CN110790219A - Chiral photonic crystal film and preparation method and application thereof - Google Patents
Chiral photonic crystal film and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a chiral photonic crystal film and a preparation method and application thereof. The chiral photonic crystal film comprises a plurality of nanowire assembly layers in a spiral structure; the length directions of the nanowires in the nanowire assembly layers are consistent, the length directions of the nanowires are the orientations of the nanowire assembly layers, and the included angle of the orientations of two adjacent nanowire assembly layers is a preset angle. The structure of the chiral photonic crystal film is controlled by controlling the orientation included angle of two adjacent nanowire assembly layers, so that the photonic band gap position is controlled; and the anisotropy factor of the chiral photonic crystal film is close to the theoretical limit, and the optical activity is strong.
Description
Technical Field
The invention belongs to the field of materials, and relates to a chiral photonic crystal film, and a preparation method and application thereof.
Background
A photonic crystal is a periodic dielectric structure with a photonic band gap. In the photonic band gap band, light waves cannot propagate in this periodic structure, but are reflected. The colors of many animal and plant aspects in nature are produced by photonic crystal effects, and these structures provide a reference for people to design and manufacture highly efficient Optics (Tadepalla, Sinimuva et al Bio-Optics and Bio-Rapid Optical materials chemical Reviews,2017,117,12705.). The chiral photonic crystal is a branch of the photonic crystal, can selectively reflect one circularly polarized light and transmit the other circularly polarized light, and shows an ultra-strong circular dichroism effect, so that the chiral photonic crystal has an application prospect in the fields of polarizing optical elements, display, sensing and the like. In the early days, researchers developed various methods for preparing chiral photonic crystals, including top-down microfabrication methods (just kyna k. gansel et al. gold heliconic photonic materials as Broadband circuit polarizer science, 2009, 325, 1513-.
Patent CN106829854A discloses a method for preparing chiral nano thin film by langmuir assembly method. However, the chiral thin film obtained by the method is based on the inherent absorption of materials, and can only generate a strong circular dichroism spectrum signal at the inherent absorption position of an assembly unit, so that the problem of uncontrollable chiral optical properties exists. Moreover, the work of preparing the chiral photonic crystal based on the assembly of inorganic nano materials in the prior art is not reported, so a new method for preparing the chiral photonic crystal is urgently needed in the field to enrich the chiral photonic crystal materials and expand the application thereof.
Disclosure of Invention
The invention provides a chiral photonic crystal film and a preparation method and application thereof, so as to achieve the effects of controllable film structure and adjustable photonic band gap position.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a chiral photonic crystal film, comprising: a plurality of nanowire assembly layers in a spiral structure;
the length directions of the nanowires in the nanowire assembly layers are consistent, the length directions of the nanowires are the orientations of the nanowire assembly layers, and the included angle of the orientations of two adjacent nanowire assembly layers is a preset angle.
The uniform length direction of the nanowires in the nanowire assembly layer means that the nanowires are arranged in parallel, so that the chiral photonic crystal film has the property of one-dimensional chiral photonic crystals, can selectively reflect circularly polarized light, and has super-strong chiral optical response. The structure of the chiral photonic crystal thin film is controllable, and the photonic band gap position can be adjusted by controlling the orientation included angle of the two adjacent nanowire assembly layers, so that the optical activity can be adjusted in the wide wavelength bands of ultraviolet, visible and near infrared regions.
Optionally, the preset angle is 360 °/N, where N >2, N ≠ 4, and N is an integer.
Wherein, N represents the number of layers of the nanowire assembly layer corresponding to one period of the chiral photonic crystal film. And the total number of layers of the chiral photonic crystal film can be the number of layers corresponding to the whole period or the number of layers corresponding to the non-whole period. The invention can obtain the chiral photonic crystal film with chiral optical response at different wave bands by selecting different N values.
Optionally, the nanowires are inorganic oxide ultrafine nanowires.
In a second aspect, the present invention provides a method for preparing a chiral photonic crystal thin film, comprising the following steps:
(1) carrying out orientation assembly on the nanowires to obtain a nanowire assembly layer;
(2) and (2) repeating the step (1) to obtain a plurality of nanowire assembly layers, sequentially transferring the nanowire assembly layers, and controlling the orientation included angle of two adjacent nanowire assembly layers to be a preset angle to obtain the chiral photonic crystal film.
Optionally, the sequentially transferring the plurality of nanowire assembly layers of step (2) comprises: and sequentially transferring a plurality of nanowire assembly layers to a substrate.
Optionally, the substrate is a transparent substrate or an opaque substrate, and a silicon wafer, a quartz wafer, a glass wafer or a polydimethylsiloxane wafer is further preferable.
Optionally, the step (2) of controlling an included angle of the orientations of two adjacent nanowire assembly layers to be a preset angle includes: and controlling the plurality of nanowire assembly layers to sequentially rotate by the preset angle along a preset direction.
Optionally, in the step (1), the nanowire assembly layer is obtained by a gas-liquid interface assembly method.
Optionally, in the step (1), the nanowire assembly layer is obtained by a langmuir gas-liquid interface assembly method.
Optionally, the preparation method of the nanowire assembly layer in step (1) includes: adding a polar solvent into the Langmuir trough, wherein the liquid level of the polar solvent is 1-3 mm higher than the edge of the Langmuir trough, dropwise adding the nanowire solution on the surface of the polar solvent in the Langmuir trough, pushing the sliding barrier, and stopping pushing the sliding barrier when the liquid level of the nanowire solution begins to wrinkle to obtain the nanowire assembly layer.
Wherein, the polar solvent is Langmuir assembled lower phase. The sliding barrier is pushed in the langmuir trough so that the interface area becomes gradually smaller.
Alternatively, the polar solvent level may be 1 mm, 1.5 mm, 2 mm, 2.5 mm, 3 mm, etc. 1 to 3 mm above the edge of the langmuir trough, and more preferably 2 mm.
Optionally, in the step (1), the orientation of the nanowire assembly layer is perpendicular to the movement direction of the sliding barrier and parallel to the plane of the nanowire solution liquid level.
Optionally, the aspect ratio of the nanowire in the step (1) is 100-.
Optionally, the polar solvent is water, ethylene glycol, dimethyl sulfoxide, or acetonitrile.
In a third aspect, the present invention provides the use of any one of the chiral photonic crystal films described above in the manufacture of a chiral material, a polarizing optical device, a sensing device, an information storage device or a cryptographic element.
The chiral photonic crystal film has the advantages of controllable structure, adjustable photonic band gap position, super-strong optical activity, wide application range and larger development space.
Compared with the prior art, the invention has the following beneficial effects:
the structure of the chiral photonic crystal film is controlled by controlling the orientation included angle of two adjacent nanowire assembly layers, so that the photonic band gap position is controlled; the anisotropy factor of the chiral photonic crystal film is close to the theoretical limit, and the optical activity is strong; the preparation method is simple, the raw materials are cheap, and the cost is low; the invention can prepare large-area defect-free chiral photonic crystal film; the invention has wide application prospect in the fields of polarization optical devices, sensing, information encryption and storage and the like.
Drawings
Fig. 1 is a circular dichroism spectrum and an absorption spectrum of a chiral photonic crystal thin film prepared in example 2.
Fig. 2 is a reflection spectrum of the chiral photonic crystal thin film prepared in example 2.
Fig. 3 is an optical anisotropy factor diagram of the chiral photonic crystal thin film prepared in example 2.
Fig. 4 is a circular dichroism spectrum of the chiral photonic crystal thin film prepared in example 3.
Fig. 5 is an absorption spectrum of the chiral photonic crystal thin film prepared in example 3.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a chiral photonic crystal film. The chiral photonic crystal film comprises a plurality of nanowire assembly layers in a spiral structure. The length directions of the nanowires in the nanowire assembly layers are consistent, the length directions of the nanowires are the orientations of the nanowire assembly layers, and the included angle of the orientations of the two adjacent nanowire assembly layers is a preset angle.
The number of the nanowire assembly layers in the helical structure may be a whole period number, for example, including 10 periods, and if the preset angle is 360 °/24, the number of the nanowire assembly layers is 240; if the preset angle is 360 °/30, the number of layers of the nanowire assembly layer is 300, and if the preset angle is 360 °/36, the number of layers of the nanowire assembly layer is 360.
The number of the nanowire assembly layers in the helical structure may also be a non-whole period number, for example, the preset angle is 360 °/17, and the number of the nanowire assembly layers is 1000.
The chiral photonic crystal film provided by the embodiment of the invention comprises a plurality of nanowire assembly layers in a spiral structure, wherein the nanowires in the nanowire assembly layers are in consistent length direction, namely the nanowires are arranged in parallel, so that the chiral photonic crystal film shows the property of one-dimensional chiral photonic crystals, can selectively reflect circularly polarized light, and shows stronger chiral optical response. The structure of the chiral photonic crystal thin film is controllable, and the photonic band gap position can be adjusted by controlling the orientation included angle of two adjacent nanowire assembly layers, so that the optical activity can be adjusted in the wide wavelength bands of ultraviolet, visible and near infrared regions. Moreover, the preparation method of the chiral photonic crystal film provided by the invention is simple, the raw materials are cheap, the cost is low, and the preparation method is favorable for preparing the chiral photonic crystal film with large area and no defects. In addition, the chiral photonic crystal film provided by the invention has wide application prospects in the fields of preparation of chiral materials, polarization optical devices, sensing devices, information storage devices or encryption elements and the like.
The embodiment of the invention provides a preparation method of various chiral photonic crystal films. In the following examples, the experimental materials used, unless otherwise specified, were purchased from conventional biochemical manufacturers. In the following examples: the centrifugation adopts a table type high-speed centrifuge (XiangYi H-1650); the CD test adopts a JASCO-1500 circular dichroism spectrometer; the langmuir trough has dimensions of 25 cm × 10 cm.
Example 2
The embodiment provides a preparation method of a chiral photonic crystal film. This example specifically illustrates a method for preparing an ultra-fine nickel molybdate nanowire in step (1), a method for preparing an ultra-fine nickel molybdate nanowire assembly layer in step (2), and a method for preparing a chiral photonic crystal thin film in step (3).
(1) Preparation of superfine nickel molybdate nanowires
6 ml of ethanol, 2 ml of oleylamine and 1 ml of oleic acid were added to a 20 ml polytetrafluoroethylene reaction vessel with vigorous stirring. Then, 0.3 ml of a 1-mol/L aqueous solution of nickel chloride and 0.3 ml of a 1-mol/L aqueous solution of sodium molybdate were added thereto, and the stirring was continued for 10 minutes. After 4 hours at 140 ℃ and cooling to room temperature, the product was dispersed in 10 ml of cyclohexane and precipitated with 20 ml of ethanol. Centrifuging at 8000 rpm for 5 min, removing supernatant, and dispersing precipitate in 20 ml cyclohexane to obtain superfine nickel molybdate nanowire cyclohexane solution.
(2) Preparation of ultrafine nickel molybdate nanowire assembly layer
And (3) dropwise adding the superfine nickel molybdate nanowire cyclohexane solution into the ethylene glycol lower phase by two times of 100 microliters by using a 50 microliter microinjector, slowly pushing the sliding barrier until the area of the gas-liquid interface is 3.75 centimeters multiplied by 10 centimeters, stopping pushing, and standing for 30 minutes to obtain the superfine nickel molybdate nanowire assembly layer.
(3) Preparation of chiral photonic crystal thin film
And (3) repeating the step (2) to obtain the M-layer superfine nickel molybdate nanowire assembly layer. And transferring the first layer of the superfine nickel molybdate nanowire assembly layer onto a quartz plate by adopting a horizontal transfer method. And continuously adopting a horizontal transfer method to transfer the second layer of the superfine nickel molybdate nanowire assembly layer to the first layer of the superfine nickel molybdate nanowire assembly layer, and rotating the second layer of the superfine nickel molybdate nanowire assembly layer for 360 degrees/N clockwise or anticlockwise on the basis of the orientation direction of the first layer. And continuously repeating the M-2 horizontal transfer methods, wherein the direction of each rotation is consistent, and thus obtaining the chiral photonic crystal film comprising the M layers of the superfine nickel molybdate nanowire assembly layers.
In example 1, M is 1000, N is 17, and a chiral photonic crystal film is obtained by adopting a counterclockwise rotation mode.
Fig. 1 is a circular dichroism spectrum and an absorption spectrum of a chiral photonic crystal thin film prepared in example 2. The dashed line in fig. 1 is a circular dichroism spectrum, corresponding to the ordinate on the left side; the solid line in fig. 1 is the absorption spectrum, corresponding to the ordinate on the right. As can be seen from the circular dichroism spectrum, the chiral photonic crystal film has a very strong circular dichroism signal at about 630 nanometers. As can be seen from the absorption spectrum, there is a distinct absorption peak at 630 nm, the intensity of which corresponds to the photonic band gap intensity.
Fig. 2 is a reflection spectrum of the chiral photonic crystal thin film prepared in example 2. The reflection spectrum in fig. 2 has a strong reflectivity around 630 nm, verifying that the absorption peak in fig. 1 results from photonic crystal reflection.
Fig. 3 is an optical anisotropy factor diagram of the chiral photonic crystal thin film prepared in example 2. The optical anisotropy factor (g-factor) is a measure of the strength of chiral optical activity and is defined as follows:
where Δ ε is the molar circular dichroism absorption and ε is the molar extinction intensity. The theoretical optical anisotropy factor ranges from-2.0 to 2.0. As seen from FIG. 3, the optical anisotropy factor of the chiral photonic crystal thin film prepared in example 1 was as low as-1.6, which is very close to the theoretical limit, and thus the optical activity was very strong.
Example 3
The embodiment provides another preparation method of the chiral photonic crystal film. This example specifically illustrates a method for preparing a gadolinium oxyhydroxide ultrafine nanowire in step (1), a method for preparing a gadolinium oxyhydroxide ultrafine nanowire assembly layer in step (2), and a method for preparing a chiral photonic crystal thin film in step (3).
(1) Preparation of hydroxyl gadolinium oxide superfine nanowire
1.2 g of gadolinium trichloride hexahydrate was dissolved in 1.5 ml of deionized water for use. 18 ml of ethanol, 6 ml of oleylamine and 3 ml of oleic acid are added into a 40 ml hydrothermal kettle, and the mixture is stirred and mixed uniformly. Then dropwise adding the prepared gadolinium trichloride aqueous solution under stirring, continuing stirring for 15 minutes, and then reacting for 8 hours at 160 ℃. Washing for three times by using a mixed solvent of ethanol and n-hexane, and finally dispersing in 500 ml of n-hexane to obtain the gadolinium oxyhydroxide superfine nanowire n-hexane solution.
(2) Preparation of gadolinium oxyhydroxide nanowire assembly layer
And (3) dropwise adding 50 microliters of gadolinium oxyhydroxide superfine nanowire n-hexane solution onto the surface of the lower ethylene glycol phase by using a 50 microliter microinjector, slowly pushing the sliding barrier until the area of a gas-liquid interface is 3.75 centimeters multiplied by 10 centimeters, stopping pushing, and standing for 30 minutes to obtain the gadolinium oxyhydroxide nanowire assembly layer.
(3) Preparation of chiral photonic crystal thin film
And (3) repeating the step (2) to obtain the M-layer hydroxyl gadolinium oxide superfine nanowire assembly layer. And transferring the hydroxyl gadolinium oxide superfine nanowire assembly layer onto a quartz plate by adopting a horizontal transfer method. And continuously adopting a horizontal transfer method to transfer the second gadolinium oxyhydroxide superfine assembly layer to the first gadolinium oxyhydroxide superfine nanowire assembly layer, and rotating the second gadolinium oxyhydroxide superfine assembly layer counterclockwise by 360 degrees/N on the basis of the orientation direction of the first gadolinium oxyhydroxide superfine nanowire assembly layer. And continuously repeating the M-2 horizontal transfer method to obtain the chiral photonic crystal film.
In example 2, 3 chiral photonic crystal thin film samples were specifically prepared, and each of the 3 chiral photonic crystal thin film samples had 10 periods. Wherein N of the first chiral photonic crystal film sample is 24, and M is 240; the N of the second chiral photonic crystal film sample is 30, and M is 300; the third chiral photonic crystal film sample had N of 36 and M of 360.
Fig. 4 is a circular dichroism spectrum of the chiral photonic crystal thin film prepared in example 3. In FIG. 4, legend A24 represents a first chiral photonic crystal film sample; legend a30 represents a second chiral photonic crystal film sample; legend a36 represents a third chiral photonic crystal film sample. As can be seen from fig. 4, the absorption peaks of the 3 samples are different in wavelength band, and the wavelength of the wavelength band in which the absorption peaks are located is longer as the number of layers is increased.
Fig. 5 is an absorption spectrum of the chiral photonic crystal thin film prepared in example 3. In FIG. 5, legend A24 represents a first chiral photonic crystal film sample; legend a30 represents a second chiral photonic crystal film sample; legend a36 represents a third chiral photonic crystal film sample. As can be seen from fig. 5, the absorption intensities of the 3 samples are different, and the absorption intensity gradually increases as the number of layers increases.
The applicant states that the present invention is illustrated by the above examples to describe a chiral photonic crystal film, a method for preparing the same and applications thereof, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be implemented. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A chiral photonic crystal film, comprising: a plurality of nanowire assembly layers in a spiral structure;
the length directions of the nanowires in the nanowire assembly layers are consistent, the length directions of the nanowires are the orientations of the nanowire assembly layers, and the included angle of the orientations of two adjacent nanowire assembly layers is a preset angle.
2. The chiral photonic crystal film of claim 1, wherein the predetermined angle is 360 °/N, where N >2, N ≠ 4, and N is an integer.
3. A preparation method of a chiral photonic crystal film is characterized by comprising the following steps:
(1) carrying out orientation assembly on the nanowires to obtain a nanowire assembly layer;
(2) and (2) repeating the step (1) to obtain a plurality of nanowire assembly layers, sequentially transferring the nanowire assembly layers, and controlling the orientation included angle of two adjacent nanowire assembly layers to be a preset angle to obtain the chiral photonic crystal film.
4. The method of claim 3, wherein the sequentially transferring the plurality of nanowire assembly layers of step (2) comprises: and sequentially transferring a plurality of nanowire assembly layers to a substrate.
5. The method for preparing a transparent substrate according to claim 4, wherein the substrate is a transparent substrate or an opaque substrate.
6. The method according to claim 3, wherein the step (2) of controlling the included angle of the orientations of the two adjacent nanowire assembly layers to be a preset angle comprises: and controlling the plurality of nanowire assembly layers to sequentially rotate by the preset angle along a preset direction.
7. The method according to claim 3, wherein the step (1) comprises obtaining the nanowire assembly layer by Langmuir gas-liquid interface assembly.
8. The method according to claim 7, wherein the nanowire assembly layer of step (1) is prepared by: adding a polar solvent into the Langmuir trough, wherein the liquid level of the polar solvent is 1-3 mm higher than the edge of the Langmuir trough, dropwise adding the nanowire solution on the surface of the polar solvent in the Langmuir trough, pushing the sliding barrier, and stopping pushing the sliding barrier when the liquid level of the nanowire solution begins to wrinkle to obtain the nanowire assembly layer.
9. The preparation method of claim 8, wherein the nanowire assembly layer in step (1) is oriented perpendicular to the movement direction of the sliding barrier and parallel to the plane of the nanowire solution surface.
10. Use of the chiral photonic crystal film of claim 1 or 2 in the preparation of a chiral material, a polarizing optical device, a sensing device, an information storage device or a cryptographic element.
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| CN111422828A (en) * | 2020-04-01 | 2020-07-17 | 南京大学 | Method for preparing high-optical chiral device by stacking crystalline state nanowire arrays |
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| CN106829854A (en) * | 2017-02-14 | 2017-06-13 | 国家纳米科学中心 | A kind of chiral nano thin-film and preparation method and application |
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Application publication date: 20200214 |