Group III nitride semiconductor nanoparticles, core-shell type particles, and methods for manufacturing the same

Abstract

The present invention provides group III nitride nanoparticles that are substantially free of impurities and have high quantum efficiency. When synthesizing group III nitride semiconductor nanoparticles with a particle size of 16 nm or less by reacting a material containing one or more group III elements M in a liquid phase, trimethylindium is used as at least one group III element material among the materials containing one or more group III elements M, and prior to the synthesis reaction of the nanoparticles, trimethylindium is dissolved in a coordination solvent to form a precursor, and the nanoparticles are synthesized by reacting this precursor with other group III element materials and a nitrogen source in a solvent at 300°C or higher under an inert atmosphere.

Description

Technology Field

[0001] The present invention relates to semiconductor nanoparticles composed of nitrides of group III elements such as Al, Ga, and In, and in particular to a method for manufacturing group III nitride semiconductor nanoparticles that does not use halogen-based materials. Background Technology

[0002] Nitride nanoparticles are materials expected to be applied in EL devices such as lighting and displays, photodetectors such as sensors and solar cells, and photocatalysts such as hydrogen generation. It is known that quantum effects are exhibited when the particle size of nitride nanoparticles is less than twice the Bohr radius, and even with nitride nanoparticles of the same composition, the energy gap can be controlled by changing the particle size, thereby significantly improving the controllability of the emission wavelength and the light absorption range.

[0003] Al x Ga y In z The Bohr radius of a group III nitride expressed as N (0≤(x, y, z)≤1, x+y+z=1) is 2.3 nm for AlN, 3.3 nm for GaN, and 8.2 nm for InN, and by controlling the composition and particle size, the emission range can be controlled from ultraviolet to infrared. In particular, by including In, nitride nanoparticles that emit light in the visible region can be manufactured, thereby improving the luminescence efficiency.

[0004] A method for manufacturing Group III nitride nanoparticles is generally a chemical synthesis method in which Group III elemental materials and nitrogen materials are synthesized in a liquid phase, and nanoparticles with a particle size of 16 nm or less that exhibit quantum effects can be manufactured by chemical synthesis. As Group III elemental materials, halogen compounds such as indium iodide and gallium iodide, which can maintain stability even when heated during chemical synthesis, are used. For example, Patent Document 1 discloses a method for manufacturing nitride nanoparticles using indium iodide and gallium iodide. Prior art literature

[0005] Patent Document 1: Japanese Patent Publication No. 2012-515803 The problem to be solved

[0006] However, when halogen compounds are used as synthetic raw materials, there is a problem in that trace amounts of halogen enter the particles of the resulting nitrides as impurities. Furthermore, during the manufacturing process of halogen-based materials, transition elements such as iron group elements and alkali metal elements such as Li and Na remain as residues, and these elements, like halogens, also enter the nitride particles as impurities. Since these impurities enter the particles and function as non-radiative centers for excited carriers, they lead to a decrease in luminous efficiency. In particular, even trace amounts of transition elements such as iron group elements or alkali metal elements such as Li and Na, on the order of a few ppm, cause a critical reduction in luminous efficiency.

[0007] Among Group III compounds other than halogen compounds, there are organic Group III compounds such as trimethylindium (hereinafter referred to as TMIn) and triethylindium. Since these compounds are of high purity and do not contain unnecessary elements in the material itself, there are instances where they are used as materials for vapor phase growth, such as MOCVD, in the manufacture of high-quality nitride thin films for LEDs. However, TMIn poses a risk of causing a violent self-decomposition reaction accompanied by an explosion when heated above 80°C. For this reason, it cannot be used in chemical synthesis where it is directly heated to react and decompose. In particular, since high thermal energy is required in the chemical synthesis of nitride nanoparticles, it is necessary to react and decompose the material at least above 100°C, preferably above 150°C, making it impossible to use TMIn as a material. Furthermore, if a self-decomposition reaction occurs, it precipitates as In metal, so it does not become nitride nanoparticles containing In, or it is not possible to obtain a nitride with the desired elemental ratio.

[0008] The present invention is made to solve the above-mentioned conventional problems and aims to provide a method for producing Group III nitride nanoparticles by chemical synthesis without using halogen materials, and accordingly, to provide Group III nitride nanoparticles that do not contain halogen. means of solving the problem

[0009] In order to solve the above problem, as a result of carefully investigating the conditions for reaction with organic Group III materials usable for chemical synthesis, it was discovered that by using trimethyl M (where M is one or more of Al, Ga, and In) as a Group III elemental material and reacting it in a coordination solvent, it is possible to produce Group III nitride nanoparticles with a desired composition and a particle size of 16 nm or less while suppressing self-decomposition. The produced Group III nitride nanoparticles do not contain halogen elements or impurity elements contained in halogen-based materials, and have a higher quantum efficiency compared to Group III nitride nanoparticles synthesized using halogen-based materials. Effects of the invention

[0010] According to the present invention, in the chemical synthesis of nitride nanoparticles, the explosive self-decomposition reaction of TMIn can be suppressed, thereby enabling the stable production of nitride nanoparticles. Furthermore, according to the present invention, nitride nanoparticles with high luminescence efficiency can be provided without substantially containing impurities that impair luminescence efficiency. Brief explanation of the drawing

[0011] Figure 1 is a diagram showing the relationship between the composition and energy gap of group III nitride nanoparticles. Figure 2 is a diagram showing the structure and energy gap of core-shell type nanoparticles. Figure 3 is a table showing the results of ICP analysis of a Group III material for manufacturing Group III nitride nanoparticles. Figure 4 is a diagram showing the X-ray diffraction analysis results of nitride nanoparticles obtained in Example 1 and Comparative Examples 2 and 3. Figure 5 is a diagram showing the results of measuring the quantum efficiency of nitride nanoparticles obtained in Example 1 and Comparative Example 3. Specific details for implementing the invention

[0012] Hereinafter, embodiments of the group III nitride nanoparticles of the present invention and the method for manufacturing the same will be described.

[0013] The Group III nitride nanoparticles of the present invention are, general formula: Al x Ga y In z N (where 0 ≤ (x, y, z) ≤ 1, x + y + z = 1), or general formula: Al x Ga y In z It is a nanoparticle represented by N (where 0 ≤ (x, y) < 1, 0 < z ≤ 1, x + y + z = 1). Meanwhile, parentheses such as '0 ≤ (x, y, z) ≤ 1' indicate that each of x, y, and z is in a relationship represented by the inequality or equality sign before and after them.

[0014] The group III nitride nanoparticles of the present invention also include core-shell type particles having a nanoparticle represented by the general formula as the core particle and a group III nitride represented by the general formula as the shell.

[0015] As shown in FIG. 1, the energy gap of the nitrides of aluminum (Al), gallium (Ga), and indium (In) is within the range of the region formed by connecting the energy gap of the univalent nitrides (AlN, GaN, InN) with the energy gap of the binary nitrides, and can be arbitrarily changed within this range by varying the ratio of these three elements. In addition, the core-shell type has a Type 1 band structure as shown in FIG. 2, and the ratio of elements constituting the core particle and the shell is determined such that the energy gap of the core particle (EGcore) and the energy gap of the shell (EGshell) is such that EGcore < EGshell. As shown in FIG. 1, the energy gap becomes higher as the amount of Al increases, and the energy gap becomes lower as the amount of In increases. Therefore, a Type 1 band structure can be realized, for example, by combining a core particle containing a relatively large amount of In and a shell containing a relatively large amount of Al. As an example, a core-shell type particle in which the core particle is InGaN and the shell is AlInN can be cited. Not limited to such examples, if the energy gap between the core particle and the shell satisfies the relationship described above, various combinations of compositions are possible. In particular, it is preferable to have group III nitride nanoparticles containing indium or core-shell particles having the same as the core particle. Accordingly, the emission range can be extended to the visible range, and the luminescence efficiency is also improved.

[0016] The proportion of Group III elements in the nitride can be adjusted in the preparation of the Group III nitride nanoparticles described below by using the compound serving as the raw material for the Group III elements in stoichiometric proportions such that the molar ratio of the Group III elements becomes the desired ratio. In the manufacturing method of the present invention, the precipitation of metals or the incorporation of impurities during the reaction is controlled, thereby enabling the realization of the desired ratio.

[0017] The nitride nanoparticles of the present invention have a particle size of 16 nm or less. A particle size of 16 nm or less is less than twice the Bohr radius of InN (8.2 nm), and accordingly, quantum effects are exhibited, and high luminescence efficiency is obtained. Generally, the particle size of nitride nanoparticles can be reduced to 16 nm or less by chemically synthesizing them with a suitable solvent under high temperature conditions; in the manufacturing method of the present invention, this can also be achieved by adjusting synthesis conditions such as the synthesis temperature, heating time, solvent, and material concentration during manufacturing. Specific synthesis conditions will be described later.

[0018] Furthermore, the nitride nanoparticles of the present invention are characterized by substantially not containing impurity elements incorporated into halogen elements and halogen compounds. Nitride nanoparticles produced by conventional chemical synthesis methods utilize halogen compounds as Group III elemental materials during synthesis, and thus inevitably contain impurities derived from the halogen compounds. The impurities derived from halogen compounds vary depending on the type of halogen compound; examples include halogen elements such as iodine (I) and bromine (Br), as well as transition elements such as fluorine, iron, manganese, and zinc, and alkali metal elements such as Li and Na. Since the nitride nanoparticles of the present invention are produced by chemical synthesis that does not utilize halogen compounds, they are free from the incorporation of such impurities and exhibit high quantum efficiency (luminescence efficiency).

[0019] The group III nitride nanoparticles / core-shell type group III nitride nanoparticles of the present invention can be widely used for general semiconductor nanoparticle applications, and in particular, by utilizing their high quantum efficiency (high energy conversion efficiency, luminescence efficiency, light absorption efficiency derived therefrom, etc.), they can be suitably used in wavelength conversion materials, photocatalysts, solar cells, EL light-emitting devices, etc.

[0020] Next, a method for manufacturing the aforementioned group III nitride nanoparticles is described.

[0021] The method for preparing Group III nitride nanoparticles of the present invention involves reacting a material containing one or more Group III elements M in a liquid phase to synthesize Group III nitride semiconductor nanoparticles with a particle size of 16 nm or less, wherein at least one Group III material among the materials containing one or more Group III elements M is used as trimethyl M. Trimethyl M is pretreated using a coordination solvent.

[0022] The Group III nitride semiconductor nanoparticles being manufactured have the general formula: Al x Ga y In z Nanoparticles represented by N (where 0 ≤ (x, y, z) ≤ 1, x + y + z = 1), or general formula: Al x Ga y In z It is a nanoparticle represented by N (where 0≤(x, y)<1, 0<z≤1, x+y+z=1).

[0023] Hereinafter, a method for manufacturing Group III nitride nanoparticles of the present invention is described in detail.

[0024] The method for manufacturing Group III nitride nanoparticles of the present invention is based on a chemical synthesis method in which a Group III material and a nitrogen material are introduced into a solvent and heated to synthesize the nitride.

[0025] Compounds of Al, Ga, and In are used as Group III materials. In the general formula described above, if y > 0, i.e., if In is included, at least trimethylindium (TMIn) is used as the In material. Among organic In compounds, in addition to TMIn, there are trialkylindium compounds with long organic chain lengths such as triethylindium, which have a similar structure. When these In compounds are reacted under high temperature, they undergo a β-dehydrogenation reaction to produce metal hydrides, and furthermore, metal is produced as a byproduct of hydrogen reduction by the metal hydrides. As a result, the stoichiometric ratio of V elements and III elements in the obtained nitride nanoparticles changes, and a nitride of the desired composition is not obtained. When TMIn is used, such hydrogen dehydrogenation is unlikely to occur, so there is no precipitation of metallic indium, and nitride nanoparticles with a stable composition can be obtained.

[0026] It is preferable to convert TMIn into a precursor by treatment with a coordination solvent prior to the reaction. The coordination solvent suppresses the vigorous self-decomposition reaction by coordinating with the In of TMIn. As a coordination solvent, trioctylphosphine (boiling point: 315°C), tributylphosphine (boiling point: 150°C / 6.7kPa conditions), trioctylamine (boiling point: 367°C), diphenyl ether (boiling point: 260°C), etc., can be used, and trioctylphosphine (hereinafter abbreviated as TOP) is particularly preferred.

[0027] Regarding Al and Ga materials, it is preferable to use trimethylaluminum (TMAl) or trimethylgallium (TMGa), but compounds other than trimethylated metals (excluding halogen compounds) may also be used. For example, aluminum acetonate may be used for Al, and gallium acetonate for Ga. However, in order to minimize impurity elements incorporated into the nitride and to maintain stoichiometric ratios, it is most preferable to use trimethylaluminum and trimethylgallium, just as with In materials.

[0028] As nitrogen materials, ammonia, metal azide compounds, metal nitrides, hydrazines, amines, metal amides, etc., can be used. In particular, metal amides such as sodium amide and lithium amide are preferred.

[0029] As a reaction solvent, general solvents used for the synthesis of nitrides can be used. Specifically, examples include tetradecylbenzene (boiling point: 356°C), 1-octadecene (boiling point: 320°C), TOP, tributylphosphine, trioctylphosphine oxide (boiling point: 238°C / 0.4 kPa conditions), diphenyl ether, etc., and tetradecylbenzene is particularly preferred.

[0030] In the manufacturing method of the present invention, first, TMIn among the Group III materials is dissolved in a coordination solvent and converted into a precursor. A precursor is a state in which TMIn is isolated by solvation, and by converting it into this state, the self-decomposition reaction is suppressed. The precursor treatment is preferably performed at 20°C or below the boiling point of the solvent, and at 88°C (the melting point of TMIn) or above, as there is a risk of explosion due to the self-decomposition reaction. The precursor is thought to have a structure in which the phosphorus (P) of TOP is coordinately bonded to a metal (indium) to which a trimethyl group is attached, for example, in the case of using TOP. Since the TMIn molecule is isolated by the coordination of bulky trioctyl groups, the high self-decomposition reaction is inhibited, making it possible to maintain a relatively stable state for a long time. Accordingly, it continuously functions as a stable Group III source even under heating of 100°C or higher.

[0031] The amount of coordinating solvent required for precursor formation is preferably such that the molar ratio between P included in TOP and the metal element of the trimethylated metal introduced as a group III material is 1:1 or greater, and more preferably 3:1 or greater.

[0032] After performing such precursor treatment, a Group III elemental material other than TMIn, a nitrogen material, and a reaction solvent are added to the reaction system, and the synthesis reaction is carried out. The concentration of the materials is not particularly limited, but the concentration of the metal element (total amount required stoichiometrically) in the reaction solvent is preferably about 3 to 36 mol / liter. In addition, the nitrogen material is preferably equal to or greater than the Group III elemental material, and the concentration in the reaction solvent is preferably about 27 to 720 mol / liter.

[0033] The reaction is carried out in an inert atmosphere at a temperature of 200°C or higher, preferably 300°C or higher, and more preferably 330°C or higher. By reacting at such a temperature, nitride nanoparticles with a particle size of 16 nm or less are produced. The reaction time is about 1 to 5 minutes, depending on the scale of the reaction. After the reaction, the particles are washed by repeated centrifugation using a specified solvent, and then recovered as particles or as a solvent dispersion.

[0034] The method for manufacturing core-shell type nanoparticles is the same as the general method for manufacturing core-shell type nanoparticles, and a group III nitride nanoparticle obtained by the above-described manufacturing method is used as the core particle, and a group III nitride that serves as the shell covering it is synthesized. To obtain a Type 1 structure, the compositions of the core particle and the shell are selected such that the energy gap of the core particle (EGcore) and the energy gap of the shell (EGshell) are such that EGcore < EGshell. For example, the core particle is composed of a relatively large amount of In, and the shell is composed of a relatively large amount of Al. In addition, as the material for the group III element constituting the shell, a material other than a halogen compound, particularly a trimethylate, is used.

[0035] The synthesis reaction for forming the shell is carried out by adding nanoparticles prepared by the manufacturing method described above, a material of a Group III element constituting the shell, and a solvent to a reaction vessel, and heating in an inert atmosphere at 200°C or higher, preferably 300°C or higher, more preferably 330°C or higher. The solvent may be the same as the solvent used to prepare the core particles. The method for recovering the core-shell particles after production is the same as that for recovering the core particles, and the core-shell particles are recovered as a dispersion by repeating centrifugation and washing using a dispersion medium.

[0036] The Group III nitride nanoparticles and core-shell type Group III nitride nanoparticles obtained by the above manufacturing method do not utilize halogen-based materials containing impurity elements such as iron; therefore, they substantially contain no impurities (e.g., undetectable in powder X-ray measurements), have high purity, and there is no decrease in luminescence efficiency caused by impurities.

[0037] Examples

[0038] Hereinafter, examples of the preparation of Group III nitride nanoparticles of the present invention are described. Meanwhile, in the following examples and comparative examples, the particle sizes were all measured using a transmission electron microscope (TEM) and a scanning transmission electron microscope (STEM).

[0039] [Example 1]

[0040] Trimethylgallium (TMGa) was used as the Ga source, TMIn as the In source, and lithium amide as the Group V source. The general ICP measurement results of TMGa and TMIn used as materials are shown in Fig. 3. For reference, the measurement results of indium iodide and gallium iodide are also shown in Fig. 3. As shown, transition metals or alkali metals were detected in the iodides, whereas such impurity elements were not detected in the materials used in this example.

[0041] First, TMIn (0.0675 mmol) was added to TOP (0.5 ml) and heated to 40°C to perform precursor treatment. Hereinafter, TMIn after precursor treatment is abbreviated as TMIn@TOP.

[0042] In a glass reaction vessel, 0.0675 mmol of TOP@TMIn, 0.0675 mmol of TMGa, and 2.7 mmol of lithium amide were added, and tetradecylbenzene (1.0 ml) was added as a reaction solvent, heated to 350°C in an inert atmosphere, and reacted for about 3 minutes.

[0043] After the reaction, the product was recovered in a centrifuge tube, and a mixed solvent of hexane and ethanol in a volume ratio of approximately 3:7 was added. Centrifugation was performed at 10,000–30,000 rpm for about 30 minutes, and the supernatant was discarded. The obtained precipitate was dispersed in hexane, and ethanol was added to perform centrifugation again under the same conditions. This process was repeated 3 to 5 times to wash the particles. Finally, the mixture was dispersed in hexane to obtain a hexane dispersion sample. The particle size of the obtained nanoparticles was 3–5 nm.

[0044] [Comparative Example 1]

[0045] As a result of using TMIn without precursor treatment instead of TMIn@TOP as the In source, explosive self-decomposition occurred during heating, and the product could not be recovered.

[0046] [Comparative Example 2]

[0047] Nitride particles were prepared by carrying out the reaction in the same manner as in Example 1, except that triethylindium (TEIn) was used instead of TMIn as the In source. Meanwhile, since TEIn does not undergo a self-decomposition reaction, it was added directly to the reaction solvent without precursor treatment. The particle size of the obtained nanoparticles was 50 to 200 nm.

[0048] [Comparative Example 3]

[0049] Nitride nanoparticles (hexane dispersion) were obtained in the same manner as in Example 1, except that indium iodide (InI3) and gallium iodide (GaI3) were used instead of TMIn and TMGa as the In and Ga sources. The particle size of the obtained nanoparticles was 3 to 5 nm.

[0050] Powder X-ray diffraction (XRD) measurements were performed on the nitride particles obtained in Example 1 and Comparative Examples 2 and 3, respectively. The results are shown in Fig. 4.

[0051] From the results of the powder X-ray measurement shown in Fig. 4, it was confirmed that nitride nanoparticles were formed in Example 1 and Comparative Examples 2 and 3, but in Comparative Example 2, it was confirmed that In metal was precipitated. From this, it was found that when the alkyl chain is lengthened, metal precipitation occurs due to the reduction reaction, so nitride particles of good purity are not obtained, and the yield also decreases.

[0052] In addition, impurity analysis and quantum efficiency were measured for the nitride nanoparticles of Example 1 and Comparative Example 3. For impurity analysis, iron (Fe) was analyzed using X-ray fluorescence analysis (XRF), and iodine (I) was analyzed using X-ray photoelectron spectroscopy (XPS) and ICP. For quantum efficiency measurement, a quantum efficiency meter (Otsuka Electronics QE-2100) was used, and excitation light (365 nm) was incident on the particle dispersion solution. The results of the impurity analysis are shown in Table 1, and the results of the quantum efficiency measurement are shown in Figure 5. Meanwhile, the impurity analysis results were calculated as the 'amount of impurities for Group III (ppm)' using the impurities and Group III values ​​detected in each measurement.

[0053] Fe(XRF) I(XPS) I(ICP) Example 1 Not detected (*1) Not detected (*2) Not detected (*3) Comparative Example 3 83 1014 876

[0054] *1: Lower detection limit: 20ppm, *2: Lower detection limit: 500ppm, *3: Lower detection limit: 100ppm

[0055] As shown in Table 1, in Comparative Example 3, which used a halogen compound as a Group III raw material, Fe was detected as an impurity in addition to the halogen element (I), whereas in Example 1, these impurity elements were not detected. From this, it can be seen that impurities other than halogens, such as Fe, are impurities originating from the material, and that nitride particles of high purity are obtained by not using a halogen compound as the material. Furthermore, as shown in Figure 5, while the quantum efficiency of the nitride nanoparticles of Example 1 was about 11%, the quantum efficiency of the nitride nanoparticles of Comparative Example 3 was lowered to about 7%, confirming that the luminescence efficiency decreased due to impurities in the material.

[0056] [Example 2]

[0057] The following precursor treatment, core particle synthesis, and shell formation were performed sequentially to produce core-shell type nitride particles. Trimethylgallium (TMGa) was used as the Ga source, TMIn as the In source, TMAl as the Al source, and lithium amide as the group V source.

[0058] In the precursor treatment, TMIn was added to TOP (0.5 ml) as in Example 1, and the precursor treatment was performed by heating to 40°C to obtain TMIn@TOP.

[0059] In the synthesis of core particles, 0.0675 mmol of TMIn@TOP, 0.0675 mmol of TMIn, 2.7 mmol of lithium amide, and 1.0 ml of tetradecylbenzene as a reaction solvent were added to a glass reaction vessel, heated to 350°C in an inert atmosphere, and reacted for about 3 minutes.

[0060] The product was recovered in a centrifuge tube, and after repeating centrifugation and washing with hexane / ethanol as in Example 1, hexane-dispersed InGaN nanoparticles (particle size 3~5 nm) were obtained.

[0061] Next, tetradecylbenzene was added to the InGaN nanoparticle dispersion and solvent exchange was performed under reduced pressure while diffusing. The InGaN nanoparticles (core particles) after solvent exchange were placed in a glass reaction vessel, and 0.054 mmol of TMAl and 0.081 mmol of TMIn@TOP were added. The proportion of the Group III element In in the added materials was 60 atomic percent. Furthermore, 2.7 mmol of lithium amide was added, and the materials were reacted by heating to 350°C in an inert atmosphere.

[0062] The product is subjected to repeated centrifugation and washing, as in the synthesis of the core particles above, to finally obtain hexane-dispersed core-shell particles (In 0.5 Ga 0.5 N / Al 0.4 In 0.6 N) was obtained. It was confirmed to be nitride nanoparticles by powder X-ray measurement. The particle size of these core-shell particles was 3–6 nm.

[0063] [Comparative Example 4]

[0064] Core-shell particles were prepared in the same manner as in Example 2, except that the In source, Ga source, and Al source were replaced with indium iodide, gallium iodide, and aluminum iodide (AlI3), respectively. From the ICP analysis results shown in Table 1 and the quantum efficiency measurement results of Comparative Example 3, it is presumed that the luminescence efficiency of Comparative Example 4 is also lower than that of Example 2. Industrial applicability

[0065] According to the present invention, nitride nanoparticles are provided that can improve the performance of wavelength conversion materials, photocatalysts, solar cells, EL light-emitting devices, etc. by being used therein.

Claims

Claim 1 A method for manufacturing Group III nitride semiconductor nanoparticles, characterized by reacting a nitrogen material, lithium amide, with a material containing one or more Group III elements M in a liquid phase, and synthesizing Group III nitride semiconductor nanoparticles with a particle size of 16 nm or less at a synthesis temperature of 100°C or higher, using trioctylphosphine as a coordination solvent, and using trimethyl M as at least one of the materials containing one or more Group III elements M. Claim 2 In claim 1, the group III nitride semiconductor nanoparticles are, general formula: Al x Ga y In z A method for manufacturing group III nitride semiconductor nanoparticles characterized by being nanoparticles represented by N (where 0 ≤ (x, y, z) ≤ 1, x + y + z = 1). Claim 3 In claim 1, the group III nitride semiconductor nanoparticles are, general formula: Al x Ga y In z A method for manufacturing group III nitride semiconductor nanoparticles characterized by being nanoparticles represented by N (where 0 ≤ (x, y) < 1, 0 < z ≤ 1, x + y + z = 1). Claim 4 A method for manufacturing Group III nitride semiconductor nanoparticles according to claim 1, wherein the Group III elemental material comprises trimethylindium, and prior to the synthesis reaction of nanoparticles, the method comprises a process of dissolving trimethylindium in a coordination solvent to form a precursor. Claim 5 A method for manufacturing Group III nitride semiconductor nanoparticles according to claim 4, wherein the Group III elemental material further comprises at least one of trimethylgallium and trimethylaluminum. Claim 6 delete Claim 7 delete Claim 8 delete Claim 9 delete Claim 10 delete

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