KR20140066906A - Quantum rod and method of fabricating the same - Google Patents

Quantum rod and method of fabricating the same Download PDF

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Publication number
KR20140066906A
KR20140066906A KR1020120133815A KR20120133815A KR20140066906A KR 20140066906 A KR20140066906 A KR 20140066906A KR 1020120133815 A KR1020120133815 A KR 1020120133815A KR 20120133815 A KR20120133815 A KR 20120133815A KR 20140066906 A KR20140066906 A KR 20140066906A
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quantum rod
core
rod
transition metal
quantum
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KR1020120133815A
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Korean (ko)
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KR102033479B1 (en
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정경석
김진욱
조성희
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엘지디스플레이 주식회사
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Priority to KR1020120133815A priority Critical patent/KR102033479B1/en
Priority to US14/085,073 priority patent/US9224920B2/en
Priority to CN201310596775.5A priority patent/CN103840052B/en
Publication of KR20140066906A publication Critical patent/KR20140066906A/en
Priority to US14/947,825 priority patent/US9543394B2/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium

Abstract

The present invention relates to a quantum rod and a manufacturing method thereof, and more specifically, to a quantum rod with the green light emitting efficiency maximized and a manufacturing method thereof. According to the present invention, a core made of ZnS based semiconductor is coated with Cu^(2+) to be biased to one side thereof in the longitudinal direction of the quantum rod. Therefore, the quantum rod has polarization characteristics by the rod-shaped core and can emit green lights with high efficiency through Cu^(2+).

Description

[0001] The present invention relates to a quantum rod and a method of fabricating the same,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quantum rod, and more particularly, to a quantum rod maximizing luminous efficiency of a green color and a method of manufacturing the same.

In general, the chemical and physical properties of solid crystals are independent of the size of the crystals. However, when the size of a solid crystal becomes a region of several nanometers, its size may be a variable that influences the chemical and physical properties of the crystal. Research to form a nanocystal, a nanocluster, or a quantum dot as a semiconductor material among nanotechnologies utilizing the unique properties of such nano-sized particles is currently being actively conducted worldwide.

In particular, conventional inorganic light-emitting devices, which have been manufactured in the form of thin films by chemical vapor deposition (CVD), have a disadvantage in that the electro-optical conversion efficiency is lowered. In recent years, there has been a growing interest in high-efficiency light emitting devices using nanomaterials. Particularly, a quantum dot having a size of several nanometers exhibits a unique behavior called a quantum effect, A semiconductor structure to be used, an emission marker of molecules in a living body, and the like.

Quantum dots and their crystal structure are Hexagonal structure, and crystals grow in uniaxial direction, and a rod shaped quantum rod emits light of different wavelength depending on its size.

Generally, the size of quantum dots and quantum rods need to be adjusted appropriately because these particles generate a short wavelength light with a small number of particles and a larger particle generates light with a long wavelength.

However, quantum dots and quantum rods are very small in particle size, so the surface-volume ratio is very high, and the atoms located on the surface are highly reactive and are likely to grow into larger particles by contact with surrounding particles.

In order to prevent this, the precipitation method, the pyrolysis method, the gas phase synthesis method, the template synthesis method, and the like have been proposed. The quantum dots and quantum rods synthesized at the beginning are II-VI, III-V, Ⅰ- Ⅲ-Ⅵ, Ⅳ-Ⅵ It consisted of a single semiconductor particles (CdSe, CdTe, CdS, GaAs , GaP, GaAs-P, Ga-Sb, InAs, InP, InSb, AlAs, AlP, AlSbCulnSe 2, CulS 2, AginS 2, PbS, PbSe, PbTe) .

The study of such quantum dots is based on changing the structure of nanocrystals such as the size and surface of nanocrystals in the nanometer range to change the properties of the crystal, that is, the band gap.

On the other hand, the quantum dots have different emission ranges, luminescent efficiencies, and chemical stability depending on their compositions, and thus the application range and application methods of each quantum dot are limited.

Particularly, in the case of a quantum rod having a high-efficiency light emission characteristic and also a polarization characteristic, the luminous efficiency is rapidly lowered as compared with the quantum dot.

This is because the quantum rod has a rod shape as opposed to a spherical quantum dot, so that the length of the shell is longer than the Bohr radius of the exiton and the quantum confinement effect is reduced to be.

Therefore, research on a quantum rod having a high-efficiency light emission characteristic and a polarization characteristic is required.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a green color light emitting quantum rod having a high efficiency light emitting characteristic and a polarization characteristic to solve the above problems.

In order to achieve the above object, the present invention provides a semiconductor device comprising: a rod-shaped core made of ZnS-based semiconductor particles; And a quantum rod including a transition metal doped on one side in the longitudinal direction of the core.

In this case, the ZnS-based semiconductor particles, ZnSe, ZnO, ZnS, Zm x Cd 1 - x Se, Zn x Cd 1 - x S composed of selected one of (0 <X <1), the transition metal is Cu 2 +, Tb 3 +, Mn 2 &Lt; / RTI &gt;

The transition metal made of Cu 2 + emits green color, and the transition metal is doped in an amount of 0.1 to 50% of the core.

The size of the core is 10 to 10000 nm.

The present invention also provides a method of fabricating a semiconductor device, comprising: forming core nanocrystals through ZnS based semiconductor particles; Doping a surface of the core nanocrystal with a transition metal; And growing the core nanocrystals in a rod shape.

In this case, the ZnS-based semiconductor particles, ZnSe, ZnO, ZnS, Zm x Cd 1 - x Se, Zn x Cd 1 - x S composed of selected one of (0 <X <1), the transition metal is Cu 2 +, Tb 3 +, Mn 2 &Lt; / RTI &gt;

The transition metal is doped with 0.1 to 50% of the core nanocrystals, and the core nanocrystals are grown to a size of 10 to 10,000 nm.

As described above on, the core made of ZnS-based semiconductor particles according to the present invention, Cu 2 + by transferring formed by proton doping biased to one side in the longitudinal direction of the bar of metal, through which the polarization properties by the rod-shaped core having at the same time through the Cu 2 + a transition metal which produces the effect of firing the green (green) color of a high efficiency.

1 schematically illustrates a quantum rod according to an embodiment of the present invention.
FIGS. 2A to 2D schematically illustrate a process of forming a quantum rod according to an embodiment of the present invention. FIG.
3 is a graph showing an emission spectrum according to an embodiment of the present invention.

Hereinafter, embodiments according to the present invention will be described in detail with reference to the drawings.

1 is a schematic view of a quantum rod according to an embodiment of the present invention.

First, the quantum rod 100 used in the present invention will be briefly described. The quantum rod 100 having a size of several nanometers exhibits a specific behavior called a quantum effect. In order to produce a highly efficient light emitting device Semiconductor structures, and emission markers of molecules in vivo.

The study of the quantum rod 100 is based on changing the structure of the nanocrystals such as the size and surface of the nanocrystals in the nanometer range to change the properties of the crystal, that is, the band gap .

Each material, including semiconducting material, combines with the atomic electron orbital as it converts to a molecular electron orbital. The molecular electron orbit involves two electron orbits in the atomic state, respectively, forming a bonding orbit (Bonding Molecular Orbital) and an antibonding molecular orbital (orbital) respectively. At this time, the band formed by many coupling orbits is called a valence band, and the band formed by many semi-coupling orbits is called a conduction band.

The highest energy level of the valence band is called the highest occupied molecular orbital (HOMO) and is called the lowest unoccupied molecular orbital (LUMO) at the lowest energy level of the conduction band. The HOMO level and the LUMO level Is defined as a band gap.

Here, the quantum rod 100 is formed of a core having a rod shape as shown in the figure. The overall size of the quantum rod 100 has a nanocrystal size of 10 to 10000 nm.

At this time, the core 110 may be in the shape of a rod having a major axis and a minor axis, and the cut surface cut in the minor axis direction of the quantum rod 100 may have any one of a circle, an ellipse, and a polygonal shape.

On the other hand, the quantum rod can have various ratios by having the ratio of the minor axis to the major axis in the range of 1: 1.1 to 1:30.

In this quantum rod 100, electrons in a state of being excited to a valence band in a conduction band are generated and fluorescence is generated.

The quantum rod 100 has a property different from a general fluorescent dye. Even if the quantum rod 100 is composed of the same material core, the fluorescence wavelength varies depending on the particle size. That is, as the size of the particle becomes smaller, it emits fluorescence of a short wavelength, and it is characterized in that almost all the light of the desired visible ray region can be obtained by controlling the particle size.

Further, the quantum rod 100 has a high quantum yield, which is another characteristic that it can generate very strong fluorescence.

In particular, the rod-shaped quantum rod 100 has a polarization characteristic that transmits only light in a specific direction and absorbs or reflects the remaining light.

That is, the quantum rod 100 has a characteristic of absorbing or reflecting only light of a specific wavelength among the light incident on the quantum rod 100. Since the polarization axis of the quantum rod 100 is formed along the longitudinal direction of the quantum rod 100, the polarized light component parallel to the longitudinal direction of the quantum rod 100 is absorbed and reflected by the quantum rod 100, The polarized light component perpendicular to the longitudinal direction is transmitted through the quantum rod.

The structure of a general quantum rod light emitting device using the quantum rod 100 having the above-described characteristics will be briefly described.

A quantum rod (100) light emitting device has a quantum rod layer between an anode electrode, which is an anode, and a cathode electrode, which is a cathode.

In the quantum rod light emitting device having such a structure, holes (+) injected from the anode electrode into the quantum rod layer through the hole injection layer and electrons injected from the cathode electrode into the quantum rod layer through the electron injection layer are recombined and excitons are formed through recombination, and light of a color corresponding to the band gap of the quantum rod layer 154 is emitted from the excitons.

Since the quantum rod 100 having such a structure is a fluorescent material, it needs a light source such as UV, and various colors can be realized by irradiating the quantum rod 100 with a UV light source.

At this time, the quantum rod 100 has a polarization characteristic so that only light of a specific wavelength is selectively transmitted through the light incident on the quantum rod 100.

When such a quantum rod (100) light emitting device is applied to a liquid crystal display device, one of a pair of polarizing plates can be eliminated, and the light loss can be minimized when the quantum rod 100 reflects light.

That is, when only light having a polarization axis perpendicular to the longitudinal direction of the quantum rod 100 among the light incident on the quantum rod 100 passes through the quantum rod 100 while the remaining light is configured to be reflected, The polarized state can be changed and reproduced with scattered light close to natural light.

The scattered light thus regenerated is again supplied to the quantum rod 100, and some of the light is again transmitted through the quantum rod 100, and the remaining light is reflected again, so that the reproduction of light is continuously repeated, The optical loss can be minimized.

Here, the quantum rod 100 according to the embodiment of the present invention is characterized in that the rod-shaped core 110 is doped with a transition metal anisotropically.

That is, the core 110 of the quantum rod 100 may be made of ZnS-based semiconductor particles. The ZnS-based semiconductor particles have a characteristic of emitting blue color, but the quantum rod 100 has a rod shape , The length of the quantum rod 100 becomes longer than the Bohr radius of the exciton, so that the quantum confinement effect is reduced, and substantially no light is emitted.

Therefore, the ZnS-based semiconductor particles are substantially transparent to visible light.

The quantum rod 100 of the present invention is doped with the Cu 2 + transition metal 120 that emits green color fluorescence to the core 110 made of ZnS based semiconductor particles, And has a polarization characteristic and simultaneously emits high-efficiency green color through the Cu 2 + transition metal 120.

That is, when the core 110 made of ZnS-based semiconductor particles is doped with the Cu 2 + transition metal 120, green color light emission is performed at about 500 nm.

Accordingly, the present invention can realize a quantum rod 100 having a high efficiency of green color emission efficiency and polarization characteristics.

Here, the ZnS semiconductor particles may be selected from ZnSe, ZnO, ZnS, Zm x Cd 1 - x Se, and Zn x Cd 1 - x S (0 <x <1).

The Cu 2 + transition metal 120 is preferably doped so as to have an amount of 0.1 to 50% of the ZnS based semiconductor particles.

At this time, in addition to the Cu 2 + transition metal 120, a green color emission may be realized by doping Tb 3 + transition metal.

Then, by doping the transition having a desired color metal, there may be implemented a variety of colors, as an example, Mn 2 + there may transition to dope a metal, a Mn 2 + transition metal core 110 made of ZnS-based semiconductor particles When doping, a red color emission of about 600 nm may be realized.

At this time, the Cu 2 + transition metal 120 is doped by being shifted to one side of the longitudinal direction of the quantum rod 100 within the rod-shaped core 110.

Which, by applying an electric field to both the bar 100, in the process of regulating the fluorescence amount or a quantity of emitted light of the two rods 100, the major and electrons Cu 2 +, which is dispersed in the core 110, the transition metal 120 So as not to be disturbed by the user.

Through this, self-absorption of electrons and holes can be reduced.

That is, before the electric field is applied in the longitudinal direction of the quantum rod 100, electrons and holes are coupled to each other in the core 110. However, when an electric field is applied in the longitudinal direction of the quantum rod 100, So that the separation of the band gap can be induced by being spatially separated from the inside.

Unlike the embodiment of the present invention, the Cu 2 + transition metal 120 may be dispersed in the quantum rod 100 in a state of being dispersed throughout the quantum rod 100, When doped, an electric field is applied in the longitudinal direction of the quantum rod 100, so that electrons and holes are disturbed by the Cu 2 + transition metal 120 in the process of being separated from the inside of the core 110.

Therefore, separation of electrons and holes may not be easy, so that separation of band gaps can not be easily induced, and some electrons collide with Cu 2 + transition metal 120 to be self-absorbed.

Therefore, in the embodiment of the present invention, Cu 2 + transition metal 120. The electrons and holes Cu 2 if the electric field in both the rod 100 by making biased doped with one side of the two-way quantum rod 100 is + The transition metal 120 from being interfered with.

This makes it possible to easily adjust the amount of emitted light and the amount of emitted light of the quantum rod 100 and prevent the occurrence of self-absorption of electrons.

Here, the quantum rod 100 of the present invention does not dope the transition metal to the completed quantum rod 100, but rather, by doping the transition metal before forming the quantum rod 100, So that it can be positioned to be positioned only on one side of the direction.

That is, in the quantum rod of the present invention,

(a) forming core (110) nanocrystals;

(b) doping the surface of the core (110) nanocrystals with a transition metal;

(c) Growth of the core (110) nanocrystals into a bar shape to form the quantum rod (100).

Here, the formation process of the quantum rod 100 of the present invention will be described in detail with reference to FIGS. 2A to 2D.

2A to 2D are schematic views illustrating a process of forming a quantum rod according to an embodiment of the present invention.

As shown in FIG. 2A, first, core 110 nanocrystals are formed through ZnS based semiconductor particles, and core 110 nanocrystals can be manufactured through a general core 110 nanocrystal manufacturing method.

2 ( b ), the core 110 nanocrystals and the Cu 2 + (120) transition metal precursor solution are mixed and reacted to form a core 110 nanocrystal doped with the Cu 2 + transition metal 120 .

Next, as shown in FIGS. 2c and 2d, core 110 nanocrystals grown with Cu 2 + transition metal 120 are grown.

In this case, when a precursor of each element is mixed with a solvent, a dispersant may be further used. Mixing of the respective reactants may be performed simultaneously or sequentially, and the order may be adjusted depending on the case.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example

Cu2 + doping in a quantum rod consisting of a zinc sulfide (ZnS) semiconductor particle core

Octadecylamine (hereinafter referred to as ODE) and octadecylamine (hereinafter referred to as ODA) were placed in a reactor and heated to 120 ° C. in a nitrogen atmosphere to heat the mixture to a temperature of 120 ° C., Remove.

Separately, a Se-TBP complex solution was prepared by dissolving Se powder in tributylphosphine (hereinafter referred to as TBP).

After heating at 300 ° C in a nitrogen stream, Se-TBP was introduced and reacted at 300 ° C for 10 minutes.

When the reaction was completed, the temperature of the reaction mixture was dropped to room temperature as soon as possible, and centrifugation was performed by adding ethanol as a non-solvent. The supernatant of the solution excluding the centrifuged precipitate is discarded, and the precipitate is dispersed in toluene to form ZnS semiconductor particles.

Then ZnS semiconductor particles were doped with Cu2 +, ZnS semiconductor particles were doped with selenourea, ODA, Zn (St) 2, and dimethylformamide (DMF) Lt; / RTI &gt;

When the reaction was completed, the temperature of the reaction mixture was dropped to room temperature as soon as possible, and centrifugation was performed by adding ethanol as a non-solvent. The supernatant of the solution except for the centrifuged precipitate was discarded, and the precipitate was dispersed in toluene to synthesize rod-shaped quantum rod formed by biasing Cu2 + on one side in the longitudinal direction.

The emission spectrum of the quantum rod emitting the green color thus produced is shown in Fig. Referring to FIG. 3, the quantum rod according to the embodiment of the present invention can realize a green color having a color wavelength of about 500 nm by doping Cu 2 + into a core made of ZnS based semiconductor particles.

The quantum rod of the present invention can be applied variously as an electronic device in fields such as a display, a sensor, etc., and is particularly useful for forming an organic thin film of an organic light emitting device, particularly a light emitting layer. When a quantum rod is to be introduced into the light emitting layer, a vacuum deposition method, a sputtering method, a printing method, a coating method, an inkjet method, an electron beam method, or the like can be used.

Here, the organic thin film refers to a film made of an organic compound formed between a pair of electrodes in an organic electroluminescent device such as an electron transport layer and a hole transport layer in addition to a light emitting layer.

Such an organic light emitting device includes a known anode / light emitting layer / cathode, anode / buffer layer / light emitting layer / cathode, anode / hole transporting layer / light emitting layer / cathode, anode / buffer layer / hole transporting layer / light emitting layer / cathode, anode / buffer layer / Layer / light emitting layer / electron transport layer / cathode, anode / buffer layer / hole transport layer / light emitting layer / hole blocking layer / cathode, but the present invention is not limited thereto.

At this time, as a material of the buffer layer, a material commonly used can be used, and preferably a material such as copper phthalocyanine, polythiophene, polyaniline, polyacetylene, polypyrrole, Polyphenylene sulfide, polyphenylene sulfide, polyphenylene sulfide, polyphenylene sulfide, and polyphenylene sulfide.

As the material of the hole transporting layer, a commonly used material can be used, and polytriphenylamine can be preferably used, but not limited thereto.

As a material of the electron transporting layer, a commonly used material can be used, and preferably, polyoxadiazole can be used, but the present invention is not limited thereto.

As the material of the hole blocking layer, materials commonly used can be used, and LiF, BaF2, MgF2 or the like may be preferably used, but the present invention is not limited thereto.

As described above, the quantum rod of the present invention is formed by doping Cu 2 + at one side in the longitudinal direction of a quantum rod on a core made of ZnS-based semiconductor particles, and thus has a polarizing property by the rod- 2 + to emit high-efficiency green color.

The present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the spirit of the present invention.

100: Quantum rod
110: core, 120: Cu 2 +

Claims (11)

A rod-shaped core made of ZnS-based semiconductor particles;
And a doped transition metal
Lt; / RTI &gt;
The method according to claim 1,
The ZnS-based semiconductor particles are made of one selected from the group consisting of ZnSe, ZnO, ZnS, Zm x Cd 1 - x Se, and Zn x Cd 1 - x S (0 <x <1).
The method according to claim 1,
The transition metal is selected from the group consisting of Cu 2 + , Tb 3 + , Mn 2 A quantum rod consisting of a selected one of.
The method of claim 3,
The transition metal made of Cu 2 + is a quantum rod emitting green color.
The method according to claim 1,
Wherein the transition metal is doped in an amount of 0.1 to 50% of the core.
The method according to claim 1,
Wherein the core has a size of 10 to 10,000 nm.
Forming core nanocrystals through ZnS based semiconductor particles;
Doping a surface of the core nanocrystal with a transition metal;
Growing the core nanocrystals in a rod shape
/ RTI &gt;
8. The method of claim 7,
Wherein the ZnS-based semiconductor particles are selected from the group consisting of ZnSe, ZnO, ZnS, Zm x Cd 1 - x Se, and Zn x Cd 1 - x S (0 <x <1).
8. The method of claim 7,
The transition metal is selected from the group consisting of Cu 2 + , Tb 3 + , Mn 2 The quantum rod forming method comprising the steps of:
8. The method of claim 7,
Wherein the transition metal dopes an amount of 0.1 to 50% of the core nanocrystals.
8. The method of claim 7,
Wherein the core nanocrystals are grown to a size of 10 to 10,000 nm.
KR1020120133815A 2012-11-23 2012-11-23 Quantum rod and method of fabricating the same KR102033479B1 (en)

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Application Number Priority Date Filing Date Title
KR1020120133815A KR102033479B1 (en) 2012-11-23 2012-11-23 Quantum rod and method of fabricating the same
US14/085,073 US9224920B2 (en) 2012-11-23 2013-11-20 Quantum rod and method of fabricating the same
CN201310596775.5A CN103840052B (en) 2012-11-23 2013-11-22 Quantum rod and its manufacture method
US14/947,825 US9543394B2 (en) 2012-11-23 2015-11-20 Quantum rod and method of fabricating the same

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040059300A (en) * 2002-12-28 2004-07-05 학교법인 포항공과대학교 Nanostructure comprising magnetic material and nanomaterial and method for manufacturing thereof
CN101842460A (en) * 2007-10-30 2010-09-22 伊斯曼柯达公司 Device containing non-blinking quantum dots
WO2012035535A1 (en) * 2010-09-16 2012-03-22 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Anistropic semiconductor nanoparticles

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040059300A (en) * 2002-12-28 2004-07-05 학교법인 포항공과대학교 Nanostructure comprising magnetic material and nanomaterial and method for manufacturing thereof
CN101842460A (en) * 2007-10-30 2010-09-22 伊斯曼柯达公司 Device containing non-blinking quantum dots
WO2012035535A1 (en) * 2010-09-16 2012-03-22 Yissum Research Development Company Of The Hebrew University Of Jerusalem Ltd. Anistropic semiconductor nanoparticles

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