WO2017034226A1 - Composite of quantum dots and polymer, and production method therefor - Google Patents

Abstract

The present invention relates to a production method for a composite of quantum dots and a polymer, the method comprising: a step of synthesising quantum dots (QD) such that same have a ligand capable of hydrosilylation; and a step of forming a composite by mixing the synthesised quantum dots with a polymer substance, and the present invention also relates to the composite of quantum dots and a polymer produced by means of said production method. According to the present invention, because of the formation of the composite of quantum dots and a polymer, it is possible have a rapid reaction rate and low reaction temperature and also to improve on physical properties that the quantum dots themselves have such as poor heat resistance and chemical resistance, and it is possible to adjust the light-emission properties of the quantum dots, and possible to achieve commercial viability and economic viability by allowing large-scale production, and it is possible to use quantum dots in various practical products by overcoming limitations on the use of quantum dots themselves.

Description

Composite of quantum dots and polymer and preparation method thereof

The present invention relates to a composite of a quantum dot and a polymer and a method for manufacturing the same, which has a fast reaction rate and a low reaction temperature and can improve the physical properties such as weak heat resistance and chemical resistance of the quantum dot itself. It relates to a complex and a method for producing the same.

In general, when a material is reduced to nanometers in size, it has new physical properties that were not seen in bulk because the material changes as its size and shape change.

Among such nanomaterials, there is a quantum dot (QD), which is a semiconductor material corresponding to a nano size of about 2 to 10 nm in diameter, and when it is smaller than a certain size, electron motion characteristics in the bulk semiconductor material are further restricted. It is a material that gives a quantum confinement effect that the emission wavelength is different from the bulk state. When the quantum dot receives light from an excitation source and reaches an energy excited state, the quantum dot emits energy according to a corresponding energy band gap. Therefore, by adjusting the size of the quantum dot it is possible to adjust the band gap, the energy of various wavelength bands can be obtained, thereby showing optical, electrical and magnetic properties that are completely different from the original physical properties.

These quantum dots have recently been studied for use in various fields, including a wide range of applications, such as displays, solar energy conversion, molecular and cellular imaging, and the like.

As a technique related to the conventional quantum dots, there is a "quantum dot-matrix thin film" of Korea Patent Publication No. 10-2013-0067137, which includes a plurality of quantum dots; An inorganic matrix embedded with a plurality of said quantum dots; And an interface layer positioned between the quantum dots and the inorganic matrix and surrounding the surface of the quantum dots.

Conventional quantum dots as well as the conventional quantum dots, as shown in Figure 1 not only has a characteristic that the emission color is changed according to the particle size, but also sensitive to the external environment has a characteristic that causes poor heat resistance and chemical resistance Therefore, this needs to be improved. In addition, the conventional quantum dots as well as the conventional quantum dots are limited in their use, so it is necessary to improve the applicability.

In order to solve the problems of the prior art as described above, an object of the present invention is to improve the physical properties such as weak heat resistance, chemical resistance, etc. that the quantum dot itself has, and to overcome the application limitation of the quantum dot itself.

Other objects of the present invention will be readily understood through the following description of the embodiments.

In order to achieve the above object, according to an aspect of the present invention, the step of synthesizing a quantum dot (QD) to have a ligand capable of hydrogen sillation (hydrosilylation); And forming a complex by mixing the synthesized quantum dots with a polymer material. A method of manufacturing a complex of a quantum dot and a polymer is provided.

In the synthesizing of the quantum dots, the ligand capable of hydrosilylation is one of an oleic acid derivative or an undecenoic acid derivative, or a terminal or internal alkene. (alkene) or alkyne (phosphine), phosphine oxide (phosphine oxide), thiol (thiol), phosphonic acid (phosphonic acid) and phosphinic acid (any one or a derivative thereof, or Phosphine, phosphine oxide, thiol, phosphonic acid and the like having terminal or internal silicon hydroxide (Si-H) It may be any one of phosphinic acid or a derivative thereof.

Synthesizing the quantum dots may be such that the quantum dots have some or all of alkene, alkyne, and Si—H bonds.

Synthesizing the quantum dot, CdO, Zn (OAc) ₂ , Oleic acid (Oleic acid (OA) and ODE (Octadecene) is mixed, but based on the CdO 0.4mmol, the Zn (OAc) ₂ Heating 1 to 10 mmol, a mixture of 10 to 25 mmol of the oleic acid (OA) and 5 to 25 ml of the ODE (Octadecene) to 150 to 210 ° C .; Degassing while cooling the mixture; Inject the mixture of TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S at 250 to 350 ° C. in the degassed mixture and grow at 250 to 300 ° C. for 5 to 15 minutes, based on 0.4 mmol of CdO. Wherein, the TOP-Se is 0.1 to 1.0 mmol Se and 1 to 10 ml TOP, and the TOP-S is 1 to 10 mmol S and 1 to 10 ml TOP; And cooling the grown mixture with an organic solvent after cooling.

Synthesizing the quantum dot, CdO, Zn (OAc) ₂ , Oleic acid (Oleic acid (OA) and ODE (Octadecene) is mixed, but based on the CdO 0.4mmol, the Zn (OAc) ₂ Heating 1 to 10 mmol, a mixture of 10 to 25 mmol of oleic acid (OA) and 5 to 25 ml of ODE (Octadecene) to 150 to 210 ° C .; Degassing while cooling the mixture; After degassing the mixture at 250 ~ 350 ℃, TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S each injected 5 to 20 seconds apart, each growth at 250 ~ 300 ℃ for 5 to 15 minutes Based on 0.4 mmol of CdO, wherein TOP-Se is 0.1 to 1.0 mmol Se and 1 to 10 ml TOP, and TOP-S is 1 to 10 mmol S and 1 to 10 ml TOP; And cooling the grown mixture with an organic solvent after cooling.

Synthesizing the quantum dots, by dissolving Se and S in tri-n-octylphosphine, respectively, to prepare a red quantum dot chalcogenide standard solution 1M TOP-Se and 1M TOP-S, respectively step; 0.1-5.0 mmol of CdO, 0.2-10 mmol of oleic acid (OA), 5-50 mL of ODE (Octadecene) was added, and the solution was heated to 150-250 ° C. until the solution became clear. Obtaining a precursor; The cadmium oleate metal precursor is heated in a vacuum to 100 ~ 200 ℃ to remove the water, remove the gas for 1 to 100 minutes, raise the temperature to 200 ~ 350 ℃, 1M TOP-Se 0.1 ~ Injecting 10 mL and 1 M of TOP-S 0.05-0.5 mL, adjusting the temperature to 180-330 ° C., and performing the reaction for 1-1000 minutes to obtain CdSe core quantum dots; Preparing a CdSe core quantum dot / ODE solution by dissolving 0.1 g of the obtained CdSe Core quantum dot in 1-100 mL of ODE; After raising the temperature of the reaction vessel to 150 ~ 250 ℃ under vacuum, and after purging the reaction vessel N ₂ again to raise the temperature to 180 ~ 330 ℃, 1 mmol of zinc stearate and the TOP-S in the reaction vessel After mixing 1 mL, further diluting TOP 5 mL to obtain a Zn-S precursor solution; And slowly dropping the Zn-S precursor solution into the CdSe core quantum dot / ODE solution, lowering the temperature to room temperature after the reaction for 1 to 6 hours, and recovering the CdSe-ZnS quantum dot by adding an organic solvent. Can be.

Synthesizing the quantum dot, dissolve 0.05 ~ 0.5g InCl ₃ and 0.01 ~ 0.5g anhydrous ZnCl ₂ in 1 ~ 100 mL of Oleyamine (OLA), raise the temperature to 150 ~ 300 ℃, and then vacuum the volatile material Removing and filling with nitrogen to prepare an In—Zn—OLA solution; And 0.01-1.0 mL of Tris (dimethylamino) phosphine (P (DA) ₃ ) in 1-10 mL of ODE (Octadecene) to prepare a P (DA) ₃ / ODE solution, and the In-Zn- at 150-300 ° C. Injecting the OLA solution, and maintaining the temperature at 150 ~ 300 ℃ for 1 ~ 1000 minutes, when the temperature of the solution is less than 60 ~ 100 ℃ by putting an organic solvent to recover the InP-ZnS quantum dot; may include; .

The forming of the complex may include: hydrosilylation of the polymer material to form a C-Si bond in the presence of an alkene or alkyne and silicon hydride (Si-H) as a catalyst It may be a material formed by the reaction.

In the forming of the complex, the polymer material may be polydimethylsiloxane (PDMS).

Forming the complex, the quantum dots, SYLGARD 184A and SYLGARD 184B of Dow Corning (Dow Corning) mixed in a weight ratio of 1: 50 to 200: 5 to 20, then 10 to 60 minutes at 80 ~ 120 ℃ Can be maintained for a while.

According to another aspect of the present invention, there is provided a composite of the quantum dots and the polymer, which is prepared by the method for producing a composite of the quantum dots and the polymer according to an aspect of the present invention.

According to the composite of the quantum dot and the polymer according to the present invention and a method for manufacturing the same, the composite of the quantum dot and the polymer has a fast reaction rate and a low reaction temperature, and also has weak physical properties such as poor heat resistance and chemical resistance. It is possible to improve the luminescence of the quantum dot, to adjust the luminescence of the quantum dot can be commercialized and economical, and to overcome the limitations of the application of the quantum dot itself can be applied to a variety of applications.

1 is a view showing a change in emission color according to the conventional quantum dot particle size.

2 is a flowchart illustrating a method of manufacturing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

Figure 3 shows as an example a ligand capable of hydrogen silicication in the method for producing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

4 is a view for explaining a double bond in the method of manufacturing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

5 is a view showing the concept of hydrogen silicic acid in the method for producing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

6 is a view showing a reaction mechanism of the method for producing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

7 is a view showing the luminescence of the quantum dots in the method for producing a composite of the quantum dots and the polymer according to an embodiment of the present invention.

8 is a view showing the luminescence of the composite prepared by the method for producing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

9 is a view showing the luminescence of the composite application product prepared by the method for producing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

As the inventive concept allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to the specific embodiments, but should be understood in a way that includes all changes, equivalents, and substitutes included in the spirit and scope of the present invention, and may be modified in various other forms. It is to be understood that the scope of the present invention is not limited to the following examples.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, and like reference numerals denote the same or corresponding elements regardless of reference numerals, and redundant description thereof will be omitted.

2 is a flowchart illustrating a method of manufacturing a composite of a quantum dot and a polymer according to an embodiment of the present invention.

As shown in FIG. 2, the method of manufacturing a composite of a quantum dot and a polymer according to an embodiment of the present invention synthesizes the quantum dot (QD) to have a ligand capable of hydrosilylation (S11). And mixing the synthesized quantum dots with a polymer material to form a complex (S12).

Synthesis of the quantum dot (S11) is a ligand capable of hydrosilylation is one of an oleic acid (OA) derivative or an undecenoic acid (UDCA) derivative, or a terminal or internal ( any one of phosphine, phosphine oxide, thiol, phosphonic acid and phosphinic acid having an alkene or alkyne of internal Phosphines, phosphine oxides, thiols, phosphonic acids with their derivatives or with terminal or internal silicon hydroxide (Si-H) phosphonic acid) and phosphinic acid, or one or a derivative thereof. This is as shown in FIG. 3. In the case of hydrosilylation process, Pt, Pd, Ni, Cobalt triad, Iron trid, Early transition metal complex, lanthanide metal complet, and actinide metal complex can be used as catalysts, and Karstedt's catalyst is the most commonly used catalyst. (Pt (II) divinylsiloxane) can be used as a catalyst. Hydrosilylation reactions are reactions in which alkenes or alkynes and silicon hydroxide (Si-H) form C-Si bonds in the presence of a catalyst (eg Pt) (Hydrosilylation; A Comprehensive Review on Recent Advances, Editors: Marciniec, Bogdan (Ed.)).

Quantum dots can be synthesized, for example, by pyrolysis, according to which, for example, by injecting a room temperature Se solution into a high temperature Cd solution to form a Cd-Se seed and by continuous supply of materials. By growing CdSe particles, quantum dots are synthesized. At this time, for example, oleic acid (Oleic acid; OA) can be synthesized using a ligand, the ligand serves to enable the dispersion of the quantum dots in the organic solvent.

On the other hand, the quantum dot is any of Si-based nanocrystals, II-VI-based compound semiconductor nanocrystals, III-V-based compound semiconductor nanocrystals, IV-VI-based compound semiconductor nanocrystals and compounds thereof within the scope to which the present invention can be applied It may comprise one nanocrystal. Here, the group II-VI compound semiconductor nanocrystals are CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, PbSe, PbS, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeS, HgSeS, HgSeS Among CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HggZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgZTSe, HdHgZTT, In addition, group III-V compound semiconductor nanocrystals are GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNPs, GaInNAs, GaInPAs, InAlNPs, InAlNAs, and InAlPAs may be any one selected from. In addition, the quantum dot may be a Cd compound such as CdS, CdSe, CdTe, CdTe, or the like, or an In compound such as InP, InN, InAs, etc., and the shell surrounding the core may be a Zn compound such as a quantum dot core and a lattice parameter. May be similar ZnS or ZnSe, and thus may include nanocrystals made of CdSe / ZnS or InP / ZnS.

As shown in FIG. 4, the step S11 of synthesizing the quantum dots may allow the quantum dots to have some or all of alkene, alkyne, and Si—H bonds, and a double bond. Can have Thus, oleic acid derivatives or undecenoic acid derivatives can be used for hydrogen silicidation, and when oleic acid and undenoic acid used for quantum dots are used to protect quantum dots and improve dispersibility in organic solvents, they are the same as carboxylate alkyl esters. It can be said to function. This is because oleic acid or undenoic acid is attached to the surface of the quantum dot. Conceptually referring to FIG. 5, as in (a), Alkyl acid is unprotected by carboxylate, does not cause a hydrosilylation reaction, and as in (b), R2 is used for Alkyl acid alkyl ester. Is protected by carboxylate and causes a hydrosilylation reaction, as in (c), the quantum dots are protected by carboxylate, and like (b) can cause a hydrosilylation reaction. Similarly, if the quantum dot ligand has silicon hydroxide (Si-H) at the terminal or internal, it reacts in the presence of alkene or alkyne and catalyst (eg Pt). To form a C-Si bond.

Synthesis of the quantum dot (S11) is, for example, a mixture of CdO, Zn (OAc) ₂ , oleic acid (OA) and ODE (Octadecene) for the synthesis of the green QD (green QD), based on 0.4 mmol CdO With Zn (OAc) ₂ Heating a mixture of 1-10 mmol, 10-25 mmol of oleic acid (OA) and 5-25 ml of ODE (Octadecene) to 150-210 ° C., and degassing while cooling the mixture. After degassing, the mixture of TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S is injected at 250 to 350 ° C. and grown at 250 to 300 ° C. for 5 to 15 minutes, based on 0.4 mmol of CdO. As a step, TOP-Se is 0.1 to 1.0 mmol Se and 1 to 10 ml TOP, and TOP-S is 1 to 10 mmol S and 1 to 10 ml TOP, and the grown product is cooled and purified by an organic solvent. It may include.

In addition, the step of synthesizing the quantum dots (S11), for example, to combine the red quantum dots (red QD), for example, CdO, Zn (OAc) ₂ , oleic acid (Oleic acid (OA) and ODE (Octadecene) mixed, but 0.4dol As a reference, Zn (OAc) ₂ Heating a mixture of 1-10 mmol, 10-25 mmol of oleic acid (OA) and 5-25 ml of ODE (Octadecene) to 150-210 ° C., and degassing while cooling the mixture. And, in the degassed mixture at 250 ~ 350 ℃, TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S each injected 5 to 20 seconds apart, each growth at 250 ~ 300 ℃ for 5 to 15 minutes On the basis of 0.4 mmol CdO, TOP-Se is 0.1-1.0 mmol Se and 1-10 ml TOP, TOP-S is 1-10 mmol S and 1-10 ml TOP, and the grown product is cooled. And then purifying with an organic solvent.

In the step of synthesizing the quantum dots (S11), Se and S were dissolved in tri-n-octylphosphine, respectively, to prepare a red quantum dot chalcogenide standard solution, 1 M TOP-Se and 1 M TOP-S, respectively. And 0.1 to 5.0 mmol of CdO, 0.2 to 10 mmol of oleic acid (OA), 5 to 50 mL of ODE (Octadecene), and heated to 150 to 250 ° C. until the solution becomes transparent. Obtaining a cadmium oleate metal precursor, heating the cadmium oleate metal precursor to 100 to 200 ° C. in a vacuum to remove water, removing gas for 1 to 100 minutes, and heating the temperature to 200 to 350 Raise to ℃, inject 0.1 ~ 10 mL of 1M TOP-Se and 0.05 ~ 0.5 mL of 1M TOP-S, adjust the temperature to 180 ~ 330 ℃, proceed the reaction for 1 ~ 1000 minutes CdSe core Obtaining a quantum dot, dissolving 0.1 g of the obtained CdSe Core quantum dot in 1-100 mL of ODE to prepare a CdSe core quantum dot / ODE solution, and under vacuum After the semi-raised the temperature of the vessel up to 150 ~ 250 ℃, again raised up to the temperature of the reaction vessel after the N ₂ purging (purging) 180 ~ 330 ℃, the TOP-S 1 mL and Zinc stearate 1 mmol in the reaction vessel After mixing, additionally dilute TOP 5 mL to obtain a Zn-S precursor solution, and slowly drop the Zn-S precursor solution into the CdSe core quantum dot / ODE solution, and then react at room temperature after 1-6 hours. After lowering to, may include the step of recovering the CdSe-ZnS quantum dots by adding an organic solvent.

In addition, the step of synthesizing the quantum dots (S11) is dissolved in 0.05 ~ 0.5g InCl ₃ and 0.01 ~ 0.5g anhydrous ZnCl ₂ in 1 ~ 100 mL of Oleyamine (OLA), raising the temperature to 150 ~ 300 ℃, and then volatile in vacuum Removing the material, filling with nitrogen to prepare an In-Zn-OLA solution, and dissolving 0.01 ~ 1.0 mL of Tris (dimethylamino) phosphine (P (DA) ₃ ) in 1-10 mL of ODE (Octadecene) ₃ ) / ODE solution was prepared, injected into the In-Zn-OLA solution at 150 ~ 300 ℃, the temperature was maintained at 150 ~ 300 ℃ 1 to 1000 minutes, and the temperature of the solution is less than 60 ~ 100 ℃ If the organic solvent may be added to recover the InP-ZnS quantum dot.

Forming the complex (S12) is a hydrogen silicide in which the polymer material catalyzes alkenes or alkynes and silicon hydrides (Si-H) to form C-Si bonds in the presence of, for example, Pt. It may be a material formed by a hydrosilylation reaction. In addition, the step (S12) of forming a composite may be a polymer material is polydimethylsiloxane (PDMS). In addition, the step of forming a complex (S12) is a quantum dot, Dow Corning (Dow Corning) SYLGARD 184A and SYLGARD 184B 1: 1: 50 ~ 200: 5 to 20 by weight ratio of 10 to 60 at 80 ~ 120 ℃ Hold for minutes. The reaction mechanism of forming such a complex (S12) is shown in FIG.

The composite of the quantum dot and the polymer according to the present invention may be prepared by the method of manufacturing a composite of the quantum dot and the polymer according to the present invention described above.

Example 1 Green Quantum Dot Synthesis

0.4 mmol CdO, 4.0 mmol Zn (OAc) ₂ , 17.6 mmol oleic acid and 10 ml of ODE were mixed, heated to 180 ° C., lowered to 130 ° C., degassed, and then degassed to TOP-Se at 300 ° C. A mixture of TOP-S was injected, Se 0.4 mmol / 3 ml TOP, S 4.0 mmol / 3 ml TOP, and the resultant was grown at 270 ° C. for 10 minutes, then cooled to room temperature and purified by EtOH. The luminescence of the green quantum dots thus synthesized is shown in FIG.

Example 2 Red quantum dot synthesis

0.4 mmol CdO, 4.0 mmol Zn (OAc) ₂ , 17.6 mmol oleic acid and 10 ml of ODE were mixed, heated to 180 ° C., and then degassed by lowering the temperature to 130 ° C., followed by degassing at 300 ° C. in TOP-. Each of Se and TOP-S is injected in turn at intervals of 10 seconds, Se 0.4mmol / 3mL TOP, S 4.0mmol / 3mL TOP, and the resultant is grown at 260 ° C for 10 minutes, and then cooled to room temperature. Purification with EtOH. The luminescence of the red quantum dots thus synthesized is shown in FIG.

Example 3 Synthesis of CdSe-ZnS Core-shell Quantum Dots

Se and S were dissolved in tri-n-octylphosphine, respectively, to prepare a red color quantum dot chalcogenide standard solution, 1M Se solution (TOP-Se) and 1M S (TOP-S) solution. In a 100 mL two neck round bottom flask, 0.128 g (1.0 mmol) of cadmium oxide, 0.634 mL (2.0 mmol) of oleic acid, 10 mL of ODE (Octadecene) were added and the solution became clear. It heated up to 180 degreeC and obtained the cadmium oleate metal precursor. The resulting water was then removed by heating in vacuo to 150 ° C. and degassing for 20 minutes. The temperature of the mixed solution was raised to 300 ° C. and 2 mL of 1 M Se solution (TOP-Se) and 0.1 mL of S solution (TOP-S) were injected. After the growth step to adjust the temperature to 280 ℃ 10 minutes to obtain a CdSe core quantum dot. 0.1 g of the CdSe Core quantum dot obtained above is dissolved in 10 mL of ODE. The temperature of the reaction vessel is raised to 200 ° C. under vacuum, and then the temperature is increased to 280 ° C. after N ₂ purging. Mix 1 mmol of zinc stearate with 1 mL of the prepared TOP-S and dilute by adding 5 mL of TOP (this is called the Zn-S precursor solution). The Zn-S precursor solution is slowly dropped into a CdSe core quantum dot / ODE solution using a syringe pump. After 1 hour of reaction, the temperature of the reaction vessel was lowered to room temperature, acetone was added to the container in excess, and quantum dots were precipitated, and the particles were recovered at 15,000 rpm using a centrifuge.

Example 4 InP-ZnS Core-shell Quantum Dot Synthesis

Dissolve 0.2g InCl ₃ and 0.12g anhydrous ZnCl ₂ in Oleyamine (OLA) and place in 100mL 1-neck RBF. Medium Medium vacuum is applied to remove volatiles in the solution and to fill the container with nitrogen. Dissolve 0.25 mL of tris (dimethylamino) phosphine (P (DA) ₃ ) in 1 mL of 1-octadecene. P (DA) ₃ / ODE solution is injected into the In-Zn-OLA solution at 220 ° C and the temperature of the vessel is maintained at 220 ° C for 3 minutes. After 3 minutes, the vessel is separated from the heating mantle, and when the temperature of the solution reaches 100 ° C. or lower, EtOH is poured to recover the InP-ZnS quantum dots. The collected quantum dots emit green light.

Example 5 Preparation of Quantum Dot-PDMS Composite

45 g of SYLGARD 184A from Dow Corning, 5 g of SYLGARD 184B, and 0.5 g of red quantum dots of Example 1 or 0.5 g of red quantum dots of Example 2 were mixed and held at 100 ° C. for 30 minutes. The luminescence of the composite thus produced is shown in FIG. 8.

Example 6 Mass Production of Quantum Dot-PDMS Complexes

Dow Corning's SYLGARD 184A 900g and SYLGARD 184B 100g, and 10g of the stock solution or any 10ml (100mg QD / mL chcloroform oor toluene) of any one of Examples 1 to 4 were mixed and maintained at 100 ° C for 30 minutes. .

Example 7

A pellet was prepared by mixing 1 kg of the quantum dot-PDMS complex prepared in Example 5 or Example 6 and 19 kg of PMMA (polymethylmethacrylate), and these pellets also showed intrinsic luminescence as shown in FIG. 9.

According to such a composite of the quantum dot and the polymer according to the present invention and a manufacturing method thereof, by forming a complex of the quantum dot and the polymer, it has a fast reaction rate and low reaction temperature, and also has a weak heat resistance, chemical resistance, etc. that the quantum dot itself has It is possible to improve the physical properties of the quantum dot, such as the emission wavelength band, emission intensity through the control of the concentration and additives of the light emitter to be used can be adjusted.

In addition, according to the composite of the quantum dot and the polymer according to the present invention and a method for producing the same, the commercial siloxane (compound) and the catalyst can be used for mass production in the commercial, it is possible to promote the commercial and economical, for example, the composite of 10kg in lab scale It can be prepared in 1 hour, and can be mixed with other polymers such as polymethylmethacrylate (PMMA), thereby overcoming the application limitations of the quantum dot itself, allowing the application of quantum dots to various applications.

As described above with reference to the accompanying drawings, the present invention, of course, various modifications and variations can be made within the scope 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 defined by the claims below and equivalents thereof.

Claims (10)

1. Synthesizing a quantum dot (QD) to have a ligand capable of hydrosilylation; And

   Mixing the synthesized quantum dots with a polymer material to form a composite;

   Including,

   Synthesizing the quantum dots,

   The ligand capable of hydrosilylation is one of an oleic acid derivative or an undecenoic acid derivative, or an alkene or alkyne of a terminal or internal. Phosphine (phosphine), phosphine oxide (phosphine oxide), thiol (thiol) having a phosphonic acid (phosphonic acid) and phosphinic acid (phosphinic acid) any one or derivative thereof, or a terminal (terminal) or internal ( phosphine, phosphine oxide, thiol, phosphonic acid and phosphinic acid with internal silicon hydroxide (Si-H) Method for producing a composite of a quantum dot and a polymer, which is one or a derivative thereof.
2. The method according to claim 1,

   Synthesizing the quantum dots,

   The quantum dot to have some or all of the alkene (alkene), alkyne (alkyne) and Si-H bonds, quantum dot and a polymer manufacturing method.
3. The method according to claim 1,

   Synthesizing the quantum dots,

   CdO, Zn (OAc) ₂ , oleic acid (Oleic acid; OA) and ODE (Octadecene) is mixed, based on 0.4 mmol CdO, Zn (OAc) ₂ Heating 1 to 10 mmol, a mixture of 10 to 25 mmol of the oleic acid (OA) and 5 to 25 ml of the ODE (Octadecene) to 150 to 210 ° C .;

   Degassing while cooling the mixture;

   Inject the mixture of TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S at 250 to 350 ° C. in the degassed mixture and grow at 250 to 300 ° C. for 5 to 15 minutes, based on 0.4 mmol of CdO. Wherein, the TOP-Se is 0.1 to 1.0 mmol Se and 1 to 10 ml TOP, and the TOP-S is 1 to 10 mmol S and 1 to 10 ml TOP; And

   Purifying the grown mixture with an organic solvent after cooling;

   Comprising a method for producing a composite of a quantum dot and a polymer.
4. The method according to claim 1,

   Synthesizing the quantum dots,

   CdO, Zn (OAc) ₂ , oleic acid (Oleic acid; OA) and ODE (Octadecene) is mixed, based on 0.4 mmol CdO, Zn (OAc) ₂ Heating 1 to 10 mmol, a mixture of 10 to 25 mmol of oleic acid (OA) and 5 to 25 ml of ODE (Octadecene) to 150 to 210 ° C .;

   Degassing while cooling the mixture;

   After degassing the mixture at 250 ~ 350 ℃, TOP (Trioctylphosphine) -Se and TOP (Trioctylphosphine) -S each injected 5 to 20 seconds apart, each growth at 250 ~ 300 ℃ for 5 to 15 minutes Based on 0.4 mmol of CdO, wherein TOP-Se is 0.1 to 1.0 mmol Se and 1 to 10 ml TOP, and TOP-S is 1 to 10 mmol S and 1 to 10 ml TOP; And

   Purifying the grown mixture with an organic solvent after cooling;

   Comprising a method for producing a composite of a quantum dot and a polymer.
5. The method according to claim 1,

   Synthesizing the quantum dots,

   Dissolving Se and S in tri-n-octylphosphine, respectively, to prepare 1 M TOP-Se and 1 M TOP-S, which are chalcogenide standard solutions for red quantum dot synthesis;

   0.1-5.0 mmol of CdO, 0.2-10 mmol of oleic acid (OA), 5-50 mL of ODE (Octadecene) was added, and the solution was heated to 150-250 ° C. until the solution became clear. Obtaining a precursor;

   The cadmium oleate metal precursor is heated in a vacuum to 100 ~ 200 ℃ to remove the water, remove the gas for 1 to 100 minutes, raise the temperature to 200 ~ 350 ℃, 1M TOP-Se 0.1 ~ Injecting 10 mL and 1 M of TOP-S 0.05-0.5 mL, adjusting the temperature to 180-330 ° C., and performing the reaction for 1-1000 minutes to obtain CdSe core quantum dots;

   Preparing a CdSe core quantum dot / ODE solution by dissolving 0.1 g of the obtained CdSe Core quantum dot in 1-100 mL of ODE;

   After raising the temperature of the reaction vessel to 150 ~ 250 ℃ under vacuum, and after purging the reaction vessel N ₂ again to raise the temperature to 180 ~ 330 ℃, 1 mmol of zinc stearate and the TOP-S in the reaction vessel After mixing 1 mL, further diluting TOP 5 mL to obtain a Zn-S precursor solution; And

   Slowly dropping the Zn-S precursor solution into the CdSe core quantum dot / ODE solution, lowering the temperature to room temperature after the reaction for 1 to 6 hours, and then recovering the CdSe-ZnS quantum dot by adding an organic solvent;

   Comprising a method for producing a composite of a quantum dot and a polymer.
6. The method according to claim 1,

   Synthesizing the quantum dots,

   Dissolve 0.05 ~ 0.5g InCl ₃ and 0.01 ~ 0.5g anhydrous ZnCl ₂ in 1 ~ 100 mL of Oleyamine (OLA), raise the temperature to 150 ~ 300 ℃, remove the volatile material by vacuum, and fill with In- Preparing a Zn-OLA solution; And

   Dissolve 0.01-1.0 mL of Tris (dimethylamino) phosphine (P (DA) ₃ ) in 1-10 mL of ODE (Octadecene) to prepare a P (DA) ₃ / ODE solution, and the In-Zn-OLA at 150-300 ° C. Injecting the solution, maintaining the temperature at 150 to 300 ° C. for 1 to 1000 minutes, and then recovering the InP-ZnS quantum dot by adding an organic solvent when the temperature of the solution is less than 60 to 100 ° C .;

   Comprising a method for producing a composite of a quantum dot and a polymer.
7. The method according to claim 1,

   Forming the complex,

   The polymer material is a material formed by a hydrosilylation reaction to form a C-Si bond in the presence of an alkene or alkyne and silicon hydride (Si-H) as a catalyst. Method for producing a composite of quantum dots and polymers.
8. The method according to claim 1,

   Forming the complex,

   The polymer material is PDMS (polydimethylsiloxane), the method of manufacturing a composite of a quantum dot and a polymer.
9. The method according to claim 8,

   Forming the complex,

   The quantum dots, SYLGARD 184A and SYLGARD 184B of Dow Corning (Dow Corning) is mixed in a weight ratio of 1: 50 ~ 200: 5 ~ 20, and then maintained for 10 to 60 minutes at 80 ~ 120 ℃, of the quantum dots and polymer Composite manufacturing method.
10. The method according to claim 1,

    A composite of a quantum dot and a polymer produced by the method for producing a composite of the quantum dot and a polymer described.

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