CN110718645B - Preparation method and product of perovskite quantum dot light-emitting diode - Google Patents

Preparation method and product of perovskite quantum dot light-emitting diode Download PDF

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CN110718645B
CN110718645B CN201910906165.8A CN201910906165A CN110718645B CN 110718645 B CN110718645 B CN 110718645B CN 201910906165 A CN201910906165 A CN 201910906165A CN 110718645 B CN110718645 B CN 110718645B
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陈蓉
耿士才
曹坤
单斌
周彬泽
刘梦佳
姜晨晨
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Huazhong University of Science and Technology
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Abstract

The present invention belongs to the preparation of light-emitting diodeThe field of the technology and particularly discloses a preparation method and a product of a perovskite quantum dot light-emitting diode. The method comprises the following steps: carrying out activation treatment on the clean ITO glass surface; depositing a layer of ZnO film and Al on the surface of the activated ITO glass in sequence2O3A film; in Al2O3Spin-coating a quantum dot solution on the surface of the film to obtain a quantum dot film; depositing a layer of Al on the surface of the quantum dot film2O3A film; in Al2O3Sequentially preparing a TPD hole transport layer and MoO on the surface of the film3A hole injection layer and an electrode aluminum. The product is prepared by the preparation method. The preparation method provided by the invention is simple and convenient in process, the prepared product has higher carrier injection, transmission capability and stability, the QLED device can be protected from being damaged, and the stability of the device is obviously improved by introducing an inorganic substance, so that the luminous performance of the device is improved.

Description

Preparation method and product of perovskite quantum dot light-emitting diode
Technical Field
The invention belongs to the field of light-emitting diode preparation, and particularly relates to a preparation method and a product of a perovskite quantum dot light-emitting diode.
Background
Quantum dots are also called semiconductor nanocrystals, are zero-dimensional nanostructures composed of a small number of atoms and having three-dimensional dimensions of usually 1nm to 100nm, have adjustable band gaps and narrow emission spectra, are widely applied to LED devices in recent years, have the advantages of self-luminescence, high color purity, low energy consumption, stable images, wide viewing angle range, rich colors and the like, are considered as a new generation of display technology following LCD and OLED (organic light emitting diode) in recent years, and have wide application prospects.
However, the perovskite quantum dot has a large specific surface area, and an unstable dangling bond is formed due to the shedding of a surface ligand, and the material of the device is easily corroded by water and oxygen, so that the current quantum dot light-emitting diode device has the defects of low luminous efficiency, poor stability, complex process, poor process compatibility, incapability of mass production and the like, and the progress of the device in commercial application is limited. In order to solve the above problems, the quantum dot per se and the device structure are mainly improved at present, and the ligand exchange method is utilized, and some ligands with stronger binding force than oleic acid oleylamine are used, so that the quantum dot has higher PLQY (photoluminescence quantum yield), the stability of the quantum dot can be improved, and the efficiency of the device can be improved.
Therefore, there is a need in the art for improvement of the existing diode manufacturing method, so that the quantum dots of the diode have higher carrier injection and transport capabilities, and PLQY and stability of the quantum dots are improved through the combined action of the quantum dots and the carrier injection and transport capabilities.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method and a product of a perovskite quantum dot light-emitting diode, wherein the characteristics of the light-emitting diode and the characteristics of the perovskite quantum dot preparation process are combined, the preparation method and the product of the perovskite quantum dot light-emitting diode are correspondingly improved, and isolating layers Al are arranged on the upper surface and the lower surface of a quantum dot film2O3The film can form protective layers on two sides of the quantum dot film, effectively prevent water and oxygen in the air from reacting with the quantum dot film, and can further fill up defects caused by unevenness of the quantum dot film. The preparation method has simple and convenient process, and the prepared productThe product has high carrier injection, transmission capability and stability, and can protect the QLED device from being damaged, and the introduction of inorganic substances can obviously improve the stability of the device, thereby improving the luminous performance of the device.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for manufacturing a perovskite quantum dot light emitting diode, comprising the steps of:
s1, carrying out activation treatment on the clean ITO glass surface;
s2 depositing a layer of ZnO film and Al on the surface of the activated ITO glass in sequence2O3A film;
s3 the Al prepared at step S22O3Spin coating quantum dot solution on the surface of the film to obtain uniform coating on the Al2O3A quantum dot film on the surface of the film;
s4 depositing a layer of Al on the surface of the quantum dot film prepared in the step S32O3A film;
s5 Al prepared in step S42O3Sequentially preparing a TPD hole transport layer and MoO on the surface of the film3Hole injection layer and electrode aluminium, thus prepare and obtain perovskite quantum dot light-emitting diode.
As a further preference, step S1 specifically includes the following substeps:
s11, carrying out ultrasonic cleaning on the ITO glass cut into the preset size and shape;
s12, drying the ITO glass by adopting nitrogen, and determining an electrode of the ITO glass by using a universal meter;
s13, placing the ITO glass into a cavity of plasma equipment, introducing oxygen into the cavity, and adjusting the working power of the plasma equipment to 300-500W to realize the activation treatment of the ITO glass.
As a further preferred, in step S2, the precursor for preparing the ZnO thin film is diethyl zinc and water; in step S2 and step S4, the Al is prepared2O3The precursor of the film is Al (CH)3)3、O2And O3。
As a further preference, step S2 specifically includes the following substeps:
s21, placing the activated ITO glass surface into a cavity of plasma equipment, setting the reaction temperature in the cavity, and then alternately and circularly introducing diethyl zinc and water into the cavity to generate a ZnO film crosslinked with the ITO glass surface on the ITO glass surface;
s22 extracting diethyl zinc and water which are not adsorbed on the surface of the ITO glass and by-products of deposition reaction, setting the reaction temperature and pressure in the cavity, and then alternately and circularly introducing the Al into the cavity for preparing the Al2O3Precursor of film to grow a layer of Al on the surface of ZnO film2O3A film;
the thickness of the ZnO film is 100 nm-200 nm, and further the thickness of the ZnO film is 150 nm; the Al is2O3The thickness of the film is 0.5 nm-10 nm, and further, the Al2O3The thickness of the film is 3 nm-8 nm; further, the Al is2O3The thickness of the film was 5 nm.
More preferably, step S3 specifically includes the following steps: transferring the ITO glass treated in the step S2 into a glove box, setting the pressure of the glove box, and spin-coating a quantum dot solution on the surface of the ITO glass by using spin-coating equipment to obtain a layer of the quantum dot solution uniformly coated on the Al2O3A quantum dot film on the surface of the film;
wherein the rotating speed of the spin coating equipment is 2000-3000 rpm, the acceleration of the spin coating equipment during spin coating is 500-2000 rpm/s, and the spin coating time is 45-60 s.
As a further preferred, the preparation method of the quantum dot solution comprises the following steps:
s41 reaction of CS2CO3Adding the cesium precursor solution into n-octanoic acid, and then magnetically stirring to form a cesium precursor solution;
s42 mixing PbX2And tetraoctyl ammonium bromide are dissolved in toluene according to a preset proportion, and Pb is formed after magnetic stirring at room temperatureX2A solution;
s43, adding DDAB into a toluene solution to prepare a DDAB ligand solution;
s44 adding the cesium precursor solution into PbX at room temperature2Magnetically stirring the solution to synthesize the perovskite quantum dots with controllable sizes;
s45, adding the DDAB ligand solution into the solution processed in the step S44 to passivate perovskite quantum dots in the solution;
s46, adding ethyl acetate into the solution processed in the step S45, centrifuging, removing the precipitate after centrifugation, and dispersing the precipitate into ethyl acetate to obtain a quantum dot solution;
wherein, X is any one of Cl, Br and I.
According to another aspect of the invention, a perovskite quantum dot light-emitting diode is provided, and is prepared by the preparation method.
Generally, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
1. the invention researches the deposition of nanometer metal oxide on an ITO glass sheet by an atomic layer deposition technology, uses ZnO with good conductivity as an electron transport layer material, enhances the carrier transport rate of a quantum dot light-emitting device, balances the carrier transport, improves the electron and hole recombination probability, and in addition, the upper surface and the lower surface of a quantum dot film are provided with isolating layers Al2O3The film can form protective layers on two sides of the quantum dot film, effectively prevent water and oxygen in the air from reacting with the quantum dot film, and can further fill up the defects caused by the unevenness of the quantum dot film, and the introduction of inorganic matters can obviously improve the stability of a device, thereby improving the luminous performance of the device.
2. In the invention, DDAB and short-chain OTAC ligands are used in the process of synthesizing the quantum dots, the carbon chain of a common oleic acid oleylamine ligand is longer, although the quantum dots also have higher PLQY, when the ligand is applied to a QLED device, the movement of a current carrier in a luminous layer is hindered due to the ligand with a longer chain on the surface, the quantum dots have stronger photoluminescence characteristic and uniform dispersibility due to the introduction of the DDAB, the synthesized quantum dot solution can be stored for several months in the atmospheric environment, the quantum dots have higher current carrier injection and transmission capacity due to the short ligand OTAC, the QLED device has higher current density, the PLQY and the stability of the quantum dots are improved due to the combined action of the two ligands, and the performance of the QLED is improved
3. The invention synthesizes quantum dots by using a room temperature method, greatly reduces the cost and time, utilizes DDAB and OTAC ligands to carry out surface passivation on the quantum dots, the DDAB ligands enable the quantum dots to have stronger photoluminescence characteristics and uniform dispersibility, the short ligands OTAC enable the quantum dots to have higher carrier injection and transmission capability, and the PLQY and the stability of the quantum dots are improved under the combined action of the DDAB ligands and the OTAC ligands. The atomic layer deposition technology is used for depositing the ZnO film to serve as the electron transmission layer, the atomic layer deposition technology can realize growth at a molecular level, the thickness of the film is accurately controlled, the grown ZnO film has high electron transmission capacity, and carrier balance of the quantum dot light-emitting device can be well balanced.
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Fig. 1 is a flow chart of a method for manufacturing a perovskite quantum dot light emitting diode according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of a perovskite quantum dot light emitting diode according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the method for preparing a perovskite quantum dot light emitting diode of the present invention specifically comprises the following steps:
step one, room temperature synthesis of perovskite quantum dots is different from a traditional heat injection method, the perovskite quantum dots with uniform and controllable sizes are synthesized by a room temperature method, the room temperature synthesis method is simple to operate, can be carried out at room temperature, does not need vacuum conditions and protection of inert gases, is controlled in temperature, and can be used for reacting after a certain amount of two precursor solutions are mixed to generate the perovskite quantum dots, and the method specifically comprises the following steps:
(1) to connect CS2CO3Adding into OTAC (n-octanoic acid), stirring by magnetic force for 5 min-20 min at room temperature to prepare 0.1M-0.3M CS2CO3A solution, thereby preparing a cesium precursor solution;
(2) mixing PbX2(X ═ Cl, Br, I) and TOAB (tetraoctylammonium bromide) were measured at a molar ratio of 1: 2-1: 10 mol percent of the raw material is dissolved in 10-50 ml of toluene, and the mixture is fully dissolved into a clear and transparent state by magnetic stirring for 20-50 min at room temperature to prepare the PbX2A toluene solution of (4);
(3) adding DDAB (didodecyldimethylammonium bromide) into a toluene solution to prepare a DDAB ligand solution of 5 mg/mL-15 mg/mL;
(4) 1-2 ml of cesium precursor solution was added rapidly to 9ml of PbX2The reaction is carried out for 1-5 min under the conditions of room temperature and open air by magnetic stirring to synthesize the perovskite quantum dots, and the quantum dots grow gradually and increase in size along with the reaction time;
(5) adding 3-5 ml of DDAB (didodecyldimethylammonium bromide) toluene solution into the solution, introducing DDAB ligand, further passivating the quantum dots, and reacting for 1-5 min;
(6) adding ethyl acetate with the volume twice that of the stock solution obtained in the step (5), centrifuging at 7000rpm for 10min, removing a supernatant, dissolving the precipitate by using n-hexane, adding ethyl acetate with a preset volume, dispersing, centrifuging, collecting the precipitate, and dispersing the precipitate in the n-hexane again.
Step two, cleaning the surface of the ITO glass, placing the ITO glass in a plasma cleaning machine for surface plasma activation after cleaning with a reagent, and specifically comprising the following steps:
(2.1) cutting the ITO glass into small sample pieces with preset sizes and shapes, and ultrasonically cleaning the small sample pieces with deionized water, acetone, isopropanol and alcohol respectively for 15 minutes each time;
(2.2) blowing the ITO glass with nitrogen in a clean room and determining the front and back of an ITO glass electrode with a multimeter;
and (2.3) putting the ITO glass into a cavity of plasma equipment, introducing oxygen, adjusting the power of the plasma equipment to be 300-500W, cleaning the front surface of the ITO glass by using oxygen plasma, and cleaning for 10-20 min to obtain the ITO glass with activated surface.
Growing an electron transmission layer ZnO film on the activated ITO glass by using atomic layer deposition equipment, and then growing a thin electron blocking layer Al on the ZnO film2O3A film, comprising in particular the steps of:
(3.1) changing a reaction source of the atomic layer deposition equipment to diethyl zinc and water;
(3.2) heating the pipeline and the cavity of the atomic layer deposition equipment to 60-120 ℃ and stabilizing;
(3.3) setting the pulse time of the diethyl zinc to be 0.1-1 s, adjusting the switch of the source bottle to enable the pulse to be 20-50 Pa, setting the pulse time of the water to be 0.1-1 s, and adjusting the switch of the source bottle to enable the pulse to be 10-30 Pa;
(3.4) setting the cycle number of ZnO growth as 100-200, alternately introducing diethyl zinc and water, and growing a ZnO film with the thickness of 100-200 nm on the ITO glass; preferably, the thickness of the ZnO film is 150 nm;
(3.5) extracting diethyl zinc and water which are not adsorbed on the surface of the ITO glass and by-products of deposition reaction, and changing reactants into Al (CH)3)3、O2And O3Al is carried out at 60-120 DEG C2O3Set Al2O3The growth cycle is 10-20 times, and Al (CH) is alternately introduced3)3、O2And O3Growing 0.5-10 nm Al on ITO glass2O3A film; preferably, the Al is2O3Thickness of the filmThe degree is 3 nm-8 nm; further, the Al is2O3The thickness of the film was 5 nm.
And step four, transferring the ITO glass processed in the step four into a glove box to prepare the quantum dot film. The method specifically comprises the following steps:
(4.1) moving the substrate to a glove box for spin coating of quantum dots, adjusting the pressure intensity of the glove box and facilitating operation;
(4.2) setting the rotating speed of the spin coating equipment to be 2000-3000 rpm, the acceleration to be 500-2000 rpm/s and the spin coating time to be 45-60 s;
(4.3) placing the ITO glass on spin-coating equipment, blowing off dust on the surface by using an ear washing ball, dripping 50-100 ul of quantum dot solution on a substrate by using a liquid transfer gun, and starting quantum dot spin-coating to obtain a layer of quantum dot solution uniformly coated on the Al2O3Quantum dot film on the surface of the film.
Step five, using atomic layer deposition equipment to perform electron barrier layer Al2O3And (5) growing the thin film. That is, the reaction source of the atomic layer deposition apparatus is changed to Al (CH)3)3、O2And O3Al is carried out at 60-120 DEG C2O3Set Al2O3The growth cycle is 10-20 times, and Al (CH) is alternately introduced3)3、O2And O3Growing 0.5-10 nm Al on ITO glass2O3A film; preferably, the Al is2O3The thickness of the film is 3 nm-8 nm; further, the Al is2O3The thickness of the film was 5 nm.
And step six, moving the substrate into a glove box to prepare the hole transport layer TPD.
(6.1) moving the substrate to a glove box for spin coating of TPD, adjusting the pressure intensity of the glove box and facilitating operation
(6.2) setting the rotating speed of the spin coating equipment to be 2000-4000 rpm, the acceleration to be 500-2000 rpm/s, and the spin coating time to be 45-60 s;
and (6.3) placing the substrate on spin coating equipment, blowing off dust on the surface by using an ear washing ball, taking 50-100 ul of quantum dot solution by using a liquid transfer gun, dripping the quantum dot solution on the substrate, and starting TPD spin coating.
Step seven, placing the base in an evaporation coating cavity, and performing hole injection layer MoO by using a direct reading method3And growth of electrode aluminum.
(7.1) moving the device into a vapor deposition cavity, enabling the sample to rotate at a constant speed to ensure the uniformity of vapor deposition, and vacuumizing until the pressure reaches 2 x 10-4Pa；
(7.2) the 1nm hole injection layer MnO was evaporated at 0.05nm/s, and the 100nm electrode Al was evaporated at 0.2nm/s, so that the evaporation rate was kept as stable as possible.
As shown in figure 2, the perovskite quantum dot light-emitting diode prepared by the preparation method comprises a ZnO film and Al which are sequentially arranged on the surface of ITO glass2O3Film, quantum dot film, and Al2O3Film, TPD hole transport layer MoO3A hole injection layer and an electrode aluminum.
Example 1
1) The room temperature synthesis of perovskite quantum dot is different from the traditional heat injection method, adopts the room temperature method to synthesize the perovskite quantum dot with the uniform and controllable size, and the room temperature synthesis method has simple operation, not only can be carried out at room temperature, but also does not need the protection of vacuum condition and inert gas, controls the temperature well, mixes a certain amount of two precursor solutions and can react to generate the perovskite quantum dot, and the specific steps are as follows:
1.1) adding CS2CO3 into OTAC (n-octanoic acid), and magnetically stirring at room temperature for 10min to prepare 0.1-0.3M CS2CO3 solution to prepare a cesium precursor;
1.2) adding PbCl2And TOAB (tetraoctylammonium bromide) in a ratio of 1: 2 in 10ml of toluene, and the mixture was sufficiently dissolved to a clear and transparent state by magnetic stirring at room temperature for 30 minutes to prepare 0.1M PbCl2A solution;
1.3) adding DDAB into a toluene solution to prepare a DDAB ligand solution of 5 mg/mL;
1.4) 1ml of cesium precursor solution was added rapidly to 9ml of PbCl2In toluene solution, the reaction is carried out at room temperature in the open airPerforming a reaction of quantum dot synthesis by magnetic stirring for 1min to synthesize perovskite quantum dots, wherein the quantum dots gradually grow and increase in size along with the reaction time;
1.5) then adding 3ml of DDAB (didodecyldimethylammonium bromide) toluene solution, introducing DDAB ligand, further passivating the quantum dots, and reacting for 1 min;
1.6) adding twice of ethyl acetate into the stock solution, centrifuging at 7000rpm for 10min, removing the supernatant, dissolving the precipitate with 6ml of n-hexane, adding 12ml of ethyl acetate, centrifuging, collecting, and dispersing in 6ml of n-hexane.
2) And cleaning the surface of the ITO glass, and after cleaning with a reagent, placing the substrate in a plasma cleaning machine for surface plasma activation.
2.1) the ITO glass was cut into small sample pieces of 20mm by 20mm and cleaned ultrasonically with deionized water, acetone, isopropanol and alcohol, respectively, for 15 minutes each time.
2.2) drying the ITO glass in a clean room by using nitrogen and determining the front and back of an ITO glass electrode by using a universal meter;
2.3) putting the ITO glass into a cavity, introducing oxygen, adjusting the power to 300W, cleaning the front surface of the ITO glass by using oxygen plasma, and cleaning for 10 min;
3) growing an electron transport layer ZnO film on the activated plasma substrate by using an atomic layer deposition device, and then growing a thin electron blocking layer Al on the ZnO film2O3A film.
3.1) changing a reaction source of the atomic layer deposition equipment into diethyl zinc and water;
3.2) heating the pipeline and the cavity of the atomic layer deposition equipment to 120 ℃ and stabilizing;
3.3) setting the pulse time of the diethyl zinc to be 0.1s, adjusting the switch of the source bottle to enable the pulse to be 20Pa, setting the pulse time of the water to be 0.1s, and adjusting the switch of the source bottle to enable the pulse to be 10 Pa;
3.4) setting the cycle number of ZnO growth as 100, alternately introducing diethyl zinc and water, and growing a 100nm ZnO film on the ITO glass;
3.5) atomic layer depositionReaction source of deposition equipment is changed into Al (CH)3)3、O2And O3Al at 120 ℃ C2O3Set Al2O3The growth cycle number is 5, and Al (CH) is alternately introduced3)3、O2And O30.5nm of Al is grown on the ITO glass2O3A film.
4) And (4) moving the substrate into a glove box to prepare the quantum dot film.
4.1) moving the substrate to a glove box for spin coating of quantum dots, adjusting the pressure intensity of the glove box and facilitating operation;
4.2) setting the rotating speed of the spin coater to be 2000rpm, the acceleration to be 500rpm/s and the spin coating time to be 45 s;
4.3) putting the ITO glass on a spin coating instrument, blowing off dust on the surface by using an ear washing ball, taking 50ul of quantum dot solution by using a liquid transfer gun, dripping the quantum dot solution on a substrate, and starting quantum dot spin coating.
5) Electron blocking layer Al using atomic layer deposition equipment2O3And (5) growing the thin film.
Changing reaction source of atomic layer deposition equipment to Al (CH)3)3、O2And O3Al at 120 ℃ C2O3Set Al2O3The growth cycle number is 5, and Al (CH) is alternately introduced3)3、O2And O30.5nm of Al is grown on the ITO glass2O3A film.
6) The substrate was transferred to a glove box for preparation of the hole transport layer TPD.
6.1) moving the substrate to a glove box for spin coating of TPD (spin-on-demand) and adjusting the pressure intensity of the glove box, thereby facilitating operation
6.2) setting the rotating speed of the spin coater to be 2000rpm, the acceleration to be 500rpm/s and the spin coating time to be 45 s;
6.3) putting the substrate on a spin coater, blowing off dust on the surface by using an ear washing ball, taking 50ul of quantum dot solution by using a pipette gun, dripping the quantum dot solution on the substrate, and starting TPD spin coating.
7) Placing the base in the evaporation chamber and using the positive readingMethod for performing hole injection layer MoO3And growth of electrode aluminum.
7.1) moving the device into an evaporation cavity, enabling a sample to rotate at a constant speed to ensure the uniformity of evaporation, and vacuumizing until the pressure reaches 2 x 10 < -4 > Pa;
7.2) evaporating a 1nm hole injection layer MnO at 0.05nm/s and evaporating a 100nm electrode Al at 0.2nm/s, wherein the evaporation rate is kept as stable as possible.
Example 2
1) The room temperature synthesis of perovskite quantum dot is different from the traditional heat injection method, adopts the room temperature method to synthesize the perovskite quantum dot with the uniform and controllable size, and the room temperature synthesis method has simple operation, not only can be carried out at room temperature, but also does not need the protection of vacuum condition and inert gas, controls the temperature well, mixes a certain amount of two precursor solutions and can react to generate the perovskite quantum dot, and the specific steps are as follows:
1.1) reaction of CS2CO3Adding into OTAC (n-octanoic acid), magnetically stirring at room temperature for 10min to obtain 0.3M CS2CO3Solution, preparing a cesium precursor;
1.2) reacting PbBr2And TOAB (tetraoctylammonium bromide) in a ratio of 1: 2 in 10ml of toluene, and the mixture was fully dissolved to a clear and transparent state by magnetic stirring at room temperature for 30min to prepare 0.1M PbBr2A solution;
1.3) adding DDAB to the toluene solution to prepare a 15mg/mL DDAB ligand solution.
1.4) quickly adding 2ml of cesium precursor solution into 9ml of PbBr2 toluene solution, carrying out a quantum dot synthesis reaction by magnetic stirring at room temperature in the open air for 5min to synthesize perovskite quantum dots, wherein the quantum dots gradually grow and increase in size along with the reaction time
1.5) then adding 5ml of DDAB (didodecyldimethylammonium bromide) toluene solution, introducing DDAB ligand, further passivating the quantum dots, and reacting for 5 min;
1.6) adding twice of ethyl acetate into the stock solution, centrifuging at 7000rpm for 10min, removing the supernatant, dissolving the precipitate with 6ml of n-hexane, adding 12ml of ethyl acetate, centrifuging, collecting, and dispersing in 6ml of n-hexane.
2) And cleaning the surface of the ITO glass, and after cleaning with a reagent, placing the substrate in a plasma cleaning machine for surface plasma activation.
2.1) the ITO glass was cut into small sample pieces of 30mm by 30mm and cleaned ultrasonically with deionized water, acetone, isopropanol and alcohol, respectively, for 15 minutes each time.
2.2) blowing the ITO sheet to dry in a clean room by using nitrogen and determining the front and back of an ITO electrode by using a universal meter
2.3) putting the ITO substrate into a cavity, introducing oxygen, adjusting the power to be 500W, cleaning the front surface of the ITO glass by using oxygen plasma, and cleaning for 20 min;
3) and growing an electron transport layer ZnO film on the activated plasma substrate by using an atomic layer deposition device, and then growing a thin electron blocking layer Al2O3 film on the ZnO film.
3.1) changing a reaction source of the atomic layer deposition equipment into diethyl zinc and water;
3.2) heating the pipeline and the cavity of the atomic layer deposition equipment to 120 ℃ and stabilizing;
3.3) setting the pulse time of the diethyl zinc to be 1s, adjusting the switch of the source bottle to enable the pulse to be 50Pa, setting the pulse time of the water to be 1s, and adjusting the switch of the source bottle to enable the pulse to be 30 Pa;
3.4) setting the cycle number of ZnO growth as 200, alternately introducing diethyl zinc and water, and growing a ZnO film of 200nm on the ITO glass;
3.5) exchange of the diethyl Zinc Source for Al (CH)3)3、O2And O3Al at 120 ℃ C2O3Set Al2O3The growth cycle was 20 times, and Al (CH) was alternately introduced3)3、O2And O3Growing 10nm Al on ITO glass2O3A film;
4) and (4) moving the substrate into a glove box to prepare the quantum dot film.
4.1) moving the substrate to a glove box for spin coating of quantum dots, adjusting the pressure intensity of the glove box and facilitating operation;
4.2) setting the rotating speed of the spin coater to be 3000rpm, the acceleration to be 2000rpm/s and the spin coating time to be 60 s;
4.3) putting the substrate on a spin coating instrument, blowing off dust on the surface by using an ear washing ball, taking 100ul of quantum dot solution by using a liquid transfer gun, dripping the quantum dot solution on the substrate, and starting quantum dot spin coating;
5) electron blocking layer Al using atomic layer deposition equipment2O3And (5) growing the thin film.
5.1) changing a reaction source of the atomic layer deposition equipment into trimethylaluminum and water;
conversion of the diethyl Zinc Source to Al (CH)3)3、O2And O3Al at 120 ℃ C2O3Set Al2O3The growth cycle was 20 times, and Al (CH) was alternately introduced3)3、O2And O3Growing 10nm Al on ITO glass2O3A film.
6) The substrate was transferred to a glove box for preparation of the hole transport layer TPD.
6.1) moving the substrate to a glove box for spin coating of TPD (spin-on-demand) and adjusting the pressure intensity of the glove box, thereby facilitating operation
6.2) setting the rotating speed of the spin coater to be 4000rpm, the acceleration to be 2000rpm/s and the spin coating time to be 60 s;
6.3) putting the substrate on a spin coating instrument, blowing off dust on the surface by using an ear washing ball, taking 100ul of quantum dot solution by using a liquid transfer gun, dripping the quantum dot solution on the substrate, and starting TPD (spin coating);
7) placing the base in an evaporation coating cavity, and performing hole injection on the MoO layer by using a direct reading method3And growth of electrode aluminum.
7.1) moving the device into a cavity for evaporation to ensure the uniformity of evaporation by rotating the sample at a constant speed, and vacuumizing until the pressure reaches 2 multiplied by 10-4Pa；
7.2) evaporating a 1nm hole injection layer MnO at 0.05nm/s and evaporating a 100nm electrode Al at 0.2nm/s, wherein the evaporation rate is kept as stable as possible.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A preparation method of a perovskite quantum dot light-emitting diode is characterized by comprising the following steps:
s1, carrying out activation treatment on the clean ITO glass surface;
s2 depositing a layer of ZnO film and Al on the surface of the activated ITO glass in sequence2O3A film; the method specifically comprises the following substeps:
s21, changing a reaction source of the atomic layer deposition equipment into diethyl zinc and water;
s22, heating the pipeline and the cavity of the atomic layer deposition equipment to 60-120 ℃ and stabilizing;
s23, setting the pulse time of diethyl zinc to be 0.1-1S, adjusting the switch of a source bottle to make the pulse of the source bottle be 20-50 Pa, setting the pulse time of water to be 0.1-1S, and adjusting the switch of the source bottle to make the pulse of the source bottle be 10-30 Pa;
s24, setting the cycle number of ZnO growth as 100-200, alternately introducing diethyl zinc and water, and growing a ZnO film of 100-200 nm on the ITO glass;
s25 extracting diethyl zinc and water which are not adsorbed on the surface of the ITO glass and by-products of deposition reaction, and changing reactants into Al (CH)3)3、O2And O3Al is carried out at 60-120 DEG C2O3Set Al2O3The growth cycle is 10-20 times, and Al (CH) is alternately introduced3)3、O2And O3Growing 0.5-10 nm Al on ITO glass2O3A film;
s3 the Al prepared at step S22O3Spin coating quantum dot solution on the surface of the film to obtain uniform coating on the Al2O3A quantum dot film on the surface of the film;
s4 at stepA layer of Al is deposited on the surface of the quantum dot film prepared by S32O3A film;
s5 Al prepared in step S42O3Sequentially preparing a TPD hole transport layer and MoO on the surface of the film3Hole injection layer and electrode aluminium, thus prepare and obtain perovskite quantum dot light-emitting diode.
2. The method of claim 1, wherein: step S1 specifically includes the following substeps:
s11, carrying out ultrasonic cleaning on the ITO glass cut into the preset size and shape;
s12, drying the ITO glass by adopting nitrogen, and determining an electrode of the ITO glass by using a universal meter;
s13, placing the ITO glass into a cavity of plasma equipment, introducing oxygen into the cavity, and adjusting the working power of the plasma equipment to 300-500W to realize the activation treatment of the ITO glass.
3. The method of claim 1, wherein: in step S2, the precursor for preparing the ZnO film is diethyl zinc and water; in step S2 and step S4, the Al is prepared2O3The precursor of the film is Al (CH)3)3、O2And O3。
4. The method of claim 1, wherein: the thickness of the ZnO film in the step S2 is 150 nm; the Al is2O3The thickness of the film is 3 nm-8 nm.
5. The production method according to any one of claims 1 to 4, characterized in that: step S3 specifically includes the following steps: transferring the ITO glass treated in the step S2 into a glove box, setting the pressure of the glove box, and spin-coating a quantum dot solution on the surface of the ITO glass by using spin-coating equipment to obtain a layer of the quantum dot solution uniformly coated on the Al2O3A quantum dot film on the surface of the film;
wherein the rotating speed of the spin coating equipment is 2000-3000 rpm, the acceleration of the spin coating equipment during spin coating is 500-2000 rpm/s, and the spin coating time is 45-60 s.
6. The method of claim 5, wherein: the preparation method of the quantum dot solution comprises the following steps:
s41 reaction of CS2CO3Adding the cesium precursor solution into n-octanoic acid, and then magnetically stirring to form a cesium precursor solution;
s42 mixing PbX2And tetraoctyl ammonium bromide are dissolved in toluene according to a preset proportion, and PbX is formed after magnetic stirring at room temperature2A solution;
s43, adding DDAB into a toluene solution to prepare a DDAB ligand solution;
s44 adding the cesium precursor solution into PbX at room temperature2Magnetically stirring the solution to synthesize the perovskite quantum dots with controllable sizes;
s45, adding the DDAB ligand solution into the solution processed in the step S44 to passivate perovskite quantum dots in the solution;
s46, adding ethyl acetate into the solution processed in the step S45, centrifuging, removing the precipitate after centrifugation, and dispersing the precipitate into ethyl acetate to obtain a quantum dot solution;
wherein, X is any one of Cl, Br and I.
7. A perovskite quantum dot light-emitting diode, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
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