CN111162187B - Double-heterojunction nanorod, preparation method thereof and light-emitting diode - Google Patents
Double-heterojunction nanorod, preparation method thereof and light-emitting diode Download PDFInfo
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- CN111162187B CN111162187B CN201911426017.2A CN201911426017A CN111162187B CN 111162187 B CN111162187 B CN 111162187B CN 201911426017 A CN201911426017 A CN 201911426017A CN 111162187 B CN111162187 B CN 111162187B
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Abstract
The invention discloses a double-heterojunction nanorod, a preparation method thereof and a light-emitting diode. The preparation method of the double heterojunction nanorod comprises the following steps: mixing a first reactant and a second reactant for reaction to prepare a nanoparticle solution; adding a third reactant into the nanoparticle solution to prepare a single heterojunction nanorod solution; and adding a fourth reactant and a fifth reactant into the single heterojunction nanorod solution to prepare the double heterojunction nanorod. The invention provides a double-heterojunction nanorod, a preparation method thereof and a light-emitting diode, and aims to solve the problem that an electroluminescent diode based on quantum dots in the prior art is short in service life.
Description
Technical Field
The invention relates to the technical field of electronic devices, in particular to a double-heterojunction nanorod, a preparation method thereof and a light-emitting diode.
Background
Quantum dots (Quantum dots) are semiconductor nanostructures that confine excitons in three spatial directions, the emission spectra of Quantum dots can be changed by changing the size and chemical composition of Quantum dots, and Quantum Dot Light Emitting Diodes (QLEDs) have the advantages of large viewing angle, high contrast, fast response speed, and flexibility that liquid crystal displays do not have, so QLEDs are expected to become the next generation of display technologies.
In the existing QLED display technology, due to the unique energy level structure of a quantum dot and the asymmetric charge injection barrier between a quantum dot light emitting layer and a cathode and an anode, the electron hole of a blue light QLED is unbalanced, so that the hole cannot be effectively injected, and finally the service life of the blue light QLED is short. In the structure of the quantum dot, the outermost wide band gap semiconductor blocks injection of electrons and also blocks injection of holes, and thus the problem of short life of the QLED cannot be fundamentally solved.
Disclosure of Invention
The invention provides a double-heterojunction nanorod, a preparation method thereof and a light-emitting diode, and aims to solve the problem that a QLED (quantum dot light-emitting diode) in the prior art is short in service life.
In order to achieve the above object, the present invention provides a double-heterojunction nanorod, which includes a first nanoparticle, a nanorod, and a second nanoparticle, wherein a first heterojunction is formed between the first nanoparticle and the nanorod, a second heterojunction is formed between the second nanoparticle and the nanorod, the first heterojunction is a type II heterojunction, and the second heterojunction is a type I heterojunction.
Optionally, the material of the first nanoparticles is cadmium telluride or zinc telluride or cadmium zinc telluride;
the material of the nano rod is cadmium selenide or cadmium selenide sulfide or cadmium zinc selenide sulfide;
the second nano-particles are made of zinc selenide or zinc sulfide or zinc sulfoselenide.
Optionally, the preparation method of the double-heterojunction nanorod comprises the following steps:
adding a second reactant into a first reactant for mixing reaction to prepare a nanoparticle solution, wherein the first reactant contains cadmium element and/or zinc element, the second reactant contains tellurium element, and the molar mass of the first reactant is larger than that of the second reactant;
adding a third reactant into the nanoparticle solution to prepare a single heterojunction nanorod solution, wherein the third reactant contains selenium and/or sulfur;
and adding a fourth reactant and a fifth reactant into the single heterojunction nanorod solution to prepare the double heterojunction nanorod, wherein the fourth reactant contains zinc element, and the fifth reactant contains selenium element and/or sulfur element.
Optionally, the step of adding a second reactant into the first reactant for mixing and reacting to prepare the nanoparticle solution includes:
adding a first reactant and a first ligand into a first container to mix to form a first mixed solution;
pumping a first container filled with a first mixed solution to a vacuum state, introducing nitrogen into the first mixed solution, continuously stirring and heating to a first temperature, wherein the first temperature is 120-180 ℃;
adding a diluent into the first mixed solution to form a second mixed solution, and heating the second mixed solution to a second temperature, wherein the second temperature is 300-350 ℃;
adding a third ligand into a second reactant to form a first precursor solution, injecting the first precursor solution into the second mixed solution, reacting the first precursor solution with the second mixed solution for 10-15 minutes to form a nanoparticle solution, and cooling the nanoparticle solution to a third temperature, wherein the third temperature is 200-250 ℃.
Optionally, the step of adding a third reactant into the nanoparticle solution to prepare a single heterojunction nanorod solution includes:
adding a third ligand into a third reactant to form a second precursor solution, injecting the second precursor solution into the nanoparticle solution, and reacting the second precursor solution and the nanoparticle solution for 10-15 minutes to form a third mixed solution;
and cooling the third mixed solution to room temperature, purifying to obtain single heterojunction nanorods, and dissolving the single heterojunction nanorods in chloroform to obtain a single heterojunction nanorod solution.
Optionally, the step of adding a fourth reactant and a fifth reactant into the single heterojunction nanorod solution to prepare the double heterojunction nanorod comprises:
adding a fourth reactant, a second ligand and a diluent into a second container, mixing to form a third precursor solution, pumping the second container filled with the third precursor solution to a vacuum state, introducing nitrogen into the third precursor solution, continuously stirring and heating, wherein the heating temperature range is a fourth temperature which is higher than 150 ℃, the heating time is 0.5-1 hour, and the temperature is reduced to 60 ℃ after the heating is finished;
forming a fourth mixed solution after the single heterojunction nanorod solution is injected into the third precursor solution, vacuumizing to remove trichloromethane in the single heterojunction nanorod solution, and heating the fourth mixed solution to a fifth temperature, wherein the range of the fifth temperature is 300 +/-0.2 ℃;
adding a fifth reactant into a third ligand to form a fourth precursor solution, injecting the fourth precursor solution into the fourth mixed solution, and forming a double-heterojunction nanorod solution after reaction;
and cooling the double-heterojunction nanorod solution to room temperature, and purifying to obtain the double-heterojunction nanorod.
Optionally, the first ligand and/or the second ligand and/or the third ligand comprise at least one of octadecyl phosphate, trioctylphosphine oxide and oleic acid.
Optionally, the molar mass ratio of the first reactant to the first ligand is 1: 2-4.
Optionally, the molar mass of the third reactant is greater than the difference between the molar masses of the first reactant and the second reactant.
Optionally, the injection speed range of the second precursor solution into the nanoparticle solution is 3-6 ml/h, and the injection speed range of the fourth precursor solution into the fourth mixed solution is 3-6 ml/h.
Optionally, the concentration of the third ligand is 0.1-1 mol/L.
In order to achieve the above object, the present application provides a light emitting diode, which is characterized in that the light emitting diode includes double heterojunction nanorods according to any one of the above embodiments.
In the technical scheme that this application provided, the double heterojunction nanorod includes first nanoparticle, nanorod and second nanoparticle, first nanoparticle with form first heterojunction between the nanorod, the second nanoparticle with form the second heterojunction between the nanorod, first heterojunction is II type heterojunction, the second heterojunction is I type heterojunction. The double-heterojunction nanorod promotes the injection of holes and simultaneously hinders the injection of electrons, so that the electron holes in the luminescent material are more balanced, and the service life of the quantum-dot-based electroluminescent diode is prolonged.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a double heterojunction nanorod according to the present invention;
FIG. 2 is a schematic diagram of a type II heterojunction of the present invention;
FIG. 3 is a schematic diagram of a type I heterojunction of the present invention;
FIG. 4 is a schematic diagram of the energy level structure of the double heterojunction nanorod of the present invention;
FIG. 5 is a schematic flow chart of an embodiment of the method for preparing double-heterojunction nanorods according to the invention;
FIG. 6 is a schematic flow chart of another embodiment of the method for preparing double-heterojunction nanorods according to the invention;
FIG. 7 is a schematic flow chart of another embodiment of the method for preparing double-heterojunction nanorods according to the invention;
FIG. 8 is a schematic flow chart of another embodiment of the method for preparing double-heterojunction nanorods according to the invention;
fig. 9 is a schematic flow chart of a method for manufacturing a light emitting diode according to an embodiment of the invention.
The reference numbers illustrate:
| reference numerals | Name (R) | Reference numerals | Name (R) |
| 10 | |
30 | |
| 20 | Nano rod |
The implementation, functional features and advantages of the present invention will be further described with reference to the accompanying drawings.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the movement situation, etc. in a specific posture (as shown in the drawing), and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are only for descriptive purposes and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In the present invention, unless otherwise expressly stated or limited, the terms "connected," "secured," and the like are to be construed broadly, and for example, "secured" may be a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; they may be directly connected or indirectly connected through intervening media, or they may be connected internally or in any other suitable relationship, unless expressly stated otherwise. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a double-heterojunction nanorod, a preparation method thereof and a light-emitting diode.
Referring to fig. 1 to 4, in order to achieve the above object, the present application also provides a double-heterojunction nanorod prepared by the method for preparing a double-heterojunction nanorod according to any of the above embodiments. Specifically, the double-heterojunction nanorod comprises a first nanoparticle 10, a nanorod 20 and a second nanoparticle 30, a first heterojunction is formed between the first nanoparticle 10 and the nanorod 20, a second heterojunction is formed between the second nanoparticle 30 and the nanorod 20, the first heterojunction is a type II heterojunction, and the second heterojunction is a type I heterojunction.
The II-type heterojunction is a straddle-type heterojunction, and the forbidden bands of wide and narrow energy gap materials of the straddle-type heterojunction are staggered with each other, so that the forbidden band of one material can not completely contain the forbidden band of the other material any more. The I-type heterojunction is a staggered heterojunction, and the conduction band bottom valence band tops of the narrow-gap semiconductor of the staggered heterojunction are all contained by the forbidden band of the wide-gap semiconductor.
In some optional embodiments, the material of the first nanoparticle is cadmium telluride or zinc telluride or cadmium zinc telluride; the material of the nano-rod 20 is cadmium selenide or cadmium selenide sulfide or cadmium zinc selenide sulfide; the second nano-particles are made of zinc selenide or zinc sulfide or zinc sulfoselenide.
Specifically, the double-heterojunction nanorod is in a dumbbell structure, the first nanoparticle 10 and the second nanoparticle 30 are connected through a nanorod 20, the nanorod 20 is a handle of the dumbbell structure, and the first nanoparticle 10 and the second nanoparticle 30 are dumbbells of the dumbbell structure, wherein as shown in fig. 4, a conduction band bottom energy level of the dumbbell structure is required to be smaller than a conduction band bottom energy level of the handle, and a valence band top energy level of the dumbbell structure is required to be larger than a valence band top energy level of the handle. The II heterojunction can delocalize holes, is beneficial to injecting holes and has the function of limiting electrons, and the I heterojunction is used for obstructing the injection of electrons and can play the role of limiting holes. Through the heterojunction II and the heterojunction I, the double-heterojunction nanorod is beneficial to hole injection and simultaneously obstructs electron injection, so that the problem of unbalanced electron holes is solved, and the service life of the QLED is prolonged.
Referring to fig. 5, the method for preparing the double heterojunction nanorod comprises:
s100, adding a second reactant into a first reactant for mixing reaction to prepare a nanoparticle solution, wherein the first reactant contains cadmium element and/or zinc element, the second reactant contains tellurium element, and the molar mass of the first reactant is larger than that of the second reactant;
the first reactant and the second reactant both include elements in the nanoparticle solution, and specifically, after the first reactant and the second reactant react, a solution containing the first nanoparticles 10 is formed in the nanoparticle solution. Specifically, the first reactant includes an element or elements of the first nanoparticle 10, and the second reactant includes an element or elements of the first nanoparticle 10.
Specifically, when the first reactant and/or the second reactant are solid, in order to ensure that the first reactant and the second reactant can normally perform a chemical reaction, the first reactant and/or the second reactant may be added to a first ligand to perform a reaction, wherein the ligand represents an atom, a molecule, and an ion that can bond with a specific atom (metal or metalloid), and is mainly used to protect a functional group or stabilize a compound that is easily reacted. The reaction environment of the first reactant and the second reactant is changed from a solid state to a liquid state by the first ligand, thereby improving the reaction environment of the first reactant and the second reactant.
S200, adding a third reactant into the nanoparticle solution to prepare a single heterojunction nanorod solution, wherein the third reactant contains selenium and/or sulfur;
after a third reactant is added to the nanoparticle solution, the nanorod 20 is formed after an element in the nanoparticle solution reacts with an element in the third reactant, the nanorod 20 grows on the first nanoparticle 10 in the nanoparticle solution, because the production process of the nanorod 20 is different from the growth mode of the first nanoparticle 10, the nanorod 20 needs to grow in a linear direction from the outside of the first nanoparticle 10 in the growth process, and in order to ensure that the growth direction of the nanorod 20 is unchanged, the production speed of the nanorod 20 is less than that of the first nanoparticle 10.
S300, adding a fourth reactant and a fifth reactant into the single heterojunction nanorod solution to prepare a double heterojunction nanorod, wherein the fourth reactant contains a zinc element, and the fifth reactant contains a selenium element and/or a sulfur element.
After the single-heterojunction nanorod solution is obtained, in order to generate the second nanoparticles 30 on the side of the nanorods 20 far away from the first nanoparticles 10, the fourth reactant and the fifth reactant are added to react with each other, and the second nanoparticles 30 are generated by the element in the fourth reactant and the element in the fifth reactant, similarly, in the process of generating the second nanoparticles 30, since the second nanoparticles need to be generated in a spherical or approximately spherical shape with the nanorods 20 as a generation starting point, the second nanoparticles cannot be generated in any direction, and thus the generation speed of the second nanoparticles 30 is lower than that of the first nanoparticles 10.
In the technical scheme provided by the application, the preparation method of the double heterojunction nanorod comprises the following steps: firstly, mixing a first reactant and a first precursor solution to form a third mixed solution, reacting to generate a single heterojunction, secondly, adding a second precursor solution into the third mixed solution, reacting to form a fourth mixed solution, generating a nanorod on the single heterojunction, secondly, adding a third precursor solution into the fourth mixed solution to form a fifth mixed solution, and generating another heterojunction on the other side of the nanorod to form the double-heterojunction nanorod. The double-heterojunction nanorod is obtained by mixing different solutions, generating a new nanorod solution and finally purifying, and inhibits the injection of electrons while promoting the injection of holes, so that the electron holes in the luminescent material are more balanced, and the service life of the quantum-dot-based electroluminescent diode is prolonged.
Referring to fig. 6, in some alternative embodiments, the step S100 includes:
s110, adding a first reactant and a first ligand into a first container to mix to form a first mixed solution;
the first ligand can improve the solubility of the reaction element in the first reactant in a solvent and improve the dispersibility of the reaction element in the first ligand, and particularly, the first ligand is a mixed solvent of octadecyl phosphoric acid and trioctylphosphine oxide.
S120, pumping a first container filled with a first mixed solution to a vacuum state, introducing nitrogen into the first mixed solution, continuously stirring, and heating to a first temperature, wherein the first temperature is 120-180 ℃;
wherein, because nitrogen is required to be introduced into the first mixed solution and stirring is carried out continuously, in order to ensure that the operation of introducing nitrogen and the continuous stirring can be carried out simultaneously and do not interfere with each other, the first container is a three-mouth flask, and a nitrogen tank for introducing nitrogen and a stirring rod for stirring extend into the three-mouth flask from different inlets respectively, thereby ensuring that stirring and nitrogen introduction are carried out simultaneously.
Specifically, the first container is vacuumized and communicated with the first container through a vacuum pump to vacuumize the first container. It is understood that, in order to avoid the breakage of the three-neck flask due to the excessively low vacuum pressure, the vacuum pump is a mechanical pump, and the vacuum degree in the vacuum state is greater than or equal to 10E-1 Pa.
S130, adding a diluent into the first mixed solution to form a second mixed solution, and heating the second mixed solution to a second temperature, wherein the second temperature is 300-350 ℃;
wherein when the first reactant is mixed with the first ligand to form a first mixed solution, the first mixed solution is a turbid and opaque solution, when the first mixed solution is heated, the first mixed solution is gradually changed from the turbid and opaque solution to a colorless and transparent solution, and a diluent is added to the first mixed solution to form a second mixed solution.
The diluent is used for diluting the first mixed solution so as to disperse elements in the first solution, and specifically, the diluent may be octadecene or o-phthalaldehyde or other diluents capable of being used for solution dilution.
S140, adding a third ligand into a second reactant to form a first precursor solution, injecting the first precursor solution into the second mixed solution, waiting for the first precursor solution and the second mixed solution to react for 10-15 minutes to form a nanoparticle solution, and cooling the nanoparticle solution to a third temperature, wherein the range of the third temperature is 200-250 ℃.
The third ligand is used for coating the second reactant, so that the first precursor solution can be conveniently prepared, the first precursor solution can conveniently react with the second mixed solution, and specifically, the third ligand can be trioctylphosphine.
Wherein, since the first nanoparticles 10 can grow in all directions, the first precursor solution can be rapidly injected into the second mixed solution, thereby accelerating the growth of the first precursor and the second mixed solution.
Specifically, the reaction time of the first precursor solution and the second mixed solution is greater than or equal to 10 minutes. And preparing the nanoparticle solution after the first precursor solution and the second mixed solution are reacted.
Referring to fig. 7, in some alternative embodiments, the step S200 includes:
s210, adding a third ligand into a third reactant to form a second precursor solution, injecting the second precursor solution into the nanoparticle solution, and reacting the second precursor solution and the nanoparticle solution for 10-15 minutes to form a third mixed solution;
and injecting the second precursor solution into the nanoparticle solution, so that the elements in the second precursor solution react with the elements in the second precursor solution to generate the nanorods 20, wherein the molar mass of the first reactant is greater than that of the first precursor solution in order to ensure that the elements in the nanoparticle solution react with the elements in the second precursor solution.
Wherein, since the nanorods 20 are generated on the first nanoparticles 10 in a designated direction, an injection speed of the second precursor solution into the nanoparticle solution is less than an injection speed of the first precursor solution into the second mixed solution. Specifically, the injection speed of the second precursor solution into the nanoparticle solution is greater than or equal to 3ml/h and less than or equal to 6ml/h, and the tool for injecting the second precursor solution into the nanoparticle solution can be a needle or other tool capable of performing slow injection.
S220, cooling the third mixed solution to room temperature, purifying to obtain single heterojunction nanorods, and dissolving the single heterojunction nanorods in chloroform to obtain a single heterojunction nanorod solution.
Wherein, the room temperature is 25 ℃. Purifying the third mixed solution by a centrifugal machine, thereby obtaining the solid of the single heterojunction nanorod.
And adding trichloromethane into the heterojunction nanorods to facilitate the next reaction of the heterojunction nanorods. Specifically, the solvent compatible with the heterojunction nanorods is not limited to chloroform, and may be other solutions capable of dissolving and separating the heterojunction nanorods.
Referring to fig. 8, in some alternative embodiments, the step S300 includes:
s310, adding a fourth reactant, a second ligand and a diluent into a second container, mixing to form a third precursor solution, pumping the second container filled with the third precursor solution to a vacuum state, introducing nitrogen into the third precursor solution, continuously stirring and heating, wherein the heating temperature range is a fourth temperature which is higher than 150 ℃, the heating time is 0.5-1 hour, and the temperature is reduced to 60 ℃ after the heating is finished;
wherein, because nitrogen is required to be introduced into the third precursor solution and stirring is carried out continuously, in order to ensure that the operation of introducing nitrogen and the continuous stirring can be carried out simultaneously and do not interfere with each other, the second container is a three-mouth flask, and a nitrogen tank for introducing nitrogen and a stirring rod for stirring extend into the three-mouth flask from different inlets respectively, so as to ensure that stirring and nitrogen introduction are carried out simultaneously.
Specifically, the second container is vacuumized and communicated with the second container through a vacuum pump to vacuumize the second container. It is understood that, in order to avoid the breakage of the three-neck flask due to the excessively low vacuum pressure, the vacuum pump is a mechanical pump, and the vacuum degree in the vacuum state is greater than or equal to 10E-1 Pa.
S320, forming a fourth mixed solution after the single heterojunction nanorod solution is injected into the third precursor solution, vacuumizing to remove trichloromethane in the single heterojunction nanorod solution, and heating the fourth mixed solution to a fifth temperature, wherein the range of the fifth temperature is 300 +/-0.2 ℃;
the boiling point of the trichloromethane is 61.3 ℃, and after the single heterojunction nanorod solution is heated, the trichloromethane in the single heterojunction nanorod solution volatilizes, so that impurities in the mixed solution are reduced.
S330, adding a third ligand into a fifth reactant to form a fourth precursor solution, injecting the fourth precursor solution into the fourth mixed solution, and forming a double-heterojunction nanorod solution after reaction;
s340, cooling the double-heterojunction nanorod solution to room temperature, and purifying to obtain the double-heterojunction nanorod.
Wherein, the room temperature is 25 ℃. Purifying the double-heterojunction nanorod solution by a centrifugal machine to obtain the solid of the double-heterojunction nanorod, and specifically, the powder of the double-heterojunction nanorod is obtained after the solid is extracted.
In some alternative embodiments, the first ligand and/or the second ligand and/or the third ligand comprise at least one of octadecyl phosphate, trioctylphosphine oxide, and oleic acid.
In some alternative embodiments, the molar mass of the first ligand is greater than the molar mass of the first reactant, in order to facilitate complete solubility of the first reactant in the first ligand of threo fox. Specifically, the molar mass ratio of the first reactant to the first ligand is 1: 2-4.
In some alternative embodiments, the molar mass of the first reactant is greater than the molar mass of the first precursor solution in order to ensure that the elements in the nanoparticle solution are present to react with the elements of the second precursor solution. The molar mass of the first reactant is greater than the molar mass of the second reactant.
In some alternative embodiments, to ensure that there is a residual element in the nanoparticle solution to react with an element in the third reactant, the molar mass of the third reactant is greater than the difference between the molar masses of the first reactant and the second reactant.
In some alternative embodiments, since the nanorods 20 are grown on the first nanoparticles 10 in a specific direction, the injection speed of the second precursor solution into the nanoparticle solution is less than that of the first precursor solution into the second mixed solution. Specifically, the injection speed range of the second precursor solution into the nanoparticle solution is 3-6 ml/h.
In some alternative embodiments, the second ligand is octadecyl phosphate and/or trioctylphosphine oxide and/or oleic acid. Specifically, the second ligand is oleic acid.
In some optional embodiments, since the second nanoparticles 30 are generated in the specific direction at the nanorods 20, the injection speed of the fourth precursor solution into the fourth mixed solution is less than that of the first precursor solution into the second mixed solution. Specifically, the injection speed range of the fourth precursor solution into the fourth mixed solution is 3-6 ml/h.
In some optional embodiments, the concentration of the third ligand is 0.1-1 mol/L.
In the first embodiment, the double-heterojunction nanorod has an asymmetric structure, the first nanoparticles 10 of the double-heterojunction nanorod are Cadmium telluride (CdTe) materials, the nanorods 20 are Cadmium selenide (CdSe) materials, and the second nanoparticles 30 are Zinc selenide (ZnSe) materials. Specifically, the first reactant is Cadmium oxide (CdO), the first ligand is octadecyl phosphate (ODPA) and trioctyl phosphine oxide (TOPO), the diluent is octadecene (1-O ctadecene, ODE), the second reactant is Tellurium powder (Tellurium, Te), the third ligand is trioctyl phosphine (Tri-n-octyphosphine, TOP), the third reactant is Selenium powder (Selenium, Se), the fourth reactant is Zinc acetate (Zn (CH3COO)2), the fifth reactant is Selenium powder (Se), and the second ligand is Oleic acid (Oleic acid).
The steps for preparing the double heterojunction nanorod of the first embodiment are as follows:
(1) taking 0.128g of cadmium oxide, 0.668g of octadecyl phosphoric acid and 2g of trioctylphosphine oxide in a 100ml three-necked bottle, vacuumizing for 30 minutes by using a mechanical pump, introducing nitrogen, stirring, heating to 150 ℃, adding 15ml of octadecene after forming a transparent solution, and then heating the mixed solution to 350 ℃ until the mixed solution is stable;
(2) 16mg of tellurium powder is dissolved in 1.5ml of trioctylphosphine to form a first precursor solution. And quickly injecting the first precursor solution into the second mixed solution, and reacting 15 to grow the CdTe nano particles. After the reaction effect is over, reducing the temperature of the mixed solution from 350 ℃ to 250 ℃;
(3) 20mg of selenium powder is dissolved in 1ml of trioctylphosphine to form a second precursor solution. Dropwise injecting the second precursor solution into the second mixed solution at the speed of 4ml/h, and then reacting for 10 minutes to grow the CdSe nanorod;
(4) after 10 minutes, cooling the single heterojunction nanorod solution to room temperature, then purifying to obtain a CdTe/CdSe single heterojunction nanorod, and dissolving in chloroform for later use;
(5) after 0.184g was taken, zinc acetate, 1.13g oleic acid, 6ml octadecene were added to another three-necked flask, evacuated for 30 minutes by a mechanical pump, then purged with nitrogen, stirred, heated to 250 ℃ and held for 1 hour. Cooling to 60 ℃ after 1 hour;
(6) injecting 2ml of the CdTe/CdSe single heterojunction nanorod solution obtained in the step (4) into a third precursor solvent, vacuumizing the precursor solution by using a mechanical pump to remove chloroform, and raising the temperature of the mixed solution from 60 ℃ to 300 ℃ and keeping the mixed solution stable;
(7) 20mg of selenium powder was dissolved in 1ml of trioctylphosphine. Dropwise injecting the third precursor solution into the fourth mixed solution at the speed of 6ml/h, then reacting for 2 minutes, and growing ZnSe at the other end of the CdTe/CdSe nanorod to form a CdTe/CdSe/ZnSe double-heterojunction nanorod;
(8) after 2 minutes, cooling the double-heterojunction nanorod solution to room temperature, and then purifying to obtain the CdTe/CdSe/ZnSe asymmetric double-heterojunction nanorod.
In a second embodiment, the double-heterojunction nanorod has an asymmetric structure, the first nanoparticle 10 of the double-heterojunction nanorod is Cadmium Zinc Telluride (ZnCdTe), the nanorod 20 is Cadmium Zinc selenide sulfide (ZnCdSeS) material, and the second nanoparticle 30 is Zinc sulfide (ZnS) material. In particular, the method comprises the following steps of,
the first reactant is cadmium oxide and zinc acetate, the first ligand is octadecyl phosphoric acid and trioctylphosphine oxide, the diluent is octadecene, the second reactant is tellurium powder (Te), the third ligand is trioctylphosphine, the third reactant is Selenium powder (Selenium, Se) and Sulfur powder (Sulfur, S), the fourth reactant is zinc acetate, the fifth reactant is Sulfur powder, and the second ligand is Oleic acid (Oleic acid).
The steps for preparing the double heterojunction nanorods of the second embodiment are as follows:
(1) taking 0.128g of cadmium oxide, 0.2g of zinc acetate, 0.668g of octadecyl phosphoric acid and 2g of trioctylphosphine oxide in a 100ml three-necked bottle, vacuumizing for 30 minutes by using a mechanical pump, introducing nitrogen, stirring, heating to 140 ℃, adding 15ml of octadecene after forming a transparent solution, and then heating the mixed solution to 340 ℃ until the mixed solution is stable;
(2) 16mg of tellurium powder is dissolved in 1.5ml of trioctylphosphine to form a first precursor solution. And quickly injecting the first precursor solution into the second mixed solution, and reacting 15 to grow ZnCdTe nanoparticles. After the reaction effect is over, reducing the temperature of the mixed solution from 350 ℃ to 250 ℃;
(3) and dissolving 20mg of selenium powder and 15mg of sulfur powder in 2ml of trioctylphosphine to form a second precursor solution. Dropwise injecting the second precursor solution into the second mixed solution at the speed of 3ml/h, and then reacting for 10 minutes to grow the ZnCdSeS nanorod;
(4) after 10 minutes, cooling the single heterojunction nanorod solution to room temperature, then purifying to obtain a ZnCdTe/ZnCdSeS single heterojunction nanorod, and dissolving in chloroform for later use;
(5) 0.184g of zinc acetate, 1.13g of oleic acid and 6ml of octadecene were taken and put into another three-necked flask, and evacuated for 30 minutes by a mechanical pump, then introduced with nitrogen, stirred, heated to 240 ℃ and kept for 1 hour. Cooling to 60 ℃ after 1 hour;
(6) injecting 2ml of ZnCdTe/ZnCdSeS single heterojunction nanorod solution into a third precursor solvent, vacuumizing the precursor solution by using a mechanical pump to remove chloroform, and raising the temperature of the mixed solution from 60 ℃ to 300 ℃ and keeping the mixed solution stable;
(7) 15mg of sulfur powder was dissolved in 1ml of trioctylphosphine. Dropwise injecting the third precursor solution into the fourth mixed solution at the speed of 5ml/h, then reacting for 2 minutes, and growing ZnS at the other end of the ZnCdTe/ZnCdSeS nanorod to form a ZnCdTe/ZnCdSeS/ZnS double-heterojunction nanorod;
(8) after 2 minutes, cooling the double-heterojunction nanorod solution to room temperature, and then purifying to obtain the ZnCdTe/ZnCdSeS/ZnS asymmetric double-heterojunction nanorod.
Referring to fig. 9, to achieve the above object, the present application further provides a method for manufacturing a light emitting diode, where the method for manufacturing a light emitting diode includes:
s400, depositing a hole injection layer on a conductive film of the light-emitting diode by adopting a high-molecular polymer PEDOT (Poly ethylene glycol Ether-Ether), namely PSS (Poly ethylene glycol ether ketone);
s500, depositing a hole transport layer on the hole injection layer by adopting tetrafluorobenzene;
s600, depositing a light-emitting layer on the hole transport layer by adopting double heterojunction nanorods;
s700, depositing an electron transport layer on the luminous layer by adopting zinc oxide nano particles;
and S800, adopting a silver deposition anode on the electron transport layer.
Specifically, the hole transport layer is deposited by a solution method, and the thickness of the hole transport layer is 10-100 nm; the light-emitting layer is deposited by a solution method, and the thickness of the light-emitting layer ranges from 10 nm to 100 nm; the electron transport layer is deposited by a solution method, and the thickness of the light-emitting layer ranges from 10 nm to 100 nm; the cathode is deposited by an evaporation method, and the thickness of the light-emitting layer is 80-200 nm.
Specifically, in the third embodiment, the method for manufacturing the light emitting diode may be:
taking a transparent conductive film as an anode, wherein the thickness range of the anode is 50 nm;
PSS is a hole injection layer, and the thickness range of the hole injection layer is 30 nm;
depositing tetrafluorobenzene on the hole injection layer by a solution method to form a hole transport layer, wherein the thickness of the hole transport layer is in a range of 30 nm;
depositing CdTe/CdSe/ZnSe double heterojunction nanorods on the hole transport layer by a solution method to serve as a light-emitting layer, wherein the thickness range of the light-emitting layer is 20 nm;
depositing zinc oxide nanoparticles on the light-emitting layer by a solution method to serve as an electron transport layer, wherein the thickness range of the light-emitting layer is 40 nm;
and depositing silver on the electron transport layer by using an evaporation method to serve as a cathode, wherein the thickness of the cathode is in a range of 100 nm.
In addition, in a fourth embodiment, the method for manufacturing the light emitting diode may be:
taking a transparent conductive film as an anode, wherein the thickness range of the anode is 60 nm;
PSS is a hole injection layer, and the thickness range of the hole injection layer is 40 nm;
depositing tetrafluorobenzene on the hole injection layer by a solution method to form a hole transport layer, wherein the thickness of the hole transport layer is in a range of 50 nm;
depositing a ZnCdTe/ZnCdSeS/ZnS double-heterojunction nanorod on the hole transport layer by a solution method to serve as a light-emitting layer, wherein the thickness of the light-emitting layer is 30 nm;
depositing zinc oxide nanoparticles on the light-emitting layer by a solution method to serve as an electron transport layer, wherein the thickness range of the light-emitting layer is 60 nm;
and depositing silver on the electron transport layer by using an evaporation method to serve as a cathode, wherein the thickness of the cathode is in a range of 150 nm.
In order to achieve the above object, the present application also provides a light emitting diode, wherein a light emitting layer of the light emitting diode is prepared by the method for preparing a light emitting diode according to any one of the above embodiments. Specifically, the light emitting layer of the light emitting diode includes the double heterojunction nanorod according to any one of the embodiments.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the contents of the present specification and the drawings, or any other related technical fields, which are directly or indirectly applied to the present invention, are included in the scope of the present invention.
Claims (12)
1. The double-heterojunction nanorod comprises a first nanoparticle, a nanorod and a second nanoparticle, wherein a first heterojunction is formed between the first nanoparticle and one end of the nanorod, a second heterojunction is formed between the second nanoparticle and the other end of the nanorod, the first heterojunction is a type II heterojunction, the second heterojunction is a type I heterojunction, the top valence band energy level of the first nanoparticle is smaller than that of the nanorod, the top valence band energy level of the second nanoparticle is larger than that of the nanorod, and the bottom conduction band energy levels of the first nanoparticle and the second nanoparticle are smaller than that of the nanorod.
2. The double heterojunction nanorod according to claim 1, wherein,
the material of the first nano particles is cadmium telluride or zinc telluride or cadmium zinc telluride;
the material of the nano rod is cadmium selenide or cadmium selenide sulfide or cadmium zinc selenide sulfide;
the second nano-particles are made of zinc selenide or zinc sulfide or zinc sulfoselenide.
3. The method for preparing double heterojunction nanorods according to claim 1, wherein the method for preparing double heterojunction nanorods comprises:
adding a second reactant into a first reactant for mixing reaction to prepare a nanoparticle solution, wherein the first reactant contains cadmium element and/or zinc element, the second reactant contains tellurium element, and the molar mass of the first reactant is larger than that of the second reactant;
adding a third reactant into the nanoparticle solution to prepare a single heterojunction nanorod solution, wherein the third reactant contains selenium and/or sulfur;
and adding a fourth reactant and a fifth reactant into the single heterojunction nanorod solution to prepare the double heterojunction nanorod, wherein the fourth reactant contains zinc element, and the fifth reactant contains selenium element and/or sulfur element.
4. The method for preparing double heterojunction nanorods according to claim 3, wherein the step of adding the second reactant into the first reactant for mixing reaction to prepare the nanoparticle solution comprises:
adding a first reactant and a first ligand into a first container to mix to form a first mixed solution;
pumping a first container filled with a first mixed solution to a vacuum state, introducing nitrogen into the first mixed solution, continuously stirring and heating to a first temperature, wherein the first temperature is 120-180 ℃;
adding a diluent into the first mixed solution to form a second mixed solution, and heating the second mixed solution to a second temperature, wherein the second temperature is 300-350 ℃;
adding a third ligand into a second reactant to form a first precursor solution, injecting the first precursor solution into the second mixed solution, reacting the first precursor solution with the second mixed solution for 10-15 minutes to form a nanoparticle solution, and cooling the nanoparticle solution to a third temperature, wherein the range of the third temperature is 200-250 ℃.
5. The method for preparing double-heterojunction nanorods according to claim 4, wherein the step of adding a third reactant into the nanoparticle solution to prepare a single-heterojunction nanorod solution comprises:
adding a third ligand into a third reactant to form a second precursor solution, injecting the second precursor solution into the nanoparticle solution, and reacting the second precursor solution and the nanoparticle solution for 10-15 minutes to form a third mixed solution;
and cooling the third mixed solution to room temperature, purifying to obtain single heterojunction nanorods, and dissolving the single heterojunction nanorods in chloroform to obtain a single heterojunction nanorod solution.
6. The method for preparing double-heterojunction nanorods of claim 5, wherein the step of adding a fourth reactant and a fifth reactant into the single-heterojunction nanorod solution to prepare double-heterojunction nanorods comprises:
adding a fourth reactant, a second ligand and a diluent into a second container, mixing to form a third precursor solution, pumping the second container filled with the third precursor solution to a vacuum state, introducing nitrogen into the third precursor solution, continuously stirring and heating, wherein the heating temperature range is a fourth temperature which is higher than 150 ℃, the heating time is 0.5-1 hour, and the temperature is reduced to 60 ℃ after the heating is finished;
forming a fourth mixed solution after the single heterojunction nanorod solution is injected into the third precursor solution, vacuumizing to remove trichloromethane in the single heterojunction nanorod solution, and heating the fourth mixed solution to a fifth temperature, wherein the range of the fifth temperature is 300 +/-0.2 ℃;
adding a fifth reactant into a third ligand to form a fourth precursor solution, injecting the fourth precursor solution into the fourth mixed solution, and forming a double-heterojunction nanorod solution after reaction;
and cooling the double-heterojunction nanorod solution to room temperature, and purifying to obtain the double-heterojunction nanorod.
7. The method of claim 6, wherein the first ligand and/or the second ligand and/or the third ligand comprise at least one of octadecyl phosphate, trioctylphosphine oxide and oleic acid.
8. The method for preparing double heterojunction nanorods of claim 4, wherein the molar mass ratio of the first reactant to the first ligand is 1: 2-4.
9. The method of preparing double heterojunction nanorods of claim 5, wherein the molar mass of the third reactant is greater than the difference between the molar masses of the first reactant and the second reactant.
10. The method for preparing double heterojunction nanorods according to claim 6, wherein the injection speed of the second precursor solution into the nanoparticle solution is in the range of 3-6 ml/h and/or the injection speed of the fourth precursor solution into the fourth mixed solution is in the range of 3-6 ml/h.
11. The method for preparing double heterojunction nanorods according to any one of claims 4 to 6, wherein the concentration of the third ligand is 0.1-1 mol/L.
12. A light emitting diode, wherein the light emitting layer of the light emitting diode comprises the double heterojunction nanorod according to claim 1 or 2, or the double heterojunction nanorod prepared according to the preparation method of the double heterojunction nanorod according to any one of claims 3 to 11.
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