CN1903566A - Method for preparing quantum point multi-layered ultra-thin film made of chitin/CdSe-ZnS with nucleus-sheel structure - Google Patents
Method for preparing quantum point multi-layered ultra-thin film made of chitin/CdSe-ZnS with nucleus-sheel structure Download PDFInfo
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Abstract
A multi-layer superfilm of the quantum dot with the chitosan/CdSe-ZnS core-shell structure is prepared through preparing chitosan solution, preparing mercaptoacetic acid modified quantum dot solution, preparing PEI solution, sticking the adhesive paper on one surface of a treated glass substrate, immersing it in PEI solution, washing, drying, and alternatively immersing in quantum solution and chitosan solution n times while washing and drying for each immersing. It has excellent non-linear optical performance.
Description
Technical field
The present invention relates to a kind of preparation method who is used for the self-assembly chitosan/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane of third-order nonlinear optical device, belong to physical chemistry and macromolecule chemical material field.
Background technology
Nonlinear optical material is significant in fields such as optical communication, optical storage, light conversion, photonic computers.The nonlinear response that desirable device for non-linear optical should be big, ultrafast signal conversion, advantages of excellent stability and machinability, preferably ultrathin membrane material.In recent years, semiconductor-quantum-point becomes the focus of nonlinear optical material research owing to its ultrafast response time, big third-order nonlinear susceptibility.But how quantum dot is transformed into the optics with operability from solution, also keep quantum dot special physicochemical performance to become puzzlement people's a difficult problem simultaneously.
Summary of the invention
The present invention overcomes the dissatisfactory shortcoming of the machinability of quanta point material in the prior art, the preparation method of a kind of shitosan/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane is provided, this method is dressed up the Nano ultrathin film by the mode of self assembly layer by layer with CdSe-ZnS nucleocapsid structure quantum dot and shitosan alternate group, this multi-layer ultrathin membrane is the desirable third order non-linear optical material of a kind of combination property, and the optical property of this material obviously is better than other and is scattered in quanta point material in solution, glass and the polymer.And the method for preparing shitosan/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane provided by the invention also has simple possible, lower-cost advantage.
Technical scheme provided by the invention is to utilize the self assembly effect of electrostatic force, mode with self assembly is layer by layer dressed up the Nano ultrathin film with CdSe-ZnS nucleocapsid structure quantum dot and shitosan alternate group, obtain shitosan/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane, the concrete preparation process that is adopted is as follows:
(1) shitosan is dissolved in is made into the solution that mass volume ratio is 0.5～2mg/ml in acetic acid-sodium acetate buffer solution, adding NaCl then, to make the molar concentration of chitosan solution be that 0.1～1mol/l is standby;
(2) the configuration quality volume ratio is the CdSe-ZnS nucleocapsid structure quantum dot aqueous solution of the TGA modification of 0.5～2mg/ml, adds NaCl then and makes the solution molar concentration be 0.1～1mol/l, and is standby;
(3) polymine PEI is dissolved in is made into the solution that concentration is 1～2mg/ml in the distilled water, add NaCl then and make the solution molar concentration be 0.1～1mol/l, standby;
(4) glass substrate was boiled in the mixed liquor of oleum and hydrogen peroxide 20～30 minutes, take out the back and clean with a large amount of distilled water, handled 20～30 minutes in absolute ethyl alcohol, deionized water for ultrasonic successively, cold wind dries up standby;
(5) glass substrate handled well is touched one side with gummed paper, be immersed in the polymine PEI solution 20～30 minutes, take out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(6) again glass substrate is immersed in the ready quantum dot solution 5～10 minutes, takes out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(7) again glass substrate is immersed in the ready chitosan solution 5～10 minutes, takes out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(8) hocket (6) and (7) step, repeat n time, promptly obtain self-assembly chitosan/CdSe-ZnS nucleocapsid structure quantum dot n layer ultrathin membrane.
Wherein used chitosan molecule amount is 10～200,000, deacetylation is 85～98%, process recrystallization purifying before using, the pH value of acetic acid-sodium acetate buffer solution is 5.6, what use is that volume ratio is 70: 30 a oleum: the mixed liquor of hydrogen peroxide, and in step (6) and (7) glass substrate the soak time in quantum dot solution, chitosan solution should be identical respectively.
As shown from the above technical solution, the present invention utilizes cheap natural polymer chitosan, by the self assembly effect of electrostatic force, only is that 100nm is with interior multi-layer quantum point ultrathin membrane assembling thickness on the glass substrate.This ultrathin membrane has not only been realized higher quantum dot filling rate, and the reunion of effectively having avoided quantum dot may occur in process, has advantages of excellent stability.Detect through femtosecond laser Z-scan, the third-order nonlinear susceptibility of this material is 1.1 * 10
-8Esu is higher than equal similar material far away, function admirable.
Self-assembly chitosan/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane by the present invention's preparation not only has the advantage of shitosan and quantum dot, and third order non-linear optical property and stability are also fine, abundant because of the shitosan raw material sources again, low price is so be with a wide range of applications in the nonlinear optical material field.And preparation method provided by the invention is a kind of cleaning, convenience, pollution-free green technology, is fit to large-scale production.
The specific embodiment
Below by specific embodiment the present invention is described in further detail.
What the present invention was used is that molecular weight is 10～200,000, and deacetylation is 85～98% shitosan, process recrystallization purifying before using.Employed CdSe-ZnS nucleocapsid structure quantum dot can be according to document .Xie, H.Y.; Liang, J.G.; Liu, Y.; Zhang, Z.L.; Pang, D.W.; He, Z.K.J.Nanosci.Nanotechnol.2005, the preparation of method described in the in press., TGA is modified CdSe-ZnS nucleocapsid structure quantum dot hydrophilic surface can be according to document Yang, Y.; Hori, M.; Hayakawa, T.; Nogami, M.Surf.Sci.2005 carries out described in 576,215.
Embodiment 1: getting the 20mg shitosan, to be dissolved in 20ml pH value be to obtain the chitosan solution that mass volume ratio is 1mg/ml in acetic acid-sodium-acetate buffer of 5.6, adds NaCl and make chitosan solution concentration to 1mol/l; The CdSe-ZnS nucleocapsid structure quantum dot that the TGA of learning from else's experience is modified becomes 1mg/ml with distilled water diluting, adds NaCl and makes quantum dot solution concentration to 1mol/l; Get 20mg PEI and be dissolved in the solution that is made into 1ml/ml in the 20ml distilled water, add NaC and make the PEI solution concentration to 1mol/l.Is 70: 30 oleum with the glass of 3cm * 2cm in volume ratio: boiled in the hydrogen peroxide 25 minutes, taking out the back cleans with a large amount of distilled water, handled 25 minutes at absolute ethyl alcohol and deionized water for ultrasonic successively, cold wind dries up, and touch with the one side of gummed paper with substrate.Substrate is immersed in the ready PEI solution 25 minutes, taking-up is cleaned in distilled water twice, cold wind dries up, alternately be immersed in quantum dot solution and the chitosan solution each 8 minutes again, dry up through 2 washings and cold wind respectively successively, so circulation is 6 times, promptly gets 6 layers of shitosan/CdSe-ZnS nucleocapsid structure quantum dot self-assembling ultrathin film.
Embodiment 2: getting the 20mg shitosan, to be dissolved in 20ml pH value be the chitosan solution that obtains 1mg/ml in acetic acid-sodium-acetate buffer of 5.6, adds NaCl and make chitosan solution concentration to 1mol/l; The CdSe-ZnS nucleocapsid structure quantum dot that the TGA of learning from else's experience is modified becomes 1mg/ml with distilled water diluting, adds NaCl and makes quantum dot solution concentration to 1mol/l; Get 20mgPEI and be dissolved in the solution that is made into 1mg/ml in the 20ml distilled water, add NaCl and make the PEI solution concentration to 1mol/l.(3cm * 2cm) is 70: 30 oleum in volume ratio: boiled in the hydrogen peroxide 30 minutes, and took out the back and clean with a large amount of distilled water, handled 30 minutes at absolute ethyl alcohol and deionized water for ultrasonic successively, cold wind dries up glass substrate, and gummed paper touch simultaneously.Substrate is immersed in the PEI solution 30 minutes, taking-up is cleaned in distilled water twice, cold wind dries up, alternately be immersed in quantum dot solution and the chitosan solution each 10 minutes again, dry up through 2 washings and cold wind respectively successively, so circulation is 12 times, promptly gets 12 layers of shitosan/CdSe-ZnS nucleocapsid structure quantum dot self-assembling ultrathin film.
Embodiment 3: get the 10mg shitosan and be dissolved in the chitosan solution that 20ml acetic acid-sodium-acetate buffer (pH=5.6) obtains 0.5mg/ml, add NaCl and make chitosan solution concentration to 0.5mol/l; The CdSe-ZnS nucleocapsid structure quantum dot that the TGA of learning from else's experience is modified becomes 0.5mg/ml with distilled water diluting, adds NaCl and makes quantum dot solution concentration to 0.5mol/l; Get 10mgPEI and be dissolved in the solution that is made into 0.5mg/ml in the 20ml distilled water, add NaCl to making PEI solution concentration 0.5mol/l.(3cm * 2cm) is 70: 30 oleum in volume ratio: boiled in the hydrogen peroxide 20 minutes, and took out the back and clean with a large amount of distilled water, handled 20 minutes at absolute ethyl alcohol and deionized water for ultrasonic successively, cold wind dries up glass substrate, and gummed paper touch simultaneously.Substrate is immersed in the PEI solution 20 minutes, taking-up is cleaned in distilled water twice, cold wind dries up, alternately be immersed in quantum dot solution and the chitosan solution each 5 minutes again, dry up through 2 washings and cold wind respectively successively, so circulation is 9 times, promptly gets 9 layers of shitosan/CdSe-ZnS nucleocapsid structure quantum dot self-assembling ultrathin film.
Embodiment 1,2,3 products therefroms are carried out third-order non-linear absorption and third-order non-linear refraction test, and test result sees the following form.
The third-order non-linear performance table of different number of plies CS/CdSe-ZnS core-shell QDs self-assembling ultrathin films
| ΔT 0-∞ | ΔΦ | β(cm/GW) | γ(cm 2/GW) | |
| 6-layer CS/QDs film 9-layer CS/QDs film 12-layer CS/QDs film | ---- -0.0223 -0.12 | 0.2069 0.4060 0.7133 | ---- 7.9×10 2 4.0×10 3 | 4.7×10 -2 5.1×10 -2 9.1×10 -2 |
By data in the table as can be known, the non-linear absorption and the nonlinear refraction of shitosan/CdSe-ZnS nucleocapsid structure quantum dot self-assembling ultrathin film all increase progressively with the increase of the number of plies.
Claims (6)
1, the preparation method of a kind of shitosan/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane, it is characterized in that: utilize the self assembly effect of electrostatic force, mode with self assembly is layer by layer dressed up the Nano ultrathin film with CdSe-ZnS nucleocapsid structure quantum dot and shitosan alternate group, obtains shitosan/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane.
2, the preparation method of shitosan according to claim 1/CdSe-ZnS nucleocapsid structure quantum dot multi-layer ultrathin membrane is characterized in that adopting following concrete steps:
(1) shitosan is dissolved in is made into the solution that mass volume ratio is 0.5～2mg/ml in acetic acid-sodium acetate buffer solution, adding NaCl then, to make the molar concentration of chitosan solution be that 0.1～1mol/l is standby;
(2) the configuration quality volume ratio is the CdSe-ZnS nucleocapsid structure quantum dot aqueous solution of the TGA modification of 0.5～2mg/ml, adds NaCl then and makes the solution molar concentration be 0.1～1mol/l, and is standby;
(3) polymine PEI is dissolved in is made into the solution that concentration is 1～2mg/ml in the distilled water, add NaCl then and make the solution molar concentration be 0.1～1mol/l, standby;
(4) glass substrate was boiled in the mixed liquor of oleum and hydrogen peroxide 20～30 minutes, take out the back and clean with a large amount of distilled water, handled 20～30 minutes in absolute ethyl alcohol, deionized water for ultrasonic successively, cold wind dries up standby;
(5) glass substrate handled well is touched one side with gummed paper, be immersed in the polymine PEI solution 20～30 minutes, take out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(6) again glass substrate is immersed in the ready quantum dot solution 5～10 minutes, takes out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(7) again glass substrate is immersed in the ready chitosan solution 5～10 minutes, takes out to be immersed in the distilled water and washs, be immersed in again in the clean distilled water after the taking-up and wash, take out cold wind and dry up;
(8) hocket (6) and (7) step, repeat n time, promptly obtain self-assembly chitosan/CdSe-ZnS nucleocapsid structure quantum dot n layer ultrathin membrane.
3, the preparation method of shitosan according to claim 2/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane, it is characterized in that: employed chitosan molecule amount is 10～200,000 in step (1), deacetylation is 85～98%, process recrystallization purifying before using.
4, the preparation method of shitosan according to claim 2/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane, it is characterized in that: the pH value of employed acetic acid-sodium acetate buffer solution is 5.6 in step (1).
5, the preparation method of shitosan according to claim 2/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane is characterized in that: used in the step (4) is that volume ratio is 70: 30 a oleum: the mixed liquor of hydrogen peroxide.
6, the preparation method of shitosan according to claim 2/CdSe-ZnS nuclear-shell quantum dot multi-layer ultrathin membrane is characterized in that: the soak time in quantum dot solution, chitosan solution should be identical respectively for glass substrate in step (6) and (7).
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| CN101980005A (en) * | 2010-10-20 | 2011-02-23 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN102053151A (en) * | 2010-10-26 | 2011-05-11 | 华南理工大学 | Fluorescent probe and method for rapidly detecting staphylococcus aureus by using same |
| CN102121030A (en) * | 2010-12-21 | 2011-07-13 | 中南林业科技大学 | Fluorescent quantum dot marked chitosan DNA nano composite vector and preparation and application thereof |
| GB2482597A (en) * | 2010-08-03 | 2012-02-08 | Honeywell Int Inc | Quantum dot solar cell and method of manufacture |
| CN104629765A (en) * | 2015-01-30 | 2015-05-20 | 天津理工大学 | Method for preparing multilayer fluorescence film by using hydrophobic semiconductor quantum dots |
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| GB2482597A (en) * | 2010-08-03 | 2012-02-08 | Honeywell Int Inc | Quantum dot solar cell and method of manufacture |
| GB2482597B (en) * | 2010-08-03 | 2014-01-29 | Honeywell Int Inc | Quantum dot solar cells and methods for manufacturing such solar cells |
| CN101980005A (en) * | 2010-10-20 | 2011-02-23 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN101980005B (en) * | 2010-10-20 | 2011-11-30 | 武汉市疾病预防控制中心 | Method for marking canine kidney cells through chitosan-quantum dot fluorescent probe |
| CN102053151A (en) * | 2010-10-26 | 2011-05-11 | 华南理工大学 | Fluorescent probe and method for rapidly detecting staphylococcus aureus by using same |
| CN102121030A (en) * | 2010-12-21 | 2011-07-13 | 中南林业科技大学 | Fluorescent quantum dot marked chitosan DNA nano composite vector and preparation and application thereof |
| CN102121030B (en) * | 2010-12-21 | 2013-01-02 | 中南林业科技大学 | Fluorescent quantum dot marked chitosan DNA nano composite vector and preparation and application thereof |
| CN104629765A (en) * | 2015-01-30 | 2015-05-20 | 天津理工大学 | Method for preparing multilayer fluorescence film by using hydrophobic semiconductor quantum dots |
| CN111450260A (en) * | 2020-04-17 | 2020-07-28 | 西南交通大学 | Bifidobacterium bifidum anti-tumor preparation, and preparation method, product and application thereof |
| CN111450260B (en) * | 2020-04-17 | 2021-06-25 | 西南交通大学 | Bifidobacterium bifidum anti-tumor preparation, and preparation method, product and application thereof |
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