CN111995836B - Polymer dispersed liquid crystal, preparation method and application - Google Patents
Polymer dispersed liquid crystal, preparation method and application Download PDFInfo
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
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- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
Abstract
The invention relates to a polymer dispersed liquid crystal which is prepared from the following components in parts by mass: 0.5-1.5 parts of nano-silver loaded graphene; 1-5 parts of semiconductor quantum dots; 20-74 parts of a photosensitive polymer; 20-78 parts of nematic liquid crystal; 1-5 parts of a photoinitiator; wherein the silver content of the nano-silver loaded graphene is not more than 45wt%, the average transverse size is not less than 5 μm, and the average longitudinal size is 0.8-1.2 μm. The invention also relates to a preparation method of the polymer dispersed liquid crystal and application of the polymer dispersed liquid crystal in a random laser. The polymer dispersed liquid crystal has the characteristics of simple and easily obtained raw materials and low cost; the obtained random laser has the advantages of short preparation period, simple preparation process, easy regulation and control of emission wavelength, low production cost, higher emission light intensity, low threshold value and the like, and has wide commercial application prospect.
Description
Technical Field
The invention belongs to the field of quantum dots, and particularly relates to a polymer dispersed liquid crystal, a preparation method and an application thereof.
Background
Laser technology has been widely used in many fields such as industry, medicine and communication. The random laser core component comprises three elements of a pumping source, a working medium and a resonant cavity. The resonant cavity selects light with certain frequency and consistent direction to carry out the most preferential amplification, and suppresses light with other frequency and direction to form standing wave oscillation, and finally the standing wave oscillation is emitted in the form of laser. The random laser uses a strong scattering, disordered and aperiodic medium as a resonant cavity, has the characteristics of low threshold, small size, no resonant cavity structure, simple process, short preparation period, low manufacturing cost and the like, and has wide application prospect in the aspects of photonic integration, optical sensing, optical fiber communication, tumor detection, wearable devices and the like.
Dyes are common laser gain media, and the corresponding dispersed liquid crystal structure formed is a dye-doped polymer dispersed liquid crystal structure. Random lasers of dye-doped polymer dispersed liquid crystals have the following disadvantages: the laser emission threshold is high, the full width of the half peak is large, the light stability is poor, the synthesis process is complex, the light-emitting wave band is not easy to change, the production period is long and the cost is high; at dispersible concentrations in the polymer dispersed liquid crystal structure, it is not convenient to prepare random lasers.
It is therefore desirable to find a new technique that overcomes the above-mentioned drawbacks of random lasers.
Disclosure of Invention
The Polymer Dispersed Liquid Crystal (PDLC) is a random laser, which is usually applied to a random laser and is called polymer dispersed liquid crystal, wherein low molecular liquid crystal and a prepolymer are mixed and subjected to polymerization reaction under certain conditions to form micron-sized liquid crystal droplets which are uniformly dispersed in a polymer network, and then the dielectric anisotropy of liquid crystal molecules is utilized to obtain a material with an electro-optic response characteristic. The conventional polymer dispersed liquid crystal structured random laser generally operates by using dispersed liquid crystal as a laser scattering medium and a specific material as a laser gain medium (working medium).
The invention of the graphene lays the foundation of two-dimensional material research, and the scalability and the flexibility of the graphene arouse great interest in realizing low-size wearable optoelectronic devices. Because the noble metal surface plasmon has complex and peculiar optical characteristics, the noble metal surface plasmon has wide application in the fields of biosensing, micro photoelectric devices and the like, and recent research shows that the metal surface plasmon also has great application value in the field of random laser. Due to collective resonance of free electrons in surface plasmons, the noble metal nanoparticles have optical scattering cross sections which are much larger than those of common nanoparticles, and the strong scattering characteristic is just the requirement on a disordered scattering medium during random laser generation, so that the nano-silver loaded graphene has unique properties. The material of the nano-silver loaded graphene is a mixed heating method. Mixing graphene and acetate of metal silver in a manual or mechanical ball milling mode, further heating in a segmented mode, keeping the temperature for a period of time when the temperature reaches the acetate decomposition temperature of the metal silver, and forming metal silver nano particles on the surface of the graphene by utilizing the characteristic that the acetate of the metal silver is heated and decomposed.
The present invention aims to ameliorate the disadvantages of the prior art by providing a polymer dispersed liquid crystal comprising semiconductor quantum dots. The polymer dispersed liquid crystal disclosed by the invention is used for a random laser, and the obtained random laser has the characteristics of short preparation period, low production cost, simple preparation process, easy regulation and control of emission wavelength, higher emission light intensity and low threshold value, and has wide potential application prospects in the aspects of photonic integration, optical sensing, optical fiber communication, tumor detection, wearable devices and the like.
In the present invention,
the term "average lateral dimension" refers to the average size dimension in the horizontal direction.
The term "average longitudinal dimension" refers to the average size dimension in the vertical direction.
An object of the present invention is to provide a polymer dispersed liquid crystal which is realized by the following technique.
A polymer dispersed liquid crystal made from:
the silver content of the nano-silver loaded graphene is not more than 45wt%, the average transverse size is not less than 5 mu m, and the average longitudinal size is 0.8-1.2 mu m.
Further, the semiconductor quantum dots are selected from ZnCdSeS/ZnS semiconductor quantum dots or perovskite semiconductor quantum dots, and the perovskite semiconductor quantum dots are CsPbX 3 And X is selected from Cl, br or I.
Further, the photosensitive polymer is selected from polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyaminoacrylate, polyhydroxypropyl acrylate or polyurethane acrylate;
the photoinitiator is selected from one or more of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-methylphenylpropane-1 one, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzyl phenyl) butanone or 2-isopropyl thioxanthone.
Further, the nematic liquid crystal molecules comprise the following components in parts by mass:
another object of the present invention is to provide a method for preparing the above polymer dispersed liquid crystal, which comprises the steps of:
(1) Mixing a photoinitiator, nematic liquid crystal, a photosensitive polymer and semiconductor quantum dots to form a mixed solution;
(2) Adding the nano-silver loaded graphene into the mixed solution, and stirring to obtain a solution A;
(3) And (3) carrying out ultraviolet curing on the solution A in the step (2) so that liquid crystal molecules are separated out to form liquid crystal microdroplets which are dispersed in the solution A.
Further, after the nano-silver loaded graphene is added into the mixed solution, ultrasonic dispersion is carried out for 1-2 hours, and then mechanical stirring is carried out for 1-3 hours.
Further, the wavelength of the ultraviolet light is 200-365nm.
Further, the ultraviolet curing time is more than or equal to 5 seconds.
Further, the steps (1) and (2) are carried out in a light-shielding environment.
The invention also aims to provide the application of the polymer dispersed liquid crystal in a random laser.
The invention has the following beneficial effects:
1. the invention provides a polymer dispersed liquid crystal and a preparation method thereof, and the adopted raw materials are common chemicals and are simple and easy to obtain; the preparation process is simple, the cost is low, the required preparation conditions are not harsh, and the method has wide commercialization prospect.
2. The invention provides a random laser containing polymer dispersed liquid crystal formed by co-doping nano-silver loaded graphene and quantum dots, which solves the problems of high light laser emission threshold and large full width at half maximum of a random laser of dispersed liquid crystal in a common dye-doped polymer; the random laser disclosed by the invention has the characteristics of short preparation period, low production cost, simple preparation process, easiness in adjustment and control of emission wavelength, higher emission light intensity and low threshold value, and has wide potential application prospects in the aspects of photonic integration, optical sensing, optical fiber communication, tumor detection, wearable devices and the like.
Drawings
FIG. 1 is a schematic view showing the microstructure of the polymer dispersed liquid crystal prepared in example 1.
FIG. 2 is an optical microscope photograph of the polymer dispersed liquid crystal prepared in example 1.
FIG. 3 is an optical microscope photograph of a polymer dispersed liquid crystal prepared in example 2.
FIG. 4 is an optical microscope photograph of the polymer dispersed liquid crystal prepared in example 3.
FIG. 5 is an optical microscopic view of the polymer dispersed liquid crystal prepared in comparative example 1.
FIG. 6 is a schematic diagram of the structure of the random laser of polymer dispersed liquid crystal in example 4.
FIG. 7 shows examples 1, dye R6G doped polymer dispersed liquid crystal, znCdSeS/ZnS semiconductor quantum dots and CsPbBr 3 The emission intensity of the random laser of the perovskite semiconductor quantum dot doped polymer dispersed liquid crystal is compared with that of the test chart.
The structure corresponding to the reference number in the attached drawings is as follows:
1-pump laser; 2-working medium and resonant cavity; 3-a spectrometer; 4-spectrometer probe; 5-random laser; 6-a focusing lens; 7-Pump Source.
Detailed Description
The following will specifically describe the polymer dispersed liquid crystal, the preparation method thereof, and the structure of the random laser according to the present invention with reference to the following embodiments. The scope of the invention as claimed should not be limited to the embodiments described herein. Unless otherwise noted, the solvents and test methods mentioned in the examples of the present patent disclosure are conventional methods known to those skilled in the art.
In the embodiment of the present invention, the first and second,
the nano silver loaded graphene is purchased from chemical coma and has the model of GRSP50;
the components in the nematic liquid crystal are purchased from Jiangsu and Chemicals Co., ltd;
ZnCdSeS/ZnS semiconductor quantum dot and CsPbBr 3 Perovskite semiconductor quantum dots are purchased from Guangdong Pujiafu photoelectric technologyA limited company.
Example 1
A polymer dispersed liquid crystal made from:
the nematic liquid crystal comprises the following components in parts by mass:
the content of silver in the nano-silver loaded graphene is 45wt%, the average transverse size is 5 mu m, and the average longitudinal size is 0.8 mu m;
the polymer dispersed liquid crystal is prepared by the following method:
(1) The nematic liquid crystal, the photosensitive polymer polymethyl methacrylate, znCdSeS/ZnS semiconductor quantum dots and the photoinitiator phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide are stirred at 50 ℃ for 5min in the dark to form a mixed solution.
(2) Adding the nano-silver loaded graphene into the mixed solution, performing ultrasonic dispersion for 1.5 hours, and mechanically stirring for 2 hours at 50 ℃ in the dark to obtain a solution A.
(3) The solution A described above was poured into a liquid crystal cell having a thickness of 50 μm by capillary action.
(4) The intensity of use is 1mW/cm 2 And ultraviolet light with the wavelength of 200nm is used for carrying out ultraviolet curing on the solution A, wherein the ultraviolet curing time is 5 seconds, so that liquid crystal molecules are separated out to form liquid crystal microdroplets which are dispersed in the solution A to form dispersed liquid crystal microdroplets, and the nano-silver loaded graphene containing the nano-silver loaded graphene and the quantum dot co-doped polymer dispersed liquid crystal are obtained.
FIG. 1 shows a schematic view of a polymer dispersed liquid crystal prepared in example 1; wherein
1-ITO glass; 2-a photopolymer; 3-ZnCdSeS/ZnS semiconductor quantum dots; 4-nematic liquid crystal;
5-nano silver loaded graphene.
Under the ultraviolet curing condition, the components jointly form a polymer dispersed liquid crystal structure codoped by the nano-silver loaded graphene and the quantum dots.
Fig. 2 shows an optical microscope image of the prepared polymer dispersed liquid crystal, which shows that when the nano-silver supported graphene is doped by 0.5 part, the nano-silver supported graphene of the nano-silver supported graphene and the semiconductor quantum dot co-doped polymer dispersed liquid crystal can form a good structural framework, and the nano-silver supported graphene can be well dispersed.
Example 2
A polymer dispersed liquid crystal made from:
the nematic liquid crystal comprises the following components in parts by mass:
the silver content of the nano-silver loaded graphene is 35wt%, the average transverse size is 6 micrometers, and the average longitudinal size is 0.9 micrometers;
the polymer dispersed liquid crystal is prepared by the following method:
(1) Mixing the nematic liquid crystal, photosensitive polymer polymethyl acrylate and CsPbBr 3 Perovskite semiconductor quantum dots and photoinitiator 2-hydroxy-methylThe phenyl propane-1-one was stirred at 50 ℃ for 5min in the dark to form a mixed solution.
(2) Adding the nano-silver loaded graphene into the mixed solution, performing ultrasonic dispersion for 1h, and mechanically stirring for 1h at 50 ℃ in a dark condition to obtain a solution A.
(3) The solution A described above was poured into a liquid crystal cell having a thickness of 50 μm by capillary action.
(4) The intensity of use is 1mW/cm 2 And ultraviolet light with the wavelength of 365nm is used for carrying out ultraviolet curing on the solution A, wherein the ultraviolet curing time is 5 seconds, so that liquid crystal molecules are separated out to form liquid crystal microdroplets which are dispersed in the solution A to form dispersed liquid crystal microdroplets, and the polymer dispersed liquid crystal containing nano silver loaded graphene and co-doped quantum dots is obtained.
Fig. 3 shows an optical microscope image of the prepared polymer dispersed liquid crystal, which shows that when the nano-silver loaded graphene is doped by 1 part, the nano-silver loaded graphene of the nano-silver loaded graphene and the quantum dot co-doped polymer dispersed liquid crystal can form a relatively good structural framework, and the nano-silver loaded graphene can be relatively well dispersed, but at this time, the dispersion state of the polymer dispersed liquid crystal is relatively sparse, which shows that the doping amount of the nano-silver loaded graphene can affect the formation of the polymer dispersed liquid crystal structure.
Example 3
A polymer dispersed liquid crystal made from:
the nematic liquid crystal comprises the following components in parts by mass:
wherein the silver content of the nano-silver loaded graphene is 30wt%, the average transverse dimension is 6 μm, and the average longitudinal dimension is 1.1 μm;
the polymer dispersed liquid crystal is prepared by the following method:
(1) And stirring the nematic liquid crystal, the photopolymer polyamino acrylate, the ZnCdSeS/ZnS semiconductor quantum dots and the photoinitiator benzoin dimethyl ether at 50 ℃ in a dark place for 5min to form a mixed solution.
(2) Adding the nano-silver loaded graphene into the mixed solution, firstly performing ultrasonic dispersion for 1h, and then mechanically stirring for 2h at 50 ℃ in the dark to obtain a solution A.
(3) The solution A described above was poured into a liquid crystal cell having a thickness of 50 μm by capillary action.
(4) The intensity of use is 1mW/cm 2 And ultraviolet light with the wavelength of 300nm is used for carrying out ultraviolet curing on the solution A for 5 seconds, so that liquid crystal molecules are separated out to form liquid crystal microdroplets which are dispersed in the solution A to form dispersed liquid crystal microdroplets, and the nano-silver loaded graphene containing the nano-silver loaded graphene and quantum dot co-doped polymer dispersed liquid crystal is obtained
Fig. 4 shows an optical microscope image of the prepared polymer dispersed liquid crystal, which shows that when the nano-silver loaded graphene is doped by 1.5 parts, the nano-silver loaded graphene of the nano-silver loaded graphene and the quantum dot co-doped polymer dispersed liquid crystal can form a structure frame, the size of the dispersed liquid crystal is large, and the nano-silver loaded graphene has a clustering phenomenon in a polymer matrix.
Comparative example 1
The composition, parts by mass, and preparation method of the polymer dispersed liquid crystal in comparative example 1 are the same as those of example 1, except that the polymer dispersed liquid crystal in comparative example 1 does not contain nano silver-supported graphene.
Fig. 5 shows an optical microscope image of the polymer dispersed liquid crystal according to comparative example 1, which shows that when the amount of the nano-silver loaded graphene added to the quantum dot co-doped polymer dispersed liquid crystal is 1 part compared to the amount of the nano-silver loaded graphene doped, the quantum dot co-doped polymer dispersed liquid crystal formed in fig. 5 is very poor, and further highlights that the nano-silver loaded graphene is beneficial to the formation of a relatively good structural framework of the polymer dispersed liquid crystal, and when the amount of the nano-silver loaded graphene doped is 1 part compared to the amount of the nano-silver loaded graphene doped, the nano-silver loaded graphene can be dispersed relatively well without cluster phenomenon, which indicates that the formation of the polymer dispersed liquid crystal structure is affected by the doping of the nano-silver loaded graphene.
Example 4
This example relates to the use of the polymer dispersed liquid crystal prepared in example 1 in a random laser.
FIG. 6 shows the structure of a random laser of polymer dispersed liquid crystal prepared in example 4. The random laser component parts and the respective parts function as follows:
pump emission laser (1): providing the energy required to pump the sample.
Working medium and resonant cavity (2): the laser generation must be carried out with a suitable working medium, which may be a gas, a liquid, a solid or a semiconductor. Population inversion can be achieved in such media to create the necessary conditions for obtaining laser light. And (3) the scattering strength of the polymer co-doped with the graphene and the quantum dots.
And the graphene and quantum dot co-doped polymer is used as a resonant cavity.
Spectrometer (3) and spectrometer probe (4): collecting the spectral information of the emergent laser.
Sample emission light (5): a light source collected by the spectrometer.
Focusing lens (6): the focusing device has the function of focusing an emission light spot, so that light energy irradiated to the surface of a polymer co-doped with nano-silver loaded graphene and quantum dots is more concentrated.
Pump source (7): the pump source reverses the population in the working medium and must deactivate the atomic system in a certain way to increase the population at the upper level to generate laser radiation. Here, a pulsed light source is used as a pump source to irradiate the working medium, and the pumping process is also called "pumping". The pulsed laser here acts as a pump source.
The working principle of the random laser is as follows: the pump laser source is an ultraviolet pulse laser, the pulse frequency is 1Hz-1000Hz, and the pulse energy is more than 1 muJ. The semiconductor quantum dots fluoresce by the pumping action of the pump laser. Fluorescence is strongly scattered by the polymer to form a random closed resonant cavity, and random laser radiation is generated after the laser threshold is reached. The nano-silver loaded graphene is used as a scatterer to enhance the random laser radiation intensity.
Correlation test
The test principle is as follows: after laser emitted by the pumping source passes through the focusing lens, the energy is more concentrated, the laser irradiates a sample to enable the number of particles in a working medium to be reversed, laser radiation is generated, data can be analyzed by collecting data through a spectrometer, and a conclusion can be obtained.
Four samples of example 1, znCdSeS/ZnS semiconductor quantum dot doped polymer dispersed liquid crystal (comparative sample 1), dye doped polymer dispersed liquid crystal (comparative sample 2), and perovskite semiconductor quantum dot doped polymer dispersed liquid crystal (comparative sample 3), respectively, were tested using a random laser tester shown in fig. 6.
The comparative sample 1 and the example 1 have the same component types, component parts by mass, and preparation methods, but the comparative sample 1 does not contain the nano silver-supported graphene described in the example 1.
The component types, the component parts by mass and the preparation methods of the comparative sample 2 and the example 1 are the same, and the difference is that the dye R6G with equal parts by mass in the comparative sample 2 replaces the ZnCdSeS/ZnS quantum dots described in the example 1, and the nano-silver loaded graphene is not contained.
The component types, the component parts by mass and the preparation methods of the comparative sample 3 and the example 2 are the same, and the difference is that the nano silver loaded graphene described in the example 2 is not contained in the comparative sample 3.
FIG. 7 is a graph showing the emission intensity of random lasers of example 1, comparative sample 2 and comparative sample 3 in the test examples.
Table 1 shows random laser threshold and emitted light intensity data for four samples.
TABLE 1 random laser threshold and emitted light intensity data for four samples
As can be seen from the above table, example 1 is significantly better than comparative samples 1-3 in both the random laser threshold and the emitted light intensity.
Claims (9)
1. A polymer dispersed liquid crystal prepared from:
wherein the silver content of the nano-silver loaded graphene is less than or equal to 45wt%, the average transverse size is greater than or equal to 5 mu m, and the average longitudinal size is 0.8-1.2 mu m;
the preparation method of the polymer dispersed liquid crystal comprises the following steps:
(1) Blending a photoinitiator, nematic liquid crystal, a photosensitive polymer and semiconductor quantum dots to form a mixed solution;
(2) Adding the nano-silver loaded graphene into the mixed solution, and stirring to obtain a solution A;
(3) And (3) carrying out ultraviolet curing on the solution A in the step (2).
2. The polymer dispersed liquid crystal of claim 1, wherein the semiconductor quantum dots are selected from ZnCdSeS/ZnS semiconductor quantum dots or perovskite semiconductor quantum dots, and the perovskite semiconductor quantum dots are CsPbX 3 And X is selected from Cl, br or I.
3. The polymer dispersed liquid crystal of claim 1, wherein the photosensitive polymer is selected from the group consisting of polymethyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyaminoacrylate, polyhydroxypropyl acrylate, and urethane acrylate;
the photoinitiator is selected from one or more of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, 2-hydroxy-methylphenylpropane-1 one, 1-hydroxycyclohexyl phenyl ketone, benzoin dimethyl ether, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzyl phenyl) butanone or 2-isopropyl thioxanthone.
4. The polymer dispersed liquid crystal of claim 1, wherein the nematic liquid crystal molecules comprise the following components in parts by mass:
5. the polymer dispersed liquid crystal of claim 1, wherein the nano silver loaded graphene is added to the mixed solution, and then is subjected to ultrasonic dispersion for 1-2 hours, and then is subjected to mechanical stirring for 1-3 hours.
6. The polymer dispersed liquid crystal according to claim 1, wherein the wavelength of the ultraviolet light is 200 to 365nm.
7. The polymer dispersed liquid crystal according to claim 1, wherein the UV curing time is 5 seconds or more.
8. The polymer dispersed liquid crystal according to claim 1, wherein the steps (1) and (2) are carried out in a light-shielding environment.
9. Use of a polymer dispersed liquid crystal according to any one of claims 1 to 8 in a random laser.
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| CN202010801315.1A CN111995836B (en) | 2020-08-11 | 2020-08-11 | Polymer dispersed liquid crystal, preparation method and application |
| PCT/CN2021/115948 WO2022033599A1 (en) | 2020-08-11 | 2021-09-01 | Polymer-dispersed liquid crystal, preparation method therefor and use thereof |
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