CN117202674A - Near-infrared quantum dot light-emitting device insensitive to thickness and preparation method thereof - Google Patents
Near-infrared quantum dot light-emitting device insensitive to thickness and preparation method thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 claims description 26
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- Luminescent Compositions (AREA)
Abstract
The invention relates to a thickness-insensitive near-infrared quantum dot light-emitting device and a preparation method thereof, belonging to the field of semiconductor devices. The near infrared quantum dot light emitting device of the present invention includes a light emitting layer; the light-emitting layer comprises a quantum dot film with a core-shell structure, and a bifunctional connecting agent is contained on the surface of the quantum dot film; the difunctional linker contains a thiol group; the thickness of the luminescent layer of the near infrared quantum dot luminescent device is more than or equal to 40nm. The luminous wavelength of the infrared luminous device is 750-2500 nm, the radiation recombination is improved by packaging the quantum dots in an I-type inorganic shell, so that 80% of high photoluminescence quantum yield is obtained, and the film is subjected to post treatment by using a bifunctional connecting agent so as to improve and balance the hole mobility and the electron mobility of the whole film, so that the infrared quantum dot luminous device which is efficient, stable and insensitive in thickness is prepared.
Description
Technical Field
The invention belongs to the field of semiconductor devices, and particularly relates to a near infrared quantum dot light-emitting device insensitive to thickness and a preparation method thereof.
Background
PbS quantum dots are a popular choice for optoelectronic device materials due to their good fabrication techniques and optical properties. In particular, the PbS bulk band gap is 0.4eV, and this small band gap makes PbS quantum dots an excellent light emitting layer for infrared light emitting diodes. By controlling the quantum dot size during the synthesis process, the absorption band edge of the PbS quantum dot can be adjusted from about 3000nm to 600nm, covering a spectrum range which cannot be achieved by the conventional silicon detection technology. The solution process of PbS quantum dots makes them particularly suitable for preparing large area films from bottom to top. Techniques for depositing PbS quantum dot films include spray coating, drop coating, dip coating, printing, and spin coating. The PbS quantum dot particles are uniform in size and can be used for preparing denser quantum dot films. Interactions between PbS quantum dot particles and coordinating solvents affect the morphology of the final film. The filling order, morphology and thickness of the film can be controlled by introducing external forces such as pressure, concentration gradients and spatial constraints. These low temperature film forming processes can be easily transferred to flexible substrates.
A typical quantum dot light emitting diode device includes: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode. Transparent glass with silver tin oxide (ITO) plated on the surface is generally used as an anode, and ITO has a low resistivity and a high work function, and has a high transmittance in the visible light region. The hole injection layer is usually made of PEDOT, PSS, poly-TPD, PVK, etc., for preventing ohmic contact between ITO substrate and top layer, and the hole transport layer is deposited on the hole injection layer for ensuring charge confinement in the active layer and enhancing exciton binding capability, and perovskite material is deposited on the hole transport layer as light emitting layer, and is usually 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]-1,3, 5-triazole (POT 2T), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 1,3, 5-tris [ (3-pyridinyl) -3-phenyl]Benzene (TmPyPB), znO and other traditional electron transport materials are used as electron transport layers, meanwhile, the electron transport layers also have an effective blocking effect on hole transport, and the electron injection layers are usually LiF, liq, csF, csCO 3 Such materials, the cathode is typically of a material having a relatively low work function such that electrons are injected into the electron transport layerIn the lowest unoccupied tracks, such as Al, ag or metal alloys, etc.
The PbS quantum dot has unique photoelectric property and is successfully applied to photoelectric devices. And the high surface defect state and the low carrier mobility are factors restricting the performance of the PbS quantum dot device. The surface morphology and stability of PbS quantum dots have very important determining effect on the final photoelectric property of the whole quantum dot light emitting diode device, so that obtaining a light emitting layer with low surface defect state and high carrier mobility is necessary for preparing efficient and stable PbS quantum dot light emitting diode device with insensitive thickness.
Disclosure of Invention
The presently available near infrared light emitting diodes are susceptible to variations in the thickness of the emissive layer: when the emissive layer thickness varies within a narrow range of 30nm, the highest External Quantum Efficiency (EQE) drops below 50% (relative to the peak EQE). This is due to thickness dependent carrier recombination rate and current density variations, resulting in batch-to-batch EQE fluctuations, limiting LED repeatability. The invention provides a near infrared quantum dot luminescent device with insensitive thickness and a preparation method thereof, wherein the radiation recombination is improved by packaging quantum dots in an I-type inorganic shell, so that 80% of high photoluminescence quantum yield is obtained, and a bifunctional connecting agent is used for carrying out post-treatment on a film so as to improve and balance hole and electron mobility of the whole film, so that the near infrared quantum dot luminescent device with high efficiency, stability and insensitive thickness is prepared.
The invention is realized by the following technical scheme:
a first object of the present invention is to provide a thickness insensitive near infrared quantum dot light emitting device,
comprises a light emitting layer;
the light-emitting layer comprises a quantum dot film with a core-shell structure, and a bifunctional connecting agent is contained on the surface of the quantum dot film; the difunctional linker contains a thiol group;
the thickness of the luminescent layer of the near infrared quantum dot luminescent device is more than or equal to 40nm.
In one embodiment of the invention, the light emitting wavelength of the thickness insensitive near infrared quantum dot light emitting device is 750nm-2500nm.
In one embodiment of the invention, the thickness of the light emitting layer is 40nm-210nm.
In one embodiment of the present invention, the thickness-insensitive near infrared quantum dot light emitting device further comprises one or more of a hole injection layer, a hole transport layer, an electron injection layer, and a cathode.
In one embodiment of the invention, the quantum dots of the core-shell structure are lead halide/lead sulfide core-shell quantum dots; the core of the lead halide/lead sulfide core-shell quantum dot is lead sulfide, and the shell is one or more of lead bromide, lead chloride and lead iodide; the lead halide coats the lead sulfide to form a core-shell structure.
In one embodiment of the invention, the bifunctional linking reagent comprises one or more of 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, and 1, 8-octanedithiol.
In one embodiment of the invention, the bifunctional linking reagent comprises 0.1% to 1% of the total concentration of the raw materials of the luminescent layer; the concentration of the quantum dot solution with the core-shell structure used in the preparation of the quantum dot film with the core-shell structure is 1mg/mL-40mg/mL.
In one embodiment of the invention, the lead halide/lead sulfide core-shell quantum dot is obtained by the following preparation method:
mixing a surfactant and a lead source in a solvent, and heating for reaction to obtain a precursor solution containing lead;
dissolving a sulfur source in a solvent, and heating for reaction to obtain a sulfur-containing precursor solution;
injecting the obtained sulfur-containing precursor solution into the obtained lead-containing precursor solution in an inert atmosphere, and nucleating and growing to obtain lead sulfide quantum dots;
and reacting the halogen-containing compound with the obtained lead sulfide quantum dot to obtain the lead halide/lead sulfide core-shell quantum dot.
In one embodiment of the invention, further comprising purifying the lead halide/lead sulfide core-shell quantum dot.
In one embodiment of the invention, one or more of the following conditions are met:
the sulfur source is selected from one or more of hexamethyldisilazane, sulfur powder and dithio-amino methane;
the conditions of the heating reaction are as follows: the heating temperature is 100-200 ℃ and the heating time is 1-2 h;
the surfactant is oleic acid and/or oleylamine; the growth, stability and optical properties of the quantum dots can be controlled by adding the surfactant;
the lead source is selected from one or more of lead acetate trihydrate, lead sulfate, lead oxide, lead chloride, lead bromide and lead iodide;
the solvent is selected from one or more of hexadecene, octadecene and eicosene; the solvent can also be used as a heat transfer medium to help promote the decomposition of lead sulfide precursors and the growth of quantum dots under heating;
the mass ratio of the surfactant to the solvent is 0.05-0.5.
In one embodiment of the invention, the halogen-containing compound includes one or more of trimethylchlorosilane, trimethylbromosilane, and trimethyliodosilane.
In one embodiment of the present invention, the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, and molybdenum oxide.
In one embodiment of the present invention, the hole transport layer is selected from one or more of poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (9-vinylcarbazole) and polytrianiline.
In one embodiment of the invention, the electron transport layer is selected from one or more of 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ] -1,3, 5-triazole, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1':3',1 "-terphenyl ] -3,3" -diyl ] bipyridine and 2,2',2"- (1, 3, 5-phenyl) triazine-3, 3',3" -triylbenzene; the electron injection layer is selected from one or more of 8-hydroxyquinoline-lithium, lithium fluoride and (tris (8-hydroxyquinoline) aluminum).
The second object of the present invention is to provide a method for manufacturing the thickness-insensitive near-infrared quantum dot light emitting device, wherein the infrared light emitting device structure comprises a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode; the thickness of the luminescent layer of the near infrared quantum dot luminescent device is more than 40nm, and the method comprises the following steps:
sequentially spin-coating a hole injection layer and a hole transport layer on the pretreated substrate;
spin-coating a quantum dot solution of a core-shell structure on the hollow transport layer to obtain a quantum dot film of the core-shell structure;
Reacting the obtained quantum dot film with the core-shell structure with a bifunctional connecting agent to obtain a luminescent layer;
and sequentially obtaining an electron transport layer, an electron injection layer and a cathode on the surface of the obtained luminescent layer by a vacuum evaporation method.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the invention provides a thickness insensitive near infrared quantum dot luminescent device and a preparation method thereof, wherein the preparation process is simple and convenient, the defect state density of the surface of the quantum dot is reduced by cladding a core shell, the quantum yield is improved, the ligand with higher quality and better effect is introduced by surface ligand exchange, the optimal balance between charge injection and radiative exciton recombination is realized, the flatness and uniformity of the surface of a quantum dot film are improved, the defect formation is effectively inhibited, the mobility of carriers in the device can be improved by high and balanced electron and hole mobility, the integral performance of the device is obviously improved, the leakage current of the device is reduced, and the recombination efficiency of the carriers is improved, so that the luminescent life and the luminescent efficiency of the quantum dot light emitting diode device are improved. The materials used in the invention are easy to obtain, have high repeatability, are favorable for preparing large-area flexible devices, and promote the development of large-scale industrialization.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic diagram of a quantum dot light emitting diode device according to an embodiment of the present invention;
FIG. 2 is an electroluminescent spectrum of a QD LED in performance test according to the present invention;
FIG. 3 is a graph of current density versus voltage for a QD LED in performance testing according to the present invention;
FIG. 4 is a graph of irradiance versus voltage for a QD LED in performance testing according to the present invention;
FIG. 5 is a graph of external quantum efficiency versus current density for a QD LED in performance testing according to the present invention;
FIG. 6 is a transmission electron microscope image of a quantum dot film in a performance test of the present invention;
FIG. 7 is an atomic force microscope image of a quantum dot film in a performance test of the present invention;
FIG. 8 is a graph of external quantum efficiency versus current density for a quantum dot film of comparative example in performance testing of the present invention;
FIG. 9 is a graph of external quantum efficiency versus current density for a quantum dot film in an example of performance testing of the present invention.
Detailed Description
In order to solve the technical problems pointed out in the background technology, the invention provides a near infrared quantum dot light-emitting device insensitive to thickness and a preparation method thereof.
The invention provides a thickness insensitive near infrared quantum dot light emitting device,
comprises a light emitting layer;
the light-emitting layer comprises a quantum dot film with a core-shell structure, and a bifunctional connecting agent is contained on the surface of the quantum dot film; the difunctional linker contains a thiol group;
further, the bifunctional connecting agent contained on the surface of the quantum dot film is obtained through ligand exchange, and the method comprises the following steps: the quantum dot solution with the core-shell structure contains a surfactant (such as oleic acid and/or oleylamine), and after being mixed with the bifunctional linking agent, the exchange of thiol groups in the oleic acid or oleylamine and the bifunctional linking agent is realized under certain conditions. Ligands with higher quality and better effect can be introduced through ligand exchange, so that the optimal balance between charge injection and radiative exciton recombination is realized.
Further, all technical means for ligand exchange in the art, such as mechanical stirring, preferably stirring at a certain speed, are meant under certain conditions.
Further, the thickness of the luminescent layer of the near infrared quantum dot luminescent device is more than or equal to 40nm, so that the lowest thickness with uniformity and no defects can be prepared; specifically 40nm to 210nm and more than 210nm; the luminous layer of the near infrared quantum dot luminous device is 40 nm-210 nm; for example 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 180nm, 190nm, 200nm, 210 nm.
In a specific embodiment, the light-emitting wavelength of the thickness-insensitive near-infrared quantum dot light-emitting device is 750nm-2500nm.
Further, the infrared light emitting device structure may further include one or more of a hole injection layer, a hole transport layer, an electron injection layer, and a cathode. Preferably, a hole transport layer, an electron injection layer, and an electron transport layer are included.
In a specific embodiment, the quantum dots of the core-shell structure are lead halide/lead sulfide core-shell quantum dots; the core of the lead halide/lead sulfide core-shell quantum dot is lead sulfide, and the shell is one or more of lead bromide, lead chloride and lead iodide; the lead halide coats the lead sulfide to form a core-shell structure.
Further, in the process of preparing the shell, various schemes may be employed, such as using lead bromide, lead chloride and lead iodide, respectively, alone or in combination with each other. Further, when the two are combined with each other, the mass ratio of the two lead halides may be selected at will, and is not particularly limited herein, and the preferred mass ratio may be 2:1 to 4:1, specifically, 2:1, 3:1, 4:1, or the like. Further, when the three are combined with each other, the mass ratio of the three lead halides may be selected at will, and is not particularly limited herein, and the preferred mass ratio may be 1:1:1 to 4:1:1, specifically 1:1:1, 2:1:1, 3:1:1, 4:1:1, or the like.
In particular embodiments, the bifunctional linking reagent comprises one or more of 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, and 1, 8-octanedithiol.
In a specific embodiment, the bifunctional linking reagent comprises 0.1% -1% of the total concentration of the luminescent layer raw materials; the concentration of the quantum dot solution with the core-shell structure used in the preparation of the quantum dot film with the core-shell structure is 1mg/mL-40mg/mL.
In one embodiment of the invention, the lead halide/lead sulfide core-shell quantum dot is obtained by the following preparation method:
mixing a surfactant and a lead source in a solvent, and heating for reaction to obtain a precursor solution containing lead;
dissolving a sulfur source in a solvent, and heating for reaction to obtain a sulfur-containing precursor solution;
injecting the obtained sulfur-containing precursor solution into the obtained lead-containing precursor solution in an inert atmosphere, and nucleating and growing to obtain lead sulfide quantum dots;
and reacting the halogen-containing compound with the obtained lead sulfide quantum dot to obtain the lead halide/lead sulfide core-shell quantum dot.
In particular embodiments, the purification of the lead halide/lead sulfide core-shell quantum dots is also included.
In specific embodiments, the sulfur source is selected from one or more of hexamethyldisilazane, sulfur powder, and dithio-aminomethane.
In a specific embodiment, the heating reaction conditions are: the heating temperature is 100-200 ℃ and the heating time is 1-2 h.
In particular embodiments, the surfactant is oleic acid and/or oleylamine; the addition of surfactants can help control the growth, stability and optical properties of the quantum dots.
In particular embodiments, the lead source is selected from one or more of lead acetate trihydrate, lead sulfate, lead oxide, lead chloride, lead bromide, and lead iodide.
In specific embodiments, the solvent is selected from one or more of hexadecene, octadecene, and eicosene; the solvent may also act as a heat transfer medium to facilitate decomposition of the lead sulfide precursor and growth of the quantum dots under heating.
In a specific embodiment, the mass ratio of the surfactant to the solvent is 0.05-0.5.
In particular embodiments, the halogen-containing compound includes one or more of trimethylchlorosilane, trimethylbromosilane, and trimethyliodosilane.
In specific embodiments, the hole injection layer is selected from one or more of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid, nickel oxide, and molybdenum oxide.
In specific embodiments, the hole transport layer is selected from one or more of poly [ bis (4-phenyl) (4-butylphenyl) amine ], poly (9-vinylcarbazole), and polytrianiline.
In specific embodiments, the electron transport layer is selected from the group consisting of 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ] -1,3, 5-triazole, 3'- [5' - [3- (3-pyridyl) phenyl ] [1,1': one or more of 3',1 "-terphenyl ] -3,3" -diyl ] bipyridine and 2,2',2"- (1, 3, 5-phenyl) triazine-3, 3',3" -triylbenzene; the electron injection layer is selected from one or more of 8-hydroxyquinoline-lithium, lithium fluoride and (tris (8-hydroxyquinoline) aluminum).
The invention also provides a preparation method of the thickness-insensitive near-infrared quantum dot light-emitting device, wherein the infrared light-emitting device structure comprises a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode, and the preparation method comprises the following steps:
sequentially spin-coating a hole injection layer and a hole transport layer on the pretreated substrate;
spin-coating a quantum dot solution of a core-shell structure on the hollow transport layer to obtain a quantum dot film of the core-shell structure;
reacting the obtained quantum dot film with the core-shell structure with a bifunctional connecting agent to obtain a luminescent layer;
and sequentially obtaining an electron transport layer, an electron injection layer and a cathode on the surface of the obtained luminescent layer by a vacuum evaporation method.
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The ITO transparent conductive glass substrates used in the following examples were purchased from Lumitec LTD. Co., lead acetate trihydrate, hexamethyldisilazane, oleylamine, octadecene and hexane were all purchased from Sigma-Aldrich, and 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ] -1,3, 5-triazole and 8-hydroxyquinoline-lithium were all purchased from SianBallate phototech Co.
Example 1
The embodiment provides a preparation method of a thickness-insensitive near-infrared quantum dot light-emitting device, which comprises the following specific steps:
step 1: and (3) rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning for 15min by using ethanol, acetone and deionized water, repeating for 3 times, putting the beaker filled with the ITO glass into a drying box after cleaning, heating and drying, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the ITO glass in an ultraviolet ozone cleaning machine for 15min to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: and (3) dissolving trimethyl bromosilane in 1-octadecene, injecting the solution into the lead sulfide quantum dot solution obtained in the step (7) for reaction for 10min, and growing to obtain the lead bromide/lead sulfide core-shell quantum dot solution.
Step 9: and transferring the lead bromide/lead sulfide core-shell quantum dot solution after the reaction is finished into a glove box filled with nitrogen, adding isopropanol with the same volume, and then centrifuging to purify the quantum dots. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead bromide/lead sulfide core-shell quantum dot material.
Step 10: and (3) dissolving the lead bromide/lead sulfide core-shell quantum dot material in normal hexane to prepare a lead bromide/lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the 40nm uniform lead bromide/lead sulfide core-shell quantum dot film.
Step 11: and diluting the 1, 6-hexanedithiol to the volume concentration of 0.5% by using acetonitrile, spin-coating the 1, 6-hexanedithiol solution on the surface of the lead bromide/lead sulfide core-shell quantum dot film at the rotating speed of 6000rpm, and realizing the surface ligand exchange of the quantum dot film to obtain a uniform luminescent layer.
Step 12: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]-1,3, 5-triazole, 8-hydroxySequentially obtaining an electron transport layer, an electron injection layer and a metal cathode electrode from quinoline-lithium and aluminum raw materials by a vacuum evaporation method, wherein the evaporation rates are respectivelyAnd->The thicknesses are respectively 60nm, 2nm and 100nm, and the quantum dot light emitting diode device is prepared, and the structure schematic diagram of the quantum dot light emitting diode device is shown in figure 1.
Example 2
The embodiment provides a preparation method of a thickness-insensitive near-infrared quantum dot light-emitting device, which comprises the following specific steps:
step 1: and (3) rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning for 15min by using ethanol, acetone and deionized water, repeating for 3 times, putting the beaker filled with the ITO glass into a drying box after cleaning, heating and drying, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the ITO glass in an ultraviolet ozone cleaning machine for 15min to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: and (3) dissolving trimethyl bromosilane in 1-octadecene, injecting the solution into the lead sulfide quantum dot solution obtained in the step (7) for reaction for 10min, and growing to obtain the lead bromide/lead sulfide core-shell quantum dot solution.
Step 9: and transferring the lead bromide/lead sulfide core-shell quantum dot solution after the reaction is finished into a glove box filled with nitrogen, adding isopropanol with the same volume, and then centrifuging to purify the quantum dots. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead bromide/lead sulfide core-shell quantum dot material.
Step 10: and (3) dissolving the lead bromide/lead sulfide core-shell quantum dot material in normal hexane to prepare a lead bromide/lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the 60nm uniform lead bromide/lead sulfide core-shell quantum dot film.
Step 11: and diluting the 1, 6-hexanedithiol to the volume concentration of 0.5% by using acetonitrile, spin-coating the 1, 6-hexanedithiol solution on the surface of the lead bromide/lead sulfide core-shell quantum dot film at the rotating speed of 6000rpm, and realizing the surface ligand exchange of the quantum dot film to obtain a uniform luminescent layer.
Step 12: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]The electron transport layer, the electron injection layer and the metal cathode electrode are sequentially obtained from the raw materials of-1, 3, 5-triazole, 8-hydroxyquinoline-lithium and aluminum by a vacuum evaporation method, and the evaporation rates are respectivelyAnd->The thicknesses are respectively 60nm, 2nm and 100nm, and the quantum dot light emitting diode device is manufactured.
Example 3
The embodiment provides a preparation method of a thickness-insensitive near-infrared quantum dot light-emitting device, which comprises the following specific steps:
step 1: and (3) rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning for 15min by using ethanol, acetone and deionized water, repeating for 3 times, putting the beaker filled with the ITO glass into a drying box after cleaning, heating and drying, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the ITO glass in an ultraviolet ozone cleaning machine for 15min to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: and (3) dissolving trimethyl bromosilane in 1-octadecene, injecting the solution into the lead sulfide quantum dot solution obtained in the step (7) for reaction for 10min, and growing to obtain the lead bromide/lead sulfide core-shell quantum dot solution.
Step 9: and transferring the lead bromide/lead sulfide core-shell quantum dot solution after the reaction is finished into a glove box filled with nitrogen, adding isopropanol with the same volume, and then centrifuging to purify the quantum dots. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead bromide/lead sulfide core-shell quantum dot material.
Step 10: and (3) dissolving the lead bromide/lead sulfide core-shell quantum dot material in normal hexane to prepare a lead bromide/lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the lead bromide/lead sulfide core-shell quantum dot film with the uniformity of 110 nm.
Step 11: and diluting the 1, 6-hexanedithiol to the volume concentration of 0.5% by using acetonitrile, spin-coating one drop of 1, 6-hexanedithiol solution on the surface of the lead bromide/lead sulfide core-shell quantum dot film at the rotating speed of 6000rpm, and realizing the surface ligand exchange of the quantum dot film to obtain a uniform luminescent layer.
Step 12: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]The electron transport layer, the electron injection layer and the metal cathode electrode are sequentially obtained from the raw materials of-1, 3, 5-triazole, 8-hydroxyquinoline-lithium and aluminum by a vacuum evaporation method, and the evaporation rates are respectivelyAnd->The thicknesses are respectively 60nm, 2nm and 100nm, and the quantum dot light emitting diode device is manufactured.
Example 4
The embodiment provides a preparation method of a thickness-insensitive near-infrared quantum dot light-emitting device, which comprises the following specific steps:
step 1: and rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning by using ethanol, acetone and deionized water for 15 minutes, repeating the ultrasonic cleaning for 2 to 3 times, putting the beaker filled with the ITO glass in a drying box after the cleaning is finished, heating and drying the beaker, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the beaker in an ultraviolet ozone cleaning machine for 15 minutes to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: and (3) dissolving trimethyl bromosilane in 1-octadecene, injecting the solution into the lead sulfide quantum dot solution obtained in the step (7) for reaction for 10min, and growing to obtain the lead bromide/lead sulfide core-shell quantum dot solution.
Step 9: and transferring the lead bromide/lead sulfide core-shell quantum dot solution after the reaction is finished into a glove box filled with nitrogen, adding isopropanol with the same volume, and then centrifuging to purify the quantum dots. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead bromide/lead sulfide core-shell quantum dot material.
Step 10: and (3) dissolving the lead bromide/lead sulfide core-shell quantum dot material in normal hexane to prepare a lead bromide/lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the 160nm uniform lead bromide/lead sulfide core-shell quantum dot film.
Step 11: and diluting the 1, 6-hexanedithiol to the volume concentration of 0.5% by using acetonitrile, spin-coating one drop of 1, 6-hexanedithiol solution on the surface of the lead bromide/lead sulfide core-shell quantum dot film at the rotating speed of 6000rpm, and realizing the surface ligand exchange of the quantum dot film to obtain a uniform luminescent layer.
Step 12: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]The electron transport layer, the electron injection layer and the metal cathode electrode are sequentially obtained from the raw materials of-1, 3, 5-triazole, 8-hydroxyquinoline-lithium and aluminum by a vacuum evaporation method, and the evaporation rates are respectivelyAnd->The thickness is 60nm, 2nm and 100nm respectively, thus the quantum dot light emitting diode is manufacturedAnd (3) a piece.
Example 5
The embodiment provides a preparation method of a thickness-insensitive near-infrared quantum dot light-emitting device, which comprises the following specific steps:
step 1: and rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning by using ethanol, acetone and deionized water for 15 minutes, repeating the ultrasonic cleaning for 2 to 3 times, putting the beaker filled with the ITO glass in a drying box after the cleaning is finished, heating and drying the beaker, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the beaker in an ultraviolet ozone cleaning machine for 15 minutes to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: and (3) dissolving trimethyl bromosilane in 1-octadecene, injecting the solution into the lead sulfide quantum dot solution obtained in the step (7) for reaction for 10min, and growing to obtain the lead bromide/lead sulfide core-shell quantum dot solution.
Step 9: and transferring the lead bromide/lead sulfide core-shell quantum dot solution after the reaction is finished into a glove box filled with nitrogen, adding isopropanol with the same volume, and then centrifuging to purify the quantum dots. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead bromide/lead sulfide core-shell quantum dot material.
Step 10: and (3) dissolving the lead bromide/lead sulfide core-shell quantum dot material in normal hexane to prepare a lead bromide/lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the 210nm uniform lead bromide/lead sulfide core-shell quantum dot film.
Step 11: and diluting the 1, 6-hexanedithiol to the volume concentration of 0.5% by using acetonitrile, spin-coating one drop of 1, 6-hexanedithiol solution on the surface of the lead bromide/lead sulfide core-shell quantum dot film at the rotating speed of 6000rpm, and realizing the surface ligand exchange of the quantum dot film to obtain a uniform luminescent layer.
Step 12: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]The electron transport layer, the electron injection layer and the metal cathode electrode are sequentially obtained from the raw materials of-1, 3, 5-triazole, 8-hydroxyquinoline-lithium and aluminum by a vacuum evaporation method, and the evaporation rates are respectivelyAnd->The thicknesses are respectively 60nm, 2nm and 100nm, and the quantum dot light emitting diode device is manufactured.
Comparative example
Step 1: and rubbing and washing the ITO glass by using a nano sponge dipping cleaning agent, washing the ITO glass with deionized water, standing the ITO glass in a beaker, putting the beaker in an ultrasonic water bath, respectively carrying out ultrasonic cleaning by using ethanol, acetone and deionized water for 15 minutes, repeating the ultrasonic cleaning for 2 to 3 times, putting the beaker filled with the ITO glass in a drying box after the cleaning is finished, heating and drying the beaker, and finally putting the ITO glass in a surface dish with the front side facing upwards, and treating the beaker in an ultraviolet ozone cleaning machine for 15 minutes to obtain the pretreated ITO glass.
Step 2: the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid solution was filtered through a 0.45 μm filter head and spin-coated on ITO glass at a rotation speed of 5000rpm for 60s, and then annealed at 150 ℃ for 20min to obtain a uniform hole injection layer.
Step 3: the poly [ bis (4-phenyl) (4-butylphenyl) amine ] solution was filtered through a 0.22 μm filter head and spun onto the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonic acid layer at 4000rpm for 60s and annealed at 150 ℃ for 15min to give a uniform hole transport layer 1 (poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer.
Step 4: the poly (9-vinylcarbazole) solution was filtered through a 0.22 μm filter and spun onto the poly [ bis (4-phenyl) (4-butylphenyl) amine ] layer at a rotation speed of 3000rpm for 60s, and annealed at 150 ℃ for 15min to give a uniform hole transport layer 2.
Step 5: mixing oleic acid and 1-octadecene according to the mass ratio of 1:10, dissolving 10mmol of lead acetate trihydrate, heating to 100 ℃ under vacuum, and stirring for 2 hours to obtain anhydrous and oxygen-free lead-containing precursor solution.
Step 6: mixing hexamethyldisilazane and 1-octadecene according to a volume ratio of 1:9, heating to 100 ℃ under vacuum and stirring for 2 hours to obtain anhydrous and oxygen-free sulfur-containing precursor solution.
Step 7: and rapidly injecting the sulfur-containing precursor solution into the lead-containing precursor solution, carrying out the reaction in a nitrogen environment, and nucleating and growing the obtained lead-containing precursor solution to obtain the lead sulfide quantum dot.
Step 8: the lead sulfide quantum dot solution after the reaction is transferred into a glove box filled with nitrogen, and the quantum dots are purified by adding isopropanol with the same volume and then centrifuging. And re-dispersing the extracted quantum dots in normal hexane, adding acetone to precipitate the quantum dots, and centrifuging to obtain the lead sulfide core-shell quantum dot material.
Step 9: and (3) dissolving the lead sulfide quantum dot material in normal hexane, preparing to obtain a lead sulfide quantum dot solution with the concentration of 25mg/mL, spin-coating 50 mu L of the solution on the hole transport layer obtained in the step (4) at the rotating speed of 3000rpm, and repeatedly superposing to obtain the 210nm uniform lead sulfide quantum dot film.
Step 10: using 2,4, 6-tris [3- (diphenylphosphinyloxy) phenyl ]]The electron transport layer, the electron injection layer and the metal cathode electrode are sequentially obtained from the raw materials of-1, 3, 5-triazole, 8-hydroxyquinoline-lithium and aluminum by a vacuum evaporation method, and the evaporation rates are respectivelyAnd->The thicknesses are respectively 60nm, 2nm and 100nm, and the quantum dot light emitting diode device is manufactured.
Performance testing
Fig. 2 is an electroluminescence spectrum of the qd led prepared in example 1, and as can be seen from fig. 2, the qd led has an electroluminescence wavelength of 1025nm.
Fig. 3 is a graph showing the relationship between the current density and the voltage of the quantum dot light emitting diode prepared in example 1, and it can be seen from fig. 3 that the turn-on voltage is 2.2V.
FIG. 4 is a graph showing the relationship between the irradiation intensity and the voltage of the Quantum dot light emitting diode prepared in example 1, and it can be seen from FIG. 4 that the highest irradiation intensity is 1.38W sr -1 m -2 。
Fig. 5 is a graph showing the relationship between the external quantum efficiency and the current density of the quantum dot light emitting diode prepared in example 1, and it can be seen from fig. 5 that the highest external quantum efficiency is 11.5%.
Fig. 6 is a transmission electron microscope image of the quantum dot film prepared in example 1, and it can be seen from fig. 6 that the quantum dots are orderly arranged and uniform in size.
Fig. 7 is an atomic force microscope image of the quantum dot film prepared in example 1, and it can be seen from fig. 7 that the surface of the quantum dot film is compact and flat.
Fig. 8 shows performance of the quantum dot light emitting diode device prepared by the comparative example, and the EQE of the comparative example obtained by fig. 8 is only 3.8%.
The quantum dot light emitting diode devices of examples 1-5 above were tested for electroluminescence, and the absolute emittance was calibrated by connecting calibrated photon multichannel PMA-12 analyzer systems Hamamatsu C10027-01 (360 nm-950 nm) and C10028-01 (950 nm-1600 nm) to an integrating sphere for collecting forward light of the device and a control current output point power supply system using PR-745 instrument Photo Research,380nm-1060nm, as shown in fig. 9: as can be taken from fig. 9, the EQE of the near infrared light emitting diode is independent of the light emitting layer thickness: the variation of EQE is less than 15% in the range of 40nm-210nm of the luminescent layer thickness.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A thickness insensitive near infrared quantum dot light emitting device is characterized in that,
comprises a light emitting layer;
the light-emitting layer comprises a quantum dot film with a core-shell structure, and a bifunctional connecting agent is contained on the surface of the quantum dot film; the difunctional linker contains a thiol group;
the thickness of the luminescent layer of the near infrared quantum dot luminescent device is more than or equal to 40nm.
2. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, wherein the light emitting wavelength of the thickness-insensitive near infrared quantum dot light emitting device is 750nm to 2500nm.
3. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, wherein the thickness of the light emitting layer is 40nm-210nm.
4. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, further comprising one or more of a hole injection layer, a hole transport layer, an electron injection layer, and a cathode.
5. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, wherein the bifunctional linker comprises one or more of 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 4-butanedithiol, 1, 5-pentanedithiol, 1, 6-hexanedithiol, 1, 7-heptanedithiol, and 1, 8-octanedithiol.
6. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, wherein the bifunctional linker comprises 0.1% -1% of the total concentration of the luminescent layer raw materials; the concentration of the quantum dot solution with the core-shell structure used in the preparation of the quantum dot film with the core-shell structure is 1mg/mL-40mg/mL.
7. The thickness-insensitive near infrared quantum dot light emitting device of claim 1, wherein the quantum dots of the core-shell structure are lead halide/lead sulfide core-shell quantum dots; the core of the lead halide/lead sulfide core-shell quantum dot is lead sulfide, and the shell is one or more of lead bromide, lead chloride and lead iodide.
8. The thickness-insensitive near infrared quantum dot light emitting device of claim 7, wherein the lead halide/lead sulfide core-shell quantum dot is obtained by the following preparation method:
mixing a surfactant and a lead source in a solvent, and heating for reaction to obtain a precursor solution containing lead;
dissolving a sulfur source in a solvent, and heating for reaction to obtain a sulfur-containing precursor solution;
injecting the obtained sulfur-containing precursor solution into the obtained lead-containing precursor solution in an inert atmosphere, and nucleating and growing to obtain lead sulfide quantum dots;
and reacting the halogen-containing compound with the obtained lead sulfide quantum dot to obtain the lead halide/lead sulfide core-shell quantum dot.
9. The thickness-insensitive near infrared quantum dot light emitting device of claim 8, wherein one or more of the following conditions are satisfied:
a) The sulfur source is selected from one or more of hexamethyldisilazane, sulfur powder and dithio-amino methane;
b) The conditions of the heating reaction are as follows: the heating temperature is 100-200 ℃ and the heating time is 1-2 h;
c) The surfactant is oleic acid and/or oleylamine;
d) The lead source is selected from one or more of lead acetate trihydrate, lead sulfate, lead oxide, lead chloride, lead bromide and lead iodide;
e) The solvent is selected from one or more of hexadecene, octadecene and eicosene;
f) The mass ratio of the surfactant to the solvent is 0.05-0.5.
10. A method for manufacturing a thickness-insensitive near infrared quantum dot light emitting device according to any one of claims 1 to 9, comprising the steps of:
sequentially spin-coating a hole injection layer and a hole transport layer on the pretreated substrate;
spin-coating a quantum dot solution of a core-shell structure on the hollow transport layer to obtain a quantum dot film of the core-shell structure;
reacting the obtained quantum dot film with the core-shell structure with a bifunctional connecting agent to obtain a luminescent layer;
and sequentially obtaining an electron transport layer, an electron injection layer and a cathode on the surface of the obtained luminescent layer by a vacuum evaporation method.
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