KR102486603B1 - Methods of perovskite-polymer composite particles and perovskite-polymer composite particles prepared thereby - Google Patents

Abstract

The present invention discloses a method for preparing perovskite-polymer composite particles and perovskite-polymer composite particles prepared through the same. The present invention comprises the steps of preparing a perovskite-polymer solution containing a perovskite compound, a polymer material and a solvent; discharging the perovskite-polymer solution from an inkjet nozzle to generate perovskite-polymer droplets; and drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in the collection container. The step of obtaining the perovskite-polymer composite particles in the collection container is characterized by adjusting the porosity of the perovskite-polymer composite particles by adjusting the distance between the nozzle of the inkjet and the collection container .

Description

Method for producing perovskite-polymer composite particles and perovskite-polymer composite particles prepared through the same

The present invention relates to perovskite-polymer composite particles and a method for producing the same, and more particularly, by discharging a perovskite-polymer solution into the air through a nozzle using an inkjet method, and perovskite-polymer A method for producing perovskite-polymer composite particles having uniform size and kinetically stable perovskite-polymer composite particles by drying the solvent included in the droplets for a short time, and the perovskite produced thereby It relates to skyte-polymer composite particles.

Organic-inorganic or inorganic halide perovskites have been developed to have photoelectric conversion efficiencies comparable to commercial solar cells while being applied to solar cells. This is because perovskite materials are suitable for photovoltaic properties such as high absorption coefficient due to direct band gap, long diffusion length of charge carriers with long lifetime, high open circuit voltage due to small exciton binding energy, and low-temperature solution processability. to be. Due to these properties, nano-sized perovskites are very attractive materials for light emitting devices, light detection sensors, and optoelectronic devices.

However, perovskite is vulnerable to moisture, and when even a small amount of moisture in the air is present, the photoelectric conversion efficiency rapidly decreases, resulting in poor stability. Therefore, in order to use perovskite in various fields such as photovoltaics, optoelectronics, biomedicine, and catalyst fields as well as solar cells, it is important to maintain stable properties even in a watery environment.

Among the conventionally proposed methods having stability against moisture as described above, in the most recent method, the hydroxyl group (OH-) on the surface of perovskite meets evaporated methylamine to form a lead hydroxide protective film on the surface to improve water resistance There are methods for synthesizing perovskite materials.

In addition, by preparing the perovskite-polymer composite particles such that the organic-inorganic or inorganic halide perovskite nanoparticles are included inside the polymer particles, the organic-inorganic or inorganic halide perovskite nanoparticles are inside the hydrophobic polymer present, and may have strong resistance to moisture.

However, the above method has a disadvantage of having a synthesis period of about 10 days, and thus has a limitation in that a large amount cannot be rapidly mass-produced.

Korean Patent Registration No. 10-1654790, "Fabrication Method for Multicompartmental Microparticles" Korean Patent Registration No. 10-1977195, "Method for Preparing Porous Polymer Composite Particles" Korean Patent Registration No. 10-1746296, "Perovskite nanocrystal particle emitters having core-shell structure, method of manufacturing the same and electroluminescence devices using the same)"

An embodiment of the present invention provides porous perovskite-polymer composite particles having a uniform diameter by completely evaporating the solvent of the perovskite-polymer droplet in a short time by adjusting the distance between the inkjet nozzle and the collection container It is intended to provide a method for producing perovskite-polymer composite particles that can be made.

In an embodiment of the present invention, perovskite-polymer composite particles can maintain light emission for a long time for oxygen-labile perovskite by controlling the luminescence duration of the perovskite-polymer composite particles by controlling the porosity. It is intended to provide perovskite-polymer composite particles.

An embodiment of the present invention completely evaporates the solvent of the perovskite-polymer droplet in a short time by adjusting the distance between the inkjet nozzle and the collection container to control the porosity of the perovskite-polymer composite particle, thereby making the perovskite - It is intended to provide a method for producing perovskite-polymer composite particles capable of controlling the rate of luminescence loss (the rate at which luminescence disappears) by controlling the amount of solvent penetrating into the polymer composite particles.

In an embodiment of the present invention, when a perovskite-polymer solution is ejected from an inkjet nozzle, by controlling the diameter of perovskite-polymer composite particles by adjusting the frequency or voltage of the inkjet, the density is controlled to form a dense layer. It is intended to provide a method for producing perovskite-polymer composite particles.

In an embodiment of the present invention, when a perovskite-polymer solution is ejected from an inkjet nozzle, uniform particles can be produced by adjusting the dwell time of the inkjet to control the generation rate of perovskite-polymer droplets. It is intended to provide a method for producing perovskite-polymer composite particles.

An embodiment of the present invention is a perovskite-polymer solution capable of producing stable perovskite in the air by controlling the porosity of the perovskite-polymer composite particles by adjusting the viscosity or the concentration of the polymer material. It is intended to provide a method for producing rovsite-polymer composite particles.

A method for producing a perovskite-polymer composite particle according to an embodiment of the present invention includes preparing a perovskite-polymer solution containing a perovskite compound, a polymer material and a solvent; discharging the perovskite-polymer solution from an inkjet nozzle to generate perovskite-polymer droplets; and drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in the collection container. The step of obtaining the perovskite-polymer composite particles in the collection container is characterized by adjusting the porosity of the perovskite-polymer composite particles by adjusting the distance between the nozzle of the inkjet and the collection container .

The perovskite-polymer composite particle production method of perovskite-polymer composite particles, characterized in that the emission duration time is adjusted according to the porosity.

The perovskite compound may be represented by Formula 1 below.

[Formula 1]

AMX ₃

(In Formula 1, A is a monovalent cation, M is a divalent metal cation, and X is a monovalent anion)

A distance between the nozzle of the inkjet and the collection container may range from 5 cm to 30 cm.

When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the diameter of the perovskite-polymer composite particle is adjusted according to the frequency applied to the inkjet, and the frequency may be 600hz to 900hz .

When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the diameter of the perovskite-polymer composite particle is adjusted according to the voltage applied to the inkjet, and the voltage may be 20V to 50V .

When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the generation rate of the perovskite-polymer droplets is controlled according to the dwell time applied to the inkjet, and the dwell time is It may be 28 μs to 32 μs.

When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the pressure applied to the inkjet may be 21 mbar to 34.75 mbar.

The concentration of the polymeric material may be 0.25wt% to 1wt%.

Perovskite-polymer composite particles are prepared by the method for preparing perovskite-polymer composite particles according to an embodiment of the present invention.

The emission duration of the perovskite-polymer composite particle may be adjusted according to the porosity of the perovskite-polymer composite particle.

The perovskite-polymer composite particle may have a combination ratio of the perovskite compound and the polymer material in a range of 1:1 to 1:0.01.

The perovskite-polymer composite particles may have a diameter of 10 μm to 100 μm.

According to an embodiment of the present invention, perovskite-polymer composite particles having a uniform diameter are prepared by completely evaporating the solvent of the perovskite-polymer droplets in a short time by adjusting the distance between the inkjet nozzle and the collection container and additives such as surfactants may be excluded.

According to an embodiment of the present invention, the perovskite-polymer composite particles can maintain light emission for a long time for oxygen-labile perovskite by controlling the light emission duration of the perovskite-polymer composite particles by controlling the porosity. Perovskite-polymer composite particles that can be provided.

According to an embodiment of the present invention, by adjusting the distance between the inkjet nozzle and the collection container to completely evaporate the solvent of the perovskite-polymer droplet in a short time to control the porosity of the perovskite-polymer composite particle, It is possible to provide a method for preparing perovskite-polymer composite particles in which the rate of luminescence loss (the rate at which luminescence disappears) can be controlled by controlling the amount of the solvent penetrating the skyte-polymer composite particles.

According to an embodiment of the present invention, when the perovskite-polymer solution is discharged from the inkjet nozzle, by adjusting the frequency or voltage of the inkjet to adjust the diameter of the perovskite-polymer composite particle, by controlling the density Densely stacked perovskite-polymer composite particles can be provided.

According to an embodiment of the present invention, when the perovskite-polymer solution is ejected from the inkjet nozzle, uniform particles are produced by adjusting the dwell time of the inkjet to control the generation rate of perovskite-polymer droplets It is possible to provide a method for producing perovskite-polymer composite particles that can be performed.

According to an embodiment of the present invention, by adjusting the viscosity of the perovskite-polymer solution or the concentration of the polymer material to control the porosity of the perovskite-polymer composite particles, stable perovskite in the air can be prepared. It is possible to provide a method for producing perovskite-polymer composite particles.

1 is a flow chart showing a method for producing perovskite-polymer composite particles according to an embodiment of the present invention.
2 is a cross-sectional view illustrating an inkjet nozzle for preparing perovskite-polymer composite particles according to an embodiment of the present invention.
3 is a cross-sectional view illustrating an inkjet process for producing perovskite-polymer composite particles according to an embodiment of the present invention.
4 is an image showing a particle generating device for producing perovskite-polymer composite particles according to an embodiment of the present invention.
5 is an optical microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.
6 is a fluorescence microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.
7 is a magnified fluorescence microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.
8 is an image showing a perovskite-polymer droplet photographed through a high-speed camera.
9 is a fluorescence microscope image of measuring water stability over time of a perovskite-polymer composite according to Example 1 of the present invention.
10 is a fluorescence microscope image of perovskite-polymer composite particles according to Example 2 of the present invention.
11 is an image of perovskite-polymer composite particles according to Example 3 of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

Terminology used herein is for describing the embodiments and is not intended to limit the present invention. In this specification, singular forms also include plural forms unless specifically stated otherwise in a phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of one or more other elements or steps in a stated component or step.

As used herein, “embodiments,” “examples,” “aspects,” “examples,” and the like should not be construed as indicating that any aspect or design described is preferred or advantageous over other aspects or designs. It is not.

Also, the term 'or' means 'inclusive or' rather than 'exclusive or'. That is, unless otherwise stated or clear from the context, the expression 'x employs a or b' means any one of the natural inclusive permutations.

Also, the singular expressions “a” or “an” used in this specification and claims generally mean “one or more,” unless indicated otherwise or clear from context to refer to the singular form. should be interpreted as

The terms used in the description below have been selected as general and universal in the related technical field, but there may be other terms depending on the development and / or change of technology, convention, preference of technicians, etc. Therefore, terms used in the following description should not be understood as limiting technical ideas, but should be understood as exemplary terms for describing the embodiments.

In addition, in certain cases, there are also terms arbitrarily selected by the applicant, and in this case, their meanings will be described in detail in the corresponding description section. Therefore, terms used in the following description should be understood based on the meaning of the term and the contents throughout the specification, not simply the name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used in this specification may be used in a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in commonly used dictionaries are not interpreted ideally or excessively unless explicitly specifically defined.

Meanwhile, in the description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted. In addition, the terminology used in this specification is a term used to appropriately express the embodiment of the present invention, which may vary according to the intention of a user or operator or customs in the field to which the present invention belongs. Therefore, definitions of these terms will have to be made based on the content throughout this specification.

1 is a flow chart showing a method for producing perovskite-polymer composite particles according to an embodiment of the present invention.

The method for preparing the perovskite-polymer composite particles according to an embodiment of the present invention includes preparing a perovskite-polymer solution containing a polymer material and a solvent (S110), and the perovskite-polymer solution from the inkjet nozzle. Discharging a polymer solution to generate perovskite-polymer droplets (S120) and drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in a collection container (S130) do.

In addition, in the step of drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in a collection container (S130), the distance between the nozzle of the inkjet and the collection container is adjusted to obtain perovskite-polymer composite particles. Control the porosity of the composite particles.

The porosity of the perovskite-polymer composite particle may refer to the size or number of pores formed in the perovskite-polymer composite particle.

Therefore, the method for producing perovskite-polymer composite particles according to an embodiment of the present invention completely evaporates the solvent of the perovskite-polymer droplets in a short time by adjusting the distance between the inkjet nozzle and the collection container, thereby producing uniform Perovskite-polymer composite particles having a diameter can be prepared.

Moreover, in the method of manufacturing the perovskite-polymer composite particles according to the embodiment of the present invention, since the perovskite-polymer droplets ejected from the nozzle of the inkjet exist in a liquid state only while staying in the air, the perovskite-polymer composite particles The use of a surfactant used to prevent fusion between skyte-polymer droplets can be eliminated. Therefore, it is possible to prevent surface properties of the perovskite-polymer composite particle from being modified by semi-permanent adsorption of the surfactant on the surface of the perovskite-polymer composite particle.

In addition, in the method for producing perovskite-polymer composite particles according to an embodiment of the present invention, the drying time of the perovskite-polymer droplet is very short because the solvent contained in the perovskite-polymer droplet volatilizes. Since this occurs instantaneously, porous perovskite-polymer composite particles can be easily prepared.

First, in the method of manufacturing a perovskite-polymer composite particle according to an embodiment of the present invention, a step (S110) of preparing a perovskite-polymer solution containing a polymer material and a solvent is performed.

The perovskite-polymer solution includes a perovskite compound, and the perovskite compound may be represented by Formula 1 below.

[Formula 1]

AMX ₃

In Formula 1, A is a monovalent cation, M is a divalent metal cation, X may be a monovalent anion, preferably, A is an organic ammonium or alkali metal material, B is a metal material, and X is It may be a halogen element.

For example, A is (CH ₃ NH ₃ )n, ((CzH ₂ z ₊₁ )nNH ₃ ) ₂ (CH ₃ NH ₃ )n, (RNH ₃ ) ₂ , (CnH ₂ n ₊₁ NH ₃ ) ₂ , (CF ₃ NH ₃ ), (CF ₃ NH ₃ )n, ((CzF _2z+1 )nNH ₃ ) ₂ (CF ₃ NH ₃ )n, ((CzF ₂ z ₊₁ )nNH ₃ ) ₂ or (CnF ₂ n _{+ 1} NH ₃ ) ₂ (n is an integer greater than 1, z is an integer greater than 1), M is a divalent transition metal, rare earth metal, alkaline earth metal, Pb, Sn, Ge, Ga, In, Al, Sb , Bi, Po or a combination thereof, and X may be Cl, Br, I or a combination thereof.

The rare earth metal at this time may be, for example, Ge, Sn, Pb, Eu or Yb. Also, the alkaline earth metal may be, for example, Ca or Sr.

Specifically, the perovskite compound is an organic/inorganic hybrid perovskite compound or an inorganic metal halide perovskite compound, depending on the type of A in Formula 1. can be

More specifically, in Formula 1, when A is a monovalent organic cation, the perovskite compound is an organic-inorganic hybrid perovskite compound composed of organic A and inorganic M and X and composed of organic and inorganic materials. can On the other hand, when A in Formula 1 is a monovalent inorganic cation, the perovskite compound may be an inorganic metal halide perovskite compound composed of inorganic materials A, M, and X, and composed entirely of inorganic materials.

In the case of an organic-inorganic hybrid perovskite compound, it has both organic and inorganic advantages, so it has high reproducibility and can improve durability and stability.

On the other hand, when the perovskite compound is an inorganic metal halide perovskite compound, in the case of an inorganic metal halide perovskite compound, durability and stability are higher than that of organic-inorganic hybrid perovskite because organic materials are not used. There are advantages to being higher.

Also, the perovskite compound may be a nanocrystal particle.

For example, the perovskite compound may be CsPbBr _{3 ,} CsPbCl ₃ or CsPbI ₃ .

The size of the perovskite compound, that is, the size of the perovskite nanocrystal particles may range from 1 nm to 900 nm, and when the size of the perovskite compound is less than 1 nm, the band gap by the particle size ( band gap) is changed, it is difficult to control the particle size distribution, and fine control is required, which is disadvantageous to mass production.

When the size of the perovskite compound exceeds 100 μm, there is a problem in that efficiency is reduced due to thermal ionization at room temperature and delocalization of charge carriers.

The perovskite-polymer solution includes a polymer material, and the concentration of the polymer material may be 0.25wt% to 1wt%. At this time, if the concentration of the polymer material is less than 0.25 wt%, the perovskite-polymer droplets are not continuously ejected, and the perovskite-polymer composite particles are too small or difficult to produce a uniform particle size. , If it exceeds 1 wt%, nozzle clogging occurs, it is difficult to control the frequency, dwell time, voltage and pressure, and the perovskite-polymer composite particles scatter, and the size of the perovskite is not uniform. -There is a problem that polymer composite particles are generated.

Preferably, when the concentration of the polymer material is 0.75wt% or 0.5wt%, it is most suitable, and more preferably, when the concentration of the polymer material is 0.5wt, it is easy to prepare perovskite-polymer composite particles. .

In the method of manufacturing perovskite-polymer composite particles according to an embodiment of the present invention, the distance between the inkjet nozzle and the collection container can be adjusted according to the concentration of the polymer material, and the distance between the inkjet nozzle and the collection container can be adjusted. Accordingly, the residence time (drying time) of the perovskite-polymer droplets discharged from the nozzle of the inkjet can be adjusted.

More specifically, since the solvent contained in the perovskite-polymer droplets is completely evaporated between the time the perovskite-polymer droplets are ejected from the nozzle of the inkjet and the time they reach the collection container, the perovskite-polymer The drying time of the droplet may be adjusted according to the distance between the inkjet nozzle and the collection container. Accordingly, the concentration of the polymer material decreases and the amount of the solvent to be evaporated decreases, so that the distance between the inkjet nozzle and the collection container can be reduced, and accordingly, the drying time of the perovskite-polymer droplet can be reduced.

Polymer materials include polystyrene, poly(lactic-co-glycolic acid) (PLGA), cellulose acetate, polyethyleneglycol (PEG), and polyvinylpyrrolidone (PVP). , Alginate, polyacrylonitrile (Polyacrylonitrile, PAN), and polymethacrylate (Polymethacrylate, PMMA).

The perovskite-polymer solution can control the porosity of the perovskite-polymer composite particles by adjusting the combination ratio of the perovskite compound and the polymer material.

Since the perovskite compound has the property of being included and fixed inside the polymer material in the process of drying the perovskite-polymer composite particles, as the content of the perovskite compound increases, the content included and fixed inside increases. can be increased

A volatile solvent may be used as a solvent included in the perovskite-polymer solution, and a frequency, voltage, dwell time or pressure applied to the inkjet may be adjusted according to the concentration of the solvent.

The concentration of the solvent may be 0.5wt% to 1wt%. At this time, if the concentration of the solvent is less than 0.5wt%, there is a problem of having a long residence time because the amount of the solvent is too large, and if it exceeds 1wt%, there is a problem of clogging the nozzle.

In addition, appropriate frequency, pressure and voltage may be adjusted according to the type of solvent included in the perovskite-polymer solution.

Preferably, the solvent is water, methanol, ethanol, propanol, butanol, isopropyl alcohol, isobutyl alcohol, ethylene glycol ，acetone，methylethylketone，cyclohexanone，hexane，diethylamine，triethylamine，octadecylamine，cyclohexane ), ethylacetate, acetone, dimethylformamide, dimethylacetamide, methylene chloride, dichloromethane, chloroform, tetrachloromethane, Dimethylsulfoxide, Dioxin, Nitromethane, Toluene，Xylnene, Dichlorobenzene, Dimethylbenzene, Trimethylbenzene, Methylnaphthalene ( methylnaphthalene), tetrahydrofurane, N-methyl-2-pyrrolidone, pyridine, acrylonitrile, aniline, sorbitol It may include at least one of carbitol, carbitolacetate, methyl cellosolve, and ethyl cellosolve.

In addition, in order to discharge the perovskite-polymer droplets from the inkjet nozzle, appropriate viscosity or surface tension of the perovskite-polymer solution is required, and the viscosity of the perovskite-polymer solution is skyte-polymer can affect the diameter of the droplet. For example, if the viscosity of the perovskite-polymer solution increases, the nozzles can become clogged.

In addition, the viscosity of the perovskite-polymer solution may affect the frequency, voltage, dwell time or pressure applied to the inkjet nozzle. For example, if the viscosity of the perovskite-polymer solution increases, the nozzle may become clogged or the frequency, voltage, and pressure of the perovskite-polymer droplet may increase, and the dwell time may decrease.

Thereafter, in the method for manufacturing perovskite-polymer composite particles according to an embodiment of the present invention, a perovskite-polymer solution is ejected from an inkjet nozzle to generate perovskite-polymer droplets (S120). proceed with

The step of generating perovskite-polymer droplets by ejecting the perovskite-polymer solution from the inkjet nozzle (S120) will be described in detail with reference to FIG. 2 .

2 is a cross-sectional view illustrating an inkjet nozzle for preparing perovskite-polymer composite particles according to an embodiment of the present invention.

The inkjet may include a nozzle 110 for discharging the perovskite-polymer droplet 120 and a piezoelectric element 111 for discharging the perovskite-polymer droplet 120 by contracting the nozzle 110. . In the inkjet, the perovskite-polymer solution injected into the inkjet is discharged as perovskite-polymer droplets 111 through the nozzle 110 by the action of a piezoelectric element, and the discharged perovskite-polymer droplets 120 ) can be dried in air to produce perovskite-polymer composite particles.

Therefore, perovskite-polymer composite particles 140 according to an embodiment of the present invention can easily form perovskite-polymer droplets 120 of uniform size using the piezoelectric element 111, , perovskite-polymer composite particles can be produced in large quantities.

When the perovskite-polymer solution is ejected from the inkjet nozzle 110, the diameter of the perovskite-polymer composite particle may be adjusted according to the frequency applied to the inkjet. More specifically, when the frequency applied to the inkjet is increased, the number of droplets ejected from the inkjet is increased, thereby reducing the size of the perovskite-polymer droplet 120 and reducing the diameter of the perovskite-polymer composite particle. In addition, when the frequency applied to the inkjet is reduced, the number of droplets ejected from the inkjet is reduced, so that the size of the perovskite-polymer droplet 120 and the diameter of the perovskite-polymer composite particle can be increased.

Therefore, when the perovskite-polymer solution is discharged from the inkjet nozzle 110, the number of perovskite-polymer composite particles may be adjusted according to the frequency applied to the inkjet. More specifically, the number of droplets ejected from the inkjet increases when the frequency applied to the inkjet increases, and the number of droplets ejected from the inkjet decreases when the frequency applied to the inkjet decreases.

At this time, the frequency applied to the inkjet may be 600hz to 900hz, and if the frequency is less than 600hz, sufficient force cannot be applied to the perovskite-polymer droplet 120 so that the perovskite-polymer droplet 120 is ejected. If it exceeds 900hz, there is a problem that the maximum frequency cannot be adjusted due to the nature of the machine.

When the perovskite-polymer solution is discharged from the nozzle 110 of the inkjet, the diameter of the perovskite-polymer composite particle may be adjusted according to the voltage applied to the inkjet. More specifically, the voltage applied to the inkjet can act similarly to a large pressure being applied to an orifice, and when the voltage applied to the inkjet is increased, the minimum force required to escape the orifice surface is applied to the tip of the orifice. When the perovskite-polymer droplet 120 is formed, and the voltage is reduced, the voltage is not sufficiently applied to discharge the perovskite-polymer droplet 120, so that the perovskite-polymer droplet 120 There is a problem that it is attached to the solvent in the orifice and cannot be discharged.

In addition, when the polymer solution is ejected from the inkjet nozzle 110, the size of the porous polymer particles may be adjusted according to the voltage applied to the inkjet. More specifically, the size may be increased when the voltage applied to the inkjet is increased, and the size may be decreased when the voltage applied to the inkjet is decreased.

Therefore, the voltage applied to the inkjet may be 20V to 50V, and if the voltage is less than 20V, there is a problem that the polymer droplet is not ejected, and if the voltage exceeds 50V, there is a problem that the nozzle is clogged.

When the perovskite-polymer solution is discharged from the inkjet nozzle 110, the generation speed of the perovskite-polymer droplets 120 may be adjusted according to the dwell time applied to the inkjet. More specifically, since the perovskite-polymer droplet 120 is not generated when the dwell time applied to the inkjet does not exceed a certain value, the perovskite-polymer droplet 120 is not generated. The dwell time is an important factor in order for the liquid droplet 120 to be ejected from the nozzle 110 of the inkjet.

Therefore, when the dwell time is increased, since the rate at which the perovskite-polymer droplets 120 are generated in the perovskite-polymer droplets 120 increases, the perovskite-polymer droplets 120 are placed at the tip of the orifice. ) may jump out convexly and clogging may occur, and conversely, if the dwell time is reduced, the time interval for applying force to the perovskite-polymer droplet 120 is shortened, so that the perovskite- The polymer droplet 120 may not be generated because the polymer droplet 120 does not receive sufficient force to be ejected.

In addition, when the perovskite-polymer solution is ejected from the inkjet nozzle 110, the number of perovskite-polymer composite particles may be adjusted according to the dwell time applied to the inkjet. More specifically, when the dwell time applied to the inkjet increases, the number of perovskite-polymer composite particles increases, and when the dwell time applied to the inkjet decreases, the number of perovskite-polymer composite particles decreases. there is.

Therefore, the dwell time may be 28 μs to 32 μs, and if the dwell time is less than 28 μs, there is a problem that the perovskite-polymer droplet 120 is not generated, and if the dwell time exceeds 32 μs, the perovskite-polymer droplet 120 There is a problem that the nozzle is clogged by

When the perovskite-polymer solution is discharged from the inkjet nozzle, whether or not the perovskite-polymer droplet 120 is generated may be determined according to the pressure applied to the inkjet. More specifically, if an appropriate pressure (mbar) is not applied to the inkjet, the minimum force to be ejected by the surface tension of the solution at the orifice cannot be obtained, so no matter how high the frequency, dwell time and voltage are applied, the perovskite-polymer droplet (120) may not be discharged.

In addition, although the perovskite-polymer droplet 120 is formed in the orifice when the pressure applied to the inkjet is increased, the nozzle 110 is easily clogged in the air, so that perovskite-polymer composite particles can be produced for a long time. Therefore, the pressure applied to the inkjet must be appropriately controlled.

Therefore, when the perovskite-polymer solution is ejected from the inkjet nozzle, the pressure applied to the inkjet may be 21 mbar to 34.75 mbar, and if the pressure is less than 21 mbar, the perovskite-polymer droplet 120 is not ejected. When the pressure exceeds 34.75 mbar, too large perovskite-polymer droplets 120 are generated, resulting in a jetting state in which perovskite-polymer droplets 120 are generated at the tip of the nozzle 110. There is a problem that the nozzle 110 is clogged.

More specifically, when the pressure is less than 21 mbar, the perovskite-polymer droplet 120 may not be discharged out of the nozzle 110 because it cannot be completely filled by the external pressure in the capillary tube.

When the pressure is in the range of 21 mbar to 34.75 mbar, the perovskite-polymer solution is completely filled in the capillary tube, and the nozzle 110 is continuously tightened by adjusting the frequency, dwell time, and voltage to form perovskite-polymer droplets. (120) can be discharged.

However, when the pressure exceeds 34.75 mbar, since the jetting state occurs, perovskite-polymer droplets ( 120) is generated (a process of kinetically stable drying does not occur if it exceeds a certain level), so it is difficult to control the size of the perovskite-polymer droplet 120, so that the perovskite-polymer in the air The droplet 120 hardens and the nozzle 110 can easily become clogged.

Therefore, by controlling the pressure, the polymer solution is generated as perovskite-polymer droplets 120 by tightening the nozzle 110 in the capillary with minimal contact with the air, thereby continuously forming the perovskite-polymer for a long time. Polymer particles can be produced.

As described above, when the perovskite-polymer droplet 120 is ejected from the inkjet nozzle 110, the frequency, voltage, dwell time, and pressure applied to form the perovskite-polymer droplet 120 If it acts as an important factor for drying, and if it is properly adjusted and dried for a sufficient time and distance, uniform perovskite-polymer composite particles can be produced, and continuously stable perovskite-polymer composite particles without clogging of the nozzle 110 Polymer droplets 120 may be generated.

Preferably, in the method of manufacturing perovskite-polymer composite particles according to an embodiment of the present invention, a perovskite-polymer solution is discharged from an inkjet nozzle 110 to form perovskite-polymer droplets 120 When generating, a frequency of 700hz, a voltage of 30v, a dwell time of 30us, and a pressure of 32.75mbar may be applied to the inkjet.

Finally, in the method for producing perovskite-polymer composite particles according to an embodiment of the present invention, perovskite-polymer composite particles are dried in a collection container by drying the perovskite-polymer composite particles (S130) includes

A step of drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in a collection container (S130) will be described with reference to FIG. 3 .

3 is a cross-sectional view illustrating an inkjet process for producing perovskite-polymer composite particles according to an embodiment of the present invention.

The collection container 130 is a place where the produced perovskite-polymer composite particles 140 are obtained, and the small diameter of the perovskite-polymer composite particles 140 minimizes the influence of wind and In order to obtain perovskite-polymer composite particles 140 of , the periphery of the collection container 130 may be blocked.

Drying the perovskite-polymer droplets 120 to obtain the perovskite-polymer composite particles 140 in the collection container 130 (S130) includes the inkjet nozzle 110 and the collection container 130 The porosity of the perovskite-polymer composite particle 140 may be adjusted by adjusting the distance d between the particles.

The perovskite-polymer droplets 120 in which the polymer material and the solvent are mixed stay in the air while being discharged from the nozzle 110 of the inkjet and falling into the collection container 130, and during the residence time, the perovskite-polymer droplets 120 Since the solvent in the polymer droplet 120 evaporates into the air in a short time, the perovskite-polymer composite particle 140 is generated in a thermodynamically unstable state, so the polymer particle can be manufactured without additives such as surfactants. .

In addition, the perovskite-polymer composite particle 140 according to an embodiment of the present invention is discharged from the nozzle 110 of the inkjet to the time it reaches the collection container 130, that is, during the time it stays in the air, Since the solvent contained in the perovskite-polymer droplet 120 is evaporated to form the perovskite-polymer composite particle 140, the distance between the inkjet nozzle 110 and the collection container 130 is adjusted to Lovskite-polymer droplets can be dried in a short time.

That is, since the perovskite-polymer droplet 120 ejected from the inkjet nozzle 110 exists in a liquid state only while staying in the air, the fusion between the perovskite-polymer droplet 120 occurs. The surfactant used to prevent coalescence can be completely excluded, and the time for the solvent contained in the perovskite-polymer droplet 120 to evaporate is very short, so that the perovskite-polymer droplet can be dried in a short time. Since this occurs, the porous perovskite-polymer composite particles 140 can be easily manufactured.

In addition, if a sufficient distance (height) between the nozzle 110 and the collection container 130 is given, the perovskite-polymer composite particles 140 having a uniform diameter can be produced.

The distance between the inkjet nozzle and the collection container may be 5 cm to 30 cm, and if the distance between the inkjet nozzle and the collection container is less than 5 cm, the solvent is not completely evaporated in the perovskite-polymer composite polymer particles 140, and the collection There is a problem in that the polymer particles 140 of the perovskite-polymer composite obtained in the container 130 burst and the polymer droplets 120 stick together, and when the size exceeds 30 cm, the perovskite-polymer composite in the collection container 130 It is difficult to collect the perovskite-polymer composite polymer particles 140 because the polymer composite droplets 120 fall randomly.

The drying time of the perovskite-polymer composite polymer particles 140 may be adjusted according to the size of the particles, and when the diameter of the perovskite-polymer composite droplet 120 is 70 μm, the perovskite-polymer The drying time of the composite polymer particle 140 may be 5 seconds.

Therefore, the perovskite-polymer composite particles 140 prepared by the method of manufacturing the perovskite-polymer composite particles 140 according to an embodiment of the present invention may have a nanometer size smaller than several micrometers. .

The diameter of the perovskite-polymer composite particle 140 prepared by the manufacturing method of the perovskite-polymer composite particle 140 according to an embodiment of the present invention may be 10 μm to 100 μm, and the porous polymer particle 140 ) When the diameter of 10 μm to 15 μm is out of range, the porous polymer particles 140 are not uniform. In particular, when the diameter of the perovskite-polymer composite particle 140 exceeds 100 μm, the perovskite-polymer There is a problem that the composite particle 140 is too large to be applied to industrialization. Preferably, the perovskite-polymer composite particle 140 may have a diameter of 10 μm to 30 μm.

In addition, the duration of light emission of the perovskite-polymer composite particle 140 according to an embodiment of the present invention may be adjusted according to the porosity of the perovskite-polymer composite particle.

In general, perovskite is unstable in air, but perovskite-polymer composite particles can have light emission with some stability in air. At this time, by controlling the size of the pores of the perovskite-polymer composite particles, it is possible to obtain information on the state of the solvent for the particles by adjusting the speed at which the solvent penetrates into the perovskite.

More specifically, when the porosity of the perovskite-polymer composite particle 140 is increased, the light emitting duration may be short because the penetration path into the perovskite-polymer composite particle 140 is wide. When the porosity of the skyte-polymer composite particle 140 is reduced, a path penetrating into the perovskite-polymer composite particle 140 is narrowed, and thus the duration of light emission may be reduced.

In addition, when the perovskite-polymer composite particle 140 is exposed to a specific solvent according to its porosity, the emission duration may vary. Therefore, by adjusting the porosity of the perovskite-polymer composite particle 140 according to the manufacturing method of the perovskite-polymer composite particle 140 according to an embodiment of the present invention, the sensitivity of the solvent sensor can be adjusted

For example, when the perovskite-polymer composite particle 140 according to an embodiment of the present invention is exposed to water, it has a light emission duration of 10 seconds, and when exposed to ethanol, methanol or isopropyl alcohol, it emits light for 1 second. It has a luminescence duration and can have a luminescence duration of 10 minutes when exposed to decaine.

The perovskite-polymer composite particle 140 according to an embodiment of the present invention manufactured according to the method for manufacturing the perovskite-polymer composite particle 140 according to an embodiment of the present invention may be used in a sensor.

Perovskite-polymer composite particles 140 according to an embodiment of the present invention can improve the sensitivity of the sensor by adjusting the permeation rate of water or solvent penetrating into the inside by adjusting the porosity.

In addition, the perovskite-polymer composite particle 140 according to an embodiment of the present invention adjusts the diameter of the perovskite-polymer composite particle 140 by adjusting the frequency or voltage of the inkjet, so that the perovskite - By reducing the diameter of the polymer composite particle 140 and attaching it densely, the size of the sensor can be reduced.

In the method of manufacturing the perovskite-polymer composite particle 140 according to an embodiment of the present invention, perovskite-polymer droplets 120 are uniformly formed dropwise, and the formed perovskite-polymer droplets ( 120) prepared by rapidly drying in air, the coefficient of variation (CV) for the diameter of the perovskite-polymer composite particle 140 may be 5% to 50%.

At this time, the smaller the coefficient of variation value means that the perovskite-polymer composite particles 140 are manufactured uniformly, and the larger the coefficient of variation value means that the perovskite-polymer composite particles 140 are manufactured non-uniformly. .

The perovskite-polymer composite particle 140 according to an embodiment of the present invention has surface properties expressed as hydrophobicity or hydrophobic, which is a characteristic of a polymer material such that a plastic material is not wetted by water. It is applied to the 　 compound, and a polymer material such as polystyrene blocks the inflow of water molecules so that the perovskite compound contained inside does not come into contact with water molecules, so that it can have moisture resistance.

[Example 1]: Preparation of PS and CsPbBr ₃

0.5 g of polystyrene (PS) was added to 100 mL of CsPbBr ₃ /chloroform and dissolved for 1 hour to prepare a 0.5 wt % perovskite-polymer solution, PS/CsPbBr ₃ solution. Then, 40 mL of the PS/CsPbBr ₃ solution was put into the chemical solution tank.

After driving the pump by applying a pressure of 100 mbar to the chloroform solution tank, the inside of the tube was cleaned for 10 minutes.

After a stabilization period of 5 minutes after installation of the nozzle, the PS/CsPbBr ₃ solution was ejected using a droplet ejection device to form PS/CsPbBr ₃ droplets, and the state of PS/CsPbBr ₃ droplet formation was confirmed with a high-speed camera. At this time, the nozzle is made of PTFE, the number of holes is 1, and the hole diameter is 70 μm.

Porous PS particles formed by drying the PS/CsPbBr ₃ droplets were collected in a collection vessel.

Porous PS/CsPbBr ₃ particles were prepared using the particle generating device shown in FIG. 5 .

[Example 2]: Preparation of PS and CsPbCl ₃

It was prepared in the same manner as in Example 1 except that CsPbCl ₃ was used as the perovskite.

[Example 3]: Preparation of PS and CsPbI ₃

It was prepared in the same manner as in Example 1, except that CsPbI ₃ was used as the perovskite.

4 is an image showing a particle generating device for producing perovskite-polymer composite particles according to an embodiment of the present invention.

The particle generating device includes an inkjet nozzle, a function generator, a pneumatic device, a high-speed camera, and a strobe illumination device.

Perovskite-polymer composite particles according to an embodiment of the present invention are produced by adjusting the frequency, pressure, dwell time or voltage applied to the inkjet nozzle of the particle generating device, and the distance between the inkjet nozzle and the collection container to obtain perovskite particles. Skyte-polymer composite particles were prepared.

5 is an optical microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.

Referring to FIG. 5, it can be seen that a large amount of perovskite-polymer composite particles prepared according to Example 1 of the present invention having a uniform size can be obtained.

6 is a fluorescence microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.

Referring to FIG. 6 , it can be seen that the perovskite-polymer composite particles prepared according to Example 1 of the present invention having a uniform size distribution emit green light well.

7 is a magnified fluorescence microscope image of perovskite-polymer composite particles according to Example 1 of the present invention.

Referring to Figure 7, it can be seen that the perovskite-polymer composite particles prepared according to Example 1 of the present invention are well formed with spherical particles of uniform size.

8 is an image showing a perovskite-polymer droplet photographed through a high-speed camera.

Referring to FIG. 8 , it can be seen that the method of manufacturing perovskite-polymer composite particles according to Example 1 of the present invention easily discharges perovskite-polymer droplets into the air without clogging the nozzle.

9 is a fluorescence microscope image of measuring water stability over time of a perovskite-polymer composite according to Example 1 of the present invention.

9 shows that the perovskite-polymer composite according to Example 1 of the present invention was measured every minute, and the perovskite-polymer composite according to Example 1 of the present invention has stability against moisture even after 10 minutes can know that

10 is a fluorescence microscope image of perovskite-polymer composite particles according to Example 2 of the present invention.

Referring to FIG. 10, it can be seen that the perovskite-polymer composite particles prepared according to Example 2 of the present invention emit blue light well.

11 is an image of perovskite-polymer composite particles according to Example 3 of the present invention.

Referring to FIG. 11, it can be seen that the perovskite-polymer composite particles prepared according to Example 3 of the present invention emit red light well.

As described above, although the present invention has been described by the limited embodiments and drawings, the present invention is not limited to the above embodiments, and those skilled in the art in the field to which the present invention belongs can make various modifications and variations from these descriptions. this is possible Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by not only the claims to be described later, but also those equivalent to these claims.

110: nozzle 111: piezoelectric element
120: perovskite-polymer droplet 130: collection container
140: perovskite-polymer composite particles

Claims (13)

Preparing a perovskite-polymer solution containing a perovskite compound, a polymer material and a solvent;
discharging the perovskite-polymer solution from an inkjet nozzle to generate perovskite-polymer droplets; and
drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in a collection container;
including,
Drying the perovskite-polymer droplets to obtain perovskite-polymer composite particles in the collection container may include adjusting the distance between the nozzle of the inkjet and the collection container to obtain the perovskite-polymer composite particles. A method for producing perovskite-polymer composite particles, characterized in that the porosity of the composite particles is controlled.
According to claim 1,
The perovskite-polymer composite particle production method of perovskite-polymer composite particles, characterized in that the emission duration time is adjusted according to the porosity.
According to claim 1,
The perovskite compound is a method for producing a perovskite-polymer composite particle, characterized in that represented by the following formula (1).
[Formula 1]
AMX ₃
(In Formula 1, A is an organic ammonium or alkali metal material, M is a divalent metal cation, and X is a halogen element)
According to claim 1,
The method for producing perovskite-polymer composite particles, characterized in that the distance between the nozzle of the inkjet and the collection container is 5 cm to 30 cm.
According to claim 1,
When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the diameter of the perovskite-polymer composite particle is adjusted according to the frequency applied to the inkjet,
The frequency is perovskite, characterized in that 600hz to 900hz - method of producing polymer composite particles.
According to claim 1,
When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the diameter of the perovskite-polymer composite particle is adjusted according to the voltage applied to the inkjet,
The voltage is 20V to 50V, characterized in that perovskite-method of producing a polymer composite particle.
According to claim 1,
When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the generation rate of the perovskite-polymer droplets is controlled according to the dwell time applied to the inkjet,
The dwell time is a method for producing perovskite-polymer composite particles, characterized in that 28μs to 32μs.
According to claim 1,
When the perovskite-polymer solution is discharged from the nozzle of the inkjet, the pressure applied to the inkjet is 21 mbar to 34.75 mbar.
According to claim 1,
Method for producing perovskite-polymer composite particles, characterized in that the concentration of the polymer material is 0.25wt% to 1wt%.
Claims 1 to 9 according to any one of the perovskite-perovskite-polymer composite particles produced by the production method of the polymer composite particles.
According to claim 10,
The perovskite-polymer composite particle, characterized in that the light emission duration of the perovskite-polymer composite particle is adjusted according to the porosity of the perovskite-polymer composite particle.
delete According to claim 10,
Perovskite-polymer composite particles, characterized in that the diameter of the particles of the perovskite-polymer composite particles is 10 μm to 100 μm.

Images