CN113355748A - Method for realizing photonic crystal by utilizing quantum dot metal organic framework (QDs @ MOFs) complex - Google Patents

Method for realizing photonic crystal by utilizing quantum dot metal organic framework (QDs @ MOFs) complex Download PDF

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CN113355748A
CN113355748A CN202110635048.XA CN202110635048A CN113355748A CN 113355748 A CN113355748 A CN 113355748A CN 202110635048 A CN202110635048 A CN 202110635048A CN 113355748 A CN113355748 A CN 113355748A
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quantum dots
mofs
photonic crystal
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CN113355748B (en
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饶海波
郭子悦
陈继伟
朱俊东
李俊毅
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University of Electronic Science and Technology of China
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    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes

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Abstract

The invention discloses a method for realizing photonic crystals by utilizing quantum dot metal organic framework (QDs @ MOFs), which comprises the following steps: firstly, a three-phase method, a hydrothermal method, a thermal injection method and the like are used for preparing the nano quantum dot material. Then preparing Metal Organic Frameworks (MOFs) materials by using a hydrothermal method, a thermal injection method and a supersaturation crystallization method. Then, a pre-synthesis method or a post-synthesis method is used for combining nano quantum dots with a certain size with Metal Organic Frameworks (MOFs) with specific apertures to form the composite photonic crystal material with periodically-changed optical path length. The invention obtains a new preparation idea of the three-dimensional photonic crystal, realizes the periodic variation regulation and control of the optical path by selecting materials, adjusting the size and changing the aperture of the three-dimensional photonic crystal, achieves the aim of selecting the output wavelength from the range from a visible light wave band to a terahertz wave band, and has important value for widening the application of the photonic crystal.

Description

Method for realizing photonic crystal by utilizing quantum dot metal organic framework (QDs @ MOFs) complex
Technical Field
The invention belongs to the technical field of photoelectricity, and particularly relates to a method for realizing photonic crystals by utilizing quantum dot metal organic frameworks (QDs @ MOFs).
Background
Photonic crystals (Photonic crystals) refer to artificial periodic dielectric structures with Photonic band gap characteristics. In practice, the crystal is an artificial crystal formed by arranging media with different dielectric constants in space according to a certain period, and the arrangement period is in the order of light wavelength. Generally, in a semiconductor material, electrons form an energy band structure due to a periodic potential field, and a band gap (such as a valence band and a conduction band) exists between bands, so that if the energy of the electrons falls in the band gap, the electrons cannot propagate further. Similarly, in a photonic crystal, since the dielectric constant varies periodically in space, there is a periodic potential field similar to that of a semiconductor crystal, and when the variation range of the dielectric constant is large and the variation period is comparable to the wavelength of light, bragg scattering by the medium also generates a band gap, that is, a photonic band gap. By photonic band gap is meant that a wave of a certain frequency range cannot propagate in the periodic structure, which is the "forbidden band" of the photonic crystal. If the photonic crystal has a periodic structure in only one direction, the photon forbidden band may only occur in this direction. If a three-dimensional periodic structure exists, an omnidirectional photon forbidden band can appear, and light falling in the forbidden band is forbidden to propagate in any direction. Accordingly, photonic crystals can be classified into one-dimensional photonic crystals, two-dimensional photonic crystals, and three-dimensional photonic crystals.
Based on the unique optical property of the photonic crystal, the photonic crystal has wide application in the fields of photonic crystal fibers, photonic crystal lasers, photonic crystal waveguides, photonic crystal reflectors, optical switches, optical communication and the like.
And Metal Organic Frameworks (MOFs) are porous inorganic-Organic hybrid materials with periodic network structures formed by self-assembly of Metal ions and Organic ligands. In general, metal organic framework compounds can be classified into three main classes according to different synthetic methods and component units: one is a network type metal organic framework material, of which MOF-5 is a representative structure. Secondly, zeolite type mitsu framework structure materials, called ZIFs for short. And thirdly, Lawa tin skeleton material, called MILs for short. The metal organic framework has the characteristics of adjustable pore diameter, large specific surface area, high porosity and the like, and has important application in the fields of hydrogen storage, gas adsorption and separation, sensors, drug slow release, catalytic reaction and the like due to the unique property.
Quantum Dots (QDs) are semiconductor nanostructures that confine excitons in three spatial directions. Because the particle size can enter nanometer level, the size confinement can cause size effect, quantum confinement effect, surface effect, macroscopic quantum tunneling effect, etc., and shows many different physicochemical properties from the macroscopic material, such as: the quantum dots have wide and continuous distribution of excitation spectrum, narrow and symmetrical emission spectrum, adjustable size, adjustable color, high photochemical stability, long fluorescence life, various synthesis methods and the like. Therefore, the method has considerable application prospect in the fields of semiconductor devices, life sciences and the like. At present, representative quantum dots which have been widely studied are: II-VI family quantum dots (such as CdSe, CdS and the like), III-V family quantum dots (such as InP, InAs and the like), graphene quantum dots, perovskite quantum dots and the like.
Is different from the traditional air hole photonic crystal. The metal organic framework is a periodic nano material with adjustable pore size. The quantum dots are materials with the size adjustable in the nanometer level, and the quantum dots prepared by different precursors with different sizes have different dielectric constants and refractive indexes. Therefore, the nanometer quantum dots and the metal organic framework material are used for forming the three-dimensional photonic crystal material, so that the three-dimensional photonic crystal material has the advantages of high surface, selectivity, adjustability and the like, and can realize transmission and emission in a wider wavelength range.
Disclosure of Invention
The invention combines nano quantum dots with different sizes with organic metal frameworks (MOFs) with specific apertures to form the adjustable three-dimensional photonic crystal composite material, and then prepares the adjustable three-dimensional photonic crystal composite material into powder or a film to replace photonic crystals in the traditional photoelectric device, thereby realizing the adjustment and control of the emission wavelength. The technology has the advantages of adjustable material structure, selectable period and various synthesis methods. The method can be widely applied to photoelectric devices such as photonic crystal fibers, photonic crystal lasers, photonic crystal LEDs and the like.
The technical scheme of the invention is as follows: a method for realizing photonic crystals by utilizing quantum dot metal organic frameworks (QDs @ MOFs) is characterized in that the preparation method comprises the following steps:
(1) preparing a quantum dot material;
(2) preparing Metal Organic Frameworks (MOFs) materials;
(3) quantum dots with certain sizes and Metal Organic Frameworks (MOFs) with specific apertures are combined to form the composite photonic crystal material with periodically-changed optical path length.
The photonic crystal is composed of quantum dots and Metal Organic Frameworks (MOFs). The periodic constant and the difference between the refractive indexes of the two dielectric materials determine the position and the width of the band gap of the photonic crystal, and the position and the width of the band gap of the photonic crystal can be changed by changing any parameter. The MOFs are nanoscale structures with controllable sizes, and can be selected to combine with different quantum dots to form a controllable nano composite material with periodically-changed optical path. Wherein n isxlyDenotes the optical path per unit period, which is the path of light propagating in the medium, nxIs the refractive index of the nano quantum dots, /)yIs the unit period aperture of Metal Organic Frameworks (MOFs).
The quantum dot material is cadmium-based quantum dots, graphene quantum dots, perovskite quantum dots or quantum dots which are prepared and synthesized in a laboratory or are directly purchased. Generally, the particle size of the quantum dots is between 0 and 100 nm. The cadmium-based quantum dots comprise common single-layer CdSe, CdS and CdTe quantum dots, core-shell CdSe/CdS, CdSe/ZnS, CdS/ZnS, CdSZnSe/ZnS, CdSe/CdS/ZnS quantum dots and the like. The particle size of the particles is from small to large (2-10 nm) can realize green light emission with main peak value of 540nm to red light emission with main peak value of 680 nm. Graphene Quantum Dots (GQDs) have attracted extensive interest to researchers because they do not contain heavy metals and are environmentally friendly. Perovskite quantum dots are commonly referred to as AMX3Wherein X is Cl, Br, I and other halogen elements, A is cation (inorganic Cs +, or organic C)4H9NH3+Etc.), M is a divalent metal (Pb, Sn, etc.), which forms perovskite crystals with each other by van der Waals force, which can regulate luminescence throughout the visible light region (425-655nm) by particle size control.
The Metal Organic Frameworks (MOFs) are mainly coordination polymer materials with porous network structures obtained by taking Metal ions or Metal clusters as centers and bridged multidentate Organic ligands through a self-assembly synthesis process. Due to the special composition structure, the material has different properties with common inorganic porous materials and organic complexes, and the rigidity of the inorganic material and the flexibility of the organic material can be well combined. Representative three types of metal organic framework materials are: reticular metal-organic framework materials, zeolite-type mica framework materials (ZIFs), Lawa tin framework Materials (MILs). Such as: MOF-74 belongs to a reticular metal organic framework material, and the regulation of the pore size from 1.14nm to 9.8nm is realized at present.
In the step (1), the quantum dots are cadmium-based quantum dots, graphene quantum dots and perovskite quantum dots, and can be prepared in a laboratory or directly purchased; cadmium-based quantum dots are CdSe/ZnS quantum dots and CdSe/CdS/ZnS quantum dots; ② the graphene quantum dots are GQDs; ③ the perovskite quantum dot is CsPbX3(X ═ Cl, Br, I) quantum dots.
In the step (1), the preparation method can be hydrothermal solvothermal method, thermal injection method, supersaturated crystallization method, chemical oxidation method, stepwise organic synthesis method, etc.; preparing CdSe/ZnS quantum dots and CdSe/CdS/ZnS quantum dots on the basis of a three-phase method and a hydrothermal method, namely forming an LSS three-phase system by using oleic acid and ethanol as a liquid phase (L), sodium oleate as a solid phase (S), a metal-containing aqueous solution and ethanol as a solution phase (S), transferring the LSS three-phase system into a hydrothermal synthesis reaction kettle after the cadmium acetate is used as a cadmium source, the selenium powder is used as a selenium source, the zinc acetate is used as a zinc source, and the sodium sulfide is used as a sulfur source, reacting at a high temperature for several hours, and centrifugally washing to obtain quantum dot products; preparing the graphene quantum dots on the basis of an improved Hummers method and a hydrothermal method, namely preparing graphite into graphene oxide by using the improved Hummers method, transferring the graphene oxide and a compound containing sulfur and nitrogen into a hydrothermal synthesis reaction kettle, reacting for several hours at high temperature, and then obtaining a sulfur and nitrogen modified quantum dot product by centrifugal washing; and thirdly, the perovskite quantum dots are prepared based on a supersaturation crystallization method, namely, the perovskite quantum dots are naturally separated and crystallized into the quantum dots through the fact that the concentration of ions to be reacted is greater than the solubility of the perovskite quantum dots in a solvent.
In the step (2), the Metal Organic Frameworks (MOFs) are porous inorganic-organic hybrid materials with periodic network structures formed by self-assembly of metal ions and organic ligands. Can be a reticular metal organic framework material, such as MOF-5, MOF-69, MOF-74 and the like; can be zeolite type imidazole framework structure materials, such as ZIF-8, ZIF-9, ZIF-11, etc.; can be Lavaltin skeleton material, such as MIL-53, MIL-100, MIL-101, etc., UiO series, PCN series, CPL series.
In the step (2), the preparation method can be a hydrothermal solvothermal method, a supersaturated crystallization method and the like; firstly, a hydrothermal solvothermal method is to use a compound containing metal ions such as Mg or Zn and long-chain organic matters as precursors, to prepare the precursors according to a certain proportion, to put the precursors into a hydrothermal synthesis reaction kettle to react for hours at a high temperature, and to obtain a metal organic framework Material (MOFs) product through centrifugal washing; ② supersaturation crystallization method, namely, naturally separating out and crystallizing into metal organic framework Materials (MOFs) by the concentration of ions to be reacted being larger than their solubility in solvent.
In the step (3), the preparation method can be a pre-synthesis method and a post-synthesis method; firstly, the synthesis method is to construct MOFs structure on the surface of nano quantum dot particles. The method specifically comprises the following steps: firstly, CdSe/ZnS quantum dots, CdSe/CdS/ZnS quantum dots, graphene quantum dots and perovskite quantum dots are synthesized in a laboratory or directly purchased. Then MOFs are constructed on the surface of the nano quantum dot particles, and the photonic crystal material which is arranged periodically in an optical path and has different internal and external refractive indexes is formed; secondly, the synthesis method is to synthesize MOFs first and synthesize the nano quantum dot particles in the holes by taking the MOFs as a template. The method specifically comprises the following steps: firstly, synthesizing MOFs with a certain pore size, taking the MOFs as a template, putting a precursor of nano quantum dot particles required by laboratory preparation into the MOFs, and further reacting to generate a MOFs-coated nano quantum dot composite structure; or directly purchased nano quantum dot particles are put into the reaction kettle for further reaction to generate the MOFs-coated nano quantum dot composite structure.
In the step (3), the photonic crystal based on the Metal Organic Frameworks (MOFs) and the nanometer quantum dot composite body is obtained. It is a three-dimensional photonic crystal that allows the passage of wavelength limits λ and the unit period n of the optical pathxlyThe change has a certain linear relation, and light waves in a certain wavelength range can be selectively passed or blocked to achieve the purpose of wavelength selection, namely, the transmission and emission of wavelengths with wider coverage ranges, such as visible light wave bands (380nm-780nm), optical communication wave bands (1260nm-1675nm), terahertz wave bands (0.03mm-3mm) and the like, can be realized.
Drawings
FIG. 1 is a photonic crystal implemented by quantum dot metal-organic frameworks (QDs @ MOFs) complex according to the present invention, wherein 1 is a metal ion, 2 is an organic ligand, 3 is a nano quantum dot particle, and N is a cycle number.
FIG. 2 is a spectrum diagram of the photonic crystal according to the present invention with wavelength selectivity in the wavelength range of 620nm-720 nm.
FIG. 3 is a diagram showing the relationship between the allowable wavelength and the optical path per unit period of the photonic crystal according to the present invention. Where λ is the limit value for allowing passage of wavelengths, nxIs the refractive index of the nano quantum dots, /)yUnit period pore size, n, of Metal Organic Frameworks (MOFs)xlyIs the unit period optical path.
Detailed Description
The invention is further described with reference to the accompanying drawings and examples:
example 1
Synthesis of CdSe/ZnS quantum dots (n) with particle size of 1nm by three-phase method and hydrothermal methodx2.3), and then directly synthesizing the UiO-68 (l) with the aperture size of 2nm on the CdSe/ZnS quantum dots by utilizing a post-synthesis method and a supersaturation crystallization methody2nm) are added, and after centrifugal washing, a composite photonic crystal material based on UiO-68 and CdSe/ZnS quantum dots is obtained, and the unit period optical length n of the composite photonic crystal material isxly4.6nm, allowing passage of wavelengths λ ≦ 492 nm. The material structure is shown in fig. 1.
Example 2
CdSe/CdS/ZnS quantum dots (n) with the particle size of 2nm are synthesized by a three-phase method and a hydrothermal methodx2.8), and directly synthesizing ZIF-70 (l) with the aperture size of 3nm on CdSe/CdS/ZnS quantum dots by utilizing a post-synthesis method and a supersaturation crystallization methody3nm) and centrifugally washing to obtain the composite photonic crystal material based on ZIF-70 and CdSe/CdS/ZnS quantum dots, wherein the unit period optical path n of the composite photonic crystal material isxly8.4nm, allowing passage of wavelength λ ≦ 568 nm.
Example 3
Synthesis of MOF-5 (l) having a pore size of 4nm by supersaturation crystallizationy4nm), then taking MOF-5 as a template, and continuously synthesizing CdSe/ZnS quantum dots (n) with the particle size of 3nm in a framework by a hydrothermal methodx2.3) to obtain a composite photonic crystal material based on MOF-5 and CdSe/ZnS quantum dots, with a unit period optical length nxly9.2nm, allowing the passage of a wavelength λ ≦ 584 nm.
Example 4
Synthesis of perovskite quantum dots (n) with particle size of 2nm by using three-phase method and hydrothermal methodx3.5), and directly synthesizing ZIF-82 (l) with the pore size of 3nm on the perovskite quantum dots by utilizing a post-synthesis method and a hydrothermal methody3nm) and centrifugally washing to obtain the composite photonic crystal material based on ZIF-82 and perovskite quantum dots, wherein the unit period optical path n of the composite photonic crystal material is as long asxly10.5nm, allowing passage of a wavelength λ ≦ 610 nm.
Example 5
CdSe/CdS/ZnS quantum dot with particle size of 3nm synthesized by thermal injection method(nx2.8), and directly synthesizing ZIF-95 (l) with the pore size of 4nm on CdSe/CdS/ZnS quantum dots by utilizing a post-synthesis method and a hydrothermal methody4nm) and centrifugally washing to obtain the composite photonic crystal material based on ZIF-95 and CdSe/CdS/ZnS quantum dots, wherein the unit period optical path n of the composite photonic crystal material isxly11.2nm, allowing passage of wavelength λ ≦ 624 nm.
Example 6
Synthesizing graphene quantum dots (n) with particle size of 2nm by using three-phase method and hydrothermal methodx4.5), and directly synthesizing ZIF-11 (l) with a pore size of 3nm on the graphene quantum dots by using a post-synthesis method and a supersaturation crystallization methody3nm) and centrifugally washing to obtain the composite photonic crystal material based on ZIF-11 and graphene quantum dots, wherein the unit period optical path n of the composite photonic crystal material isxly13.5nm, allowing passage of a wavelength λ ≦ 670 nm.
Example 7
Synthesis of CdSe/ZnS quantum dots (n) with particle size of 5nm by three-phase method and hydrothermal methodx2.3), and then directly synthesizing the MOF-545 (l) with the aperture size of 6nm on the CdSe/ZnS quantum dots by utilizing a post-synthesis method and a hydrothermal methody6nm) are added, and after centrifugal washing, a composite photonic crystal material based on MOF-545 and CdSe/ZnS quantum dots is obtained, and the unit period optical distance n of the composite photonic crystal material isxly13.8nm, let through wavelength λ ≦ 676 nm.
Example 8
Synthesis of MIL-101 (l) with a pore size of 7nm by supersaturation crystallizationy7nm), and then synthesizing CdSe/ZnS quantum dots (n) with the particle size of 6nm in a frame by using MIL-101 as a template and continuously using a supersaturation crystallization methodx2.3) to obtain a composite photonic crystal material based on MIL-101 and CdSe/ZnS quantum dots, with a unit period optical length nxly16.1nm, allowing passage of wavelengths λ ≦ 722 nm.
Example 9
Synthesis of MIL-53 (l) with a pore size of 4nm by supersaturation crystallizationy4nm), and then synthesizing graphene quantum dots (n) with the particle size of 3nm in a frame by using MIL-53 as a template and a hydrothermal methodx＝4And 5) obtaining a composite photonic crystal material based on MIL-53 and graphene quantum dots, wherein the unit period optical distance n of the composite photonic crystal materialxly18nm, allowing passage of wavelengths λ ≦ 760 nm.
Example 10
Synthesis of MIL-100 (l) with 6nm pore size by supersaturated crystallizationy6nm), and then synthesizing the perovskite quantum dots (n) with the particle size of 5nm in the framework by using MIL-100 as a template and continuously using a supersaturation crystallization methodx3.5) to obtain a composite photonic crystal material based on MIL-100 and perovskite quantum dots, and the unit period optical path length n of the composite photonic crystal materialxly21nm, allowing passage of a wavelength λ ≦ 820 nm.
Example 11
Synthesizing graphene quantum dots (n) with particle size of 4nm by using thermal injection methodx4.5), and then directly synthesizing MOF-69 (l) with the pore size of 5nm on the graphene quantum dots by utilizing a post-synthesis method and a supersaturated crystallization methody5nm) are obtained, and after centrifugal washing, a composite photonic crystal material based on MOF-69 and graphene quantum dots is obtained, and the unit period optical path n of the composite photonic crystal materialxly22.5nm, allowing passage of wavelengths λ ≦ 850 nm.
Example 12
Synthesis of PCN-333 (l) with pore size of 8nm by hydrothermal methody8nm), and then, taking PCN-333 as a template, and continuously synthesizing the perovskite quantum dots (n) with the particle size of 7nm in the framework by a supersaturation crystallization methodx3.5) to obtain a PCN-333 and perovskite quantum dot-based composite photonic crystal material with a unit period optical path length nxly28nm, allowing passage of wavelengths λ ≦ 960 nm.
Example 13
Synthesis of PCN-18 (l) with pore size of about 8nm by thermal injectiony8nm), and then using PCN-18 as a template to continuously synthesize the graphene quantum dots (n) with the particle size of 5nm in the frame by a supersaturation crystallization methodx4.5) to obtain a composite photonic crystal material based on PCN-18 and graphene quantum dots, and the unit period optical path length n of the composite photonic crystal materialxly36nm, allowing passage of wavelength λ ≦ 1120 nm.
Example 14
Synthesis of PCN-14 (l) with a pore size of 12nm by supersaturation crystallizationy12nm), and then the PCN-14 is taken as a template to continue hydrothermal method to synthesize perovskite quantum dots (n) with the particle size of 11nm in the frameworkx3.5) to obtain a composite photonic crystal material based on PCN-14 and perovskite quantum dots, and the unit period optical path length n of the composite photonic crystal materialxly42nm, allowing passage of wavelength λ ≦ 1240 nm.
Example 15
Synthesis of UiO-66 (l) with pore size of 18nm by supersaturated crystallizationy18nm), and then using UiO-66 as a template to continuously synthesize CdSe/CdS/ZnS quantum dots (n) with the particle size of 17nm in a frame by a hydrothermal methodx2.8) to obtain a composite photonic crystal material based on UiO-66 and CdSe/CdS/ZnS quantum dots, with a unit period optical length nxly50.4nm, allowing passage of wavelength λ ≦ 1408 nm.
Example 16
Synthesis of MOF-808 (l) with a pore size of 14nm by hydrothermal methody14nm), and then taking MOF-808 as a template to continue synthesizing the graphene quantum dots (n) with the particle size of 13nm in the framework by a supersaturation crystallization methodx4.5) to obtain a composite photonic crystal material based on MOF-808 and graphene quantum dots, and the unit period optical path length n of the composite photonic crystal materialxly63nm, allowing passage of wavelength λ ≦ 1660 nm.

Claims (10)

1. A method for realizing photonic crystals by utilizing quantum dot metal organic frameworks (QDs @ MOFs) is characterized in that the preparation method comprises the following steps:
(1) preparing a nano quantum dot material;
(2) preparing Metal Organic Frameworks (MOFs) materials;
(3) nanometer quantum dots with certain sizes and Metal Organic Frameworks (MOFs) with specific apertures are combined to form a composite photonic crystal material with periodically-changed optical path length.
2. The method of claim 1, wherein the quantum dot is a quantum dotThe method for realizing the photonic crystal by the framework (QDs @ MOFs) complex is characterized by comprising the following steps: in the step (1), the nano quantum dots are as follows: the cadmium-based quantum dots are CdSe/ZnS quantum dots and CdSe/CdS/ZnS quantum dots; the graphene quantum dots are GQDs; the perovskite quantum dot is CsPbX3(X ═ Cl, Br, I) quantum dots. The quantum dots may be prepared in the laboratory or purchased directly.
3. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: in the step (1), the cadmium-based quantum dots are prepared by a three-phase method and a hydrothermal solvothermal method, namely, oleic acid and ethanol are used as a liquid phase (L), sodium oleate is used as a solid phase (S), an aqueous solution containing metal ions and ethanol are used as a solution phase (S) to form an LSS three-phase system, cadmium acetate is used as a cadmium source, selenium powder is used as a selenium source, zinc acetate is used as a zinc source, and sodium sulfide is used as a sulfur source, after one-pot proportioning is finished at normal temperature, the LSS three-phase system is transferred to a hydrothermal synthesis reaction kettle, and after reaction is carried out for a plurality of hours (4 to 10 hours) at high temperature (120 ℃ to 220 ℃), the corresponding CdSe/ZnS quantum dots and CdSe/CdS/ZnS quantum dots are obtained through centrifugal washing.
4. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: in the step (1), the graphene quantum dots are prepared by a hydrothermal solvothermal method, namely, firstly, graphite is prepared into graphene oxide based on an improved Hummers method, then, the graphene oxide and a compound containing sulfur and nitrogen (such as hydrazine hydrate, ammonia water and the like) are transferred into a hydrothermal synthesis reaction kettle, and after the graphene oxide and the compound containing sulfur and nitrogen are reacted for several hours (4 to 12 hours) at a high temperature (120 ℃ to 220 ℃), the graphene quantum dots modified by sulfur and nitrogen are obtained by centrifugal washing.
5. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: in the step (1), the perovskite quantum dots are prepared by a thermal injection method or a supersaturated crystallization method. In the supersaturated crystallization method, PbX2 and CsX (X ═ Cl, Br and I) are dissolved in DMF or DMSO at room temperature, OA and Oam are added for stabilization to form a precursor solution, and the precursor solution is added to a certain amount of toluene under vigorous stirring, so that the CsPbX3(X ═ Cl, Br and I) quantum dots can be obtained. In the thermal injection method, a precursor solution is injected instantaneously at a high concentration in a vacuum and high-temperature solution environment, and thus CsPbX3(X ═ Cl, Br, and I) quantum dots are rapidly synthesized.
6. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: the cadmium-based quantum dots (CdSe/ZnS quantum dots, CdSe/CdS/ZnS quantum dots), the Graphene Quantum Dots (GQDs), the perovskite quantum dots CsPbX3(X ═ Cl, Br, I) was prepared directly according to the laboratory conditions equipment and synthesis procedures, parameters.
7. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: in the step (2), the metal organic framework Materials (MOFs) are porous inorganic-organic hybrid materials with periodic network structures formed by self-assembly of metal ions and organic ligands. The metal-organic framework material may be a network type metal-organic framework material represented by an MOF-5 structure. Can be zeolite-type mica skeleton material of ZIFs series. Can be Laval tin skeleton material of MILs series. The synthesis method can be a hydrothermal method, a thermal injection method and a supersaturation crystallization method.
8. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: in the step (3), the nano quantum dots with certain sizes and Metal Organic Frameworks (MOFs) with specific apertures are combined to form the composite photonic crystal material with periodically-changed optical path length. The formation method can be a pre-synthesis method and a post-synthesis method. The synthesis method comprises the steps of constructing an MOFs structure on the surface of nano quantum dot particles, namely synthesizing the nano quantum dots based on the method, and growing the MOFs on the surfaces of the quantum dots. The post-synthesis method is to synthesize MOFs firstly and synthesize nano quantum dot particles in the holes by taking the MOFs as a template, namely, the MOFs frame is synthesized firstly on the basis of the method, and the nano quantum dot is continuously synthesized in the MOFs frame by taking the MOFs as the template. Finally, the photonic crystal material with periodically arranged optical paths and different internal and external refractive indexes can be formed.
9. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: the MOFs with different pore sizes and the nanometer quantum dots with different sizes are prepared by the following steps: cadmium-based quantum dots (CdSe/ZnS quantum dots, CdSe/CdS/ZnS quantum dots), Graphene Quantum Dots (GQDs), perovskite quantum dots CsPbX3The compound photonic crystal material (X ═ Cl, Br, I) and the like are combined to form a novel compound photonic crystal material which is periodically arranged and has different internal and external refractive indexes, is an effective synthesis idea of the three-dimensional photonic crystal, and can be expanded and used for the synthesis of the combination of any hole material and nano particles.
10. The method of claim 1 for implementing photonic crystals using quantum dot metal-organic frameworks (QDs @ MOFs) composites, wherein: the composite photonic crystal allows the passing of wavelength limit and optical path (n)xly，nxIs the refractive index of the nano quantum dots, /)yA certain linear relationship exists for the periodic variation of the unit period aperture of Metal Organic Frameworks (MOFs), light waves in a certain wavelength range can be selectively passed or blocked, the purpose of wavelength selection is achieved, and the method is suitable for different scenes and applications.
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