JP7215650B1 - Method for producing luminescent particles and luminescent particle-containing composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a method for producing luminescent particles that are highly stable against moisture, light, and heat, and that are capable of producing luminescent particles with controlled emission wavelengths and particle sizes at a high yield. It is in. A further object of the present invention is to provide a method for producing a composition containing the luminescent particles. The present invention provides a flow reactor 100 in a method for producing a luminescent particle comprising a core containing semiconductor nanoparticles and a ligand layer bonded to the core via an amino group, wherein the ligand layer contains a siloxane bond. , at least one first liquid containing a raw material or precursor of luminescent particles and the first liquid containing the raw material or precursor of luminescent particles and the first liquid introducing at least one second liquid having a different component from the luminescent particles into the channels 111 and 121 and mixing them, and producing a colloidal solution containing the luminescent particles in the mixed fluid. A method of making particles is provided.

Description

The present invention relates to a method for producing luminescent particles and a method for producing a composition containing the obtained luminescent particles.

Nanometer-order particles (nanoparticles) are known to exhibit physical properties different from those of bulk materials due to the quantum size effect. For example, CdSe quantum dots, which are nanoparticles of compound semiconductors, emit light at room temperature, and the emission wavelength can be controlled by changing the particle size. being considered. Conventionally, CdSe quantum dots have been produced using a batch reactor, but in order to obtain light emission with high color purity at the target wavelength, it is required to have an appropriate particle size and little variation in particle size. ing. Therefore, in order to obtain such quantum dots, a production method using a flow reactor has been proposed (Patent Documents 1 and 2). Since the flow reactor performs chemical reactions in microspaces in a fluid, it is possible to suitably control the particle size of nanoparticles.

In recent years, quantum dots with a perovskite structure, which are a type of semiconductor nanoparticles made of metal halides, have been found and are mainly produced by batch reactors. Perovskite quantum dots are represented, for example, by a chemical formula such as CsPbX ₃ (X=Cl, Br, I), and it is possible to adjust the emission wavelength by changing the particle size and halide ion composition (Non-Patent Document 1). . Perovskite quantum dots have a high photoluminescence quantum yield (PLQY) and a narrow full width at half maximum (FWHM) of an emission spectrum, so they are attracting attention as quantum dots to replace CdSe-based materials. Furthermore, as a method for producing perovskite quantum dots with controlled emission wavelength and particle size, a method using a flow reactor has been reported (Patent Document 3, Non-Patent Document 2 and Non-Patent Document 3).

On the other hand, perovskite quantum dots are required to have improved stability against moisture, light and heat. So far, studies have been reported on improving the stability of perovskite quantum dot particles by forming a ligand layer containing siloxane bonds using 3-aminopropyltriethoxysilane on the outside of perovskite quantum dot particles (patent Document 4 and non-patent document 4). However, in the manufacturing method using a batch reactor, it is necessary to add the precursor solution of the luminescent particles to an excessive amount of the poor solvent. There is a problem that the particle size of the obtained luminescent particles is different, the content of the luminescent particles having the target particle size is decreased, and the quality variation is increased. In addition, when scaled up to a mass production scale, when rapidly cooling a large amount of the reaction solution in the reaction vessel from a high temperature state, the cooling efficiency becomes low, and the particle size of the luminescent particles varies, resulting in an undesired result. There is a problem that the content of light-emitting particles having a particle size corresponding to that of the light-emitting particles is decreased.

WO2009/008393 WO2009/020188 Chinese Patent Application Publication No. 109456764 Japanese Patent Application Laid-Open No. 2020-122901

Nano Letters, 2015, Vol. 15, No. 6, pp. 3692-3696 Nano Letters, 2016, Vol. 16, No. 3, pp. 1869-1877 Japanese Journal of Applied Physics, 2020, Vol.59, SIIG02 Advanced Materials, 2016, 28, 10088-10094

The problem to be solved by the present invention is to provide a method for producing luminescent particles, which is highly stable against moisture, light and heat, and can produce luminescent particles with controlled emission wavelength and particle size at a high yield. It is in. A further object of the present invention is to provide a method for producing a composition containing the luminescent particles.

The present inventors have conducted intensive studies to solve the above problems, and as a result, have developed a method for producing luminescent particles that includes specific production steps. That is, the present invention provides a method for producing a luminescent particle comprising a core containing a semiconductor nanoparticle and a ligand layer bonded to the core via an amino group, wherein the ligand layer contains a siloxane bond, wherein a plurality of At least one first liquid containing raw materials or precursors for producing the luminescent particles is introduced from the different introduction parts using a flow reactor equipped with a flow path capable of merging and mixing different liquids introduced from the introduction parts of and at least one second liquid whose components are different from those of the first liquid, are introduced into the flow path and mixed to produce a colloidal solution containing the luminescent particles in the mixed fluid. A method for producing luminescent particles is provided.

Further, the present invention provides a luminescent particle-containing composition obtained by mixing a colloidal solution containing the luminescent particles obtained by the above method for producing luminescent particles or luminescent particles recovered from the colloidal solution and a photopolymerizable compound. Provided is a method for producing a luminescent particle-containing composition, comprising the step of producing

According to the method for producing luminescent particles of the present invention, luminescent particles having high stability against moisture, light and heat, and controlled emission wavelength and particle size can be produced at a high yield. Furthermore, a luminescent particle-containing composition containing the luminescent particles can be produced.

FIG. 1 shows a schematic diagram of luminescent particles produced by a production method according to an embodiment of the present invention. FIG. 2 shows a structural schematic diagram of the surface of the luminescent particles produced by the production method of the embodiment of the present invention. FIG. 3 shows an example of an apparatus configuration used in a continuous laminar flow reactor. FIG. 4 shows an example apparatus configuration for use in a droplet-based flow reactor. FIG. 5 shows an apparatus configuration example used in a forced thin film type flow reactor. FIG. 5(a) shows a cross-sectional view of the device, and FIG. 5(b) shows a cross-sectional view taken along line B-B' in FIG. 5(a). FIG. 6 shows the continuous laminar flow reactor apparatus used to produce the luminescent particles of Examples 1-13. FIG. 7 shows the droplet-based flow reactor apparatus used to produce the luminescent particles of Examples 14-23. FIG. 8 shows the forced thin film flow reactor apparatus used to produce the luminescent particles of Examples 24-33. FIG. 9 shows the continuous laminar flow reactor apparatus used to produce the luminescent particles of Examples 34-41. FIG. 10 shows the droplet-based flow reactor apparatus used to produce the luminescent particles of Examples 42-49. FIG. 11 shows the forced thin film flow reactor apparatus used to produce the luminescent particles of Examples 50-57.

The present invention relates to a method for producing a luminescent particle comprising a core containing semiconductor nanoparticles and a ligand layer bonded to the core via an amino group, the ligand layer containing siloxane bonds. FIG. 1 shows a schematic diagram of luminescent particles produced by the production method of the embodiment of the present invention. According to the present invention, when producing the above-mentioned luminescent particles, a flow reactor equipped with a channel capable of merging and mixing different liquids introduced from a plurality of introduction parts is used, and raw materials for producing the above-mentioned luminescent particles or At least one first liquid containing a precursor and at least one second liquid having a different component from the first liquid are introduced into the channel and mixed, and in the mixed fluid Provided is a method for producing luminescent particles, comprising a step of producing a colloidal solution containing the luminescent particles, and a method for producing a luminescent particle-containing composition containing the luminescent particles and a photopolymerizable compound. . An embodiment of a method for producing luminescent particles will be described below.

The semiconductor nanoparticles constituting the luminescent particles produced by the production method of the present embodiment are preferably compound semiconductors from the viewpoint of ease of adjustment of optical properties, and are group III-V compound semiconductors and group II-VI semiconductors. Compound semiconductors selected from the group consisting of compound semiconductors and metal halide compound semiconductors are more preferred, and A, B and X (wherein A represents a monovalent cation, B represents a metal ion, and X represents It is particularly preferable to use a compound semiconductor containing a halide ion. FIG. 2 shows a structural schematic diagram of the surface of the luminescent particles. In FIG. 2 , the circles hatched downward to the right indicate monovalent cations A, the circles hatched downward to the left indicate metal ions B, and the black circles indicate halide ions X. From the viewpoint of ease of synthesis, emission wavelength, quantum yield and robustness of crystal structure, A is Cs, Rb, methylammonium, formamidinium, ammonium, 2-phenylethylammonium, pyrrolidinium, piperidinium, 1-butyl- A is preferably a cation selected from the group consisting of 1-methylpiperidinium, tetramethylammonium, tetraethylammonium, benzyltrimethylammonium and benzyltriethylammonium, and A is selected from Cs, Rb, methylammonium and formamidinium. A cation is more preferred, and A is particularly preferably a cation selected from Cs, methylammonium and formamidinium. From the viewpoint of ease of synthesis, emission wavelength, quantum yield and robustness of crystal structure, B is Pb, Sn, Ge, Bi, Sb, Ag, In, Cu, Yb, Ti, Pd, Mn, Eu, Zr. and Tb, and B more preferably represents a metal ion selected from the group consisting of Pb, Sn, Bi, Sb, Ag, In, Cu, Mn and Zr, More preferably B represents a metal ion selected from the group consisting of Pb, Sn and Cu, and particularly preferably B represents Pb. From the viewpoint of ease of synthesis, emission wavelength, quantum yield and robustness of crystal structure, X preferably represents a halide ion selected from the group consisting of F, Cl, Br and I, X is Cl, Br More preferably, X represents a halide ion selected from the group consisting of and I, and X particularly preferably represents Br. The semiconductor nanoparticles may have any crystal structure, but from the viewpoints of ease of synthesis, emission wavelength, quantum yield, and robustness of the crystal structure, the semiconductor nanoparticles should have a perovskite structure or a structure similar to perovskite. It is preferable that the semiconductor nanoparticles have a perovskite structure. In the compound semiconductor containing A, B and X, each of A, B and X may be composed of a single type, or may be composed of a plurality of types. Also, the semiconductor nanoparticles may be doped with other ions.

The core containing semiconductor nanoparticles may be composed only of semiconductor nanoparticles, or may contain components such as a shell in addition to semiconductor nanoparticles. Moreover, the core may be composed of a single semiconductor nanoparticle, or a plurality of semiconductor nanoparticles may be bound, aggregated or combined. From the standpoints of dispersion stability when forming a solution or composition and smoothness when applied in the form of a film, the core containing the semiconductor nanoparticles is particularly preferably composed of only a single semiconductor nanoparticle.

（式中、Ｒ^１、Ｒ^２及びＲ^３は各々独立して水素原子、ハロゲン原子、ヒドロキシル基、炭素原子数１から１０の直鎖状又は分岐状アルキル基及び炭素原子数１から１０の直鎖状又は分岐状アルコキシ基からなる群から選ばれる基を表し（ただし、Ｒ^１、Ｒ^２及びＲ^３のうち少なくとも１つはハロゲン原子、ヒドロキシル基及びアルコキシ基からなる群から選ばれる基を表す。）、
Ｒ^４及びＲ^５は各々独立して水素原子及び炭素原子数１から２０の直鎖状又は分岐状アルキル基、炭素原子数３から２０の非芳香族炭化水素環基、及び炭素原子数６から２０の芳香族炭化水素環基からなる群から選ばれる基を表すが、当該アルキル基及び炭化水素環基中の任意の水素原子はハロゲン原子、非芳香族炭化水素環基又は芳香族炭化水素環基に置換されても良く、当該アルキル基中の１又は２以上の－ＣＨ_２－が各々独立して－Ｏ－、－Ｓ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－又は－Ｃ≡Ｃ－に置き換えられても良く、Ｒ^４とＲ^５とが直接又は結合基を介して結合して環を形成しても良く、
Ｓｐ^１は各々独立して炭素原子数１から２０の直鎖状又は分岐状アルキレン基、炭素原子数３から２０の非芳香族炭化水素環基、及び炭素原子数６から２０の芳香族炭化水素環基からなる群から選ばれる基を表すが、当該アルキレン基中の任意の水素原子がハロゲン原子に置換されても良く、当該アルキレン基中の１又は２以上の－ＣＨ_２－が各々独立して－ＣＨ＝ＣＨ－又は－Ｃ≡Ｃ－に置き換えられても良いが、Ｓｐ^１が複数存在する場合それらは同一であっても異なっていても良く、
Ｚ^１は各々独立して－Ｏ－、－Ｓ－、－ＮＨ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＣＯ－Ｓ－、－Ｓ－ＣＯ－、－Ｏ－ＣＯ－Ｏ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－、－ＣＨ（ＣＨ_２ＣＨ_２ＮＨ_２）－、－Ｎ（ＣＨ_２ＣＨ_２ＮＨ_２）－、－ＮＨＣ（＝ＮＨ）－又は単結合を表すが、Ｚ^１が複数存在する場合それらは同一であっても異なっていても良く、
ｍ１は１から２０の整数を表す。）で表される化合物から形成される構造を含むことがより好ましく、配位子層が下記の一般式（Ｌ１１）

（式中、Ｒ^１１、Ｒ^２１及びＲ^３１は各々独立して炭素原子数１から１０の直鎖状アルキル基及び炭素原子数１から１０の直鎖状アルコキシ基からなる群から選ばれる基を表し（ただし、Ｒ^１１、Ｒ^２１及びＲ^３１のうち少なくとも１つはアルコキシ基を表す。）、
Ｒ^４１及びＲ^５１は各々独立して水素原子及び炭素原子数１から２０の直鎖状又は分岐状アルキル基、及び炭素原子数６から２０の芳香族炭化水素環基からなる群から選ばれる基を表すが、当該アルキル基及び炭化水素環基中の任意の水素原子は芳香族炭化水素環基に置換されても良く、
Ｓｐ^１１は各々独立して炭素原子数２から２０の直鎖状アルキレン基を表すが、Ｓｐ^１１が複数存在する場合それらは同一であっても異なっていても良く、
Ｚ^１１は各々独立して－ＮＨ－、－ＣＯ－ＮＨ－、－ＮＨ－ＣＯ－又は単結合を表すが、Ｚ^１１が複数存在する場合それらは同一であっても異なっていても良く、
ｍ１１は１から５の整数を表す。）で表される化合物から形成される構造を含むことがさらに好ましく、配位子層が下記の一般式（Ｌ１１１）

（式中、Ｒ^１１１、Ｒ^２１１及びＲ^３１１は各々独立してメチル基、メトキシ基及びエトキシ基からなる群から選ばれる基を表し（ただし、Ｒ^１１１、Ｒ^２１１及びＲ^３１１のうち少なくとも１つはメトキシ基又はエトキシ基を表す。）、
Ｓｐ^１１１は各々独立して炭素原子数２から２０の直鎖状アルキレン基を表すが、Ｓｐ^１１１が複数存在する場合それらは同一であっても異なっていても良く、
Ｚ^１１１は各々独立して－ＮＨ－又は単結合を表すが、Ｚ^１１１が複数存在する場合それらは同一であっても異なっていても良く、
ｍ１１１は１又は２を表す。）で表される化合物から形成される構造を含むことがさらにより好ましく、配位子層が下記の一般式（Ｌ１１１１）

（式中、Ｒ^１１１１、Ｒ^２１１１及びＲ^３１１１はメトキシ基又はエトキシ基を表す。）で表される化合物から形成される構造を含むことが特に好ましい。A luminescent particle produced by the production method of the present embodiment comprises a core containing semiconductor nanoparticles and a ligand layer bonded to the core via an amino group, wherein the ligand layer contains a siloxane bond. . The ligand layer preferably contains a structure formed from a compound having a silyl group and an amino group from the viewpoint of ease of synthesis, structural stability of the luminescent particles, and quantum yield. The following general formula (L1)

(Wherein, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms and a straight chain having 1 to 10 carbon atoms. represents a group selected from the group consisting of chain or branched alkoxy groups (provided that at least one of R ¹ , R ² and R ³ represents a group selected from the group consisting of halogen atoms, hydroxyl groups and alkoxy groups ),
R ⁴ and R ⁵ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon ring group having 3 to 20 carbon atoms, and 6 to represents a group selected from the group consisting of 20 aromatic hydrocarbon ring groups, but any hydrogen atom in the alkyl group and hydrocarbon ring group is a halogen atom, a non-aromatic hydrocarbon ring group or an aromatic hydrocarbon ring 1 or 2 or more —CH ₂ — in the alkyl group are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO— S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- R ⁴ and R ⁵ may combine directly or via a linking group to form a ring,
Sp ¹ is each independently a linear or branched alkylene group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon cyclic group having 3 to 20 carbon atoms, and an aromatic hydrocarbon having 6 to 20 carbon atoms represents a group selected from the group consisting of cyclic groups, any hydrogen atom in the alkylene group may be substituted with a halogen atom, and one or more —CH ₂ — in the alkylene group are each independently may be replaced with -CH=CH- or -C≡C-, but when there are multiple Sp ^1s , they may be the same or different,
Z ¹ each independently represents -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O- , -CO-NH-, -NH-CO-, -CH(CH ₂ CH ₂ NH ₂ )-, -N(CH ₂ CH ₂ NH ₂ )-, -NHC(=NH)- or a single bond , Z ¹ may be the same or different when there are more than one,
m1 represents an integer of 1 to 20; ) and the ligand layer preferably contains a structure formed from a compound represented by the following general formula (L11)

(wherein R ¹¹ , R ²¹ and R ³¹ are each independently a group selected from the group consisting of a linear alkyl group having 1 to 10 carbon atoms and a linear alkoxy group having 1 to 10 carbon atoms; (provided that at least one of R ¹¹ , R ²¹ and R ³¹ represents an alkoxy group),
R ⁴¹ and R ⁵¹ are each independently a group selected from the group consisting of a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms; represents, any hydrogen atom in the alkyl group and the hydrocarbon ring group may be substituted with an aromatic hydrocarbon ring group,
Each Sp ¹¹ independently represents a straight-chain alkylene group having 2 to 20 carbon atoms, and when there are a plurality of Sp ¹¹ , they may be the same or different,
Z ¹¹ each independently represents -NH-, -CO-NH-, -NH-CO-, or a single bond, and when there are a plurality of Z ¹¹ , they may be the same or different,
m11 represents an integer of 1 to 5; ), wherein the ligand layer has the following general formula (L111)

(wherein R ¹¹¹ , R ²¹¹ and R ³¹¹ each independently represents a group selected from the group consisting of a methyl group, a methoxy group and an ethoxy group (provided that at least one of R ¹¹¹ , R ²¹¹ and R ³¹¹ represents a methoxy group or an ethoxy group.),
Each Sp ¹¹¹ independently represents a straight-chain alkylene group having 2 to 20 carbon atoms, and when there are a plurality of Sp ¹¹¹ , they may be the same or different,
Each of Z ¹¹¹ independently represents -NH- or a single bond, and when there are multiple Z ¹¹¹ , they may be the same or different,
m111 represents 1 or 2; ), wherein the ligand layer comprises the following general formula (L1111)

(wherein R ¹¹¹¹ , R ²¹¹¹ and R ³¹¹¹ represent a methoxy group or an ethoxy group).

As shown in FIG. 2, the compound represented by the general formula (L1) has amino groups coordinated to the core containing the semiconductor nanoparticles. The Si-halogen bond or Si-alkoxy bond contained in the compound represented by the general formula (L1) is hydrolyzed to produce silanol, and the condensation reaction can form a siloxane bond between adjacent molecules. As a result, as shown in FIGS. 1 and 2, a ligand layer containing siloxane bonds is formed on the core containing semiconductor nanoparticles via amino groups. Water may or may not be added to the reaction solution to promote the hydrolysis reaction. When no water is added, the hydrolysis reaction proceeds with a trace amount of water contained in the reaction system.

で表される化合物が挙げられる。As the compound represented by the general formula (L1), specifically, the following formulas (L1-1) to (L1-36)

The compound represented by is mentioned.

The luminescent particles obtained by the production method of the present embodiment are provided with a ligand layer bonded to a core containing semiconductor nanoparticles via an amino group. In order to control crystal growth in the process of forming semiconductor nanoparticles, the ligand layer contains, in addition to compounds having amino groups, ligands such as carboxylic acid, phosphoric acid, sulfonic acid, carboxylate, It is preferable to use a phosphate, a sulfonate, or the like in combination. Specifically, oleic acid (OA), 2-hexyldecanoic acid (DA), decanoic acid (CA), propanoic acid (PA), octanoic acid (OTAc), lauric acid (LA), benzenesulfonic acid, dodecylbenzenesulfone acid, octyl phosphate, n-octylphosphonic acid, 1-tetradecyl phosphate, bis(2,4,4-trimethylpentyl)phosphinic acid (TMPPA), trioctylphosphine oxide (TOPO), trioctylphosphine (TOP) , sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and the like. Further, when a compound represented by general formula (L1) is used as the compound having an amino group, a compound having an amino group may be used in combination with the compound represented by general formula (L1). Specific examples include oleylamine (OAm), octylamine (OLA), phenethylamine (PEA), and butylamine (BLA). In addition, an ammonium salt may be added as an additive. Specifically, didodecyldimethylammonium bromide (DDAB), phenethylammonium bromide (PEAB), phenethylammonium iodide (PEAI), methyltrioctylammonium bromide, tetraoctylammonium bromide, didecyldimethylammonium bromide, ditetradecyldimethyl ammonium bromide, tetraoctylammonium bromide (TOAB);

The ligand layer may include a structure formed from another compound in addition to the structure formed from the compound represented by the general formula (L1). The other compound for forming the ligand layer may be any compound capable of forming a siloxane bond, preferably a compound selected from the group consisting of silazanes, polysilazanes and alkoxysilanes. Specific examples of silazanes include octamethylcyclotetrasilazane and 1,3-diphenyltetramethyldisilazane. Specific examples of polysilazane include "NN120-10", "NN120-20" (manufactured by AZ Electronic Materials), "Durazane 1500 Slow Cure" (Durazane is a registered trademark), and "Durazane 1500 Rapid Cure" ( (manufactured by Merck Performance Materials Co., Ltd.). Specific examples of alkoxysilanes include tetraethyl orthosilicate, tetramethyl orthosilicate, tetraisopropyl orthosilicate, tetrapropyl orthosilicate, trimethoxy(methyl)silane, dimethoxydimethylsilane, and "methylsilicate 51" (manufactured by Colcoat Co., Ltd.). ).

The manufacturing method of the present embodiment uses a flow reactor equipped with a flow path capable of merging and mixing different liquids introduced from a plurality of inlets, and contains raw materials or precursors for producing the luminescent particles from the different inlets. At least one kind of first liquid and at least one kind of second liquid having a component different from that of the first liquid are introduced into the channel and mixed, and the luminescent particles are emitted in the mixed fluid. A step of producing a colloidal solution containing

At least one of the first liquid and the second liquid preferably contains the compound represented by the general formula (L1) described above. Thereby, a luminescent particle having a ligand layer including a structure formed from the compound represented by general formula (L1) can be produced.

Then, from the viewpoint of ease of synthesis, quantum yield, yield, and uniformity of particle size, either the first liquid or the second liquid contains a monovalent cation A, and the other It preferably contains metal ions B and halide ions X.

Preferably, the first liquid containing the monovalent cation A contains a solvent in addition to the monovalent cation A. From the viewpoint of the stability and yield of the luminescent particles, it is preferable to use a solvent having low polarity, a high boiling point, and high dispersibility of the luminescent particles. A specific example of the solvent is 1-octadecene. Moreover, the monovalent cation A is preferably dissolved in a solvent, for example, preferably in the form of an oleate or the like. The oleate can be prepared by heating and mixing a carbonate, halide, acetate or oxide of monovalent cation A with oleic acid in a solvent.

The second liquid containing the metal ions B and the halide ions X preferably contains a solvent in addition to the metal ions B and the halide ions X. From the viewpoint of the stability and yield of the luminescent particles, it is preferable to use a solvent having low polarity, a high boiling point, and high dispersibility of the luminescent particles. A specific example of the solvent is 1-octadecene. In order to control the crystal growth in the process of forming semiconductor nanoparticles, the liquid containing metal ions B and halide ions X contains a compound having an amino group, a compound having a carboxyl group, or groups of both of them. It is preferred that a compound having Specific examples include the same compounds as the ligands described above.

From the viewpoint of quantum yield and yield of luminescent particles, the first liquid and the second liquid are preferably dehydrated before being used in the reaction. Moisture removal can be performed by reducing the pressure while heating the liquid. The heating temperature is preferably 40° C. or higher and 250° C. or lower, more preferably 60° C. or higher and 200° C. or lower, and particularly preferably 80° C. or higher and 150° C. or lower. Moisture can also be removed using a desiccant such as molecular sieves or silica gel.

In the production method of the present embodiment, at least two kinds of liquids containing raw materials or precursors for producing luminescent particles are introduced from different channels and reacted in the fluid to produce a colloidal solution containing the luminescent particles. including the step of It is preferable that all components are dissolved when the first liquid and the second liquid are mixed. The temperature during mixing is preferably 100° C. or higher and 220° C. or lower, preferably 120° C. or higher and 200° C. or lower, and particularly preferably 140° C. or higher and 180° C. or lower. After the first liquid and the second liquid are mixed and homogenized, the mixed liquid is cooled to deposit nano-sized luminescent particles. The cooling temperature is preferably -50°C or higher and 100°C or lower, more preferably -20°C or higher and 50°C or lower, and particularly preferably 0°C or higher and 30°C or lower. By rapidly cooling the mixed solution, a colloidal solution containing luminescent particles with less variation in particle size can be obtained.

In the process of producing the colloidal solution, when simplicity of production equipment and ease of work are emphasized, either one of the first liquid and the second liquid is a monovalent cation A and a metal ion B and a halide ion X and a first solvent, and the other preferably contains a second solvent in which the semiconductor nanoparticles have a lower solubility than the first solvent. By mixing the first liquid and the second liquid, the luminescent particles can be precipitated and a colloidal solution containing the luminescent particles can be obtained. In this case, the solvent used for the first liquid is preferably a polar solvent capable of dissolving the raw material or precursor of the luminescent particles in as small a quantity as possible. Specific examples of the solvent to be used include N,N-dimethylformamide, dimethylsulfoxide and N-methylformamide. The second liquid preferably contains a low-polarity solvent. Specific examples of solvents to be used include toluene, hexane, cyclohexane, and heptane. In order to control crystal growth in the process of forming semiconductor nanoparticles, at least one of the first liquid and the second liquid preferably contains a compound having an amino group, a carboxylic acid, or both. . Specific examples include the same compounds as the ligands described above.

From the viewpoint of quantum yield and yield of luminescent particles, the first liquid and the second liquid are preferably dehydrated before being used in the reaction. Moisture removal may be performed by reducing the pressure while heating the liquid, or may be performed using a desiccant such as a molecular sieve or silica gel.

According to the production method of the present embodiment, luminescent particles with controlled emission wavelength and particle size can be obtained. From the viewpoints of uniformity of the particle size of the luminescent particles, high quantum yield, narrow half-width of the emission spectrum, and rapid temperature control, the cross-sectional area of the fluid flow path should be 400 mm ² or less. is preferably 100 mm ² or less, more preferably 25 mm ² or less, and particularly preferably 4 mm ² or less. In this embodiment, the cross section means a cross section perpendicular to the flow direction in the channel, and the cross sectional area means the area. The cross-sectional shape of the channel is substantially square, rectangular including rectangular, polygonal such as trapezoid, parallelogram, triangle, and pentagon (including shapes with rounded corners and slit shapes with high aspect ratios). , a star shape, a substantially perfect circle, a semicircle, and a substantially elliptical shape. Moreover, the cross-sectional shape of the flow path may not be constant.

The layout of the channels may be straight, branched, comb-shaped, curved, spiral, zig-zag, or any other shape. The channel may be installed in a heat conductive container, or may be immersed in an oil bath, a water bath, or the like. Furthermore, as a device comprising a heat-conducting container in which a flow path is formed, a device having a structure in which heat-conducting plate-like structures having a plurality of grooves formed on their surfaces are laminated may be used.

Examples of the method of introducing the liquid include a method using a syringe connected to a syringe pump capable of controlling the liquid-feeding speed, and a method using a liquid-feeding pump. The liquids introduced from each introduction part are mixed by a mixer through respective channels. After that, the mixed liquid passes through the channel and is discharged from the discharge part. The discharge part may be provided with a container for receiving the discharged liquid, for example, a mixing field, an extraction field, a separation field, a flow measurement part, a detection part, a reservoir, a membrane separation mechanism, a device connection port, entanglement path, development path for chromatography or electrophoresis, part of the valve structure (portion surrounding the valve), pressurization mechanism, decompression mechanism, or the like. In addition, the number of introduction parts may be increased as appropriate in order to increase the types of liquids to be introduced or to introduce the same type of liquid from a plurality of introduction parts. In that case, channels and mixers can be added as appropriate. The shape of the mixer may be T-shaped, Y-shaped, or any other shape. Moreover, when three or more types of liquids are mixed at one place, a cross shape may be used.

The flow reactor is preferably of continuous laminar flow, droplet base or forced thin film type. Continuous laminar flow reactors are preferred because they facilitate rapid cooling from a high temperature, especially when high quantum yield of the luminescent particles and cost are important. When the narrowness of the half-value width of the emission spectrum of the luminescent particles is particularly important, it is preferable to use a droplet-based flow reactor because the reaction proceeds only in droplets. When the high concentration of the luminescent particles is particularly important, it is preferable to use a forced thin film type flow reactor, since the change in flow rate due to the viscosity increase of the reaction solution is unlikely to occur and the concentration can be easily increased.

FIG. 3 shows an example of the configuration of an apparatus used in the continuous laminar flow reactor. In the continuous laminar flow reactor device 100 , two liquids containing raw materials or precursors for producing luminescent particles are introduced through different inlets 110 and 120 . The liquids introduced from each introduction part pass through the channels 111 and 121 and are mixed in the T-shaped mixer 101 . After that, the mixed liquid passes through the channel 131 and is discharged from the discharge section 130 .

A droplet-based flow reactor comprises one or more liquid phase streams and an immiscible liquid phase stream as a carrier liquid to generate droplets. Since the liquid introduced is divided into independent portions, backmixing is suppressed. Specific droplet generation designs include configurations using T-shaped mixers, Y-shaped mixers, and cruciform mixers. FIG. 4 shows an example of equipment configuration used for a droplet-based flow reactor using a T-shaped mixer. In droplet-based flow reactor apparatus 200 , two liquids containing raw materials or precursors for producing luminescent particles are introduced through different inlets 210 and 220 . The liquids introduced from each introduction part pass through the channels 211 and 221 and are mixed in the T-shaped mixer 201 . The mixed liquid then flows through channel 231 into T-shaped mixer 202 . A carrier liquid immiscible with the liquid flowing from channel 231 is introduced through another inlet 240 . The carrier liquid enters T-mixer 202 via channel 241 and forms droplets of liquid entering from channel 231 . Liquid droplets and carrier liquid flowing from the channel 231 pass through the channel 251 and are discharged from the discharge portion 250 . A colloidal solution containing luminescent particles can be obtained by separating the carrier liquid from the discharged liquid.

Forced thin film flow reactors form a forced thin film of liquid by channeling the microscopic space between two relatively rotating discs. A specific example of the forced thin film type flow reactor is the forced thin film type microreactor ULREA (manufactured by M Technic). FIG. 5 shows an example of the device configuration used for the forced thin film type flow reactor. FIG. 5(a) is a cross-sectional view of the device, and FIG. 5(b) is a cross-sectional view taken along line B-B' in FIG. 5(a). In the thin-film flow reactor device 300 , two liquids containing raw materials or precursors for producing luminescent particles are introduced from different inlets 310 and 320 . The liquid introduced from the introduction part 310 passes through the flow path 311 to the flow path 331 formed between the rotatable disk 302 and the disk 301 that can approach and separate from the disk 302. 312 is pumped. The liquid is then introduced into channels formed in the processing surface 303 . The liquid introduced from the introduction part 320 passes through the channel 321, is introduced into the channel formed in the processing surface 303 through the annular connection part 322, and is mixed with the liquid introduced from the introduction part 310. be. After that, the mixed liquid is collected in the recovery section 304 provided on the outer circumference of the two discs 301 and 302 . The liquid collected in the recovery section 304 is discharged from the discharge section 330 via the flow path 332 . A portion of the disk 301 in contact with the processing surface 303 is provided with a channel for flowing a cooling or heating medium, and the temperature of the channel formed on the processing surface 303 can be controlled.

The luminescent particles produced by the production method of the present embodiment preferably have a volume average diameter of 9 nm or more and 80 nm or less from the viewpoint of emission wavelength and dispersion stability when forming a solution or composition. The diameter is more preferably 11 nm or more and 60 nm or less, the volume average diameter is more preferably 13 nm or more and 40 nm or less, and the volume average diameter is particularly preferably 15 nm or more and 30 nm or less.

The luminescent particles produced by the production method of the present embodiment have the following formula (1) from the viewpoint of the emission wavelength, the half width of the emission spectrum, and the smoothness when applied in a film form.
SD=(d84%-d16%)/2 (1)
(In the formula, d84% represents the particle diameter (nm) at the point where the cumulative curve is 84% when the cumulative curve is obtained with the total volume of the luminescent particles as 100%, and d16% represents the total volume of the luminescent particles at 100%. When the cumulative curve is obtained as %, the particle diameter (nm) at the point where the cumulative curve is 16%.) is preferably 1 nm or more and 40 nm or less, and the SD value is 2 nm or more. , more preferably 30 nm or less, more preferably an SD value of 3 nm or more and 25 nm or less, even more preferably an SD value of 4 nm or more and 20 nm or less, and an SD value of 5 nm or more and 15 nm or less. It is particularly preferred to have

The volume average diameter, d84% and d16%, of the luminescent particles produced by the production method of the present embodiment can be measured using a commercially available particle size distribution analyzer. In the present embodiment, the volume average diameters d84% and d16% are determined by dynamic light scattering using a particle size distribution analyzer NanotracWave II-UT151 (manufactured by Microtrac Bell, Nanotrac is a registered trademark). rice field. Software "Microtrac Application ver. 11.1.0-257H" (manufactured by Microtrac Bell) was used for data measurement and analysis under the following conditions.
Solvent: Toluene Cell temperature: 25°C
Solvent refractive index: 1.50
Solvent viscosity: 0.590 cP (20°C), 0.526 cP (30°C)
Measurement time: 300 seconds Number of measurements: 1 Particle refractive index: 1.81
Permeability: Permeable Particle shape: Non-spherical Particle density: 4.42 g/cm ³

The luminescent particles produced by the production method of this embodiment can be obtained as a colloidal solution dispersed in a solvent. The resulting colloidal solution containing luminescent particles is preferably purified to remove excess production raw materials or precursors, ligands, impurities, particles having undesirable particle sizes, and the like. Purification methods include filtration, reprecipitation, extraction, centrifugation, adsorption, recrystallization, column chromatography and the like. From the viewpoints of workability and cost, it is preferable to purify the resulting colloidal solution containing luminescent particles by centrifugation. The purified luminescent particles may be re-dispersed in an organic solvent, or may be dried and taken out as a solid. When not used immediately in the next step, the purified luminescent particles are preferably made into a colloidal solution from the viewpoint of stability of optical properties and dispersion stability. A low-polarity solvent is preferable as the organic solvent in which the purified luminescent particles are dispersed. Specific examples of organic solvents include toluene, hexane, heptane, cyclohexane, and methylcyclohexane. From the viewpoint of stability of optical properties, it is preferable that the resulting colloidal solution containing luminescent particles does not contain impurities such as water and alcohol as much as possible. In the resulting colloidal solution containing luminescent particles, water or alcohol is preferably 1.0% or less, more preferably 0.1% or less, and water or alcohol is 100 ppm or less. It is particularly preferred to have

In the production method of the present embodiment, at least two kinds of liquids containing raw materials or precursors for producing luminescent particles are introduced from different channels and reacted in the fluid to produce a colloidal solution containing the luminescent particles. and mixing the luminescent particles and the photopolymerizable compound to produce a luminescent particle-containing composition. In the step of producing the luminescent particle-containing composition, the colloidal solution containing the luminescent particles may be directly mixed with the photopolymerizable compound, or the colloidal solution containing the luminescent particles may be mixed with the photopolymerizable compound after removing the solvent from the colloidal solution containing the luminescent particles. You can mix. The photopolymerizable compound to be mixed is preferably a photoradical polymerizable compound that is polymerized by irradiation with light, and may be a photopolymerizable monomer or oligomer. These are used together with a photoinitiator. A photopolymerizable compound may be used individually by 1 type, and may use 2 or more types together. A (meth)acrylate compound is mentioned as a photoradically polymerizable compound. The (meth)acrylate compound may be a monofunctional (meth)acrylate having one (meth)acryloyl group, or may be a polyfunctional (meth)acrylate having multiple (meth)acryloyl groups. Monofunctional (meth)acrylate from the viewpoint of excellent fluidity when preparing an ink composition, excellent ejection stability, and ability to suppress deterioration in smoothness due to curing shrinkage during the production of a luminescent particle coating film. and a polyfunctional (meth)acrylate are preferably used in combination. The amount of the photopolymerizable compound contained in the luminescent particle-containing composition is preferably 40% by mass or more and 80% by mass or less, more preferably 45% by mass or more and 75% by mass or less, and 50% by mass. % or more and 70 mass % or less is particularly preferable. The photopolymerization initiator is preferably at least one selected from the group consisting of alkylphenone compounds, acylphosphine oxide compounds and oxime ester compounds.

Components other than the photopolymerizable compound and the photopolymerization initiator may be mixed in the step of producing the luminescent particle-containing composition. Specific examples include polymerization inhibitors, antioxidants, dispersants, leveling agents, and light-scattering particles.

Specific examples of polymerization inhibitors include quinone compounds such as p-methoxyphenol, cresol, t-butylcatechol, 3,5-di-t-butyl-4-hydroxytoluene, p-phenylenediamine, and 4-aminodiphenylamine. , N,N'-diphenyl-p-phenylenediamine and other amine compounds, phenothiazine, distearylthiodipropionate and other thioether compounds, 2,2,6,6-tetramethylpiperidine-1-oxyl free radical, N-oxyl compounds such as 2,2,6,6-tetramethylpiperidine, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine , and N-nitrosodinaphthylamine. The amount of the polymerization inhibitor to be added is preferably 0.01% by mass or more and 1.0% by mass or less, and preferably 0.02% by mass, based on the total amount of the photopolymerizable compound contained in the luminescent particle-containing composition. More than 0.5% by mass or less is particularly preferable.

Specific examples of antioxidants include pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate (“IRGANOX1010” (IRGANOX is a registered trademark)), thiodiethylenebis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (“IRGANOX 1035”), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (“IRGANOX 1076 ”). The amount of the antioxidant to be added is preferably 0.01% by mass or more and 2.0% by mass or less, and preferably 0.02% by mass, based on the total amount of the photopolymerizable compound contained in the luminescent particle-containing composition. Above, it is especially preferable that it is 1.0 mass % or less.

Specific examples of dispersants include phosphorus atom-containing compounds such as TOP (trioctylphosphine), TOPO (trioctylphosphine oxide), hexylphosphonic acid (HPA), nitrogen atoms such as oleylamine, octylamine, and trioctylamine. Containing compounds, 1-decanethiol, octanethiol, sulfur atom-containing compounds such as dodecanethiol, acrylic resins, polyester resins, polymeric dispersants such as polyurethane resins, DISPERBYK (manufactured by BYK-Chemie, registered trademark), TEGO Dispers (manufactured by Evonik, TEGO is a registered trademark), EFKA (manufactured by BASF, registered trademark), SOLSPERSE (manufactured by Nippon Lubrizol, registered trademark), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd., registered trademark), DISPARLON ( Kusumoto Kasei Co., Ltd., registered trademark) and Floren (Kyoeisha Chemical Co., Ltd.). The amount of the dispersant added is preferably 0.05% by mass or more and 10% by mass or less, and preferably 0.1% by mass or more and 5 % by mass or less is particularly preferred.

Specific examples of the leveling agent include "Megafac F-114", "Megafac F-251", "Megafac F-281" (manufactured by DIC, Megafac is a registered trademark), "Futa Futagent 100", "Futagent 100C", "Futagent 110" (manufactured by Neos, Futagent is a registered trademark), "BYK-300", "BYK-302", "BYK-306" ( BYK is a registered trademark), "TEGO Rad2100", "TEGO Rad2011", "TEGO Rad2200N" (manufactured by Evonik, TEGO is a registered trademark), "DISPARLON OX-880EF ”, “DISPARLON OX-881”, “DISPARLON OX-883” (manufactured by Kusumoto Kasei Co., Ltd., DISPARLON is a registered trademark), “Polyflow No. 7”, “Floren AC-300”, “Floren AC- 303” (manufactured by Kyoeisha Chemical Co., Ltd.). The amount of the leveling agent added is preferably 0.005% by mass or more and 2% by mass or less, and 0.01% by mass or more and 0 0.5% by mass or less is particularly preferred.

The light-scattering particles are preferably optically inactive inorganic fine particles. Specific examples of light-scattering particles include titanium oxide, barium sulfate, and calcium carbonate.

Although the embodiments of the method for producing luminescent particles and the method for producing a luminescent particle-containing composition of the present invention have been described above, the present invention is not limited to the configurations of the above-described embodiments. For example, the method for producing a luminescent particle and the method for producing a luminescent particle-containing composition of the present invention may each have any other configuration in addition to the configurations of the above-described embodiments, and have similar functions. It may be replaced with any effective configuration. In addition, the method for producing a luminescent particle of the present invention may have steps for other arbitrary purposes in the configurations of the above-described embodiments, and can be replaced with arbitrary steps that exhibit similar effects. .

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these. "Parts" in the examples represent "parts by mass", and "%" represents "% by mass". MA represents methylammonium and FA represents formamidinium.
1. Preparation of Liquid Containing Raw Materials or Precursors for Manufacturing Luminescent Particles <<Preparation of Liquid Containing Monovalent Cation A>>
(Liquid LR1-1)
Under an argon atmosphere, 2.4 g of cesium carbonate, 25 mL of oleic acid, and 250 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The vacuum was released while the argon atmosphere was maintained. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR1-2)
Under an argon atmosphere, 2.4 g of rubidium carbonate, 1.5 g of cesium carbonate, 25 mL of oleic acid, and 260 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (9±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The vacuum was released while the argon atmosphere was maintained. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR1-3)
Under an argon atmosphere, 3.2 g of methylammonium bromide (MABr), 25 mL of oleic acid, and 250 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (17±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The vacuum was released while the argon atmosphere was maintained, and the mixture was stirred until a uniform solution was obtained.
(Liquid LR1-4)
Under an argon atmosphere, 3.2 g of formamidine acetate, 100 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The vacuum was released while the argon atmosphere was maintained, and the mixture was stirred until a uniform solution was obtained.

<<Preparation of Liquid Containing Metal Ion B and Halide Ion X>>
(Liquid LR2-1)
Under an argon atmosphere, 2.7 g of lead (II) bromide, 20 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, and 20 mL of the compound represented by formula (L1-1) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR2-2)
Under an argon atmosphere, 3.6 g of lead (II) bromide, 60 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (20±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The pressure was released while the argon atmosphere was maintained, and 60 mL of the compound represented by formula (L1-1) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR2-3)
Under an argon atmosphere, 2.7 g of lead (II) bromide, 20 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (6±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, and 20 mL of the compound represented by formula (L1-2) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR2-4)
Under an argon atmosphere, 2.7 g of lead (II) bromide, 20 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, and 20 mL of the compound represented by formula (L1-3) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR2-5)
Under an argon atmosphere, 2.0 g of lead (II) bromide, 0.9 g of lead (II) iodide, 20 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (10±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, and 20 mL of the compound represented by formula (L1-1) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR2-6)
Under an argon atmosphere, 0.2 g of lead (II) chloride, 2.4 g of lead (II) bromide, 20 mL of oleic acid, 10 mL of trioctylphosphine, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, 20 mL of the compound represented by formula (L1-1) was added, the temperature was raised to 150° C., and the mixture was stirred until a homogeneous solution was obtained.
(Liquid LR2-7)
Under an argon atmosphere, 2.7 g of lead (II) bromide, 36 mL of oleic acid, and 310 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The reduced pressure was released while the argon atmosphere was maintained, and 20 mL of the compound represented by formula (L1-1) was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.
(Liquid LR3-1)
Under an argon atmosphere, 2.7 g of lead (II) bromide, 20 mL of oleic acid, and 200 mL of 1-octadecene were added to a three-necked flask. While reducing the pressure with a vacuum pump (15±3 kPa), the mixture was heated and stirred at 120° C. for 30 minutes. The pressure reduction was released while the argon atmosphere was maintained, and 20 mL of oleylamine was added. The temperature was raised to 140° C. and stirred until a homogeneous solution was obtained.

<<Preparation of liquid containing monovalent cation A, metal ion B and halide ion X>>
(Liquid LR4-1)
Under an argon atmosphere, 1.7 g of cesium bromide, 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. 4 mL of the compound represented by formula (L1-1) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-2)
Under an argon atmosphere, 0.9 g of rubidium bromide, 0.5 g of cesium bromide, 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. rice field. 4 mL of the compound represented by formula (L1-1) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-3)
In an argon atmosphere, 0.9 g of methylammonium bromide (MABr), 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. 4 mL of the compound represented by formula (L1-1) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-4)
Under an argon atmosphere, 1.7 g of cesium bromide, 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. 4 mL of the compound represented by formula (L1-2) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-5)
Under an argon atmosphere, 1.7 g of cesium bromide, 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. 4 mL of the compound represented by formula (L1-3) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-6)
Under an argon atmosphere, 1.3 g of cesium bromide, 0.4 g of cesium iodide, 2.2 g of lead (II) bromide, 0.9 g of lead (II) iodide, and dehydrated N,N-dimethylformamide were placed in a three-necked flask. 200 mL was added and dissolved by stirring at room temperature. 4 mL of the compound represented by formula (L1-1) was added and stirred until a homogeneous solution was obtained.
(Liquid LR4-7)
Under an argon atmosphere, 0.1 g of cesium chloride, 1.2 g of cesium bromide, 0.2 g of lead (II) chloride, 2.6 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were placed in a three-necked flask. It was added and dissolved by stirring at room temperature. 4 mL of the compound represented by formula (L1-1) was added and stirred until a homogeneous solution was obtained.
(Liquid LR5-1)
Under an argon atmosphere, 1.7 g of cesium bromide, 2.9 g of lead (II) bromide, and 200 mL of dehydrated N,N-dimethylformamide were added to a three-necked flask and stirred at room temperature to dissolve. 4 mL of oleylamine was added and stirred until a homogeneous solution was obtained.

<<Preparation of liquid containing ligand>>
(Liquid LR6-1)
In an argon atmosphere, 4 mL of oleic acid and 200 mL of dehydrated toluene were added to a three-necked flask and stirred at room temperature to dissolve.

2. Production of Luminescent Particles (Comparative Example 1) Production Using a Batch Reactor Under an argon atmosphere, 4 mL of liquid LR2-1 was added to a three-necked flask, and the mixture was heated and stirred at 140.degree. 1 mL of liquid LR1-1 was collected with a syringe and quickly injected into a 3-necked flask. After heating and stirring at 140° C. for 5 seconds, the three-necked flask was rapidly cooled with ice water. After the reaction solution was cooled until it solidified, it was heated to room temperature to obtain a colloidal solution containing luminescent particles. 15 mL of methyl acetate was added to a glass vial equipped with a stir bar. 5 mL of the colloidal solution containing the resulting luminescent particles was pipetted and added with stirring. The resulting suspension was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 1 minute using a high-speed refrigerated centrifuge Avanti JE (manufactured by Beckman Coulter, Avanti is a registered trademark). The supernatant liquid was removed, and 10 mL of toluene was added to the obtained solid matter and shaken to dissolve. The resulting colloidal solution was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 3 minutes. The precipitate was removed to obtain a purified colloidal solution containing luminescent particles containing _CsPbBr3 .

(Comparative Example 2) Production Using a Batch Reactor Luminescent particles containing Rb _0.7 Cs _0.3 PbBr ₃ were produced in the same manner as in Comparative Example 1, except that liquid LR1-1 was replaced with liquid LR1-2. A purified colloidal solution containing

(Comparative Example 3) Production Using a Batch Reactor A purified colloidal solution containing luminescent particles containing MAPbBr ₃ was prepared in the same manner as in Comparative Example 1, except that liquid LR1-1 was replaced with liquid LR1-3. Obtained.

(Comparative Example 4) Production Using a Batch Reactor A purified colloidal solution containing luminescent particles containing CsPbBr ₃ was prepared in the same manner as in Comparative Example 1, except that liquid LR2-1 was replaced with liquid LR2-2. Obtained.

(Comparative Example 5) Production Using a Batch Reactor Luminescent particles containing CsPbBr _2.25 I _0.75 were produced in the same manner as in Comparative Example 1, except that liquid LR2-1 was replaced with liquid LR2-5. A purified colloidal solution was obtained.

(Comparative Example 6) Production Using a Batch Reactor Luminescent particles containing CsPbCl _0.3 Br _2.7 were produced in the same manner as in Comparative Example 1, except that liquid LR2-1 was replaced with liquid LR2-6. A purified colloidal solution was obtained.

(Comparative Example 7) Production Using a Batch Reactor In the same manner as in Comparative Example 1, except that liquid LR1-1 was replaced with liquid LR1-4, and liquid LR2-1 was replaced with liquid LR2-7, _FAPbBr3 was prepared. A purified colloidal solution containing luminescent particles was obtained.

(Comparative Example 8) Production Using Batch Reactor Under an argon atmosphere, 6 mL of liquid LR6-1 was added to a three-necked flask equipped with a stirrer. 0.3 mL of liquid LR4-1 was taken with a syringe and quickly injected into a 3-necked flask while stirring. A colloidal solution containing luminescent particles was obtained by stirring at room temperature. 18 mL of methyl acetate was added to a glass vial equipped with a stir bar. 6 mL of the colloidal solution containing the resulting luminescent particles was pipetted and added with stirring. The resulting suspension was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 1 minute using a high-speed refrigerated centrifuge Avanti JE (manufactured by Beckman Coulter, Avanti is a registered trademark). The supernatant liquid was removed, and 10 mL of toluene was added to the obtained solid matter and shaken to dissolve. The resulting colloidal solution was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 3 minutes. The precipitate was removed to obtain a purified colloidal solution containing luminescent particles containing _CsPbBr3 .

(Comparative Example 9) Production Using Batch Reactor Luminescent particles containing Rb _0.7 Cs _0.3 PbBr ₃ were produced in the same manner as in Comparative Example 8, except that liquid LR4-1 was replaced with liquid LR4-2. A purified colloidal solution containing

(Comparative Example 10) Production Using a Batch Reactor A purified colloidal solution containing luminescent particles containing MAPbBr ₃ was prepared in the same manner as in Comparative Example 8, except that liquid LR4-1 was replaced with liquid LR4-3. Obtained.

(Comparative Example 11) Production using a batch reactor Purified colloidal solution containing luminescent particles containing CsPbBr ₃ was prepared in the same manner as in Comparative Example 8, except that the amount of liquid LR4-1 was changed to 0.6 mL. got

(Comparative Example 12) Production Using a Batch Reactor Luminescent particles containing CsPbBr _2.25 I _0.75 were produced in the same manner as in Comparative Example 8, except that liquid LR4-1 was replaced with liquid LR4-6. A purified colloidal solution was obtained.

(Comparative Example 13) Production Using a Batch Reactor Luminescent particles containing CsPbCl _0.3 Br _2.7 were produced in the same manner as in Comparative Example 8, except that liquid LR4-1 was replaced with liquid LR4-7. A purified colloidal solution was obtained.

Regarding the purified colloidal solution containing the luminescent particles produced in Comparative Examples 1 to 13, yield, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM), volume Mean diameter (MV) and SD values were measured. The measurement results are shown in Tables 1 and 2 below. The yields in Comparative Examples 1 to 12 are based on the monovalent cation A, and the yields in Comparative Example 13 are based on the halide ion X. ABX ₃ is the semiconductor nanoparticle component contained in the purified colloidal solution containing the luminescent particles, and is obtained as a ratio of the substance amount of ABX ₃ to the substance amount of the monovalent cation A or halide ion X used as the raw material. rice field. The amount of the semiconductor nanoparticle component ABX ₃ contained in the purified colloidal solution containing the luminescent particles was determined by measuring the absorbance at 400 nm of the purified colloidal solution containing the luminescent particles with a spectrophotometer (UV-Vis/NIR) U -4100 (manufactured by Hitachi High-Tech Science) was used. The molar extinction coefficient of the semiconductor nanoparticle component ABX ₃ is the ε value for CsPbBr ₃ nanoparticles (2.42 ± 0 .04)×10 ⁻² ×d ³ (cm ⁻¹ ·μM ⁻¹ ) was used, where d represents the average edge length of the semiconductor nanoparticle component ABX ₃ . The average edge length d of the semiconductor nanoparticle component ABX ₃ was obtained using an atomic resolution electron microscope JEM-ARM300F GRAND ARM (manufactured by JEOL Ltd.) and taking TEM images of 250 particles present in various regions on the grid. Then, the length was measured from the obtained TEM image, and the average value was obtained. Absolute quantum yield (PLQY), emission spectrum peak value (λem) and emission spectrum half width (FWHM) were measured using an absolute PL quantum yield measurement device Quantaurus-QY (manufactured by Hamamatsu Photonics, registered trademark) at an excitation wavelength of 400 nm. obtained by The volume mean diameter (MV) and SD value were obtained using the measurement device, analysis software and conditions described above.

(Examples 1 to 13) Production Using Continuous Laminar Flow Reactor Luminescent particles of Examples 1 to 13 were produced using a continuous laminar flow reactor apparatus 400 shown in FIG. Liquids LR1-1 to LR1-4 containing the monovalent cation A are used as the first liquid, and liquids LR2-1 to LR2-7 containing the metal ion B and the halide ion X are used as the second liquid. Used as a liquid. In the continuous laminar flow reactor device 400, the gas-tight syringes (manufactured by Hamilton) that sampled the first liquid and the second liquid were fixed to a syringe pump (manufactured by Cetoni), and the luer lock connector of the gas-tight syringe was connected. They were connected to the introduction part 410 and the introduction part 420 respectively. Pipe 411 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm), pipe 421 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm), pipe 431 (inner diameter 0.5 mm, outer diameter 1/16", length 20 cm) and piping 432 (inner diameter 0.8 mm, outer diameter 1/16", length 50 cm) were both stainless steel tubes. As the T-shaped mixer 401, a stainless steel micromixer (manufactured by Sanko Seiki Kogyo Co., Ltd.) having a channel inner diameter of 0.25 mm was used. Piping 411, piping 421, piping 431 and T-shaped mixer 401 were immersed in oil bath 402 and set to the temperatures shown in Table 3 below. The pipe 432 was immersed in the cooling bath 403 at 20°C. A vial was placed in the discharge section 430 to receive the discharged liquid. The example number, type and flow rate of the first liquid, type and flow rate of the second liquid, set temperature of the oil bath, and calculated values for the concentration of the resulting semiconductor compound ABX ₃ are shown in Table 3 below.

15 mL of methyl acetate was added to a glass vial equipped with a stir bar. 5 mL of the colloidal solution containing the resulting luminescent particles was pipetted and added with stirring. The obtained suspension was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 1 minute using a high-speed cooling centrifuge Avanti JE (manufactured by Beckman Coulter). The supernatant liquid was removed, and 10 mL of toluene was added to the obtained solid matter and shaken to dissolve. The resulting colloidal solution was centrifuged at 25° C. and 10,000 rpm (12,096×g) for 3 minutes. The precipitate was removed to obtain a purified colloidal solution containing luminescent particles. Yield, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM), volume average diameter (MV) and SD of the purified colloidal solution containing the obtained luminescent particles values were measured. The measurement results are shown in Table 4 below. The yields in Examples 1 to 12 are based on the monovalent cation A, and the yields in Comparative Example 13 are based on the halide ion X. ABX ₃ is the semiconductor nanoparticle component contained in the purified colloidal solution containing the luminescent particles, and the ratio of the substance amount of ABX ₃ to the substance amount of the monovalent cation A or halide ion X used as the raw material asked. The amount of the semiconductor nanoparticle component ABX ₃ contained in the purified colloidal solution containing the luminescent particles was determined by measuring the absorbance at 400 nm of the purified colloidal solution containing the luminescent particles with a spectrophotometer (UV-Vis/NIR) U -4100 (manufactured by Hitachi High-Tech Science) was used. The molar extinction coefficient of the semiconductor nanoparticle component ABX ₃ is the ε value for CsPbBr ₃ nanoparticles (2.42 ± 0 .04)×10 ⁻² ×d ³ (cm ⁻¹ ·μM ⁻¹ ) was used, where d represents the average edge length of the semiconductor nanoparticle component ABX ₃ . The average edge length d of the semiconductor nanoparticle component ABX ₃ was obtained using an atomic resolution electron microscope JEM-ARM300F GRAND ARM (manufactured by JEOL Ltd.) and taking TEM images of 250 particles present in various regions on the grid. Then, the length was measured from the obtained TEM image, and the average value was obtained. Absolute quantum yield (PLQY), emission spectrum peak value (λem) and emission spectrum half width (FWHM) were determined using an absolute PL quantum yield measurement device Quantaurus-QY (manufactured by Hamamatsu Photonics) at an excitation wavelength of 400 nm. . The volume mean diameter (MV) and SD value were obtained using the measurement device, analysis software and conditions described above.

It can be seen that the luminescent particles produced by the production methods of Examples 1 to 13 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 1 to 7. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 1 to 13 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little

(Comparative Example 14) Production Using Continuous Laminar Flow Reactor Luminescent particles were produced in the same manner as in Example 1, except that liquid LR2-1 was replaced with liquid LR3-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 5 below.

(Examples 14 to 23) Production using a droplet-based flow reactor Luminescent particles were produced using a droplet-based flow reactor apparatus 500 shown in Fig. 7 . In the droplet-based flow reactor device 500, gas-tight syringes (manufactured by Hamilton) in which the perfluoropolyether fluorine-based fluid Galden PFPE (manufactured by SOLVAY) was collected as the first liquid, the second liquid, and the carrier liquid were used as syringes. It was fixed to a pump (manufactured by Cetoni), and luer lock connectors of gas-tight syringes were connected to the introduction section 510, the introduction section 520, and the introduction section 530, respectively. Pipe 511 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm), pipe 521 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm), pipe 531 (inner diameter 0.5 mm, outer diameter 1/16", 20 cm long), tubing 541 (0.5 mm ID, 1/16" OD, 20 cm length) and tubing 542 (0.5 mm ID, 1/16" OD, 50 cm length) are In both cases, tubes made of tetrafluoroethylene/perfluoroalkoxyethylene copolymer resin (PFA) were used.The cross-shaped mixer 501 had a through hole diameter of 0.50 mm and a polyether ether ketone resin union joint (manufactured by IDEX Health & Science). The piping 511, piping 521, piping 531, piping 541, and cross mixer 501 were immersed in an oil bath 502 and set to the temperatures shown in Table 6. The piping 542 was placed in a cooling bath 503 at 20°C. A glass bottle for receiving the discharged liquid was installed in the discharge part 540. Example number, first liquid type and flow rate, second liquid type and flow rate, carrier liquid flow rate, oil The set temperature of the bath and the resulting calculated concentration of the semiconducting compound ABX ₃ are shown in Table 6 below, provided that the semiconducting compound ABX ₃ is not included in the carrier liquid, and the concentration in the liquid excluding the carrier liquid is calculated. value.

The carrier liquid was separated from the resulting mixture of the colloidal solution containing the luminescent particles and the carrier liquid by liquid separation treatment. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1-10. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 7 below.

It can be seen that the luminescent particles produced by the production methods of Examples 14 to 23 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 1 to 7. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 14 to 23 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little In addition, the luminescent particles produced using the droplet-based flow reactor, as shown in Examples 14-23, are comparable to the luminescent particles produced using the continuous laminar flow reactor, shown in Examples 1-13. It can be seen that the PLQY is comparable and the FWHM is smaller compared to the particles.

(Comparative Example 15) Production using a droplet-based flow reactor Luminescent particles were produced in the same manner as in Example 14, except that liquid LR3-1 was used instead of liquid LR2-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 8 below.

(Examples 24 to 33) Production Using Forced Thin Film Type Flow Reactor Luminescent particles were produced using a forced thin film type flow reactor apparatus 600 shown in FIG. As a reactor main body constituting this device 600, a forced thin film type microreactor ULREA (manufactured by M Technic Co., Ltd.) was used. The reactor body comprises an approachable and retractable disc 601 , a rotatable disc 602 , a processing surface 603 and a collection section 604 . In the forced thin film flow reactor device 600, a gas-tight syringe (manufactured by Hamilton) that collected the first liquid was fixed to a syringe pump (manufactured by Cetoni), and a luer lock connector of the gas-tight syringe was connected to the introduction part 620. . A gas-tight syringe (manufactured by Hamilton) for sampling the second liquid was fixed to a syringe pump (manufactured by Cetoni), and a luer lock connector of the gas-tight syringe was connected to the introduction portion 610 . Pipe 611 (inner diameter 0.5 mm, outer diameter 1/16″, length 50 cm), pipe 621 (inner diameter 0.5 mm, outer diameter 1/16″, length 50 cm), and pipe 632 (inner diameter 0.8 mm, outer diameter 1/16" in diameter and 100 cm in length) were both stainless steel tubes. The pipes 611 and 621 were immersed in an oil bath 605 and set to the temperatures shown in Table 9 below. The processing surface of the disk 601 A cooling medium of 20° C. was circulated in the portion in contact with 603. A glass bottle for receiving the discharged liquid was installed in the discharge section 630. The rotational speed of the disc was 1000 rpm.The supply pressure of the second liquid. Example number, type and flow rate of the first liquid, type and flow rate of the second liquid, set temperature of the oil bath, and calculated values for the concentration of the resulting semiconductor compound _ABX3 are shown below. Table 9 shows.

The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 10 below.

It can be seen that the luminescent particles produced by the production methods of Examples 24 to 33 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 1 to 6. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 24 to 33 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little In addition, the luminescent particles produced using the forced thin film flow reactor, as shown in Examples 24-33, are comparable to the luminescent particles produced using the continuous laminar flow reactor shown in Examples 1-13. It can be seen that the PLQY is slightly lower and the FWHM is comparable compared to the particles. The luminescent particles produced using the forced thin film flow reactor, as shown in Examples 24-33, are comparable to the luminescent particles produced using the droplet-based flow reactor shown in Examples 14-23. By comparison, it can be seen that the PLQY is slightly lower and the FWHM is slightly larger. Also, as shown in Example 29, when a forced thin film flow reactor was used to produce a highly concentrated colloidal solution of luminescent particles, the continuous laminar flow reactor and droplets shown in Examples 8 and 19 were used. Compared to production using a base flow reactor, the yield is high, the PLQY is high, and the FWHM is small. It turns out that it is possible to produce luminescent particles with properties.

(Comparative Example 16) Production Using Forced Thin Film Type Flow Reactor Luminescent particles were produced in the same manner as in Example 24, except that the liquid LR2-1 was replaced with the liquid LR3-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 11 below.

(Examples 34 to 41) Production Using Continuous Laminar Flow Reactor Luminescent particles were produced using a continuous laminar flow reactor 700 shown in FIG. In the continuous laminar flow reactor 700, the gas-tight syringes (manufactured by Hamilton) that collected the first liquid and the second liquid were fixed to a syringe pump (manufactured by Cetoni), and the luer lock connectors of the gas-tight syringes were connected to each other. It was connected to the introduction part 710 and the introduction part 720 . Pipe 711 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm), pipe 721 (inner diameter 0.5 mm, outer diameter 1/16″, length 20 cm) and pipe 731 (inner diameter 0.5 mm, outer diameter 1/16", length 200 cm) used a stainless steel tube. The T-shaped mixer 701 used a stainless steel micromixer (manufactured by Sanko Seiki Kogyo Co., Ltd.) with a channel inner diameter of 0.25 mm. A glass bottle was set up to receive the drained liquid.The example number, the type and flow rate of the first liquid, the type and flow rate of the second liquid, and the resulting calculated concentration of the semiconducting compound ABX ₃ are given below. Table 12 shows.

The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 13 below.

It can be seen that the luminescent particles produced by the production methods of Examples 34 to 41 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 8 to 13. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 34 to 41 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little

(Comparative Example 17) Production Using Continuous Laminar Flow Reactor Luminescent particles were produced in the same manner as in Example 34, except that liquid LR4-1 was replaced with liquid LR5-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 14 below.

Examples 42 to 49 Production Using a Droplet-Based Flow Reactor Luminescent particles were produced using a droplet-based flow reactor 800 shown in FIG. In the droplet-based flow reactor 800, gas-tight syringes (manufactured by Hamilton), each of which is a first liquid, a second liquid, and a perfluoropolyether fluorine-based fluid Galden PFPE (manufactured by SOLVAY) as a carrier liquid, are collected by a syringe pump. (manufactured by Cetoni), and luer lock connectors of gas-tight syringes were connected to the introduction section 810, the introduction section 820, and the introduction section 830, respectively. Piping 811 (inner diameter 0.5 mm, outer diameter 1/16", length 20 cm), piping 821 (inner diameter 0.5 mm, outer diameter 1/16", length 20 cm), piping 831 (inner diameter 0.5 mm, outer diameter 1/16", length 20 cm) and piping 841 (inner diameter 0.5 mm, outer diameter 1/16", length 300 cm) are both tetrafluoroethylene/perfluoroalkoxyethylene copolymer resin (PFA) tubes. Using. The cross-shaped mixer 801 used a polyetheretherketone resin union joint (manufactured by IDEX Health & Science) with a through-hole diameter of 0.50 mm. A vial was placed in the drain 840 to receive the drained liquid. The example number, the type and flow rate of the first liquid, the type and flow rate of the second liquid, the flow rate of the carrier liquid and the resulting calculated concentration of the semiconducting compound ABX ₃ are shown in Table 15 below. However, the semiconductor compound ABX ₃ was not contained in the carrier liquid, and the concentration in the liquid excluding the carrier liquid was used as the calculated value.

The carrier liquid was separated from the resulting mixture of the colloidal solution containing the luminescent particles and the carrier liquid by liquid separation treatment. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 16 below.

It can be seen that the luminescent particles produced by the production methods of Examples 42 to 49 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 8 to 13. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 42 to 49 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little Additionally, luminescent particles produced using a droplet-based flow reactor, as shown in Examples 42-49, are comparable to luminescent particles produced using a continuous laminar flow reactor, as shown in Examples 34-41. It can be seen that the PLQY is comparable and the FWHM is smaller compared to the particles.

(Comparative Example 18) Production using a droplet-based flow reactor Luminescent particles were produced in the same manner as in Example 39, except that liquid LR4-1 was replaced with liquid LR5-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 17 below.

(Examples 50 to 57) Production Using Forced Thin Film Type Flow Reactor Luminescent particles were produced using a forced thin film type flow reactor apparatus 900 shown in FIG. As a reactor main body constituting this device 900, a forced thin film type microreactor ULREA (manufactured by M Technic Co., Ltd.) was used. The reactor body comprises an approachable and retractable disc 901 , a rotatable disc 902 , a processing surface 903 and a collection section 904 . In the forced thin film type flow reactor device 900, a gas-tight syringe (manufactured by Hamilton) that collected the first liquid was fixed to a syringe pump (manufactured by Cetoni), and a luer lock connector of the gas-tight syringe was connected to the introduction part 920. . A gas-tight syringe (manufactured by Hamilton) for sampling the second liquid was fixed to a syringe pump (manufactured by Cetoni), and a luer lock connector of the gas-tight syringe was connected to the introduction portion 910 . Pipe 911 (0.5 mm inner diameter, 1/16″ outer diameter, 50 cm length), pipe 921 (0.5 mm inner diameter, 1/16″ outer diameter, 50 cm length), and pipe 932 (0.8 mm inner diameter, outer 1/16" in diameter and 100 cm in length), a stainless steel tube was used. A glass bottle was placed in the discharge part 930 to receive the discharged liquid. The rotation speed of the disk was 1000 rpm. The supply pressure of was 0.2 MPa.The example number, the type and flow rate of the first liquid, the type and flow rate of the second liquid, and the calculated concentration of the resulting semiconductor compound ABX ₃ are shown in Table 18 below. Indicated.

The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 19 below.

It can be seen that the luminescent particles produced by the production methods of Examples 50 to 57 have a higher yield than the luminescent particles produced using the batch reactors shown in Comparative Examples 8 to 13. In addition, the high PLQY and small FWHM indicate excellent optical properties. In addition, the luminescent particles produced by the production methods of Examples 50 to 57 have a smaller volume average diameter and a smaller SD value than the luminescent particles produced using a batch reactor. It can be seen that there is little Additionally, luminescent particles produced using a forced thin film flow reactor, as shown in Examples 50-57, were similar to luminescent particles produced using a continuous laminar flow reactor, as shown in Examples 34-41. It can be seen that the PLQY is higher and the FWHM is the same or slightly lower than the particles. Luminescent particles produced using the forced film flow reactor, as shown in Examples 50-57, are comparable to luminescent particles produced using the droplet-based flow reactor shown in Examples 42-49. By comparison, it can be seen that the PLQY is high and the FWHM is comparable or slightly lower. Also, as shown in Example 53, when a forced thin film flow reactor was used to produce a highly concentrated colloidal solution of luminescent particles, the continuous laminar flow reactor and droplets shown in Examples 37 and 45 Compared to production using a base flow reactor, the yield is high, the PLQY is high, and the FWHM is small. It turns out that it is possible to produce luminescent particles with properties.

(Comparative Example 19) Production Using Forced Thin Film Type Flow Reactor Luminescent particles were produced in the same manner as in Example 50, except that liquid LR4-1 was replaced with liquid LR5-1. The resulting colloidal solution containing luminescent particles was purified by the same method as in Examples 1 to 13. Regarding the purified colloidal solution containing the obtained luminescent particles, yield based on monovalent cation A, absolute quantum yield (PLQY), emission spectrum peak value (λem), emission spectrum half width (FWHM ), volume mean diameter (MV) and SD values were measured by similar methods. The measurement results are shown in Table 20 below.

(Examples 58 to 114, Comparative Examples 20 to 38) Production of Luminescent Particle-Containing Compositions, Production and Evaluation of Films Containing Luminescent Particles 9 mL of methyl acetate was added to a glass vial equipped with a stirring bar. . 3 mL each of the purified colloidal solutions containing luminescent particles produced in Examples 1 to 54 and Comparative Examples 1 to 18 were pipetted and added with stirring. The resulting suspension was centrifuged at 10,000 rpm for 5 minutes using a centrifuge IKA GL (manufactured by IKA). A solid substance containing luminescent particles was obtained by removing the supernatant liquid.
Light acrylate LA (manufactured by Kyoeisha Chemical Co., Ltd.) 65 parts by mass and light acrylate 1.6HX-A (manufactured by Kyoeisha Chemical Co., Ltd.) are added to a glass vial equipped with a stirrer in a clean room in which light with a wavelength of 500 nm or less is cut. 32 parts by mass and 3 parts by mass of Omnirad TPO (manufactured by IGM Resin) were added and dissolved by stirring at room temperature. A luminescent particle-containing composition was produced by adding 1.5 parts by mass of a solid matter containing luminescent particles and stirring at room temperature to dissolve. The resulting luminescent particle-containing composition was filtered through a membrane filter (pore size 0.50 μm). The obtained luminescent particle-containing composition after filtering was dropped onto a glass substrate Eagle XG (manufactured by Corning) and spin-coated using a spin coater MS-B100 (manufactured by Mikasa) to a film thickness of about 10 μm. bottom. A film containing luminescent particles was produced by irradiating the obtained coating film with UV light having a dominant wavelength of 395 nm in a nitrogen atmosphere so that the integrated light quantity was 10 J/cm ² .

(Evaluation of heat resistance)
Each film containing the obtained luminescent particles was heated in the air at 80° C. and 50% RH for 5 hours while shielded from light. The absolute quantum yield (PLQY) of the film was measured before and after heating, and the PLQY retention rate (%) after heat treatment was determined. PLQY retention rate (%) after heat treatment was calculated by the following formula (a).
PLQY retention rate after heat treatment (%) =
(PLQY of film after heating)/(PLQY of film before heating) * 100 (a)

(Evaluation of light resistance)
Each film containing the obtained luminescent particles was irradiated with blue light having a peak emission wavelength of 450 nm for 2 hours at a stage temperature of 30° C. and 60 mW/cm ² in air using a light resistance tester (manufactured by CCS Corporation). bottom. The absolute quantum yield (PLQY) of the film was measured before and after light irradiation, and the PLQY retention rate (%) after light irradiation treatment was determined. PLQY retention rate (%) after light irradiation treatment was calculated by the following formula (b).
PLQY retention rate after light irradiation treatment (%) =
(PLQY of film after light irradiation)/(PLQY of film before light irradiation) * 100 (b)
For each film containing the obtained luminescent particles, the example number of the purified colloidal solution containing the luminescent particles, the PLQY retention rate after heat treatment (%), and the PLQY retention rate after light irradiation treatment (%) are shown below. Tables 21 to 28 show.

The films produced by the production methods of Examples 58 to 114 contain the luminescent particles produced by the production methods of Examples 1 to 57, while the films produced by the production methods of Comparative Examples 33 to 38 contains the luminescent particles produced by the production methods of Comparative Examples 13 to 19, and the luminescent particles do not contain a siloxane bond in the ligand layer. The films produced by the production methods of Examples 58 to 114 are Compared to the films produced by the production methods of Comparative Examples 33 to 38, the PLQY retention rate (%) after heat treatment and the PLQY retention rate (%) after light irradiation treatment are both high, so moisture, light and It can be seen that the stability against heat is high. In addition, the films produced by the production methods of Examples 58 to 114 had PLQY after heat treatment compared with the films containing luminescent particles produced using the batch reactors shown in Comparative Examples 20 to 32. It can be seen that both the retention rate (%) and PLQY retention rate (%) after light irradiation treatment are slightly high. This is because the luminescent particles produced by the production methods of Examples 1 to 57 have a small SD value and little variation in particle size, so that when a film is formed, unevenness is reduced, and contact with water molecules and oxygen radicals is reduced. It is presumed that the cause is that the area is small and deterioration is difficult to occur.

As described above, it is clear that, according to the production method of the present invention, luminescent particles having high stability against moisture, light and heat and having controlled emission wavelength and particle size can be produced at a high yield.

10 Luminescent Particle 11 Core 12 Ligand 13 Ligand Layer 14 Siloxane Bond 20 Structural Schematic Diagram of Luminescent Particle Surface 100 Continuous Laminar Flow Reactor Apparatus 101 T-Shaped Mixers 110, 120 Introduction Portions 111, 121, 131 Channel 130 Outlet 200 Droplet-based flow reactor devices 201, 202 T-shaped mixers 210, 220, 240 Inlet 211, 221, 231, 241, 251 Channel 250 Outlet 300 Forced thin film flow reactor device 300a Device cross-section 300b BB′ line cross-sectional view 301 of the device Approachable/separable disk 302 Rotatable disk 303 Processing surface 304 Recovery parts 310, 320 Introduction parts 311, 321, 331, 332 Flow paths 312, 322 Connection part 330 Discharge part 400 continuous laminar flow reactor device 401 T-shaped mixer 402 oil bath 403 cooling baths 410, 420 inlets 411, 421, 431, 432 channel 430 outlet 500 droplet-based flow reactor device 501 cruciform mixer 502 oil bath 503 Cooling baths 510 , 520 , 530 Introduction parts 511 , 521 , 531 , 541 , 542 Flow path 540 Discharge part 600 Forced thin film type microreactor device 601 Approachable and separated disk 602 Rotatable disk 603 Processing surface 604 Collection part 605 oil baths 610, 620 inlets 611, 621, 631, 632 channels 612, 622 connection 630 outlet 700 continuous laminar flow reactor apparatus 701 T-shaped mixers 710, 720 inlets 711, 721, 731 channel 730 outlet Part 800 droplet-based flow reactor device 801 cruciform mixers 810, 820, 830 inlets 811, 821, 831, 841 channel 840 outlet 900 forced thin film microreactor device 901 approachable and reversible disc 902 rotatable disc 903 Processing surface 904 Recovery parts 910, 920 Introduction parts 911, 921, 931, 932 Flow paths 912, 922 Connection part 930 Discharge part

Claims (13)

A method for producing a luminescent particle comprising a core containing semiconductor nanoparticles and a ligand layer bonded to the core via an amino group, wherein the ligand layer contains a siloxane bond,
Using a flow reactor equipped with a channel capable of merging and mixing different liquids introduced from a plurality of inlets, at least one first liquid containing raw materials or precursors for producing the luminescent particles is introduced from the different inlets. A liquid and at least one second liquid whose components are different from those of the first liquid are introduced into the channel and mixed to produce a colloidal solution containing the luminescent particles in the mixed fluid. A method for producing luminescent particles, comprising steps. At least one of the first liquid and the second liquid has the following general formula (L1)

(Wherein, R ¹ , R ² and R ³ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms and a straight chain having 1 to 10 carbon atoms. represents a group selected from the group consisting of chain or branched alkoxy groups (provided that at least one of R ¹ , R ² and R ³ represents a group selected from the group consisting of halogen atoms, hydroxyl groups and alkoxy groups ),
R ⁴ and R ⁵ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon ring group having 3 to 20 carbon atoms, and 6 to represents a group selected from the group consisting of 20 aromatic hydrocarbon ring groups, but any hydrogen atom in the alkyl group and hydrocarbon ring group is a halogen atom, a non-aromatic hydrocarbon ring group or an aromatic hydrocarbon ring 1 or 2 or more —CH ₂ — in the alkyl group are each independently —O—, —S—, —CO—, —COO—, —OCO—, —CO— S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-, -CF=CF- or -C≡C- R ⁴ and R ⁵ may combine directly or via a linking group to form a ring,
Sp ¹ is each independently a linear or branched alkylene group having 1 to 20 carbon atoms, a non-aromatic hydrocarbon cyclic group having 3 to 20 carbon atoms, and an aromatic hydrocarbon having 6 to 20 carbon atoms represents a group selected from the group consisting of cyclic groups, any hydrogen atom in the alkylene group may be substituted with a halogen atom, and one or more —CH ₂ — in the alkylene group are each independently may be replaced with -CH=CH- or -C≡C-, but when there are multiple Sp ^1s , they may be the same or different,
Z ¹ each independently represents -O-, -S-, -NH-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O- , -CO-NH-, -NH-CO-, -CH(CH ₂ CH ₂ NH ₂ )-, -N(CH ₂ CH ₂ NH ₂ )-, -NHC(=NH)- or a single bond , Z ¹ may be the same or different when there are more than one,
m1 represents an integer of 1 to 20; 2. The method for producing a luminescent particle according to claim 1, wherein the compound represented by ) is contained. 3. The method according to claim 1 or claim 2, wherein one of the first liquid and the second liquid contains monovalent cations A and the other contains metal ions B and halide ions X. A method for producing luminescent particles. One of the first liquid and the second liquid contains a monovalent cation A, a metal ion B, a halide ion X, and a first solvent, and the other contains the solubility of the semiconductor nanoparticles 3. A method for producing luminescent particles according to claim 1 or claim 2, comprising a second solvent having a lower V than the first solvent. The semiconductor nanoparticles are composed of a compound semiconductor containing A, B and X (wherein A represents a monovalent cation, B represents a metal ion, and X represents a halide ion). 3. A method for producing a luminescent particle according to claim 1 or 2. 3. The method for producing luminescent particles according to claim 1, wherein the semiconductor nanoparticles have a perovskite crystal structure. 3. The method for producing luminescent particles according to claim 1, wherein the luminescent particles have a volume average diameter of 9 nm or more and 80 nm or less. Equation (1) below
SD=(d84%-d16%)/2 (1)
(In the formula, d84% represents the particle diameter (nm) at the point where the cumulative curve is 84% when the cumulative curve is obtained with the total volume of the luminescent particles as 100%, and d16% represents the total volume of the luminescent particles at 100%. 3. The SD value represented by ) is 1 nm or more and 40 nm or less. A method for producing luminescent particles. 3. The method for producing luminescent particles according to claim 1, wherein the step of producing the colloidal solution containing the luminescent particles is performed using a continuous laminar flow reactor. 3. The method for producing luminescent particles according to claim 1 or 2, wherein the step of producing a colloidal solution containing luminescent particles is performed using a droplet-based flow reactor. 3. The method for producing luminescent particles according to claim 1 or 2, wherein the step of producing a colloidal solution containing the luminescent particles is performed using a forced thin film flow reactor. A luminescent particle-containing composition comprising a step of producing a luminescent particle-containing composition by mixing a colloidal solution containing the luminescent particles obtained by the production method according to claim 7 and a photopolymerizable compound. Production method. a step of removing the solvent from the colloidal solution obtained by the production method according to claim 7 to recover the luminescent particles;
A method for producing a luminescent particle-containing composition, comprising a step of producing a luminescent particle-containing composition by mixing the collected luminescent particles and a photopolymerizable compound.

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