CN113046082B - Photonic crystal, preparation method thereof and light-emitting diode - Google Patents
Photonic crystal, preparation method thereof and light-emitting diode Download PDFInfo
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- CN113046082B CN113046082B CN201911383366.0A CN201911383366A CN113046082B CN 113046082 B CN113046082 B CN 113046082B CN 201911383366 A CN201911383366 A CN 201911383366A CN 113046082 B CN113046082 B CN 113046082B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
- C09K11/881—Chalcogenides
- C09K11/886—Chalcogenides with rare earth metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/02—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
- H01L33/16—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
- H01L33/18—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous within the light emitting region
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a photonic crystal, a preparation method thereof and a light-emitting diode. The photonic crystal comprises a body structure and a plurality of quantum dots, wherein the body structure is made of rare earth luminescent materials, the quantum dots are dispersed in the body structure, the quantum dots can absorb part of emitted light generated by the rare earth luminescent materials, and the quantum dots and the rare earth luminescent materials form a compound. The photonic crystal has good stability and luminescence property, and has good application in the fields of display and luminescence.
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a photonic crystal, a preparation method thereof and a light-emitting diode.
Background
A Photonic Crystal (PC) is a periodic dielectric structure having a significant Photonic Band Gap (PBG) characteristic, which is a microstructure formed by periodic arrangement of two or more media of different refractive indices. A photonic band gap, which may also be referred to as a photonic band gap, is a range of photonic energies (similar to the concept of electronic band gaps in semiconductor materials) that satisfy certain conditions and cannot be transported in a photonic crystal. Through the characteristics of the photonic crystal structure, people can purposefully select the light wave of a certain waveband to pass through the structure and forbid the light waves of other wavebands to pass through, so that the photonic crystal has potential application value in the field of photonic devices, particularly optical communication. In the research aspect of regulating and controlling the luminescence of fluorescent materials, the photonic crystal has also made great progress: such as modulation of the excitation spectrum, emission spectrum, frequency of emitted light waves, direction of propagation, radiative and non-radiative rates of the fluorescent material, and enhancement of the fluorescence intensity of certain fluorescent materials.
As a new nano material, semiconductor Quantum Dots (QDs) are increasingly studied and paid more attention as their synthesis and performance are increasingly studied. The quantum dots have very considerable application prospect due to the unique performance of the quantum dots, for example, the quantum dots can be used for connecting with biological molecules and endocytosis in cells in the aspect of biomedicine, realize the marking of biological cell tissues, peptides, proteins, DNA and the like, and show breakthrough potential in the aspects of clinical diagnosis, genomics, drug screening and the like; there is also great potential in opto-electronic devices, especially for white light emitting diodes, which are currently referred to as "fourth generation illumination sources". The surface modification of quantum dots, the preparation of novel quantum dots and the application of the quantum dots as fluorescent materials in the aspects of photoelectric devices and the like are the hot areas of leading-edge research at present. In the field of display or illumination, quantum dots are typically spin-coated as a light-emitting layer between an electron-transporting layer and a hole-transporting layer. However, the electron transport layer or the hole transport layer has a certain functional group or a solvent used in the spin coating process has a certain influence on the stability of the quantum dot, resulting in a decrease in the light emitting performance of the quantum dot.
Therefore, the prior art is in need of improvement.
Disclosure of Invention
The invention aims to provide a photonic crystal, a preparation method thereof and a light-emitting diode, and aims to solve the technical problem that the luminescent performance of quantum dots is reduced due to the instability of a luminescent material of the quantum dots to a certain extent.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a photonic crystal, which comprises a body structure and a plurality of quantum dots, wherein the body structure is made of rare earth luminescent materials, the quantum dots are dispersed in the body structure, the quantum dots can absorb part of emitted light generated by the rare earth luminescent materials, and the quantum dots and the rare earth luminescent materials form a compound.
In the photonic crystal provided by the invention, a plurality of quantum dots are dispersed in a body structure formed by the rare earth luminescent material, and the quantum dots and the rare earth luminescent material form a compound, so that the quantum dots in the photonic crystal have good stability; when the luminescent crystal emits light, the light emitted by the luminescent center can be regulated and controlled by utilizing the photonic band gap of the photonic crystal, and part of the emitted light of the rare earth luminescent material can be absorbed by the quantum dots, so that the energy transfer between the rare earth luminescent material and the quantum dots is promoted, and the luminous efficiency of the quantum dots is improved; therefore, the photonic crystal has good stability and luminescence property, and has good application in the fields of display and luminescence.
The invention also provides a preparation method of the photonic crystal, which comprises the following steps:
forming a mixed solution containing a rare earth luminescent material precursor and quantum dots;
providing a structural template, adding the mixed solution into gaps of the structural template, and removing the structural template through calcination treatment to form the photonic crystal.
The preparation method of the photonic crystal provided by the invention directly adds the prepared mixed solution containing the rare earth luminescent material precursor and the quantum dots into the gaps of the structural template, then carries out calcination treatment to remove the structural template, and obtains the photonic crystal, and the finally obtained photonic crystal has good stability and luminescent property, and has good application in the fields of display and luminescence.
Finally, the invention also provides a light-emitting diode which comprises an anode, a cathode and a light-emitting layer positioned between the anode and the cathode, wherein the light-emitting layer consists of the photonic crystal or the photonic crystal obtained by the preparation method.
The light emitting diode provided by the invention is a luminophor crystal light emitting diode, namely, a light emitting layer of the light emitting diode consists of the special photonic crystal; the photonic crystal can improve the stability and the luminous efficiency of the quantum dots, so that the light-emitting diode has good luminous performance.
Drawings
FIG. 1 is a schematic diagram of a photonic crystal having an inverse opal structure provided by an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for preparing a photonic crystal with an inverse opal structure according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a process for forming a photonic crystal having an inverse opal structure according to an embodiment of the present invention;
fig. 4 is a schematic structural diagram of a light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In one aspect, an embodiment of the present invention provides a photonic crystal, where the photonic crystal includes a body structure and a plurality of quantum dots, the body structure is made of a rare earth luminescent material, the quantum dots are dispersed inside the body structure, the quantum dots are capable of absorbing a part of emitted light generated by the rare earth luminescent material, and the quantum dots and the rare earth luminescent material form a composite.
In the photonic crystal provided by the invention, a plurality of quantum dots are dispersed in a body structure formed by the rare earth luminescent material, the quantum dots and the rare earth luminescent material form a compound, and the quantum dots are dispersed in the body structure of the rare earth luminescent material and are separated from the outside, so that the quantum dots in the photonic crystal have good stability; when the luminescent crystal emits light, the light emitted by the luminescent center can be regulated and controlled by utilizing the photonic band gap of the photonic crystal, and part of the emitted light of the rare earth luminescent material can be absorbed by the quantum dots, so that the energy transfer between the rare earth luminescent material and the quantum dots is promoted, and the luminous efficiency of the quantum dots is improved; therefore, the photonic crystal has good stability and luminescence property, and has good application in the fields of display and luminescence.
The photonic crystal of the embodiment of the invention can exist in various structural forms, and the photonic crystal has a photonic band gap which can regulate and control light emitted by a luminescent center, improve the luminous efficiency of quantum dots, and realize the composite luminescence of the rare earth luminescent material and the quantum dots, which are all in the range of the embodiment of the invention. In one embodiment, the bulk structure is an inverse opal structure, i.e. the photonic crystal is a photonic crystal with an inverse opal structure; as shown in fig. 1, the photonic crystal is an inverse opal structure photonic crystal. The body structure 1 is formed with a microcavity 3 capable of containing air. The side wall of the micro-cavity 3 is composed of the rare earth luminescent material and the quantum dots 2 dispersed in the rare earth luminescent material, namely, the materials around the micro-cavity 3 are the rare earth luminescent material and the quantum dots 2 dispersed in the rare earth luminescent material. The quantum dots 2 are dispersed inside the bulk structure. The quantum dots 2 are capable of absorbing a portion of the emitted light generated by the rare earth luminescent material. The quantum dots 2 and the rare earth luminescent material form a compound capable of emitting light. Because the photonic crystal of the inverse opal structure is provided with a large number of micro-cavities, on one hand, the micro-cavity structure has good heat dissipation capability, and can effectively inhibit the current from passing through a luminescent layer (the luminescent crystal is used for an electroluminescent device) formed by the luminescent crystal or the local heat effect generated by external ultraviolet light excited quantum dots and rare earth luminescent materials (the luminescent crystal is used for a photoluminescent device), thereby inhibiting the non-radiation process of a luminescent center; on the other hand, the powder material can generate energy transfer with the particles contacted with the periphery, and the photonic crystal structure of the inverse opal structure is a thin-wall structure, so that the energy transfer process can only be along the thin wall, and unnecessary long-range energy transfer can be reduced. Therefore, the photonic crystal with the inverse opal structure can further improve the energy transfer efficiency, thereby further improving the luminous efficiency of the quantum dots; in one embodiment, the bulk structure of the inverse opal structure has microcavities with a diameter of 200-500nm, and the bulk structure of the inverse opal structure is a film with a thickness of 1-10 μm, i.e. the photonic crystal film has a thickness of 1-10 μm (e.g. 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm or 8 μm, and in one embodiment, about 10 μm); within the size range, the energy transfer long range can be further reduced, and the energy transfer efficiency is improved.
In one embodiment, the photonic band gap of the photonic crystal is capable of partially suppressing emitted light generated by the rare earth luminescent material inside the photonic crystal and not absorbed by the quantum dots. Since the light emitted by the rare earth ions is not monochromatic light, the light emitted by the rare earth ions is transferred from various different energy levels and emitted in the form of mixed light, besides the light with the part of the wavelength absorbed by the quantum dots, the light with other wavelengths can affect the light emitting performance of the whole material (the emission half-peak width is wide and has a hetero peak, namely, the color is not pure), and since the photonic crystal has the photonic band gap, the light emitted by the light emitting center can be regulated, when the light not absorbed by the quantum dots in the light emitted by the rare earth ions in the photonic crystal is inhibited by the photonic band gap, the inhibited light can be subjected to resonance conversion into non-radiative energy and transferred to the quantum dots, so that the light emitting efficiency of the quantum dots is further improved.
The photonic crystal is a periodic dielectric structure having a Photonic Band Gap (PBG) characteristic. The photonic bandgap of a photonic crystal means that a wave of a certain frequency range cannot propagate in the periodic structure, i.e. the structure itself has a "forbidden band".
In one embodiment, the surface of the quantum dots in the photonic crystal are coated with a layer of silicon dioxide. The silicon dioxide layer can protect the quantum dots, so that the quantum dots are more stable, and the quantum dots are prevented from being damaged by different treatments in subsequent reactions in the preparation process; furthermore, if the acceptor is in close contact with the donor during the energy transfer, a surface wave (i.e., a surface loss) is generated, energy is released in the form of heat and fluorescence quenching is caused, and the quantum dots in the photonic crystal and the rare earth luminescent material can be separated by the silica layer, so that the occurrence of fluorescence quenching is avoided. Further, the thickness of the silicon dioxide layer is 0.5-1nm, if the coating thickness of the silicon dioxide is too small, the separation effect on the quantum dots and the rare earth luminescent material is not ideal, fluorescence quenching is easy to occur, and if the coating thickness is too thick, the luminescent performance is further reduced.
In one embodiment, a silane coupling agent is connected to the surface of the silica layer, wherein a silane oxygen group in the silane coupling agent is combined with the silica layer, and an organic functional group in the silane coupling agent is combined with the rare earth luminescent material; the silane coupling agent can prevent the silica from continuing to grow in the process of coating the silica, control the thickness of the silica, and enable more ions to be adsorbed on the quantum dots through the electrostatic action and the subsequent action of the rare earth luminescent material precursor so as to combine the generated rare earth luminescent material. The silane coupling agent can be vinyl silane coupling agent, amino silane coupling agent, epoxy silane coupling agent (i.e. organic functional group Y in the silane coupling agent respectively corresponds to vinyl, amino and epoxy), including vinyl trichlorosilane, phenylaminopropyl trimethoxysilane, gamma-isocyanate propyl triethoxysilane, acryloxypropyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane, etc.; vinyl silane coupling agents are preferred in embodiments of the present invention.
In one embodiment, the surface of the quantum dot is bound with a thiol-group-containing ligand, and the thiol-group-containing ligand is located between the quantum dot and the silica layer. The ligand containing sulfydryl can improve the dispersibility of the quantum dots, and the silicon dioxide precursors can be better combined on the surfaces of the quantum dots when the silicon dioxide coating layers are coated, so that the coating effect is improved. Specifically, surface ligands include mercaptoacids and mercaptoamines; wherein the mercapto acid comprises thioglycolic acid, mercaptosuccinic acid, mercaptopropionic acid, dimercaptosuccinic acid, 16-mercaptohexadecanoic acid, 6-mercaptohexanoic acid, etc.; wherein the mercaptoamine includes mercaptoethylamine, 2-mercaptoaniline, 3-mercapto-1-propylamine, etc.
In one embodiment, the ratio of the molar amount of the rare earth luminescent material to the mass of the quantum dot is (1-4) mol: (50-100) mg; that is, every 1-4mol of the rare earth luminescent material is composed of a bulk structure, 50-100mg of quantum dots are dispersed: if the quantum dots are too few, the luminescent effect of the photonic crystal is poor, and if the quantum dots are too many, the reabsorption of radiation can occur among the quantum dots to cause the luminescent effect to be poor, so that the composite luminescent effect of the photonic crystal is optimal within the proportion range.
In one embodiment, the rare earth phosphorThe material is selected from inorganic nano material doped with rare earth ions; wherein the rare earth ions in the rare earth luminescent material are selected from Ce 3+ 、Ce 4+ 、Pr 3+ 、Pr 4+ 、Pr 5+ 、Nd 3+ 、Sm 2+ 、Sm 3+ 、Eu 2+ 、Eu 3+ 、Gd 3 + 、Tb 3+ 、Tb 4+ 、Dy 3+ 、Dy 4+ 、Er 3+ 、Tm 3+ 、Yb 2+ 、Yb 3+ At least one of; in a particular embodiment, the rare earth luminescent material is selected from CaF 2 :Eu 2+ 、Y 2 O 3 :Er 3+ 、CaWO 3 :Eu 3+ And the like.
The quantum dots are selected from at least one of II-VI compounds, III-V compounds, II-V compounds, III-VI compounds, IV-VI compounds, I-III-VI compounds, II-IV-VI compounds and IV elementary substances. Specifically, CdSe, ZnSe, PbSe, CdTe, ZnO, InP, GaN, GaP, AlP, InN, ZnTe, InAs, GaAs, CaF 2 、Cd 1- x Zn x S、Cd 1-x Zn x Se、CdSeyS 1-y 、PbSeyS 1-y 、ZnXCd 1-X Te、CdS/ZnS、Cd 1-x Zn x S/ZnS、Cd 1-x Zn x Se/ZnSe、CdSe/ZnS、CdSe 1-x S x /CdSe y S 1-y /CdS、CdSe/Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、Cd1-xZnxSe/ZnS、Cd 1-x Zn x Se/CdyZn 1-y Se/ZnSe、CdS/Cd 1-x Zn x S/Cd y Zn 1-y S/ZnS、Cd 1-x ZnxSeyS 1-y 、CdSe/CdS/ZnS、CdSe/ZnSe/ZnS。
On the other hand, the embodiment of the present invention further provides a preparation method of a photonic crystal, as shown in fig. 2, the preparation method includes the following steps:
s01: forming a mixed solution containing a rare earth luminescent material precursor and quantum dots;
s02: providing a structural template, adding the mixed solution into gaps of the structural template, and removing the structural template through calcination treatment to form the photonic crystal.
According to the preparation method of the photonic crystal provided by the embodiment of the invention, the prepared mixed solution containing the rare earth luminescent material precursor and the quantum dots is directly added into the gaps of the structural template, then the structural template is removed by calcination, the rare earth luminescent material precursor generates the rare earth luminescent material to form a body structure, the quantum dots are dispersed in the body structure, so that the photonic crystal is obtained, and the finally obtained photonic crystal has good stability and luminescent performance and has good application in the fields of display and luminescence.
The photonic crystal prepared by the preparation method of the photonic crystal comprises a body structure and a plurality of quantum dots, wherein the body structure is made of rare earth luminescent materials, the quantum dots are dispersed in the body structure, and the quantum dots and the rare earth luminescent materials form a compound capable of emitting light.
The photonic crystal of the embodiment of the invention is obtained by the preparation method of the embodiment of the invention. In an embodiment, the structural template is an opal template, and the bulk structure of the finally obtained photonic crystal is an inverse opal structure, that is, the photonic crystal with the inverse opal structure according to the embodiment of the present invention is obtained by the above preparation method according to the embodiment of the present invention.
The specific preparation steps for forming the mixed solution containing the rare earth luminescent material precursor and the quantum dots can include: providing a quantum dot solution, and adding a rare earth luminescent material precursor into the quantum dot solution to obtain a mixed solution containing the rare earth luminescent material precursor and quantum dots. Wherein the surface of the quantum dot is combined with a ligand containing sulfhydryl. The method comprises the following specific steps of; and (2) adding excessive surface ligand with sulfydryl into 5-10mL of 10mg/mL quantum dot chloroform solution, performing ultrasonic stirring until the clear quantum dot solution has a large amount of precipitates, centrifuging the obtained mixed liquid in a centrifuge, removing supernatant, washing lower-layer quantum dots by chloroform for multiple times, and finally dispersing the obtained quantum dots in deionized water.
Specifically, the surface of the quantum dot is coated with a silicon dioxide layer; the method comprises the following specific steps: taking 0.2-1mmol of CTAB (forming a molecular layer on the surface of the quantum dot to be beneficial to combination with subsequent silicate ester), 1-5mL of 0.1mol/L ammonia water and 5-10mL of deionized water in a round bottom flask, stirring to completely dissolve CTAB, adding the quantum dot solution, continuing stirring for 30-45min to completely disperse the quantum dot in the solution, then quickly injecting 10-15 mu L of silicon dioxide precursor (such as silicate ester: ethyl orthosilicate), and reacting for 24-30h at 40-60 ℃; and finally, adding 10-20 mu L of silane coupling agent (preventing the silica from continuously growing and enabling more ions to be adsorbed on the quantum dots through the action of static electricity and the follow-up rare earth luminescent material precursor), continuously stirring for 10-20h, cleaning and dialyzing to obtain the silica-coated quantum dots, and preparing into a 5-15mg/mL quantum dot aqueous solution.
The rare earth luminescent material precursor comprises a rare earth compound and an inorganic matrix precursor; the step of preparing the mixed solution comprises: taking 5-10mL of the silicon dioxide coated quantum dot aqueous solution, adding 0.01-0.05mol of rare earth compound (such as rare earth chloride or rare earth nitrate) and 1-4mol of inorganic matrix precursor (anions and cations are added according to a stoichiometric ratio), stirring for 30-60min, enabling the rare earth luminescent material precursor to generate electrostatic interaction with a silane coupling agent on the surface of silicon dioxide as far as possible, and enabling the rare earth luminescent material precursor to be adsorbed on the silicon dioxide to obtain a mixed solution containing the rare earth luminescent material precursor and quantum dots; in one embodiment, the ratio of the molar amount of the inorganic matrix precursor in the rare earth luminescent material precursor to the mass of the quantum dot is (1-4) mol: (50-100) mg, and the doped rare earth element is 0.01-0.05 mol.
In one embodiment, the structural template is an opal template, which is composed of polymer microspheres 4 with a diameter of 200-500nm, as shown in fig. 3. And adding the mixed solution into the gaps of the structural template, and carrying out burning treatment to remove the polymer microspheres 4 of the structural template so as to form photonic crystals (the polymer microspheres 4 are removed to form a microcavity 3, and the materials around the microcavity 3 are the rare earth luminescent material and the quantum dots 2 dispersed in the rare earth luminescent material, wherein the quantum dots 2 are dispersed in the body structure 1, and the quantum dots 2 and the rare earth luminescent material form a compound capable of emitting light).
The preparation of the opal template comprises the following steps: synthesizing polymer microspheres with the sphere diameter of 200-500nm by using the conventional technology, adding 40-60mL of deionized water into a beaker, adding 3mL of polymer microsphere suspension of 50-100mg/mL, and vertically inserting a glass substrate into the beaker after uniformly stirring; then transferring the beaker into an oven, keeping the beaker at 30-40 ℃ for 24 hours, and gradually depositing the polymer microspheres on the surface of the glass substrate under the hydrophilic action due to gradual evaporation of water to form an opal template; finally, the opal template is taken out and placed in an oven and kept for 30-50 minutes at the temperature of 100-120 ℃ to enhance the physical stability. The polymer microspheres comprise polymethyl methacrylate microspheres, polyethylene microspheres, polystyrene and the like;
in one embodiment, the step of adding the mixed solution into the gaps of the structural template comprises: and mixing the mixed solution with the structural template, and then standing for treatment (such as 20-25h) to enable the mixed solution to permeate into gaps of the structural template. The step of calcining treatment comprises: heating to 400-1000 ℃ at a heating rate of 0.5-2 ℃/min for calcination; the temperature rise rate can form a stable rare earth luminescent material. Specifically, the temperature is raised to 400-.
The photonic crystal is formed by compounding the quantum dots and the rare earth luminescent material, can improve the luminescent performance of the quantum dots from multiple aspects, and is beneficial to the application of the photonic crystal in the display or luminescent field. In particular, it is possible to produce photoluminescent or electroluminescent diodes, such as phosphor-crystal light-emitting diodes in electroluminescent diodes.
In an embodiment, the embodiment of the present invention further provides a light emitting diode, as shown in fig. 4, the light emitting diode includes an anode 5, a cathode 6, and a light emitting layer 7 located between the anode 5 and the cathode 6, where the light emitting layer 7 is composed of the photonic crystal according to the embodiment of the present invention or the photonic crystal obtained by the above-described preparation method according to the embodiment of the present invention.
The light emitting diode provided by the embodiment of the invention is a luminophor crystal light emitting diode, namely, a light emitting layer of the light emitting diode consists of the special photonic crystal of the embodiment of the invention; the photonic crystal can improve the stability and the luminous efficiency of the quantum dots, so that the light-emitting diode has good luminous performance.
Further, in the above light emitting diode, a hole function layer (e.g., a hole transport layer, or a hole injection layer and a hole transport layer which are stacked, wherein the hole injection layer is adjacent to the anode) may be provided between the anode and the light emitting layer, and an electron function layer (e.g., an electron transport layer, or an electron injection layer and an electron transport layer which are stacked, wherein the electron injection layer is adjacent to the cathode) may be provided between the cathode and the light emitting layer.
The invention is described in further detail with reference to a part of the test results, which are described in detail below with reference to specific examples.
Example 1
A preparation method of photonic crystals comprises the following steps:
(1) preparing mixed solution containing quantum dot and rare earth luminescent material precursor
Taking 5mL of 10mg/mL synthesized CdSe quantum dot chloroform solution, adding excessive thioglycolic acid into the CdSe quantum dot chloroform solution, ultrasonically stirring until the clear quantum dot chloroform solution has a large amount of precipitates, then placing the clear quantum dot chloroform solution into a centrifuge for centrifugation, removing supernatant, washing lower quantum dots with chloroform for multiple times, and finally dispersing the lower quantum dots in deionized water to obtain the thioglycolic acid modified CdSe quantum dot solution;
taking 0.4mmol CTAB, 3mL of 0.1mol/L ammonia water and 8mL of deionized water in a round-bottom flask, stirring to completely dissolve CTAB, adding the mercaptoacetic acid modified CdSe quantum dot solution, continuously stirring for 35min to completely disperse the quantum dots in the solution, then quickly injecting 10 mu L of ethyl orthosilicate, and reacting for 25h at 50 ℃; finally, adding 15 mu L of vinyl trichlorosilane, continuously stirring for 15h, cleaning and dialyzing to obtain CdSe quantum dots coated by silicon dioxide, and preparing into a 10mg/mLCdSe quantum dot aqueous solution;
taking 5mL of the CdSe quantum dot aqueous solution coated by the silicon dioxide, adding 0.02mol of europium chloride, 1mol of calcium chloride and 2.5mol of ammonium fluoride, stirring for 30min to enable the rare earth luminescent material precursor to generate electrostatic interaction with the silane coupling agent vinyl trichlorosilane on the surface of the silicon dioxide as much as possible, and adsorbing the electrostatic interaction to obtain the quantum dot/rare earth luminescent material precursor solution (namely CdSe/CaF) 2 Eu precursor solution).
(2) Preparation method of photonic crystal
Synthesizing polymethyl methacrylate microspheres, wherein the sphere diameter of the polymethyl methacrylate microspheres is 300nm, adding 45mL of deionized water into a beaker, adding 3mL of 60mg/mL polymethyl methacrylate microsphere suspension, and vertically inserting a glass substrate into the beaker after uniformly stirring; then transferring the beaker into an oven, keeping the beaker at 35 ℃ for 24 hours, and gradually depositing the polymer microspheres on the surface of the glass substrate under the hydrophilic action due to gradual evaporation of water to form an opal template; finally, the opal template was removed and placed in an oven at 110 ℃ for 35 minutes to enhance its physical stability.
Then adding CdSe/CaF 2 Slowly permeating the Eu precursor solution into gaps of the opal template, and standing for 24 hours; finally, in the hydrogen atmosphere, the temperature of the tubular furnace is raised to 700 ℃ at the speed of 1 ℃ per minute, the PMMA opal template is removed by calcining for 12 hours, and CaF is synthesized 2 :Eu 2+ Finally cooling to room temperature to obtain an inverse opal photonic crystal sample (CdSe/CaF) 2 :Eu 2+ Representation).
Example 2
A preparation method of photonic crystals comprises the following steps:
(1) preparing mixed solution containing quantum dot and rare earth luminescent material precursor
Adding excessive dimercaptosuccinic acid into 8mL of 10mg/mL CdTe quantum dot chloroform solution, ultrasonically stirring until the clear quantum dot chloroform solution is precipitated in a large amount, centrifuging the obtained mixed liquid in a centrifuge, removing supernatant, washing lower quantum dots with chloroform for multiple times, and finally dispersing in deionized water to obtain a thioglycolic acid modified CdTe quantum dot solution;
taking 0.5mmol CTAB, 5mL of 0.1mol/L ammonia water and 7mL of deionized water in a round bottom flask, stirring to completely dissolve CTAB, adding the CdTe quantum dot solution, continuously stirring for 45min to completely disperse the quantum dots in the solution, quickly injecting 12 mu L of ethyl orthosilicate, and reacting for 27h at 45 ℃; finally, 18 mu L of gamma-methacryloxypropyl trimethoxy silane is added, the stirring is continued for 160h, and the CdTe quantum dots coated by silicon dioxide are obtained after cleaning and dialysis and are prepared into 5mg/mL quantum dot aqueous solution;
adding 0.03mol of erbium nitrate and 1.3mol of yttrium nitrate into 7mL of the CdTe quantum dot aqueous solution coated by the silicon dioxide, stirring for 40min to enable the rare earth luminescent material precursor to generate electrostatic interaction with the silane coupling agent gamma-methacryloxypropyl trimethoxysilane on the surface of the silicon dioxide as much as possible, and adsorbing the electrostatic interaction to obtain the quantum dot/rare earth luminescent material precursor solution (namely CdTe/Y) 2 O 3 :Er 3+ Precursor solution).
(2) Preparation method of photonic crystal
Synthesizing polyethylene microsphere microspheres, wherein the sphere diameter of the polyethylene microsphere microspheres is 350nm, adding 55mL of deionized water into a beaker, adding 3mL of 70mg/mL polyethylene microsphere suspension, and vertically inserting a glass substrate into the beaker after uniformly stirring; then transferring the beaker into an oven, keeping the beaker at 38 ℃ for 24 hours, and gradually depositing the polymer microspheres on the surface of the glass substrate under the hydrophilic action due to the gradual evaporation of water to form an opal template; finally, taking out the opal template, placing the opal template in an oven, and keeping the opal template at 115 ℃ for 45 minutes to enhance the physical stability of the opal template;
then the CdTe/Y is put in 2 O 3 :Er 3+ Slowly permeating the precursor solution into gaps of the opal template, and standing for 24 hours; finally, the temperature is raised to 900 ℃ in a tubular furnace at the speed of 1 ℃ per minute, the polyethylene opal template is removed by calcination for 10 hours, and Y is synthesized 2 O 3 :Er 3+ Finally cooling to room temperature to obtain a photonic crystal sample (CdTe/Y) with an inverse opal structure 2 O 3 :Er 3+ Representation).
Example 3
A preparation method of photonic crystals comprises the following steps:
(1) preparing mixed solution containing quantum dot and rare earth luminescent material precursor
Taking 9mL of 10mg/mL synthesized CdSe/ZnSe/ZnS quantum dot chloroform solution, adding excessive mercaptoethylamine into the solution, ultrasonically stirring until the clear quantum dot chloroform solution has a large amount of precipitates, then placing the solution into a centrifuge for centrifugation, removing supernatant, washing lower quantum dots with chloroform for multiple times, and then dispersing the lower quantum dots in deionized water to finally obtain the CdSe/ZnSe/ZnS quantum dot solution;
taking 0.9mmol CTAB, 3.5mL of 0.1mol/L ammonia water and 6mL of deionized water in a round-bottom flask, stirring to completely dissolve CTAB, adding the quantum dot solution, continuously stirring for 38min to completely disperse the quantum dots in the solution, then quickly injecting 14 mu L of ethyl orthosilicate, and reacting for 24h at 60 ℃; finally, adding 20 mu L of methacryloxypropyl trimethoxy silane, continuing stirring for 20h, cleaning and dialyzing to obtain the CdSe/ZnSe/ZnS quantum dots coated with silicon dioxide, and preparing into a 15mg/mL quantum dot aqueous solution;
taking the 10mL of the silicon dioxide coated CdSe/ZnSe/ZnS quantum dot aqueous solution, adding 0.05mol of europium chloride, 1mol of calcium chloride and 3mol of ammonium metatungstate, stirring for 60min to ensure that CaWO is formed 3 :Eu 3+ The precursor of the rare earth luminescent material generates electrostatic interaction with the silane coupling agent on the surface of the silicon dioxide as much as possible to enable the precursor to be adsorbed, and the quantum dot/rare earth luminescent material precursor solution (namely CdSe/ZnSe/ZnS/CaWO) is obtained 3 :Eu 3+ Precursor solution).
(2) Preparation method of photonic crystal
Synthesizing polystyrene microspheres, wherein the sphere diameter of the polystyrene microspheres is 450nm, adding 60mL of deionized water into a beaker, adding 3mL of 90mg/mL polystyrene microsphere suspension, and vertically inserting a glass substrate into the beaker after uniformly stirring; then transferring the beaker into an oven, keeping the beaker at 34 ℃ for 24 hours, and gradually depositing the polystyrene microspheres on the surface of the glass substrate under the hydrophilic action due to the gradual evaporation of water to form an opal template; finally, taking out the opal template, placing the opal template in an oven, and keeping the opal template at 120 ℃ for 50 minutes to enhance the physical stability of the opal template;
then the CdSe/ZnSe/ZnS/CaWO 3 :Eu 3+ Slowly permeating the precursor solution into gaps of the opal template, and standing for 24 hours; finally, the temperature is raised to 850 ℃ in a tubular furnace at the speed of 1 ℃ per minute, the opal template is removed by calcination for a certain time, and CaWO is synthesized 3 :Eu 3+ Finally cooling to room temperature to obtain a photonic crystal sample with an inverse opal structure (CdSe/ZnSe/ZnS/CaWO) 3 :Eu 3+ Representation).
Example 4
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO substrate, the hole transport layer is made of TFB, the electron transport layer is made of zinc oxide, the cathode is made of Al, and the light emitting layer is made of the photonic crystal with the inverse opal structure obtained by the preparation method of example 1.
Example 5
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO substrate, the hole transport layer is made of TFB, the electron transport layer is made of zinc oxide, the cathode is made of Al, and the light emitting layer is made of the photonic crystal with the inverse opal structure obtained by the preparation method of the embodiment 2.
Example 6
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. Wherein the substrate is made of a glass sheet, the anode is made of an ITO substrate, the hole transport layer is made of TFB, the electron transport layer is made of a zinc oxide material, the cathode is made of Al, and the light emitting layer is composed of the photonic crystal of inverse opal structure obtained by the preparation method of the above embodiment 3.
Comparative example 1
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. The substrate is made of a glass sheet, the anode is made of an ITO (indium tin oxide) substrate, the hole transport layer is made of TFB (polycrystalline silicon), the electron transport layer is made of a zinc oxide material, the cathode is made of Al, and the light emitting layer is composed of CdSe quantum dots.
Comparative example 2
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. The substrate is made of glass sheets, the anode is made of an ITO (indium tin oxide) base plate, the hole transport layer is made of TFB (blue fluorescent layer), the electron transport layer is made of zinc oxide, the cathode is made of Al, and the light emitting layer is composed of CdTe quantum dots.
Comparative example 3
A light emitting diode includes a stacked structure of an anode and a cathode which are oppositely disposed, a light emitting layer disposed between the anode and the cathode, an electron transport layer disposed between the cathode and the light emitting layer, a hole transport layer disposed between the anode and the light emitting layer, and the anode is disposed on a substrate. The material of the substrate is a glass sheet, the material of the anode is an ITO base plate, the material of the hole transport layer is TFB, the material of the electron transport layer is a zinc oxide material, the material of the cathode is Al, and the light-emitting layer is composed of CdSe/ZnSe/ZnS quantum dots.
Performance testing
(1) Stability of
The stability of the photonic crystals with inverse opal structure prepared in examples 1-3 and the corresponding quantum dots was tested and the final data are shown in table 1.
TABLE 1
The data from table 1 above show that: the photonic crystals with inverse opal structures prepared in examples 1-3 of the present invention had better stability than quantum dots.
(2) Luminous efficiency
The light emitting diodes of examples 4 to 6 and comparative examples 1 to 3 were subjected to an External Quantum Efficiency (EQE) test: measured using an EQE optical test instrument. The external quantum efficiency test is for the corresponding light emitting diode device, i.e.: anode/hole transport layer/light emitting layer/electron transport layer/cathode.
The final data are shown in table 2.
TABLE 2
| Item group classification | External Quantum Efficiency (EQE)/(%) |
| Example 4 | 13％ |
| Comparative example 1 | 6％ |
| Example 5 | 11％ |
| Comparative example 2 | 5％ |
| Example 6 | 18％ |
| Comparative example 3 | 8％ |
The data in table 2 above show that: the external quantum efficiency of the light emitting diodes provided in examples 4 to 6 of the present invention (the light emitting layer is composed of the photonic crystal specific to the examples of the present invention) is significantly higher than that of the light emitting diode in the comparative example, which shows that the light emitting diode in the examples of the present invention has better light emitting efficiency.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (8)
1. A photonic crystal is characterized by comprising a body structure and a plurality of quantum dots, wherein the body structure is provided with a microcavity capable of containing air, the side wall of the microcavity is composed of a rare earth luminescent material and quantum dots dispersed in the rare earth luminescent material, the quantum dots can absorb part of emitted light generated by the rare earth luminescent material, and the quantum dots and the rare earth luminescent material form a compound; the photonic band gap of the photonic crystal is capable of partially suppressing emission light generated by the rare earth luminescent material inside the photonic crystal and not absorbed by the quantum dots, the rare earth luminescent material being selected from rare earth ion doped inorganic nanomaterials, rare earth ions in the rare earth luminescent materialSelected from Ce 3+ 、Ce 4+ 、Pr 3+ 、Pr 4+ 、Pr 5+ 、Nd 3+ 、Sm 2+ 、Sm 3+ 、Eu 2+ 、Eu 3+ 、Gd 3+ 、Tb 3+ 、Tb 4+ 、Dy 3+ 、Dy 4+ 、Er 3+ 、Tm 3+ 、Yb 2+ 、Yb 3+ At least one quantum dot selected from the group consisting of group II-VI compounds, group III-V compounds, group II-V compounds, group III-VI compounds, group IV-VI compounds, group I-III-VI compounds, group II-IV-VI compounds, and group IV simple substance.
2. The photonic crystal of claim 1, wherein said bulk structure is an inverse opal structure; and/or the presence of a gas in the gas,
the surface of the quantum dot is coated with a silicon dioxide layer.
3. The photonic crystal of claim 2, wherein the bulk structure has a microcavity with a diameter of 200-500nm, and the sidewall of the microcavity is composed of the rare-earth luminescent material and quantum dots dispersed in the rare-earth luminescent material; and/or
The bulk structure is a film having a thickness of 1-10 μm; and/or the presence of a gas in the gas,
the thickness of the silicon dioxide layer is 0.5-1 nm; and/or the presence of a gas in the gas,
the surface of the silicon dioxide layer is connected with a silane coupling agent, wherein a silane oxygen group in the silane coupling agent is combined with the silicon dioxide layer, and an organic functional group in the silane coupling agent is combined with the rare earth luminescent material; and/or the presence of a gas in the gas,
and a ligand containing sulfydryl is combined on the surface of the quantum dot, and the ligand containing sulfydryl is positioned between the quantum dot and the silicon dioxide layer.
4. The photonic crystal of claim 1, wherein a ratio of a molar amount of the rare earth luminescent material to a mass of the quantum dot is (1-4) mol: (50-100) mg.
5. A preparation method of photonic crystals is characterized by comprising the following steps:
forming a mixed solution containing a rare earth luminescent material precursor and quantum dots;
providing a structural template, adding the mixed solution into gaps of the structural template, and removing the structural template through a calcination treatment to form the photonic crystal as claimed in claim 1.
6. The method for preparing a photonic crystal according to claim 5, wherein the surface of the quantum dots in the mixed solution is coated with a silica layer; and/or the presence of a gas in the gas,
a ligand containing sulfydryl is combined on the surface of the quantum dot in the mixed solution; and/or the presence of a gas in the gas,
the rare earth luminescent material precursor in the mixed solution comprises a rare earth compound and an inorganic matrix precursor; and/or the presence of a gas in the gas,
the ratio of the molar quantity of the inorganic matrix precursor in the rare earth luminescent material precursor in the mixed solution to the mass of the quantum dots is (1-4) mol: (50-100) mg.
7. The method of preparing a photonic crystal according to claim 5, wherein the mixed solution is added to the gaps of the structural template: mixing the mixed solution with the structural template, and then standing; and/or the presence of a gas in the gas,
the step of calcining treatment comprises: heating to 400-1000 ℃ at a heating rate of 0.5-2 ℃/min for calcination; and/or the presence of a gas in the gas,
the structural template is an opal template and consists of polymer microspheres with the diameter of 200-500 nm.
8. A light-emitting diode comprising an anode, a cathode and a light-emitting layer disposed between the anode and the cathode, wherein the light-emitting layer is composed of the photonic crystal according to any one of claims 1 to 4 or the photonic crystal obtained by the manufacturing method according to any one of claims 5 to 7.
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