阅读说明：本技术 甲脒卤化铅钙钛矿量子点的制备方法 (preparation method of formamidine lead halide perovskite quantum dots ) 是由 增田泰造 佐佐木清人 沈青 刘锋 张耀红 丁超 于 2019-05-22 设计创作，主要内容包括：本发明涉及甲脒卤化铅钙钛矿量子点的制备方法。提供能够制备实现比从前高的发光量子产率的甲脒卤化铅钙钛矿量子点的方法。本发明的方法包括：制备卤化铅溶液的工序,使卤化铅(II)、油酸和油胺溶解在非极性溶剂中；制备甲脒溶液的工序,使甲脒醋酸盐和油酸溶解在非极性溶剂中；形成量子点的工序,将甲脒溶液和卤化铅溶液混合；和对形成了量子点的混合液进行离心分离,将得到的沉淀物分散在非极性溶剂中,将得到的粗量子点溶液与醋酸甲酯混合,然后进行离心分离,得到作为精制的量子点的沉淀物的工序。通过在60℃～90℃的温度条件下向甲脒溶液中注入卤化铅溶液,从而稳定地形成具有耐久性的量子点。(The invention relates to a preparation method of formamidine lead-perovskite halide quantum dots. Provided is a method capable of producing lead perovskite halide quantum dots which achieve a higher luminescence quantum yield than ever. The method of the invention comprises the following steps: a step for preparing a lead halide solution by dissolving a lead halide (II), oleic acid and oleylamine in a nonpolar solvent; a step of preparing a formamidine solution by dissolving formamidine acetate and oleic acid in a nonpolar solvent; a step of forming quantum dots, in which a formamidine solution and a lead halide solution are mixed; and a step of obtaining a precipitate as a purified quantum dot by centrifuging the mixed solution in which the quantum dot is formed, dispersing the obtained precipitate in a nonpolar solvent, mixing the obtained crude quantum dot solution with methyl acetate, and then centrifuging the mixture. The durable quantum dots are stably formed by injecting a lead halide solution into a formamidine solution at a temperature of 60 to 90 ℃.)

1. A method for preparing formamidine lead halide perovskite quantum dots comprises the following steps:

A step for preparing a lead halide solution by dissolving a lead halide (II), oleic acid and oleylamine in a nonpolar solvent;

A step of preparing a formamidine solution by dissolving formamidine acetate and oleic acid in a nonpolar solvent;

A step of forming formamidine lead halide perovskite quantum dots, wherein the formamidine solution and the lead halide solution are mixed; and

And a step of purifying the quantum dots, in which a mixture solution of the formamidine solution and the lead halide solution in which the quantum dots are formed is centrifuged, the obtained precipitate is dispersed in a nonpolar solvent, the obtained crude quantum dot solution is mixed with methyl acetate, and then the crude quantum dot solution mixed with the methyl acetate is centrifuged to obtain a precipitate as the purified quantum dots.

2. The method according to claim 1, wherein, in the step of purifying the quantum dots, the volume ratio of the methyl acetate to the crude quantum dot solution when mixed is about 1: 1.

3. The method according to claim 1 or 2, wherein the formamidine solution and the lead halide solution are mixed at a temperature of 60 to 90 ℃ in the step of forming the quantum dots.

4. The method according to any one of claims 1 to 3, wherein, in the step of forming the quantum dots, the formamidine solution and the lead halide solution are mixed by injecting the lead halide solution into the formamidine solution.

5. a method for preparing formamidine lead halide perovskite quantum dots comprises the following steps:

A step for preparing a lead halide solution by dissolving a lead halide (II), oleic acid and oleylamine in a nonpolar solvent;

A step of preparing a formamidine solution by dissolving formamidine acetate and oleic acid in a nonpolar solvent; and

and a step of forming formamidine lead halide perovskite quantum dots, in which the lead halide solution is injected into the formamidine solution heated to 60-90 ℃.

6. The method according to any one of claims 1 to 5, wherein, in the step of forming the quantum dot, the ratio of the molar ratio of the lead ion to the formamidine ion is 1: 3.75-1: 15, mixing the formamidine solution and the lead halide solution.

7. The method according to claim 6, wherein, in the step of forming the quantum dot, the ratio of the molar ratio of the lead ion to the formamidine ion is about 1: 11.25 mixing the formamidine solution and the lead halide solution.

Technical Field

The present invention relates to a method for preparing quantum dots, and more particularly, to a method for preparing formamidine lead halide perovskite quantum dots.

Background

In recent years, perovskite quantum dots (quantum dots having a perovskite crystal structure) have attracted attention as fluorescent materials having a high luminescence quantum yield (photoluminescence quantum yield: the ratio of the number of photons emitted from a substance to the number of photons absorbed by the substance) and capable of adjusting the luminescence wavelength in a relatively wide range. As to the perovskite quantum dots, it is known that perovskite quantum dots formed using a plurality of components, particularly perovskite quantum dots composed of formamidine lead halide such as formamidine lead iodide, have a high emission quantum yield, have a characteristic of continuously absorbing light in a region on a shorter wavelength side than the emission wavelength thereof with an emission wavelength region of about 800nm, and have a narrow width of the emission wavelength region (the full width at half maximum of the peak in the emission wavelength region in the emission spectrum is about 50nm or less), and therefore, energy of a wide wavelength region component such as sunlight can be absorbed, the energy can be compressed at a high density, and the absorbed energy can be emitted as light of a specific relatively narrow wavelength region component (spectrum compression), and therefore, application to various technologies utilizing solar energy is expected. An example of a method for producing such a perovskite quantum dot composed of lead formamidine halide and an example of application thereof to an LED are described in, for example, non-patent document 1. Patent document 1 discloses an example of perovskite crystal particles made of lead formamidine halide or the like which can also be used as quantum dots. Patent document 2 discloses: a light-absorbing layer formed by mixing a perovskite compound composed of lead formamidine halide or the like and quantum dots composed of lead sulfide or the like is used to form a photoelectric conversion element and a solar cell having excellent durability and photoelectric conversion efficiency in the near infrared region.

Disclosure of Invention

Problems to be solved by the invention

In brief, non-patent document 1 reports: when a perovskite quantum dot having an emission wavelength peak of 770-780nm and a luminescence quantum yield of more than 70% is prepared by forming a formamidine lead perovskite quantum dot in a lead iodide solution by injecting a FA acetic acid solution (formamidine acetate/oleic acid/octadecane solution) into a heated lead iodide solution (lead (II) iodide powder/oleic acid/oleylamine/octadecane mixed solution) (thermal injection method) and further dispersing the crude product in an acetonitrile solution (toluene: acetonitrile 3: 1) and centrifuging the dispersion to remove impurities, followed by purification. In this regard, the present inventors have found, in their studies, that formamidine lead perovskite halide quantum dots that achieve a higher luminescence quantum yield (about 80% to 100%) than before can be produced by improving a method of removing impurities from a crude product of the quantum dots and purifying the crude product. Further, according to experiments conducted by the present inventors, when quantum dots are produced by the method of non-patent document 1, the solution often becomes transparent and loses its light-emitting ability after about 2 hours from the production (as described later, the measured value of the luminescence quantum yield is also 0%). This is considered to be caused by low durability of the formed quantum dot and early decomposition of the quantum dot. Therefore, the present inventors have studied a method for forming quantum dots, and as a result, have found a method for forming quantum dots, which can stably form formamidine lead perovskite halide quantum dots that maintain a luminescence quantum yield without losing luminescence ability for at least 1 month.

accordingly, an object of the present invention is to provide a method for producing quantum dots capable of producing formamidine lead perovskite halide quantum dots that achieve a higher luminescence quantum yield than before.

Another object of the present invention is to provide a method for producing quantum dots, which can form highly durable formamidine lead-haloperovskite quantum dots that can maintain luminescence quantum yield without losing luminescence ability for 1 month or more stably than before.

means for solving the problems

According to one embodiment of the present invention, the above object is achieved by a method for producing formamidine lead-perovskite halide quantum dots, comprising:

A step for preparing a lead halide solution by dissolving a lead halide (II), oleic acid and oleylamine in a nonpolar solvent;

A step of preparing a formamidine solution by dissolving formamidine acetate and oleic acid in a nonpolar solvent;

A step of forming formamidine lead halide perovskite quantum dots, in which the formamidine solution and the lead halide solution are mixed; and

And a step of purifying the quantum dots, in which a mixture solution of the formamidine solution and the lead halide solution in which the quantum dots are formed is centrifuged, the obtained precipitate is dispersed in a nonpolar solvent, the obtained crude quantum dot solution is mixed with methyl acetate, and the crude quantum dot solution mixed with the methyl acetate is centrifuged to obtain a precipitate as the purified quantum dots.

In the above-described configuration, the "formamidine lead perovskite halide quantum dot" is a quantum dot in which Formamidine (FA) ions, halogen ions, and lead ions form a perovskite crystal structure. The halogen ion is typically an iodide ion, but is not limited thereto, and at least a part of the halogen ion may be a bromide ion or a chloride ion instead of the iodide ion. Thus, the lead (II) halide is typically lead (II) iodide, at least a portion of which may be lead (II) bromide or lead (II) chloride. The nonpolar solvent in the "step of preparing a lead halide solution" and the "step of preparing a formamidine solution" may be any solvent in which a solute such as lead (II) halide, oleic acid, oleylamine, and formamidine acetate is dispersed and dissolved, and may be typically any nonpolar solvent having a boiling point higher than the temperature required for the dispersion and dissolution treatment of the solute, and the dehydration and deoxidation treatment in the solvent (for example, about 120 ℃ or 130 ℃) and capable of stably dispersing the solute in the solution, such as octadecane. In the step of preparing the lead halide solution and the step of preparing the formamidine solution, it is preferable to perform dehydration treatment and/or deoxidation treatment by performing degassing treatment while heating as appropriate. The "nonpolar solvent" used in the "step of purifying the quantum dots" may be any nonpolar solvent such as toluene in which formamidine lead perovskite halide quantum dots formed by mixing a formamidine solution and a lead halide solution are stably dispersed in a colloidal state. In the following description, the term "quantum dot" refers to a formamidine lead-perovskite quantum dot unless otherwise specified.

In the above-described method for producing quantum dots according to the present invention, as a step of purifying the quantum dots formed in the mixed solution by mixing the lead halide solution in which the lead halide (II) is dissolved in the nonpolar solvent together with the formamidine solution in which the formamidine acetate and the oleic acid are dissolved in the nonpolar solvent, the mixed solution in which the quantum dots are formed is centrifuged as described above, the obtained precipitate is dispersed in the nonpolar solvent to prepare the crude quantum dot solution, the crude quantum dot solution is mixed with methyl acetate, and the mixed solution is centrifuged. In this way, impurities in the crude quantum dot solution, for example, lead (II) halide, formamidine acetate, ions thereof, oleic acid, and solutes such as oleylamine, which do not form quantum dots, are contained in the supernatant, and quantum dots are obtained as precipitates. When the quantum dots (precipitates) obtained here are dispersed in a nonpolar solvent such as toluene and the luminescence quantum yield is measured, surprisingly, it is found that a value (80% to 100%) that greatly exceeds the luminescence quantum yield (about 70%) of quantum dots prepared by the conventional method is obtained. That is, it was found that when quantum dots were purified from a crude quantum dot solution, quantum dots that achieved luminescence quantum yields that greatly exceeded previous luminescence quantum yields could be produced by using only methyl acetate as a solvent for purification. Further, it was found that: in the case of using methyl acetate, as described in the present invention, it is necessary to repeat the operation of dispersing into an acetonitrile solution and centrifuging at least 2 times, but in the case of using methyl acetate, the solute which does not form quantum dots is removed by only 1 centrifugation after mixing the crude quantum dot solution with methyl acetate, and quantum dots exhibiting the above-mentioned emission quantum yield of 80% to 100% can be produced. In the step of purifying the quantum dots, the volume ratio of the crude quantum dot solution to methyl acetate when mixed is typically about 1: 1.

Further, as a result of the studies conducted by the inventors of the present invention concerning the step of forming quantum dots in the above-described method for producing quantum dots according to the present invention, it was found that quantum dots having high durability and maintaining the luminescence quantum yield can be formed without losing the luminescence ability for 1 month or more continuously when the formamidine solution and the lead halide solution are mixed at a temperature of 60 to 90 ℃. Therefore, in the step of forming the quantum dots in the method of the present invention, the formamidine solution and the lead halide solution are preferably mixed at a temperature of 60 to 90 ℃.

Further, as for the process of forming the quantum dots, according to the study conducted by the inventors of the present invention, it was found that: preferably, lead ion (Pb)²⁺) The molar ratio to formamidine ions was 1: 3.75-1: 15, more preferably, the molar ratio of lead ions to formamidine ions is from about 1: 11.25, quantum dots having durability as described above and exhibiting a luminescence quantum yield of 80% to 100% can be formed. Therefore, in the above-mentioned inventionIn the step of forming quantum dots in the method of the present invention, it is preferable that the molar ratio of lead ions to formamidine ions is 1: 3.75-1: 15, more preferably in such a manner that the molar ratio of lead ions to formamidine ions is from about 1: 11.25 the formamidine solution and lead halide solution were mixed.

In the mixing of the formamidine solution and the lead halide solution used for the formation of the above-described quantum dots, in order to form the quantum dots which have durability and exhibit a luminescence quantum yield of 80% to 100% as described above, it is preferable that formamidine ions are considerably larger than lead ions in the molar ratio in the mixed solution, and it is preferable that the volume amount of the formamidine solution is considerably larger than the volume amount of the lead halide solution. Furthermore, it is preferred that the formamidine solution and the lead halide solution are mixed as rapidly as possible. In this regard, as in the conventional method, when the formamidine solution is injected into the heated lead halide solution using a syringe or the like, the solution is mixed quickly, but when a large amount of the formamidine solution to be injected is filled into the syringe or the like, the temperature is lowered, and then when the formamidine solution is injected into the lead halide solution, the temperature of the mixed solution is easily lowered, and thus it is difficult to stably form quantum dots having durability with good reproducibility. Therefore, the inventors of the present invention have conducted studies and found that a quantum dot having durability can be stably formed with good reproducibility by injecting a lead halide solution into a heated formamidine solution (in this case, the amount of the lead halide solution injected is smaller than that of the formamidine solution in terms of volume amount, and therefore the temperature of the mixed solution is less likely to decrease and the mixing of the solution is rapidly achieved.). Therefore, in the step of forming the quantum dots in the method of the present invention described above, it is preferable that the formamidine solution and the lead halide solution be mixed by injecting the lead halide solution into the formamidine solution.

further, according to the above knowledge, quantum dots having durability are stably formed with good reproducibility by injecting a lead halide solution into a formamidine solution. In another aspect of the present invention, the above object is achieved by a method for producing formamidine lead perovskite quantum dots, comprising:

a step for preparing a lead halide solution by dissolving a lead halide (II), oleic acid and oleylamine in a nonpolar solvent;

A step of preparing a formamidine solution by dissolving formamidine acetate and oleic acid in a nonpolar solvent; and

And a step of forming formamidine lead halide perovskite quantum dots, in which the lead halide solution is injected into the formamidine solution heated to 60 to 90 ℃.

Effects of the invention

thus, according to the present invention described above, in the method for producing quantum dots, in the step of purifying the quantum dots from the crude quantum dot solution, methyl acetate is used as a solvent for purification without using an acetonitrile solution, whereby lead-camtite formamidine halide quantum dots having emission wavelength characteristics in which the emission wavelength region is around 800nm and the full width at half maximum of the peak in the emission wavelength region is around 50nm or less can be produced, and a higher emission quantum yield than before can be achieved. In the step of purifying the quantum dots, the operation of mixing with methyl acetate and centrifugal separation can be performed only 1 time, and thus there are advantages in that the production process is shortened and the amount of solvent used is reduced. In addition, in the step of mixing the formamidine solution and the lead halide solution to form the quantum dots, the lead halide solution is injected into the formamidine solution, so that the molar ratio of the lead ions to the formamidine ions and the temperature condition which are preferable for the formation of the quantum dots can be satisfied, and the quantum dots with durability can be stably formed with good reproducibility.

Other objects and advantages of the present invention will become more apparent from the following description of the preferred embodiments of the present invention.

drawings

Fig. 1(a) of fig. 1 is a view schematically showing the appearance of a step of mixing a lead halide solution and a formamidine solution to form quantum dots in the method for producing quantum dots according to the present invention. Fig. 1(B) is a schematic diagram of a quantum dot formed in the method of the present invention. Fig. 1(C) is a diagram schematically showing the procedure of purifying quantum dots in the method of the present invention.

Fig. 2 is a schematic diagram of a system for measuring the quantum yield of the quantum dot prepared in the present embodiment.

Fig. 3 shows a luminescence spectrum of a quantum dot prepared according to the method of preparing a quantum dot according to the present invention. The ratio of each curve in the figure represents the mixed molar ratio of lead ions to formamidine ions (lead ions/formamidine ions).

Description of the reference numerals

10 … three-neck flask

12 … cover heater

14 … temperature sensor

16 … Syringe

18 … gas delivery pipe

Detailed Description

Several preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings. In the drawings, the same reference numerals denote the same parts.

Preparation process of quantum dots

In the preparation of the formamidine lead-perovskite halide quantum dot according to the invention, the following steps are carried out: (a) the preparation method comprises the following steps of (a) preparing a lead halide solution, (b) preparing a formamidine solution, (c) mixing the lead halide solution and the formamidine solution (forming quantum dots), and (d) refining the quantum dots. The respective steps will be described in more detail below.

(a) Preparation of lead halide solutions

In the preparation of the lead halide solution, powders of the lead halide (II) are mixed in a nonpolar solvent, and further, oleic acid and oleylamine are added and mixed until the lead halide (II) is completely dissolved. As the lead (II) halide, typically, lead (II) iodide, at least a part of which may be lead (II) bromide or lead (II) chloride. The nonpolar solvent is typically octadecane or the like, and may be any solvent that dissolves lead (II) halide, formamidine acetate, oleic acid, and oleylamine. Further, since moisture and oxygen in the nonpolar solvent are preferably removed, the nonpolar solvent or the nonpolar solvent mixed with lead halide may be degassed under a temperature condition of, for example, water evaporation, for example, 120 to 130 ℃, subjected to dehydration deoxidation treatment, and then filled with nitrogen (nitrogen substitution). In the case of oleic acid and oleylamine, it is preferable to add them after dehydration deoxidation treatment and nitrogen substitution in order to avoid their denaturation as much as possible. The solution in which the lead (II) halide is dissolved (lead halide solution) may be stored at room temperature under a nitrogen atmosphere until later use.

(b) Preparation of the formamidine solution

In the preparation of the formamidine solution, formamidine acetate was mixed in a non-polar solvent and oleic acid was added. The nonpolar solvent may typically be octadecane or the like, as in the case of the lead halide solution. The solution in which formamidine acetate and oleic acid are mixed is also preferably subjected to dehydration and deoxidation treatment by removing water and oxygen from the nonpolar solvent, and therefore, it is possible to store the solution at room temperature under a nitrogen atmosphere until it is used later by performing deaeration at room temperature, followed by nitrogen substitution and deaeration at a temperature at which water is evaporated, for example, at about 120 ℃.

(c) Mixing of lead halide solution with formamidine solution (formation of quantum dots)

The lead halide solution and the formamidine solution prepared as described above are mixed at a higher temperature than room temperature, specifically at 60 to 90 ℃, thereby forming formamidine lead halide perovskite quantum dots in the mixed solution. In this regard, the inventors of the present invention have conducted studies and found that: as schematically shown in FIG. 1A, a lead halide solution is injected into a formamidine solution kept at 60 to 90 ℃ in a flask 10 or the like by using a mantle heater 12 or the like, and lead ions (Pb) are injected by using a syringe 16²⁺) The molar ratio to Formamidine (FA) ion became 1: 3.75-1: 15, the quantum dot having a stable light-emitting ability for a long period of time, specifically, having little change in light-emitting ability even after 1 month of production, can be formed. Therefore, in the present embodiment, it is preferable that the lead halide solution is injected into the formamidine solution kept at 60 to 90 ℃ by using the syringe 16 as described above to mix the two solutions (in the conventional method (the method of non-patent document 1 and the like), the formamidine solution is injected into the lead halide solution kept at 80 ℃ in the flask by using the syringe, and lead ions (Pb) are injected²⁺) The molar ratio to Formamidine (FA) ion became 1: 2.7, in this case, after preparation, the solution becomes transparent and loses its light-emitting ability after about 2 hours. This is considered perhaps to be forMeets Pb²⁺: FA is 1: 2.7 when a relatively large amount of formamidine solution was filled into the syringe, the temperature of the solution was lowered to around room temperature, and the formamidine solution was injected into the lead halide solution in this state, so that the temperature at the time of mixing the lead halide solution and the formamidine solution was lowered, and it became difficult to form stable quantum dots. ). Further, the mixing of the lead halide solution and the formamidine solution is preferably performed in a degassed state or under a nitrogen atmosphere in order to avoid mixing of moisture and oxygen in the air. The temperature at the time of mixing the two solutions is monitored by a temperature sensor 14 or the like, and degassing or nitrogen filling in the flask can be performed through a gas transfer tube 18. Then, after the lead halide solution and the formamidine solution are mixed, quantum dots, which are fine particles of formamidine lead-perovskite halide crystals whose surroundings are covered with ligands (oleic acid, oleylamine), are formed relatively quickly, for example, for about 1 minute as schematically depicted in fig. 1(B), and therefore, thereafter, the reaction of forming quantum dots is stopped by cooling to room temperature or less.

(d) Purification of Quantum dots

The quantum dot targeted by the present invention is formed in the mixed solution of the lead halide solution and the formamidine solution, but the precursor such as unreacted lead ions, formamidine ions, halogen ions, etc., which has not yet formed the quantum dot, remains, and the apparent light emission capability of the quantum dot is decreased (the unreacted precursor reabsorbs light emitted from the quantum dot, etc., and fluorescence emitted from the solution containing the quantum dot is decreased). Therefore, a quantum dot purification step for removing unreacted precursors from the mixed solution in which quantum dots are formed, that is, quantum dot cleaning, is performed. In this regard, in a conventional method (a method of non-patent document 1 or the like), the mixed solution is centrifuged, the precipitate is collected and redispersed in toluene (a crude quantum dot solution), and acetonitrile is added to the crude quantum dot solution to adjust the ratio of toluene: acetonitrile 3: the present inventors have found that a quantum dot dispersion solution exhibiting an emission quantum yield of up to about 70% can be obtained by destabilizing the colloid, centrifuging the mixture, discarding the supernatant, collecting the precipitate, redispersing the precipitate in toluene, and repeating the above cycle 2 times to purify the quantum dot (it is assumed that the emission quantum yield of the quantum dot dispersion solution in the conventional method using acetonitrile remains about 70% because the ligand on the surface of the quantum dot is detached due to acetonitrile). The inventors of the present invention have made studies and found that: after the mixed solution in which the quantum dots are formed is centrifuged, the precipitate is collected, and redispersed in an arbitrary nonpolar solvent such as toluene, in which the quantum dots can be stably dispersed in a colloidal state, to prepare a crude quantum dot solution, methyl acetate is added to the crude quantum dot solution so that the crude quantum dot solution: methyl acetate typically becomes approximately 1: 1, stirring, centrifugally separating the crude quantum dot solution added with the methyl acetate, dispersing the precipitate in a nonpolar solvent, and performing the operation only once to obtain the quantum dot dispersion solution with the luminous quantum yield of 80-100%. Therefore, in the present embodiment, as a purification step of the quantum dots, methyl acetate of substantially the same volume amount is added to the crude quantum dot solution, and the precipitate obtained by centrifuging the solution can be recovered as the quantum dots. The recovered quantum dots are typically redispersed in a nonpolar solvent such as toluene and used in various applications. Furthermore, the precipitate obtained by centrifuging the crude quantum dot solution to which methyl acetate has been added may be dried by blowing nitrogen (after scattering methyl acetate) and then dispersed in a nonpolar solvent such as toluene (if methyl acetate remains, this may cause the quantum dots to become colloidally unstable).

Thus, according to the method of the present embodiment described above, by performing the preparation of quantum dots, as exemplified in the column of examples below, it is possible to stably and reproducibly prepare quantum dots having emission wavelength characteristics in which the emission wavelength region is in the vicinity of 800nm and the full width at half maximum of the peak of the emission wavelength region is about 50nm or less, and the emission quantum yield is extremely higher than before, and the light emission capability is maintained for at least 1 month continuously.

In order to verify the effectiveness of the invention described above, the following experiments were performed. It should be noted that the following examples are illustrative of the effectiveness of the present invention and do not limit the scope of the present invention.