KR100616472B1 - Semiconductor nanoparticles, their precursors, and preparation method therof - Google Patents

Abstract

The present invention provides a single organometallic precursor for semiconductor nanoparticles and a method of synthesizing it. In the above method, the pyrolysis temperature is lower than 300 ° C., and the semiconductor nanoparticles obtained from the single organometallic precursor have low internal defects of particles, which have high quantum efficiency and excellent particle size uniformity, and have a half-height butterfly value of 20 nm or less. Can fluoresce.

Semiconductor Nanoparticles, Single Organometallic Precursor, Fluorescence, Pyrolysis, Half Height Butterfly (FWHM), Particle Size Uniformity

Description

Semiconductor nanoparticles and precursors thereof, and methods for their preparation {SEMICONDUCTOR NANOPARTICLES, THEIR PRECURSORS, AND PREPARATION METHOD THEROF}

1 is a thermal analysis (TG / DSC) graph of Zn (SPh) ₂ (( t -BuNH ₂ ) ₂ .

2 is a thermal analysis (TG / DSC) graph of [Cd (SePh) ₂ ] ₁₂ ( t- BuNH ₂ ) ₂ .

3 is a fluorescence spectra of nanoparticles synthesized at 250 ° C.

4 is a fluorescence spectra of nanoparticles synthesized at 300 ° C.

5 is a transmission electron microscope (TEM) image of the nanoparticles synthesized in a 30 minute reaction at 300 ℃.

Figure 6 is an X-ray diffraction (XRD) pattern of the nanoparticles synthesized in 30 minutes reaction at 300 ℃.

The present invention relates to nanoparticles and their precursors. More specifically, the present invention relates to a single organometallic precursor for producing semiconductor nanoparticles and a method for synthesizing the same, and a semiconductor nanopowder prepared using the single organometallic precursor and a method for synthesizing the same. The present invention can be used in various fields such as diagnosis and treatment of diseases, gene analysis, optical materials, etc. through the role of a probe (probe) for obtaining a medical image.

Semiconductor nanoparticles are also referred to as semiconductor nanocrystals, semiconductor nanopowders, etc., and are commonly known as quantum dots. Since the semiconductor nanoparticles have a radius smaller than the bulk exciton bohr radius, the semiconductor nanoparticles have a kind of intermediate property different from that of the bulk material and different from the molecule. Due to the quantum confinement effect of electrons and holes in three-dimensional space, the band gap increases as the size of crystal grains decreases. Therefore, as the size of the nanocrystals decreases, the absorption and emission spectra of the semiconductor nanocrystals shift toward blue, that is, toward high energy.

Semiconductor nanoparticles are crystalline semiconductor materials made of inorganic compounds, and have unique photophysical, photochemical, and nonlinear optical properties due to quantum size effects, and thus have potential applications in various fields such as medical applications, photocatalysts, charge transfer devices, and analytical chemistry. There is a great deal of attention due to sex.

Many documents have been reported on how to make semiconductor nanoparticles. Preparation in glass [Ekimov et al., JETP Letters 34: 345 (1981)] and in aqueous solution using reverse micelles, zeolites, LB films, chelating polymers, etc. [Fendler et al., J. Chem. Society, Chem. Commun. 90:90 (1984) and Henglein et al., Ber. Bunsenges. Phys. Chem . 88: 969 (1984)], and the preparation by thermal decomposition of organometallic precursors in hot coordinating solvents [Murray et al., J. Am. Chem. Soc . 115: 8706 (1993) and Katari et al., J. Phys. Chem. 98: 4109 (1994). The first two formulations have low quantum efficiency or wide particle size distribution, poor stability of colloidal particles, many internal defects, and weak particle individuality and independence.

Recently, studies on the production of semiconductor nanoparticles by thermal decomposition of organometallic precursors in coordinating solvents have been actively conducted. As a result, the size distribution, quantum efficiency, stability, internal defects, and independence of the nanoparticles are significantly improved over the previous two methods. However, most of the semiconductor nanoparticle manufacturing methods directly react with the Group 12 metal precursors and the Group 16 precursors, and thus, there is a limit in maintaining the decomposition and bonding reactions of the two materials. Therefore, there is a limit to maintaining the particle size distribution uniformly, and there is a limit to the control of internal defects.

As a method for overcoming this problem, a method of preparing a complex of a ligand such as tetratradecylphosphonic acid and a Group 12 metal ion in advance, and decomposing it with a Group 16 precursor has been reported [Peng et al., J. Am. Chem. Soc . 123: 183-184 (2001). However, this method has a disadvantage in that a low yield and high toxicity by-products are generated.

Another attempt is to synthesize single precursors containing Group 12 elements and Group 16 elements in one molecule and synthesize them through pyrolysis, reported methods [Y.-W. Jun et al., Chem. Commun ., 1243 (2000)] has a high decomposition temperature of its single precursor and must react for a long time (1 hour) at high temperatures (320 to 385 ° C.), so the full-width at half maximum (FWHM) 50 nm) was not very narrow. Therefore, there is a limit in the control of particle size uniformity, internal defect, etc. of the semiconductor nanopowder obtained therefrom. Particle size uniformity is related to the half-height of the absorption and emission spectra, and the more uniform the particle size, the narrower the spectrum line width. Therefore, the sensitivity is better and the multiple probes can be used simultaneously to make various diagnosis. have. The smallest half-height butterfly value in the fluorescence spectrum of semiconductor nanoparticles reported to date is known to be 25 nm in the ideal case. In addition, as the internal defects decrease, quantum efficiency increases, so that an excellent image can be obtained with a small amount.

Therefore, there is a need for the development of a single organometallic precursor that can be easily pyrolyzed at an appropriate temperature (preferably below 300 ° C.) to leave only semiconductor components. From this, it is possible to manufacture semiconductor nanoparticles of various sizes that can emit narrow line width fluorescence with high quantum efficiency and excellent particle size uniformity in addition to the stability, individuality, and independence of colloidal particles. It remains a priority in the development and improvement of diagnostic and therapeutic techniques.

Accordingly, it is an object of the present invention to develop a single organometallic precursor which can be easily pyrolyzed at a suitable temperature (preferably below 300 ° C.) to become a semiconductor nanopowder and a method for synthesizing it.

In addition, from the single organometallic precursor, in addition to the stability, individuality, and independence of the semiconductor nanoparticles, the internal defects of the particles are small, so that the quantum efficiency is high, and the particle size uniformity is excellent. It is an object of the present invention to prepare semiconductor nanoparticles of various sizes.

In order to achieve the above object, the present invention includes a Group 12 element or europium (Eu) and Group 16 elements in one molecule, and the decomposition temperature is relatively low so that decomposition reaction and crystal growth can be performed by appropriate heat. Provided is a single precursor of Formula 1 and a method for synthesizing them.

[Formula 1]

[M (EAr ') ₂ ] _x (NH ₂ R) _y

Where M = Zn, Cd, Hg, Eu and E = S, Se, Te,

Ar '= phenyl or phenyl [phenyl or substituted phenyl (eg 4-methylphenyl, 4- t -Butylphenyl)],

R = branched hydrocarbon or cyclic hydrocarbon or heterocyclic hydrocarbon having 3 to 10 carbon atoms (e.g. t -Butyl, neopentyl, phenyl, cyclohexyl, N-methylimidazol)

If M is Zn, x is 1, y is 1 or 2,

When M is Cd, Hg, Eu, x is an integer between 10 and 20, more preferably an integer between 12 and 18, y is 2.

The single organometallic precursor of Chemical Formula 1 developed in the present invention was synthesized through the following three steps.

In a first step, as in Scheme 1, a halogen salt of Group 12 or Eu metal and bistrimethylsilylamino sodium [NaN (SiMe ₃ ) ₂ ] are reacted with Group 12 or Eu metal precursor M [N (SiMe ₃ )] ₂ Synthesized.

Scheme 1

2 NaN (SiMe ₃ ) ₂ + MX _2- > M [N (SiMe ₃ ) ₂ ] ₂ + 2 NaX

Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺ .

X = I, Br, Cl

In a second step, organometallic polymers were synthesized by binding a group 12 or Eu metal precursor, which is a member of the semiconductor nanopowder, and an arylchalcogenide ligand as in Scheme 2.

Scheme 2

n {M [N (SiMe ₃ ) ₂ ] ₂ + 2 Ar'EH}-> [M (EAr ') ₂ ] _n + 2n HN (SiMe ₃ ) ₂

Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺ ,

E = S, Se, Te

Ar '= phenyl or phenyl with substituents [Phenyl, substituted phenyl (eg 4-methylphenyl, 4- t -Butylphenyl)].

In the third step, as in Scheme 3, a primary amine ligand was added to the organometallic polymer synthesized in step 2 to synthesize a single molecule or a polymer precursor having a low molecular weight. In the present invention, the primary amine having a branched hydrocarbon or a cyclic hydrocarbon or a heterocyclic hydrocarbon having 3 to 10 carbon atoms has a high steric effect and a coordination ability of the primary amine, so that the organometallic polymer is a single molecule. The single organometallic precursor was designed based on the fact that it has an effect of stabilizing with an oligomer to an oligomer.

Scheme 3

[M (EAr ') ₂ ] _n + xy / n (NH ₂ R)-> n / x [M (EAr') ₂ ] _x (NH ₂ R) _y

Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺

E = S, Se, Te

Ar '= phenyl or phenyl with substituents [Phenyl, substituted phenyl (eg 4-methylphenyl, 4- t -Butylphenyl)].

R = branched hydrocarbon or cyclic hydrocarbon or heterocyclic hydrocarbon having 3 to 10 carbon atoms (e.g. t -Butyl, neopentyl, phenyl, cyclohexyl, N-methylimidazol)

In addition, the present invention, from the thermal decomposition reaction of a single organometallic precursor synthesized through the three-step reaction described above, in addition to the stability, individuality, and independence of the particles, there are few internal defects, high quantum efficiency, excellent particle size uniformity and FWHM value Provided are semiconductor nanoparticles of various sizes and a method for synthesizing the same, which can emit 20 nm or less.

As in Scheme 4, the organometallic precursor [M (EAr ') ₂ ] _x (NH ₂ R) _y synthesized in Scheme 3 was thermally decomposed in a coordinating solvent to provide a surface protected formula (ME). Semiconductor nanopowders were synthesized. Examples of the coordinating solvent include amines, alkyl phosphines, alkyl phosphine oxides, fatty acids, ethers, furans, and phosphates. Phospho-acids, pyridines, or mixed solvents thereof. In addition, the coordinating solvent may include a mixture of any one of the above materials and a nonpolar organic solvent.

Scheme 4

[M (EAr ') ₂ ] _x (NH ₂ R) _y- > ME + x (Ar' ₂ E) + y (NH ₂ R)

Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺

E = S, Se, Te

Ar '= Phenyl, substituted phenyl (e.g. 4-methylphenyl, 4- t -Butylphenyl).

R = branched hydrocarbon or cyclic hydrocarbon or heterocyclic hydrocarbon having 3 to 10 carbon atoms (e.g. t -Butyl, neopentyl, phenyl, cyclohexyl, N-methylimidazol)

Nano powder synthesis of Scheme 4 was prepared through the following process.

First step: One or more coordinating solvents were taken to degassing and kept at high temperature (200-390 ° C.).

Second Step: A solution in which a single organometallic precursor of Formula 1 was dissolved in one or more coordinating solvents was prepared.

Third step: The solution prepared in the second step was instantaneously added to the solution prepared in the first step.

Fourth step: The solution of the third step was held at a high temperature (200-390 ° C.) for 2 minutes to 2 hours each, then taken up in an amount, cooled (50-150 ° C.) and excess methanol was added. The formed nanoparticles were centrifuged, washed with methanol and dried.

In addition, the present invention shells the semiconductor nanoparticle core (core) through the following process in the same manner as the synthesis of semiconductor nanoparticles from the thermal decomposition reaction of a single organometallic precursor synthesized through the three-step reaction described above It provides a method for synthesizing a composite material (shell) formed. Here, a single organometallic precursor should be selected so that the shell energy difference (valence band and conduction band energy difference) is greater than the core energy difference, which leads to stabilization of nanoparticle cores, thereby increasing quantum efficiency.

(a) The nanoparticles are dispersed in one or more coordinating solvents.

(b) Prepare a solution of a single organometallic precursor of Formula 1 dissolved in one or more coordinating solvents.

(c) The temperature of the solution (a) is raised and (b) the solution is added instantaneously to synthesize the shell on the nanoparticle cores.

(d) The solution (c) is held at a high temperature (200-390 ° C.) for 2 minutes to 2 hours each, then taken up by an amount, cooled (50-150 ° C.) and excess methanol is added. The formed nanoparticles are centrifuged, washed with methanol and dried.

Through this process, a semiconductor nanopowder in a composite form of core @ shell (composite structure in which the surface is covered with a shell) is synthesized.

Hereinafter, the embodiment of the present invention will be described in more detail. However, the present invention is not limited at all by these examples.

Example 1.

Scheme 2, synthesis of [Zn (SPh) ₂ ] _n

Synthesis of [Zn (SPh) ₂ ] _n improved the method reported in YW Jun, JW Cheon, Chem. Commun., 2000, 1243. 1.32 g (4.692 mmol) of Zn [N (SiMe ₃ )] ₂ was dissolved in 50 mL of distilled toluene under argon atmosphere, and 1.032 g (9.383 mmol) of phenol sulfide (thiophenol) was slowly added thereto for 30 minutes. A white solid formed into a suspension and the solution was stirred for 12 hours at room temperature. 50 mL of heptane was added, the solid was filtered off, washed with 50 mL of heptane and dried in a vacuum desiccator to obtain 1.194 g (4.208 mmole, 90% yield) of [Zn (SPh) ₂ ] _n compound.

Scheme 3, synthesis of Zn (SPh) ₂ ( t -BuNH ₂ ) ₂

30 mL of toluene was added to 0.5 g (1.76 mmole) of [Zn (SPh) ₂ ] _n to make a suspension, followed by addition of 0.309 g (4.23 mmole) of t-butylamine. This mixed solution became a pale yellow transparent solution within 1 minute, and after 2 hours, a white solid began to precipitate. After 1 day, 30 mL of heptane was added and stored at -24 ° C for 12 hours. The solid was filtered, washed with heptane and dried in a vacuum desiccator to give 0.546 g (1.275 mmole, 72% yield) of Zn (SPh). ₂ ( t- BuNH ₂ ) ₂ was obtained.

Example 2.

Scheme 1, synthesis of Cd [N (SiMe ₃ )] ₂

In argon atmosphere, 14.67 g (0.08 mole) of NaN (SiMe ₃ ) _{2 was} dissolved in 33 mL of distilled diethyl ether, cooled to −78 ° C., and 14.65 g (0.04 mole) of anhydrous CdI ₂ was added thereto. The temperature of the mixed solution was gradually raised to room temperature and then refluxed for 1 hour. The solution was cooled, the solid was filtered off, the filtrate was concentrated and distilled under reduced pressure (95 ° C./1 mmHg) to obtain 11.18 g (25.8 mmole, 65% yield) of a light off-white liquid Cd [N (SiMe ₃ )] ₂ .

Scheme 2, synthesis of [Cd (SePh) ₂ ] _n

Under argon atmosphere, 4.7 g (10.85 mmol) of Cd [N (SiMe ₃ )] ₂ was dissolved in 60 mL of distilled toluene, followed by stirring and slowly stirring 3.4 g (21.68 mmol) of selenophenol for 50 minutes. A white solid formed into a suspension and the solution was stirred for 12 hours at room temperature. 30 mL of heptane was added, the solid was filtered off, washed with 50 mL of heptane and dried in a vacuum desiccator to obtain 4.1 g (9.7 mmole, 89% yield) of [Cd (SePh) ₂ ] _n .

Scheme 3, synthesis of [Cd (SePh) ₂ ] _x ( t -BuNH ₂ ) _y

To 0.5 g (1.178 mmole) of [Cd (SePh) ₂ ] _n , 30 mL of toluene was added to form a suspension, followed by addition of 0.207 g (2.83 mmole) of t-butylamine. This mixed solution became a pale yellow transparent solution within 5 minutes, and gradually pale off-white solids were precipitated and stirred for 1 day. 25 mL of heptane was added and stored at −24 ° C. for 12 hours. The solid was filtered, washed with heptane and dried in a vacuum desiccator to give 0.312 g of [Cd (SePh) ₂ ] _x ( t -BuNH ₂ ) _y . Got it.

Here, as a result of analysis of the compound [Cd (SePh) ₂ ] _x ( t -BuNH ₂ ) _y , t-butylamine is bonded to cadmium (Cd) at both ends of several repeating Cd (SePh) ₂ units. The molecular formula determined from elemental analysis and nuclear magnetic resonance spectra is [Cd (SePh) ₂ ] ₁₂ ( t -BuNH ₂ ) ₂ .

The results of physical properties, elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectra, etc., of the compounds synthesized in Examples 1 and 2 are summarized in Tables 1 and 2.

Table 1 Analysis results of the compounds synthesized in Examples 1 and 2

compound Yield,% Melting Point, Decomposition Temperature, ℃ Exterior Elemental Analysis Calculated Value (experimental value),% [Zn (SPh) ₂ ] _n 90 195-200 350 White solid C: 50.8 (49.1) H: 3.6 (3.8) S: 22.6 (19.2) Zn (SPh) ₂ ( t -BuNH ₂ ) ₂ 87 102 265 White solid C: 55.9 (55.1) H: 7.5 (7.2) S: 14.9 (13.8) N: 6.5 (6.3) [Cd (SePh) ₂ ] _n 89 -300-310 Off-white solid C: 34.0 (34.7) H: 2.4 (2.6) Se: 37.2 (36.6) [Cd (SePh) ₂ ] ₁₂ ( t -BuNH ₂ ) ₂ -190 Off-white solid C: (34.45) H: (2.65) S: (36.0) N: (0.3)

Table 2 Spectroscopic Analysis of the Compounds Synthesized in Examples 1 and 2

compound Infrared spectroscopy, cm ^-1 Nuclear Magnetic Resonance Spectrum (Pyridine d ₆ Solvent), ppm [Zn (SPh) ₂ ] _n 3053 (aromatic C-H) 1941,1868,1790,1729 (combination band of mono-substituted Ar ring) 1578,1477,1437 (Ar C = C) 8.02 (m, 2H, o -CH) 7.11 (m, 2H, m -CH) 6.98 (m, 1H, p -CH) Zn (SPh) ₂ ( t -BuNH ₂ ) ₂ 3266,3245,3209 (N-H) 3062 (aromatic C-H) 2968 (aliphatic C-H) 1941,1868,1790,1729 (combination band of mono-substituted Ar ring) 1576,1475,1436 (Ar C = C) 7.48 (m, 2H, o- CH) 7.08 (m, 3H, m- & p- CH) 1.80 (s, 2H, NH ₂ ) 1.08 [s, 9H, C (CH ₃ ) ₃ ] [Cd (SePh) ₂ ] _n 3066, 3051 (aromatic C-H) 1937, 1859, 1791, 1732 (combination band of mono-substituted Ar ring) 1573, 1473, 1435 (Ar C = C) 8.00 (m, 2H, o -CH) 7.00 (m, 3H, m- & p -CH) [Cd (SePh) ₂ ] ₁₂ ( t -BuNH ₂ ) ₂ 3303 (trace N-H) 3066,3052 (aromatic C-H) 2989 (trace aliphatic C-H) 1937,1855,1790,1729 (combination band of mono-substituted Ar ring) 1573,1473, 1435 (Ar C = C) 8.00 (m, 48H, o-CH) 6.99 (m, 72H, m- & p- CH) 2.237 (s, 4H, NH ₂ ) 1.162 [s, 18H, C (CH ₃ ) ₃ ]

Example 3.

Zn (SPh) ₂ (( t -BuNH ₂ ) ₂ synthesized in Examples 1 and ₂ and TG / DSC analysis was performed to investigate the thermal decomposition properties of [Cd (SePh) ₂ ] _x ( t -BuNH ₂ ) _y and the results are shown in FIGS. 1 and 2.

Example 4.

Synthesis of CdSe Nanopowder at 250 ℃

(a) 3.89 g (10.1 mmole) of TOPO was degassed and maintained at 250 ° C.

(b) A solution of 0.5 g of [Cd (SePh) ₂ ] ₁₂ ( t -BuNH ₂ ) ₂ was dissolved in 10 mL of trioctylphosphine.

(c) The solution prepared in (b) was instantaneously added to the solution (a).

(d) The solution of (c) was held at 250 ° C. for 20, 40, and 60 minutes, and then, taken in constant amounts, cooled to 80 ° C., and excess methanol was added.

The formed nanoparticles were centrifuged, washed with methanol and dried. The fluorescence spectra of the synthesized nanoparticles were examined and the results are shown in FIGS. 3 and 3.

[Table 3] Fluorescence energy and half-height of nanoparticles synthesized at 250 ° C

Reaction time, min Fluorescent energy, nm Half-height butterfly, nm 20 555 19 40 561 18 60 563 20

Example 5.

Synthesis of CdSe Nanopowder at 300 ℃

(a) 3.89 g (10.1 mmole) of TOPO was degassed and maintained at 300 ° C.

(b) A solution of 0.5 g of [Cd (SePh) ₂ ] ₁₂ ( t -BuNH ₂ ) ₂ was dissolved in 10 mL of trioctylphosphine.

(c) The solution prepared in (b) was instantaneously added to the solution (a). (I replaced 1, 2, 3 with a, b, c for consistency.)

(d) The solution of (c) was held at 300 ° C. for 10, 20, and 30 minutes, and then, taken in constant amounts, cooled to 80 ° C., and excess methanol was added.

The formed nanoparticles were centrifuged, washed with methanol and dried. The fluorescence spectra of the synthesized nanoparticles were examined and the results are shown in FIGS. 4 and 4. TEM images and XRD patterns of nanopowders obtained by reaction at 300 ° C. for 30 minutes are shown in FIGS. 5 and 6.

[Table 4] Fluorescence energy and half height butterfly of nanoparticles synthesized at 300 ℃

Reaction time, min Fluorescent energy, nm Half-height butterfly, nm 10 463 18 20 466 18 30 644 19

As described above, the present invention has a single bond capable of producing semiconductor nanoparticles by pyrolysis at an appropriate temperature by having chemical bonds of Group 12 or Eu metal and Group 16 components of the semiconductor nanoparticles in a single precursor. Provided are organometallic precursors and methods for their synthesis. In addition to the stability, individuality, and independence of the semiconductor nanoparticles from these precursors, there are few internal defects, resulting in high quantum efficiency, excellent particle size uniformity, and various sizes of semiconductor nanoparticles capable of emitting fluorescence with a half-height butterfly value of 20 nm or less. Can be prepared. By using the semiconductor nanoparticles of various sizes according to the present invention as a probe for medical imaging at the same time, the diagnosis and treatment of various diseases can be simultaneously performed with high sensitivity.

Claims (9)

The following formula; [M (EAr ') ₂ ] _x (NH ₂ R) _y Where M = Zn, Cd, Hg, Eu and E = S, Se, Te, Ar '= phenyl or phenyl with substituents, R = branched hydrocarbon or cyclic hydrocarbon or heterocyclic hydrocarbon having 3 to 10 carbon atoms, If M is Zn, x is 1, y is 1 or 2, If M is Cd, Hg, Eu, x is an integer between 10 and 20, y is 2 Single organometallic precursor for semiconductor nanoparticles represented by. According to Scheme 1 below, a first step of synthesizing a metal precursor by reacting a halogen salt of group 12 or Eu metal with bistrimethylsilylamino sodium [NaN (SiMe ₃ ) ₂ ]; Scheme 1 2 NaN (SiMe ₃ ) ₂ + MX _2- > M [N (SiMe ₃ ) ₂ ] ₂ + 2 NaX Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺ . X = I, Br, Cl A second step of synthesizing an organometallic polymer by combining the metal precursor with an arylchalcogenide ligand according to Scheme 2 below; Scheme 2 n {M [N (SiMe ₃ ) ₂ ] ₂ + 2 Ar'EH}-> [M (EAr ') ₂ ] _n + 2n HN (SiMe ₃ ) ₂ Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺ , E = S, Se, Te Ar '= phenyl or phenyl with substituents, According to Scheme 3 below, a third step of synthesizing a mono-molecule or a polymer precursor having a low molecular weight by adding a t -butylamine ligand to the organometallic polymer; Scheme 3 [M (EAr ') ₂ ] _n + xy / n (NH ₂ R)-> n / x [M (EAr') ₂ ] _x (NH ₂ R) _y Where M = Zn ²⁺ , Cd ²⁺ , Hg ²⁺ , Eu ²⁺ E = S, Se, Te Ar '= phenyl or phenyl with substituents, R = branched hydrocarbon or cyclic hydrocarbon or heterocyclic hydrocarbon having 3 to 10 carbon atoms Single organometallic precursor synthesis method for semiconductor nanoparticles comprising a. (a) degassing at least one coordinating solvent to maintain at 200 to 390 ° C .; (b) mixing the single organometallic precursor according to claim 1 in one or more coordinating solvents; (c) instantaneously adding the solution prepared according to (b) to the solution according to (a) to produce a nanoparticle nucleus; (d) maintaining the solution according to (c) at 200 to 390 ° C. for 2 minutes to 2 hours to grow nanocrystals; (e) cooling the solution according to (d) at 50 to 150 ° C. to stop further crystal growth. Method of manufacturing semiconductor nanoparticles. The method of claim 3, wherein the coordinating solvent is amines (alkyl phosphines), alkyl phosphine oxides (alkyl phosphine oxides), fatty acids (ethers), ethers (furans) ( furans), phospho-acids (phospho-acids), pyridines (pyridines) or any one selected from a combination thereof. The method of claim 3, wherein the coordinating solvent is a non-polar organic solvent and the following groups: amines, alkyl phosphines, alkyl phosphine oxides, fatty acids, ethers Consisting of one or more selected from the group consisting of ethers, furans, phospho-acids and pyridines Method of manufacturing semiconductor nanoparticles. The method of claim 3, wherein the nucleation and crystal growth temperature are maintained at 250 to 300 ° C. 5. The method of manufacturing a semiconductor nanoparticle according to claim 3, wherein the crystal growth time is maintained at 2 to 30 minutes. The method of claim 3, wherein the semiconductor nanoparticle manufacturing method is maintained at 60 to 100 ° C. to stop further crystal growth. A semiconductor nanopowder synthesized according to the method of claim 3 and having a half-height butterfly value of 20 nm or less.

Images