阅读说明：本技术 一种钙钛矿量子点的图案化方法 (Patterning method of perovskite quantum dots ) 是由 孙小卫 王恺 方凡 于 2019-11-14 设计创作，主要内容包括：本发明提供了一种钙钛矿量子点的图案化方法。所述方法包括以下步骤：(1)将钙钛矿量子点前驱体溶于非极性溶剂中,将得到的前驱体溶液打印在基板上形成前驱体图案；(2)将所述前驱体图案置于极性溶剂的蒸气中进行反应,形成钙钛矿量子点图案。发明提供的钙钛矿量子点的图案化方法基于打印实现图案化,并且不是直接打印钙钛矿量子点,而是先打印钙钛矿量子点的前驱体,然后再将图案化的前驱体转变为钙钛矿量子点。这能很好地的避免直接打印钙钛矿量子点而导致喷头堵塞的问题,图案化精度高,适于进行大面积钙钛矿量子点图案化。(The invention provides a patterning method of perovskite quantum dots. The method comprises the following steps: (1) dissolving a perovskite quantum dot precursor in a nonpolar solvent, and printing the obtained precursor solution on a substrate to form a precursor pattern; (2) and placing the precursor pattern in vapor of a polar solvent for reaction to form a perovskite quantum dot pattern. The patterning method of the perovskite quantum dot provided by the invention realizes patterning based on printing, and instead of directly printing the perovskite quantum dot, a precursor of the perovskite quantum dot is printed first, and then the patterned precursor is converted into the perovskite quantum dot. The problem that the spray head is blocked due to direct printing of the perovskite quantum dots can be well solved, the patterning precision is high, and the method is suitable for patterning the large-area perovskite quantum dots.)

1. A method of patterning perovskite quantum dots, the method comprising the steps of:

(1) dissolving a perovskite quantum dot precursor in a nonpolar solvent, and printing the obtained precursor solution on a substrate to form a precursor pattern;

(2) and (2) placing the precursor pattern in the step (1) in vapor of a polar solvent for reaction to form a perovskite quantum dot pattern.

2. The method of claim 1, wherein the perovskite quantum dots are inorganic perovskite quantum dots;

preferably, the perovskite quantum dots consist of a cation a, a cation B and an anion X;

preferably, the cation A comprises Cs⁺And/or Rb⁺；

Preferably, the cation B comprises Pb²⁺；

Preferably, the anion X comprises Cl^-、Br^-Or I^-Any ofOne or a combination of at least two;

preferably, the perovskite quantum dot precursor of step (1) comprises a cation a precursor, a cation B precursor and optionally an anion X precursor;

preferably, the cation a precursor comprises Cs₂CO₃、CsAc、CsCl、CsBr、CsI、Rb₂CO₃Any one or combination of at least two of RbAc, RbCl, RbBr or RbI;

preferably, the cationic B precursor comprises PbCl₂、PbBr₂、PbI₂PbO or Pb (Ac)₂Any one or a combination of at least two of;

preferably, the anionic X precursor comprises NH₄Cl、NH₄Br、NH₄I. Any one or the combination of at least two of CsCl, CsBr, CsI, RbCl, RbBr or RbI;

preferably, in the perovskite quantum dot precursor in the step (1), the molar ratio of the cation A to the cation B to the anion X is (0.9-1.1): 3, and preferably 1:1: 3.

3. The method of claim 1 or 2, wherein the non-polar solvent comprises any one of octadecene, liquid paraffin, dodecane, octane, or hexane, or a combination of at least two thereof;

preferably, the concentration of the precursor in the precursor solution is 0.05-5 mol/L.

4. The method of any one of claims 1-3, wherein the substrate of step (1) comprises a host material;

preferably, the host material comprises any one of ITO glass, polyethylene film, polypropylene film, polyethylene terephthalate film, or methyl methacrylate film;

preferably, the main body material is cleaned;

preferably, the method of cleaning comprises: carrying out primary cleaning, ultrasonic cleaning and secondary cleaning on the main body material;

preferably, the method for one-time cleaning comprises the following steps: washing with a surfactant for 5-10 minutes;

preferably, the method of ultrasonic cleaning comprises: sequentially carrying out ultrasonic treatment in a surfactant, acetone and isopropanol for 20-40 minutes;

preferably, the method of secondary cleaning comprises: and cleaning with an ultraviolet ozone cleaning machine.

5. The method of claim 4, wherein the body material has a film on one side;

preferably, the film is a film of a non-polar material;

preferably, the film comprises any one of or a combination of at least two of a polyvinylcarbazole film, a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film, or a zinc oxide film, preferably a combination of a polyvinylcarbazole film and a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film;

preferably, when the film is a combination of a polyvinylcarbazole film and a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film is located on the host material, and the polyvinylcarbazole film is located on the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film;

preferably, the method of preparing a film on one side of the host material comprises: dripping a film raw material solution on one surface of the main body material, carrying out spin coating on the main body material, and then annealing;

preferably, the dropping amount of the dropwise adding is 60-120 microliters;

preferably, the spin coating is performed by a spin coater;

preferably, the rotating speed of the spin coating is 2000-4000 revolutions per minute;

preferably, the spin coating time is 30-60 seconds;

preferably, the annealing is performed on a hot stage;

preferably, the annealing temperature is 100-140 ℃;

preferably, the annealing time is 15-20 minutes.

6. The method according to any one of claims 1-5, wherein the printing of step (1) is ink jet printing;

preferably, the inkjet printing is performed with an inkjet printer;

preferably, the ink jet printer is a non-contact ink jet printer;

preferably, the diameter of the spray head of the printer is 5-100 micrometers.

7. The method according to any one of claims 1 to 6, wherein the temperature of the printing of step (1) is 15 to 35 ℃.

8. The method according to any one of claims 1 to 7, wherein the polar solvent of step (2) comprises any one of water, ethanol, isopropanol or isobutanol, or a combination of at least two thereof.

9. The method according to any one of claims 1 to 8, wherein the flow rate of the vapor of the polar solvent in the step (2) is 1 to 100L/min;

preferably, the temperature of the reaction in the step (2) is 0-100 ℃;

preferably, the reaction time of the step (2) is 15-120 s.

10. Method according to any of claims 1-9, characterized in that the method comprises the steps of:

(1) cleaning the ITO glass with a surfactant for 5-10 minutes, then sequentially carrying out ultrasonic treatment in the surfactant, acetone and isopropanol for 20-40 minutes, and finally cleaning with an ultraviolet ozone cleaning machine to obtain the cleaned ITO glass;

(2) dripping 60-120 microliters of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture solution on one surface of the cleaned ITO glass in the step (1), spin-coating for 30-60 seconds at a rotating speed of 2000-4000 revolutions per minute by using a spin coater, annealing for 15-20 minutes at a temperature of 100-140 ℃ on a hot table, dripping 60-120 microliters of polyvinyl carbazole solution on the obtained poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film, spin-coating for 30-60 seconds at a rotating speed of 2000-4000 revolutions per minute by using a spin coater, annealing for 15-20 minutes at a temperature of 100-140 ℃ on the hot table to form a polyvinyl carbazole film, and obtaining the ITO glass with a film as a substrate;

(3) dissolving a cation A precursor, a cation B precursor and an optional anion X precursor in a nonpolar solvent to obtain a precursor solution with the precursor concentration of 0.05-5 mol/L, wherein the element ratio of A, B to X in the precursor is 1:1:3, A is Cs⁺B is Pb²⁺X is any one or a combination of at least two of Br-, I-or Cl-, and the precursor solution is printed on the substrate in the step (2) by using ink jet with the diameter of a nozzle of 5-100 micrometers at 15-35 ℃ to form a precursor pattern;

(4) placing the precursor pattern obtained in the step (3) in steam of a polar solvent with the flow rate of 1-100L/min, and reacting at the temperature of 0-100 ℃ for 15-120 s to form a perovskite quantum dot pattern;

and (3) preparing a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film of the ITO glass with the film in the step (2), wherein the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film is positioned on one surface of the ITO glass, and the polyvinyl carbazole film is positioned on the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film.

Technical Field

The invention belongs to the technical field of perovskite quantum dots, and particularly relates to a patterning method of perovskite quantum dots.

Background

The inorganic perovskite quantum dot has the advantages of simple synthesis method, adjustable emission spectrum, narrow half-peak width, high luminous efficiency and capability of covering the whole visible light range, thereby attracting the attention of many fields, particularly the field of display illumination. Compared with an Organic Light Emitting Diode (OLED), the electroluminescent diode (PeLED) taking the inorganic perovskite quantum dots as the light emitting layer has the advantages of high light emitting color purity, adjustable wavelength, high efficiency, good stability, full solution processing and the like, so the PeLED has great potential in the fields of future display, solid state lighting and the like.

Micro LEDs are a new generation of display technology, with higher brightness, better luminous efficiency, but lower power consumption than existing OLED technologies. In 2017, in 5 months, apples have started the development of a new generation of display technology. In 2018, 2 months, samsung released a Micro LED television on CES 2018. With the development and research of inorganic perovskite quantum dots, the PeLED technology has enjoyable achievements in the aspects of preparation process, device efficiency and the like, and the final application target is high-resolution dynamic full-color display. Therefore, the light-emitting layer needs to be processed to a certain extent, that is, the light-emitting layer must include three color light-emitting dots of red (R), green (G) and blue (B) that are aligned side by side, so that the pixel can be formed. Thus, high requirements are put forward on the precision (generally micron level) and accurate positioning of the light-emitting layer and large area. However, conventional patterning methods such as stencil method, transfer printing method, photolithography and the like cannot satisfy this requirement at the same time. The ink-jet printing technology is a low-consumption, high-precision (can reach micron level) and maskless patterning technology, and can realize printing of high-precision pixel points. OLEDs are produced by means of inkjet printing technology (reference: Makoto Mizukami, Seung-Il Cho, Kaori Watanabe, Miho Abiko, Yoshiyuki Suzuri, ShizuoTokito, and Junji Kido, IEEE ELECTRON DEVICE LETTERS 2018.) and QLEDs (reference: Kim, B.H.; Onses, M.S.; Lim, J.B.; Nam, S.; Oh, N.; Kim, H.; Yu, K.J.; Lee, J.W.; Chem J.H.; Kang, S.K.; Lee, C.H.; Lee, J.Shin, J.H.; Kim, N.H.; Leal, C.; Chem Roger, Rong, J.A, Nanolettt, Lee, J.H.; Lee, J.K.; Shin, K.H.; Lee, J.H.; Lee, J.H.; Leal, C.; Chem Kang, Roger, Rong, E, W.K.; Miq.H.; Lee, W.W.K.; Lee, W.H.; Lee, W.H.; Lee, W.W.S.S.S.H.; E, W.S.S.S.S.S.H.; Lee, W.S.S.H.; E, W.S.H.; E, W.H.; E, W.S.S.S, the above requirements cannot be satisfied.

CN109321036A discloses a perovskite quantum dot ink for ink-jet printing and a preparation method thereof, wherein the preparation method of the scheme comprises the following steps: s1, mixing a first precursor of the perovskite raw material with first ink to obtain a first dispersion liquid; s2, mixing a second precursor of the perovskite raw material with second ink to obtain a second dispersion liquid; and S3, mixing the first dispersion liquid and the second dispersion liquid at 140-200 ℃, and reacting to obtain the perovskite quantum dot ink for ink-jet printing. This scheme is direct to carry out the inkjet printing to perovskite quantum dot, because perovskite quantum dot crystal grain grows up and makes inkjet printer's shower nozzle plug up easily, interrupts production easily in the volume production.

CN108192593A discloses an optical film based on an eutectic structure of inorganic perovskite quantum dots and conjugated organic small molecules, wherein in the scheme, the optical film is a composite dispersion liquid formed by dispersing the inorganic perovskite quantum dots and the conjugated organic small molecules in an organic solvent; and forming a film by the composite dispersion liquid through dip-coating, ink-jet printing or spin coating, thus obtaining the optical film based on the eutectic structure of the inorganic perovskite quantum dots and the conjugated organic micromolecules. The scheme has the problems that ink-jet printing is directly carried out on perovskite quantum dots, a nozzle of the ink-jet printer is easily blocked, and high-precision and large-area dot matrix groups cannot be prepared by other methods.

CN109321038A discloses a quantum dot ink based on inkjet printing, wherein the quantum dot ink in this scheme comprises quantum dots and an organic solvent. The quantum dot material comprises a core-shell quantum dot system such as CdS or an inorganic perovskite quantum dot; the organic solvent is a single solvent or a mixed solvent, and is a low-polarity or non-polar solvent. The scheme also has the problems that ink-jet printing is directly carried out on the perovskite quantum dots, the nozzle of the ink-jet printer is easily blocked due to the growth of perovskite quantum dot crystal particles, and the production is easily interrupted in the mass production.

Disclosure of Invention

In view of the above-mentioned shortcomings in the prior art, the present invention aims to provide a patterning method for perovskite quantum dots. The perovskite quantum dot patterning method provided by the invention has high precision, does not block a spray head of a printer, is suitable for large-area patterning,

in order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a patterning method of perovskite quantum dots, which comprises the following steps:

(1) dissolving a perovskite quantum dot precursor in a nonpolar solvent, and printing the obtained precursor solution on a substrate to form a precursor pattern;

(2) and (2) placing the precursor pattern in the step (1) in vapor of a polar solvent for reaction to form a perovskite quantum dot pattern.

According to the perovskite quantum dot patterning method provided by the invention, perovskite quantum dots are not directly printed, but precursors of the perovskite quantum dots are printed firstly, and then the patterned precursors are converted into the perovskite quantum dots. According to the method, the perovskite precursor cannot generate an ionization agglomeration phenomenon in a nonpolar solvent, so that the problem of nozzle blockage caused by direct printing of perovskite quantum dots can be well avoided.

When the patterning method based on in-situ growth is adopted to pattern perovskite quantum dots, firstly, perovskite quantum dot precursors are dissolved in a nonpolar solution to be printed, the perovskite quantum dot precursors do not react in the nonpolar solvent to become quantum dots, and after the patterning method is adopted, vapor of a polar solvent is used to enable the precursors to generate a series of changes such as ionization, crystallization and the like, and the perovskite quantum dots are generated by reaction.

In the present invention, the advantage of using the vapor of the polar solvent without using other phases is that the vapor of the polar solvent does not damage the printed pattern while ensuring the reaction.

The perovskite quantum dot patterning method provided by the invention can be used for preparing the perovskite quantum dot luminescent layer.

The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.

According to a preferred technical scheme of the invention, the perovskite quantum dots are inorganic perovskite quantum dots.

Preferably, the perovskite quantum dots consist of a cation a, a cation B and an anion X. Here, the cation a is an a-site cation of the perovskite, the cation B is a B-site cation of the perovskite, and the anion X is an X anion of the perovskite. ABX is composed of cation A, cation B and anion X₃A perovskite structure.

Preferably, the cation A comprises Cs⁺And/or Rb⁺。

Preferably, the cation B comprises Pb²⁺。

Preferably, the anion X comprises Br^-Any one or a combination of at least two of I-or Cl-, typically but not limited to a combination of Cl^-And Br^-Combination of (A) and (B)^-And I^-Combination of (A) and (B), Cl^-And I^-Combinations of (a), (b), and the like.

Preferably, the perovskite quantum dot precursor of step (1) comprises a cation a precursor, a cation B precursor and optionally an anion X precursor. When the cation a precursor or the cation B precursor contains the anion X, the anion X precursor may not be used.

Preferably, the cation a precursor comprises Cs₂CO₃CsAc (cesium acetate), CsCl, CsBr, CsI, Rb₂CO₃Any one or a combination of at least two of RbAc (rubidium acetate), RbCl, RbBr or RbI.

Preferably, the cationic B precursor comprises PbCl₂、PbBr₂、PbI₂PbO or Pb (Ac)₂(lead acetate) or a combination of at least two thereof.

Preferably, the anionic X precursor comprises NH₄Cl、NH₄Br、NH₄I. Any one or the combination of at least two of CsCl, CsBr, CsI, RbCl, RbBr or RbI;

preferably, in the perovskite quantum dot precursor in the step (1), the molar ratio of the cation a, the cation B and the anion X is (0.9-1.1): 3, such as 0.9:1:3, 0.95:1:3, 1:1:3, 1.1:0.9:3, 1:1.1:3, etc., but not limited to the enumerated values, and other non-enumerated values within the numerical range are equally applicable, preferably 1:1: 3.

In a preferred embodiment of the present invention, the non-polar solvent includes any one or a combination of at least two of octadecene, liquid paraffin, dodecane, octane, or hexane.

Preferably, the concentration of the precursor in the precursor solution is 0.05 to 5mol/L, for example, 0.05mol/L, 0.1mol/L, 0.5mol/L, 1mol/L, 2mol/L, 3mol/L, 4mol/L or 5mol/L, but not limited to the recited values, and other values not recited in the range of the values are also applicable. In the invention, if the concentration of the precursor is too high, the precursor can not react completely; if the precursor concentration is too low, the reaction will produce less quantum dots. In the present invention, the concentration of the precursor refers to the total concentration of all precursors.

As a preferred embodiment of the present invention, the substrate in the step (1) includes a host material.

Preferably, the host material includes any one of ITO glass, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, or a methyl methacrylate film.

Preferably, the host material is cleaned host material.

Preferably, the method of cleaning comprises: and carrying out primary cleaning, ultrasonic cleaning and secondary cleaning on the main body material.

Preferably, the method for one-time cleaning comprises the following steps: and cleaning with a surfactant for 5-10 minutes. The primary wash is aimed at removing large particles. The surfactant for one-time cleaning can be used as a detergent.

Preferably, the method of ultrasonic cleaning comprises: and sequentially carrying out ultrasonic treatment in a surfactant, acetone and isopropanol for 20-40 minutes. The surfactant used herein may be an ITO cleaning solution.

Preferably, the method of secondary cleaning comprises: cleaning with ultraviolet ozone (UV-O)₃A washer).

In a preferred embodiment of the present invention, the main material has a film on one surface thereof. The deposition on the host material contributes to the improvement of the patterning accuracy of the perovskite quantum dot, and also contributes to the subsequent use of the patterned product, for example, when the host material is used as a light-emitting layer, the deposition is a pre-step required for the subsequent use of the light-emitting layer.

Preferably, the film is a film of a non-polar material. Because the precursor solution in the step (1) uses the nonpolar solvent, the nonpolar material film is used, the printing precursor solution can be better infiltrated, the contact angle is smaller, liquid drops are avoided, and the patterning precision is improved.

Preferably, the film includes any one of a Polyvinylcarbazole (PVK) film, a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture (PEDOT: PSS) film, or a zinc oxide film or a combination of at least two thereof, preferably a Polyvinylcarbazole (PVK) film and a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture (PEDOT: PSS) film.

Preferably, when the film is a combination of a polyvinylcarbazole film and a poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film, the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film is located on the host material, and the polyvinylcarbazole film is located on the poly 3, 4-ethylenedioxythiophene-polystyrene sulfonate mixture film.

Preferably, the method of preparing a film on one side of the host material comprises: and dripping the film raw material solution on one surface of the main body material, carrying out spin coating on the main body material, and then annealing.

If a multilayer film is produced, the above process may be repeated.

Preferably, the dropping amount is 60 to 120 microliters, such as 60 microliters, 70 microliters, 80 microliters, 90 microliters, 100 microliters, 110 microliters, or 120 microliters, but not limited to the recited values, and other values in the range of the values are also applicable.

Preferably, the spin coating is performed with a spin coater.

Preferably, the spin coating is performed at a speed of 2000 to 4000 rpm, such as 2000 rpm, 2500 rpm, 3000 rpm, 3500 rpm or 4000 rpm, but not limited to the recited values, and other values not recited in the range are also applicable.

Preferably, the spin coating time is 30 to 60 seconds, for example, 30 seconds, 35 seconds, 40 seconds, 45 seconds, 50 seconds, 55 seconds, 60 seconds, etc., but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the annealing is performed on a hot stage.

Preferably, the annealing temperature is 100 to 140 ℃, for example, 100 ℃, 110 ℃, 120 ℃, 130 ℃ or 140 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.

Preferably, the annealing time is 15 to 20 minutes, such as 15 minutes, 16 minutes, 17 minutes, 18 minutes, 19 minutes, or 20 minutes, but not limited to the recited values, and other values not recited within the range of values are equally applicable.

As a preferable technical solution of the present invention, the printing in the step (1) is ink-jet printing.

Compared with other patterning methods (such as a template method, a transfer printing method, a photoetching method and the like), the method for preparing the dot matrix group with high precision and large area by adopting the ink-jet printing is more favorable.

Preferably, the inkjet printing is performed with an inkjet printer.

Preferably, the inkjet printer is a non-contact inkjet printer.

Preferably, the diameter of the nozzle of the printer is 5 to 100 micrometers, such as 5 micrometers, 10 micrometers, 20 micrometers, 30 micrometers, 35 micrometers, 40 micrometers, 50 micrometers, 60 micrometers, 70 micrometers, 80 micrometers, 90 micrometers or 100 micrometers, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

In a preferred embodiment of the present invention, the printing temperature in the step (1) is 15 to 35 ℃, for example, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, but the printing temperature is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.

In a preferred embodiment of the present invention, the polar solvent in step (2) includes any one or a combination of at least two of water, ethanol, isopropanol, and isobutanol.

In a preferred embodiment of the present invention, the flow rate of the polar solvent vapor in the step (2) is 1 to 100L/min, for example, 1L/min, 10L/min, 25L/min, 50L/min, 75L/min, or 100L/min, but the flow rate is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable. Here, too large a flow of polar solvent vapor may cause the polar solvent vapor to condense into droplets, destroying the printed pattern; if the flow of the polar solvent vapor is too low, incomplete reaction of the precursor may result.

Preferably, the reaction temperature in step (2) is 0 to 100 ℃, for example, 0 ℃, 10 ℃, 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable. Here, if the reaction temperature is too high, decomposition of the formed quantum dots may be caused; if the reaction temperature is too low, the growth rate of the quantum dots is slow.

Preferably, the reaction time in step (2) is 15-120 s, such as 15s, 30s, 50s, 70s, 90s, 100s, 110s or 120s, but not limited to the recited values, and other values not recited in the range of the values are also applicable.

As a further preferred technical scheme of the method of the basic invention, the method comprises the following steps:

(1) cleaning the ITO glass with a surfactant for 5-10 minutes, then sequentially carrying out ultrasonic treatment in the surfactant, acetone and isopropanol for 20-40 minutes, and finally cleaning with an ultraviolet ozone cleaning machine to obtain the cleaned ITO glass;

(2) dripping 60-120 microliters of poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture solution on one surface of the cleaned ITO glass in the step (1), spin-coating for 30-60 seconds at a rotating speed of 2000-4000 revolutions per minute by using a spin coater, annealing for 15-20 minutes at a temperature of 100-140 ℃ on a hot table, dripping 60-120 microliters of polyvinyl carbazole solution on the obtained poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film, spin-coating for 30-60 seconds at a rotating speed of 2000-4000 revolutions per minute by using a spin coater, annealing for 15-20 minutes at a temperature of 100-140 ℃ on the hot table to form a polyvinyl carbazole film, and obtaining the ITO glass with a film as a substrate;

(3) dissolving a cation A precursor, a cation B precursor and an optional anion X precursor in a nonpolar solvent to obtain a precursor solution with the precursor concentration of 0.05-5M, wherein the element ratio of A, B to X in the precursor is 1:1:3, A is Cs⁺B is Pb²⁺X is any one or a combination of at least two of Br-, I-or Cl-, and the precursor solution is printed on the substrate in the step (2) by using ink jet with the diameter of a nozzle of 5-100 micrometers at 15-35 ℃ to form a precursor pattern;

(4) placing the precursor pattern obtained in the step (3) in steam of a polar solvent with the flow rate of 1-100L/min, and reacting at the temperature of 0-100 ℃ for 15-120 s to form a perovskite quantum dot pattern;

and (3) preparing a poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film of the ITO glass with the film in the step (2), wherein the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film is positioned on one surface of the ITO glass, and the polyvinyl carbazole film is positioned on the poly (3, 4-ethylenedioxythiophene) -polystyrene sulfonate mixture film.

Compared with the prior art, the invention has the following beneficial effects:

(1) the patterning method of the perovskite quantum dot provided by the invention realizes patterning based on printing, and the printed precursor pattern is subjected to in-situ reaction to be changed into the perovskite quantum dot pattern, so that the method is high in precision, suitable for large-area perovskite quantum dot patterning, capable of being used for preparing a perovskite quantum dot light-emitting layer, and good in application prospect in the fields of photoelectric display and illumination.

(2) According to the patterning method of the perovskite quantum dots, provided by the invention, the perovskite quantum dots are not directly printed, but precursors of the perovskite quantum dots are printed firstly, and then the patterned precursors are converted into the perovskite quantum dots. The problem of nozzle blockage caused by direct printing of perovskite quantum dots can be well avoided, and the yield of the obtained perovskite quantum dots is over 57%.

Drawings

Fig. 1 is a fluorescence microscope photograph of the patterned perovskite quantum dot provided in example 1 of the present invention.

Detailed Description

In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

The following are typical but non-limiting examples of the invention: