KR101723850B1

KR101723850B1 - Method for manufacturing of quantum dots including phosphorus and quantum dot thereof

Info

Publication number: KR101723850B1
Application number: KR1020150071145A
Authority: KR
Inventors: 김재일; 임태윤
Original assignee: 큐디브릭 주식회사
Priority date: 2015-05-21
Filing date: 2015-05-21
Publication date: 2017-04-06
Also published as: KR20160136913A

Abstract

The present invention relates to a process for the preparation of a compound of formula (I), comprising the steps of activating phosphorus (P) compound using a reducing agent; Adding an indium (In) ion to the activated phosphorus (P) compound to synthesize an InP core; And forming a shell layer surrounding the InP core. The present invention also relates to a quantum dot manufacturing method and a quantum dot manufactured thereby.
According to the present invention, by using chemically stable phosphorus (P) directly in the InP chemical reaction, it is possible to manufacture the quantum dot at a low cost by reducing the manufacturing cost, and the manufacturing can be performed at room temperature and atmospheric pressure, Safety can be ensured.

Description

[0001] The present invention relates to a quantum dot manufacturing method and a quantum dot manufacturing method,

TECHNICAL FIELD The present invention relates to a quantum dot manufacturing method and a quantum dot manufactured thereby, and more particularly, to a quantum dot manufacturing method including chemically stable phosphor and a quantum dot produced thereby.

In general, when a material is reduced in size to nanometers, it will have new physical properties not seen in the bulk state, as the materials become smaller and become nanometer-scale in size, This is because the ratio becomes abnormally large.

Among such nanomaterials, there is a quantum dot (QD), which is a semiconductor material having a diameter of about 2 to 10 nm, which is smaller than a certain size. When the electron mobility in a bulk semiconductor material becomes more restrictive And is a material which exhibits a quantum confinement effect in which the emission wavelength is different from the bulk state. These quantum dots emit light from an excitation source and emit energy corresponding to their corresponding energy band gaps when they reach the energy excited state. Therefore, by adjusting the size of the quantum dots, it is possible to control the bandgap and obtain various wavelengths of energy, thereby exhibiting optical, electrical, and magnetic characteristics completely different from the original physical properties.

Such quantum dots are in recent years under investigation for use in a wide variety of applications including displays, solar energy conversion, molecular and cellular imaging, and the like.

As a related technology related to quantum dots, Korean Patent Laid-Open No. 10-2009-0114112 entitled " QD-nanoparticles having a core-multiple shell structure and its use "has been proposed. An inner shell formed on the core and comprising an In compound; And a core-multiple shell structure of an outer shell formed on the surface of the quantum dot core-inner shell and containing a Zn compound.

Thus, conventional quantum dots have been focused on quantum dots based on Cd compounds, particularly CdSe (Cadmium Selenide). In recent years, however, the demand for Cd-free QDs has increased and commercialization is required. Use of Cd in accordance with Restriction of Hazardous Substances in EEE (RoHS) Although this regulation was deferred until 2018, in accordance with these regulations, InP-based substances are used instead of CdSe-based substances. InP (Indium Phosphide) based quantum dots are comparable to CdSe in luminescence, so that there is an increasing tendency in the market.

In the conventional InP method, there is a method of dissolving an indium (In) precursor in a solvent and injecting phosphorus (P) precursor at a high temperature. However, this method has a problem of using expensive (P) (TMS) ₃ which is a toxic substance. In another conventional InP method, there is a method of forming particles by simultaneously introducing an indium precursor and phosphorus precursor and gradually raising the temperature, but it has a problem that it is difficult to produce a material emitting a luminescent color other than green-yellow.

Further, the phosphorus precursor known to date has a problem that it is expensive, difficult to store and use, and inconvenient to handle at room temperature and atmospheric pressure.

In order to solve the problems of the prior art as described above, it is an object of the present invention to reduce the manufacturing cost of quantum dots and ensure safety by directly using chemically stable phosphorus (P) for the InP chemical reaction.

Other objects of the present invention will become readily apparent from the following description of the embodiments.

According to an aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: activating phosphorus (P) compound using a reducing agent; Adding an indium (In) ion to the activated phosphorus (P) compound to synthesize an InP core; And forming a shell layer surrounding the InP core. &Lt; IMAGE >

The step of activating the phosphorus (P) compound comprises reacting the reducing agent with a metal hydride, a metal borohydride, an alkyl amine, an aryl amine, and a terminal olefin olefin. < / RTI >

The step of activating the phosphorus (P) compound may activate the phosphorus (P) compound by mixing and heating the phosphorus (P) compound, the reducing agent and the organic solvent.

The step of activating the phosphorus (P) compound may be performed by mixing 0.05 to 5 mmol of the phosphorus (P) compound and 0.05 to 5 mmol of the reducing agent, based on 10 ml of the organic solvent, at 100 to 340 ° C for 0.1 to 48 hours The phosphorus (P) compound can be activated.

The step of synthesizing the InP core may include an In source corresponding to the metal salt in which In ^{3 +} is present, and a combination of any one of a myristic acid, an alkyl acid, and an aryl acid, Mixing and heating the solvent to dissolve the solution, and cooling the solution to prepare an indium solution; And injecting the indium solution into the activated phosphorus (P) compound to grow the particles.

The step of preparing the indium solution may be carried out by mixing 0.05 to 5 mmol of the In source with one of myristic acid, alkyl acid and aryl acid, based on 10 ml of the organic solvent. 0.1 to 10 mmol are mixed and dissolved in a vacuum at 50 to 340 ° C for 0.1 to 48 hours and then cooled at room temperature.

The step of forming the shell layer may include a step of firstly injecting zinc salt into the result of the growth of the particles, Any one of an alkyl thiol, an alkyl thioisocyanate, an aryl thiol and an aryl thioisocyanate may be added to the resultant product after the first heat treatment, ; And a step of dropping the particles by adding a solvent to the resultant product after the secondary heat treatment and recovering the particles.

The step of cooling after the primary heat treatment may be performed by adding 0.1 to 10 mmol of the zinc salt based on 10 ml of the organic solvent at room temperature, heating the mixture to 100 to 340 ° C, performing the heat treatment for 0.1 to 48 hours, .

The step of cooling after the secondary heat treatment may be performed by using the alkyl thiol, the alkyl thioisocyanate, the aryl thiol, and the aryl thioisocyanate based on 10 ml of the organic solvent at room temperature. 0.1 to 20 mmol of any one of them is added, and the temperature is raised to 100 to 340 ° C, followed by heat treatment for 0.1 to 48 hours, followed by cooling at room temperature.

The step of synthesizing the InP core may be performed by using an In source corresponding to a metal salt containing In ³⁺ , a zinc salt, a myristic acid, an alkyl acid, and an aryl acid acid, and an organic solvent are mixed and heated to dissolve and then cooled to form an indium solution; And injecting the indium solution into the activated phosphorus (P) compound to grow the particles.

The step of preparing the indium solution may include 0.05 to 5 mmol of the In source, 0.1 to 10 mmol of the zinc salt, 0.1 to 10 mmol of the myristic acid, alkyl acid, And aryl acid in an amount of 0.1 to 10 mmol, and the resulting mixture is dissolved in a vacuum at 100 to 200 ° C for 0.1 to 48 hours, followed by cooling at room temperature.

According to another aspect of the present invention, there is provided a quantum dot including phosphorus, which is produced by a method for manufacturing a quantum dot including phosphor according to an aspect of the present invention.

According to the method of manufacturing a quantum dot including phosphorus according to the present invention and the quantum dot produced by the method, the manufacturing cost can be reduced by directly using a chemically stable phosphorus (P) compound for the InP chemical reaction, And atmospheric conditions of normal pressure, so that it is easy to deal with and safety can be ensured.

1 is a flow chart illustrating a method of fabricating a quantum dot including phosphorus according to one embodiment of the present invention.
2 is a view for explaining the production of InP in the method of manufacturing a quantum dot including phosphor according to an embodiment of the present invention.

The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated and described in detail in the drawings. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but is to be understood to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention, And the scope of the present invention is not limited to the following examples.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the accompanying drawings, wherein like or corresponding elements are denoted by the same reference numerals, and redundant explanations thereof will be omitted.

FIG. 1 is a flow chart illustrating a method of manufacturing a quantum dot including phosphorus according to an embodiment of the present invention, and FIG. 2 is a view for explaining manufacturing of InP in a method of manufacturing a quantum dot including phosphorus according to an embodiment of the present invention to be.

Referring to FIGS. 1 and 2, a method of manufacturing a quantum dot including phosphor according to an embodiment of the present invention includes activating a phosphorus (P) compound using a reducing agent (S11) A step (S12) of adding an indium (In) ion (In3 ⁺ ) to an InP core to form an InP core, and a step (S13) of forming a shell layer surrounding the InP core.

Step (S11) of activating the phosphorus (P) compound forcibly activates the phosphorus (P) compound corresponding to a chemically stable element by using a reducing agent and makes it available to form InP particles.

In the present invention, the reducing agent may be any one selected from the group consisting of a metal hydride, a metal borohydride, an alkyl amine, an aryl amine, and a terminal olefin. However, it is possible to use not only long chain alkyl amines such as oleylamine and octadecylamicne, but also substances which supply hydride (H-). Reducing agent may be illustratively NaBH ₄ or LiAlH _4. Also, in the metal hydride and the metal borohydride, the metal may be Na, K, Li, LiAl, and the like. As a molecule having a terminal olefin, ODE (1-octadecene) can be exemplified.

Step (S11) of activating phosphorus (P) compound can activate phosphorus (P) compound by mixing and heating phosphorus (P) compound, reducing agent and organic solvent. In this case, The phosphorus (P) compound can be activated by mixing 0.05 to 5 mmol of the phosphorus (P) compound and 0.05 to 5 mmol of the reducing agent and maintaining the temperature at 100 to 340 ° C for 0.1 to 48 hours. Examples of the phosphorus (P) compound in the present invention include white phosphorus, red phosphorus, black phosphorus, phosphorus (P ₂ O ₅ ), and the like. In the present invention, examples of the organic solvent include ODE (1-octadecene), TOPO, TOP, Tri-cotylamine, and other organic solvents having high boiling points.

The step of synthesizing the InP core (S12) may be carried out, for example, by using an In source corresponding to a metal salt in which In ³⁺ is present and at least one of an myristic acid, an alkyl acid, and an aryl acid And an organic solvent may be mixed and heated to dissolve and then cooled to form an indium solution. The indium solution may be added to the activated phosphorus (P) compound to grow the particles. The In source may be indium acetate, for example. Here, the step of preparing the indium solution may be performed by using 0.05 to 5 mmol of In source and 0.1 to 10 mmol of any one of myristic acid, alkyl acid and aryl acid, based on 10 ml of the organic solvent Mixed and dissolved in a vacuum at 50 to 340 ° C for 0.1 to 48 hours, and then cooled at room temperature.

As another example, the step of synthesizing the InP core (S13) may be performed by using an In source corresponding to a metal salt in which In ³⁺ exists, a zinc salt, a myristic acid, an alkyl acid, Mixing an organic solvent and an organic solvent with an organic solvent to dissolve and then dissolving the organic solvent and cooling the solution to form an indium solution; and injecting the indium solution into the activated phosphorus (P) compound to grow the particles . As the In source corresponding to the metal salt in which In ^{3 +} exists, for example, indium acetate can be mentioned. The zinc salt may be, for example, zinc acetate. Here, the step of preparing the indium solution is performed by using 0.05 to 5 mmoles of In source, 0.1 to 10 mmoles of zinc salt, myristic acid, alkyl acid and aryl acid (based on 10 ml of the organic solvent aryl acid in an amount of 0.1 to 10 mmol may be mixed and dissolved in a vacuum at 100 to 200 ° C for 0.1 to 48 hours, followed by cooling at room temperature.

The step of forming the shell layer (S13) comprises the steps of: firstly injecting zinc salt into the resultant product of the growth of the particles, cooling the mixture by heat treatment; and cooling the mixture after the first heat treatment to form an alkylthiol, , An alkyl thioisocyanate, an aryl thiol and an aryl thioisocyanate, followed by a second heat treatment and then a second heat treatment. After the second heat treatment, the resultant product is cooled, And dropping and collecting the particles. Here, the first cooling step is a step of cooling 0.1 to 10 mmol of zinc salt based on 10 ml of the organic solvent at room temperature, heating the mixture to 100 to 340 ° C. for 0.1 to 48 hours, . Further, the step of cooling after the second heat treatment may be carried out at a temperature of room temperature using any one of an alkyl thiol, an alkyl thioisocyanate, an aryl thiol, and an aryl thioisocyanate based on 10 ml of an organic solvent 0.1 to 20 mmol is added, the temperature is raised to 100 to 340 ° C, and the resultant is heat-treated for 0.1 to 48 hours, and then cooled at room temperature.

The quantum dot including phosphorus according to the present invention can be manufactured by the method of manufacturing a quantum dot including phosphor according to the present invention described above and the InP is used as a core and the shell surrounding the core is a Zn compound such as ZnS or ZnSe Thus, for example, it may be a semiconductor quantum dot of a nanocrystal made of InP / ZnS core / shell. Hereinafter, a method of manufacturing a quantum dot including phosphorus according to the present invention will be described by way of example.

[Example 1]

1. Elemental (P) compound activation

(P), 0.5 mmol of LiAlH ₄ and 10 ml of ODE (1-octadecene) were mixed, the temperature was raised to 280 ° C., and this state was maintained for 24 hours to prepare an activated phosphorus (P) precursor solution.

2. InP synthesis using activated phosphorus (P) compound

0.2 mmol of indium acetate, 0.65 mmol of myristic acid and 10 mL of ODE (1-octadecene) were mixed and completely dissolved in a vacuum at 120 ° C. for 3 hours, And the cooled indium solution is added to the phosphorus (P) precursor solution activated in the previous process to grow the particles for a certain period of time. On the other hand, InP can be recovered by recovering the particles by dropping the particles by adding excess ethanol to the resultant particles.

3. InP / ZnS core / shell quantum dot synthesis using activated phosphorus (P) compound

0.2 mmol of zinc acetate was added to the resultant of the growth of the particles in the previous step, and then the mixture was heated to 280 ° C. and then heat-treated for 30 minutes and then cooled at room temperature. After cooling, 1 mmol of 1-dodecanethiol (DDT) was added at room temperature, and the temperature was raised to 280 ° C. After 30 minutes of heat treatment, the resultant was cooled at room temperature and then ethanol was added to the InP / ZnS core / shell Collect the quantum dots.

[Practical example 2]

In the case of Example 2, the process for synthesizing InP using the activated P (P) compound is the same as the process of Example 1 described above.

InP synthesis using activated phosphorus (P) compound

0.2 mmol of indium acetate, 0.2 mmol of zinc acetate, 1.1 mmol of myristic acid and 10 ml of ODE (1-octadecene) were mixed and completely dissolved in a vacuum at 120 ° C for 3 hours Next, the indium solution is prepared by cooling to room temperature, and the cooled indium solution is added to the phosphorus (P) precursor solution activated in the previous process to grow particles for a predetermined period of time. In this case, InP can also be recovered by dropping the particles by adding an excess amount of ethanol to the resultant product.

As described above, according to the present invention, by using chemically stable phosphorus (P) directly for InP chemical reaction, it is possible to manufacture the quantum dots at low cost by reducing the manufacturing cost, It is not only convenient but also safe.

Although the present invention has been described with reference to the accompanying drawings, it is to be understood that various changes and modifications may be made without departing from the spirit of the invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined by the scope of the appended claims and equivalents thereof.

Claims

Activating the phosphorus (P) compound using a reducing agent;
Adding an indium (In) ion to the activated phosphorus (P) compound to synthesize an InP core; And
Forming a shell layer surrounding the InP core;
Lt; / RTI >
The step of activating the phosphorus (P)
Wherein the reducing agent is any one selected from the group consisting of a metal hydride, a metal borohydride, an alkyl amine, an aryl amine, and a terminal olefin,
The phosphorus (P) compound, the reducing agent and the organic solvent are mixed and heated to activate the phosphorus (P) compound,
(P) compound is activated by mixing 0.05 to 5 mmol of the phosphorus (P) compound and 0.05 to 5 mmol of the reducing agent based on 10 ml of the organic solvent and maintaining the mixture at 100 to 340 ° C for 0.1 to 48 hours,
The step of synthesizing the InP core comprises:
An In source corresponding to a metal salt in which In ³⁺ is present is mixed with an organic solvent and any one of myristic acid, alkyl acid and aryl acid, , Cooling to form an indium solution; And
Introducing the indium solution into the activated phosphorus (P) compound to grow particles;
Lt; / RTI >
The step of making the indium solution comprises:
0.05 to 5 mmol of the In source and 0.1 to 10 mmol of any one of myristic acid, alkyl acid and aryl acid are mixed with 10 ml of the organic solvent to prepare 50 To < RTI ID = 0.0 > 340 C < / RTI > under vacuum for 0.1 to 48 hours,
The step of forming the shell layer comprises:
Introducing a zinc salt into the resultant of the growth of the particles, firstly heat-treating and then cooling;
Any one of an alkyl thiol, an alkyl thioisocyanate, an aryl thiol and an aryl thioisocyanate may be added to the resultant product after the first heat treatment, ; And
Adding a solvent to the resultant product cooled by the second heat treatment, dropping the particles and recovering the particles;
&Lt; / RTI > wherein the quantum dot comprises phosphorus.

delete

The method according to claim 1,
The step of cooling after the first heat treatment includes:
0.1 to 10 mmol of zinc salt is added thereto at a room temperature based on 10 ml of the organic solvent and the mixture is heated to 100 to 340 ° C. and then heat treated for 0.1 to 48 hours and then cooled at room temperature. Way.

The method according to claim 1,
The step of cooling after the secondary heat treatment includes:
0.1 to 20 mmol of any one of the alkyl thiol, the alkyl thioisocyanate, the aryl thiol and the aryl thioisocyanate is added to the solution at room temperature based on 10 ml of the organic solvent, Wherein the temperature is raised to 100 to 340 ° C, the heat treatment is performed for 0.1 to 48 hours, and then the temperature is cooled at room temperature.

delete

A quantum dot comprising phosphorus produced by the method of manufacturing a quantum dot comprising phosphorus according to any one of claims 1 to 9.