in reactor, are warmed up to 180 ° of C reaction 0.5h after 60min.After reaction product is cooled to room temperature, add the ethanol precipitation, centrifugation gets CdHgTe@ZnS quantum dot.
8, take the polyethyleneglycol modified Thioctic Acid of 200mg Thioctic Acid and 60mg and join in the 10mL ultrapure water, add the 300mg sodium borohydride, reaction 2h transfers to 11 with sodium hydroxide with pH value of solution
9. getting the 100mg quantum dot joins in the 5mL chloroform and dissolves, add 10ml Thioctic Acid solution, concussion, the centrifuging and taking supernatant liquor, filtrate is removed in ultrafiltration, be that 7.4 phosphoric acid buffer dissolves medium with pH, the gadolinium ion that adds 5mg/mL, filtrate is removed in ultrafiltration, obtains possessing the semiconductor nano material of near infrared imaging and nuclear magnetic resonance function.
Embodiment 4
1, the preparation of Te precursor: in glove box, 0.0128g Te powder is added in the 20mL vial, then add the 0.1g tributylphosphine, cover lid also takes out from glove box, ultrasonic (can be heated to 100 ° of C) until Te dissolve fully.
2, Hg precursor: under room temperature condition, mercuric acetate 1mmol is added dropwise in the 3ml methanol solution that contains 0.606g potassium hydroxide of Dodecyl Mercaptan 3mmol, and reaction 20min then with sedimentation and filtration, and respectively washes once vacuum-drying with methyl alcohol and ether.Get 0.0245g and add in the 0.5ml chloroform, stand-by.
3, single precursor: in glove box, 0.07g zinc diethyldithiocarbamate, 0.8g octadecylene and 0.8g tributylphosphine are added in the 20mL vial, cover lid also takes out from glove box, and is ultrasonic until dissolving fully.
4,0.0257gCdO, 6.4g octadecylene, 1g oleyl amine and 0.122g tetradecyl phosphoric acid are joined in three mouthfuls of round-bottomed flasks of 100mL logical N
2And be heated to 300 ° of C.Te precursor solution 0.02mmol is expelled in reactor.Cooling to 240 ° of C increases quantum dot.
5, etc. after reaction product is cooled to room temperature, add the centrifugal precipitation that makes it of acetone, 10000 rev/mins of centrifugation 5min discard supernatant liquid, and throw out is taken out, and add the dissolving of 10ml chloroform.
6. get above-mentioned quantum dot solution 2ml, add the 0.025mlHg precursor solution, reaction 2h, adding volume ratio is normal hexane and the methanol solution of 1:2, centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution, in the CdHgTe quantum dot solution, mercury content is that the ratio of amount of substance of amount of substance and (mercury+cadmium) of mercury is 0.12:1.
7. get 2g trioctylphosphine oxygen phosphorus, 4g oleyl amine and 5g octadecylene join above-mentioned quantum dot solution, at 60 ° of C, vacuumize 30min, then are warmed up to 80 ° of C, drip the 0.3mL single precursor in reactor, are warmed up to 150 ° of C reaction 4h after 10min.After reaction product is cooled to room temperature, add the ethanol precipitation, centrifugation gets CdHgTe@ZnS quantum dot.
8, take the polyethyleneglycol modified Thioctic Acid of 20mg Thioctic Acid and 6mg and join in the 2mL ultrapure water, add the 30mg sodium borohydride, reaction 2h transfers to 9 with sodium hydroxide with pH value of solution
9. getting the 10mg quantum dot joins in the 0.5mL chloroform and dissolves, add 1ml Thioctic Acid solution, concussion, the centrifuging and taking supernatant liquor, filtrate is removed in ultrafiltration, be that 7.4 borate buffer dissolves medium with pH, the gadolinium ion that adds 0.1mg/mL, filtrate is removed in ultrafiltration, obtains possessing the semiconductor nano material of near infrared imaging and nuclear magnetic resonance function.
Embodiment 5
Preparation CdHgTe quantum dot.
To add the methyl alcohol of 3 times of volumes in the CdHgTe quantum dot solution in the step 6 of embodiment 3, then centrifugation, the rotating speed of centrifugation is 10000 rev/mins, the time of centrifugation is 5 minutes, obtains the CdHgTe quantum dot.
Embodiment 6
Preparation CdHgTe quantum dot.
To add the methyl alcohol of 5 times of volumes in the CdHgTe quantum dot solution in embodiment 3 steps 6, then centrifugation, the rotating speed of centrifugation is 4000 rev/mins, the time of centrifugation is 10 minutes, obtains the CdHgTe quantum dot.
Embodiment 7
Get the quantum dot solution 2ml in embodiment 3 steps 5, add volume ratio to be normal hexane and the methanol solution of 1:1, centrifugal, the sucking-off upper solution namely obtains the CdTe quantum dot solution, and wherein the content of Hg is 0.
In embodiment 8(figure, Hg content is 0.51)
Get the quantum dot solution 2ml in embodiment 3 steps 5, add the 0.1mlHg precursor solution, reaction 2h, adding volume ratio is normal hexane and the methanol solution of 1:2, centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution, and wherein mercury content is that the ratio of amount of substance of amount of substance and (mercury+cadmium) of mercury is 0.51: 1.
Embodiment 9
Get the quantum dot solution 2ml in embodiment 3 steps 5, add the 0.15mlHg precursor solution, reaction 2h, adding volume ratio is normal hexane and the methanol solution of 1:2, centrifugal, the sucking-off upper solution namely obtains the CdHgTe quantum dot solution, and wherein mercury content is that the ratio of amount of substance of amount of substance and (mercury+cadmium) of mercury is 0.77:1.
Embodiment 10
Get the Gd-CdHgTe@ZnS semiconductor nano material 2mL borate buffer dissolving that embodiment 3 step 9 ultrafiltration obtain, getting 0.5mL pH and be 7.4 borate buffer doubling dilution, to obtain concentration for four times be 4 μ mol/L, 2 μ mol/L, 1 μ mol/L, 0.5 the Gd-CdHgTe ZnS(concentration of μ mol/L is calculated with the concentration of Gd, Gd concentration records by ICP-OES), then take the Gd-CdHgTe@ZnS borate buffer of 0 μ mol/L as blank, measure magnetic resonance imaging signal, test result as shown in Figure 4.As can be seen from Figure 4 along with the increase of Gd concentration, the magnetic resonance imaging signal of material is stronger, and linear in the finite concentration scope.
See also Fig. 5, Fig. 5 is the fluorescence emission spectrogram of the CdHgTe quantum dot solution in embodiment 3,4,7 ~ 9.The increase of Hg content as can be seen from Figure 5, the fluorescent emission wavelength red shift gradually of CdHgTe quantum dot.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.Should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the preparation method of a CdHgTe quantum dot solution, is characterized in that, comprises the steps:
Tellurium is dissolved in obtains the tellurium precursor in organic phosphine, wherein, described organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine, and the mass ratio of described tellurium and described organic phosphine is (0.0128 ~ 0.128): (0.1 ~ 1);
Mercuric acetate is joined react in the methyl alcohol that contains potassium hydroxide and Dodecyl Mercaptan and be precipitated in 20 minutes ~ 40 minutes, obtain the mercury precursor in chloroform with being dissolved in after the dry washing of described precipitation, wherein, the mol ratio of described mercuric acetate and described Dodecyl Mercaptan is (1 ~ 5): (3 ~ 15);
under the protection of nitrogen, with Cadmium oxide, oleyl amine, tetradecyl phosphoric acid and octadecylene mixing post-heating to 280 ℃ ~ 310 ℃, add the tellurium precursor, be cooled to 240 ℃ ~ 260 ℃ reaction 15s ~ 600s and obtain reaction solution, wherein, described Cadmium oxide, the mass ratio of described oleyl amine and described tetradecyl phosphoric acid is (0.0257 ~ 0.257): (1 ~ 10): (0.122 ~ 1.22), the solid-to-liquid ratio of described Cadmium oxide and octadecylene is (0.0257g ~ 0.257g): (8ml ~ 40ml), tellurium in described tellurium precursor and the mass ratio of described Cadmium oxide are (0.01276 ~ 0.1276): (0.0257 ~ 0.257), and
Centrifugation after described reaction solution is mixed with acetone is dissolved in the centrifugal throw out that obtains in chloroform, adds the mercury precursors reaction two hours, adds the mixed solution of normal hexane and methyl alcohol, and the upper solution that obtains after centrifugal is the CdHgTe quantum dot solution.
2. the preparation method of CdHgTe quantum dot solution according to claim 1, is characterized in that, makes described tellurium be dissolved in described organic phosphine by ultrasonic under 80 ℃ ~ 100 ℃.
3. the preparation method of CdHgTe quantum dot solution according to claim 1, it is characterized in that, in the described methyl alcohol that contains potassium hydroxide and Dodecyl Mercaptan, the mass ratio of described potassium hydroxide and described Dodecyl Mercaptan is 1:2 ~ 1:3, and the concentration of described Dodecyl Mercaptan is 0.1g/mL ~ 0.2g/mL.
4. the preparation method of CdHgTe quantum dot solution according to claim 1, it is characterized in that, after described reaction solution is mixed with acetone, in the step of centrifugation, the rotating speed of centrifugation is 4000 rev/mins ~ 10000 rev/mins, and the time of centrifugation is 5 minutes ~ 10 minutes.
5. the preparation method of CdHgTe quantum dot solution according to claim 1, is characterized in that, the volume ratio of normal hexane and described methyl alcohol described in the mixed solution of described normal hexane and methyl alcohol is 1:1 ~ 1:2.
6. the preparation method of a CdHgTe quantum dot, is characterized in that, comprises the following steps:
Adopt the preparation method of the described CdHgTe quantum dot solution of claim 1 ~ 5 any one to prepare the CdHgTe quantum dot solution; And
Add excessive methanol in described quantum dot solution, then centrifugation, the rotating speed of centrifugation is 4000 rev/mins ~ 10000 rev/mins, the time of centrifugation is 5 minutes ~ 10 minutes, obtains the CdHgTe quantum dot.
7. the preparation method of a bimodal semiconductor nano material, is characterized in that, comprises the following steps:
Adopt the preparation method of the described CdHgTe quantum dot solution of claim 1 ~ 5 any one to prepare the CdHgTe quantum dot solution;
Be (0.07 ~ 0.7) with mass ratio: (0.8 ~ 8): after the zinc diethyldithiocarbamate of (0.8 ~ 8), octadecylene and organic phosphine mix, ultrasonic dissolution obtains zinc diethyldithiocarbamate solution, and described organic phosphine is selected from least a in tri octyl phosphine and tributylphosphine;
Trioctylphosphine oxygen phosphorus, oleyl amine and octadecylene are added described CdHgTe quantum dot solution, vacuumize 30 ~ 60 minutes under 30 ℃ ~ 80 ℃, be warming up to 80 ℃ ~ 130 ℃, add described zinc diethyldithiocarbamate solution, react and be warming up to 150 ℃ ~ 180 ℃ reactions 0.5 hour ~ 4 hours after 10 minutes ~ 60 minutes, add the ethanol precipitating after being cooled to room temperature, obtain CdHgTe@ZnS quantum dot after centrifugation, wherein@represents to coat;
Be (20 ~ 200) with mass ratio: the Thioctic Acid of (6 ~ 60) and polyethyleneglycol modified Thioctic Acid add in ultrapure water, add sodium borohydride reaction 1 ~ 2 hour, regulating the pH value with sodium hydroxide is 9 ~ 11 to obtain Thioctic Acid solution, and the mass ratio of wherein said Thioctic Acid and described sodium borohydride is (20 ~ 200): (30 ~ 300);
Described CdHgTe@ZnS quantum dot is added in chloroform dissolve, add Thioctic Acid solution, centrifugal after concussion, get supernatant liquid, after ultrafiltration, filter residue is used the dissolving of neutral buffered liquid, add the solution that contains gadolinium ion, remove filtrate after ultrafiltration and obtain the bimodal semiconductor nano material.
8. the preparation method of bimodal semiconductor nano material according to claim 7, is characterized in that, in the described solution that contains gadolinium ion, the concentration of gadolinium ion is 0.1 ~ 5mg/mL.
9. the preparation method of bimodal semiconductor nano material according to claim 7, is characterized in that, the solid-to-liquid ratio of described CdHgTe@ZnS quantum dot and described chloroform is (10mg ~ 100mg): (0.5ml ~ 5ml).
10. a bimodal semiconductor nano material, is characterized in that, by preparation method's preparation of the described bimodal semiconductor nano material of claim 7 ~ 9 any one.
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