KR20160146333A - Polymer solution for fabricating nano structures - Google Patents

Abstract

A polymer containing metal atoms capable of forming metal nanoparticles in a short time by a commercially available low cost, simple method and a solution thereof are disclosed.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a polymer solution for nanoparticle production,

As various embodiments of the present invention, a method for preparing a polymer solution for nanoparticle production is provided.

The nanostructure exhibits characteristics such as quantum confinement effect, Hall petch effect, lowering of melting point, resonance phenomenon, and excellent carrier mobility compared with conventional bulk and thin film type structures. Therefore, it is being applied to devices requiring high integration and high efficiency, such as chemical batteries, solar cells, semiconductor devices, chemical sensors, and photoelectric devices.

Such nanostructures are manufactured in a top-down manner and a bottom-up manner. As a bottom-up method, a vapor-liquid-solid (VLS) growth method and a liquid phase growth method have been proposed. The VLS growth method can be applied to various types of growth methods such as thermal chemical vapor deposition (CVD), metal-organic chemical vapor deposition (MOCVD), pulsed laser deposition (PLD) (Atomic layer deposition (ALD)). Self-assembly technology and hydrothermal synthesis are proposed as the liquid growth method.

On the other hand, the conventional bottom up method is a method in which nanoparticles are made in advance and the nanoparticles are attached to a surface-modified substrate. However, this method has a limit to decrease the reproducibility and reliability of a nano-semiconductor device that utilizes the inherent characteristics of nanoparticles because the size of the nanoparticles is limited, . That is, the method of forming the nanostructure by simply attaching the already prepared nanoparticles to the substrate can not improve the performance of the nanodevice until the nanoparticle synthesis technology is highly improved.

In order to overcome these limitations, it is possible to produce nanoparticles in a top-down manner such as lithography, but in this case, it is very costly to use a high-grade lithography apparatus. In addition, the process is complicated and there is a limit to mass production. Further, even if etching is performed using an electron beam, there is a limit in reducing the size of the nanoparticles to a certain size or less.

A problem to be solved by the embodiments of the present invention is to provide a method for producing a polymer solution containing metal atoms capable of forming nanoparticles in a short time by a simple and low cost method which can be used commercially.

A method for preparing a metal atom containing polymer solution according to an embodiment of the present invention comprises:

Mixing a metal precursor and an organic material into a solvent; And adding a stabilizer for preventing precipitation to the solvent.

Preferably, the metal precursor may be any one selected from the group consisting of a halide, a chalcogenide, a hydrochloride, a nitrate, a sulfate, an acetate, and an ammonium salt of a transition metal.

More specifically, the metal precursor may be selected from the group consisting of HAuCl ₄ , AuCl, AuCl ₃ , Au ₄ Cl ₈ , KAuCl ₄ , NaAuCl ₄ , NaAuBr ₄ , AuBr ₃ , AuBr, AuF ₃ , AuF ₅ , AuI, AuI ₃ , KAu ) ₂ , Au ₂ O ₃ , Au ₂ S, Au ₂ S ₃ , AuSe, and Au ₂ Se ₃ .

Preferably, the organic material may include a functional group capable of binding to the metal atom.

More specifically,

But are not limited to, mercaptopropyl trimethoxysilane (3-MPTMS), mercaptopropyl triethoxysilane, 11-mercaptoundecyl trimethoxysilane, Mercaptomethyl methyl diethoxysilane octyltrichlorosilane (OTS), hexamethyldisilazane (HMDS), octadecyltrichlorosilane (ODTS), (3-aminopropyl) trimethylene Aminopropyl) trimethoxysilane (APS), (3-aminopropyl) triethoxysilane, N- (3-aminopropyl) -dimethyl-ethoxysilane (N- 3-aminopropyl) -dimethyl-ethoxysilane (APDMES) Perfluorodecyltrichlorosilane (PFS), mercaptopropyl trimethoxysilane (MPTMS), N- Trimethoxysilane (N- (2-aminoethyl) -3aminopropyltrimethoxysilane), (3-trimethoxysilylpropyl) diethylenetriamine ((3-

Octadecyltrimethoxysilane (OTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane ((Heptadecafluoro-1,1,2,2- tetrahydrodecyl trichlorosilane (FDTS), dichlorodimethylsilane (DDMS), N- (trimethoxysilylpropyl) ethylenediamine triacetic acid, hexadecanethiol (HDT), and epoxy And may be any one selected from the group of hexyltriethoxysilane.

Preferably, the functional group may be any one of a thiol group, an amine group and a phosphine group.

Preferably,

Methanol, Ethanol, 1-Propanol, 2-Propanol, 1-Pentanol, 2-Butoxyethanol, Ethylene glycol, Acetone, 2-Butanone, 4-Methyl-2-Pranone, Acetic Acid, Pentanes, Hexane, Decane, Cyclohexane, 1-Chloropropane, 2-Chloropropane, 1-Chloropropane, Bromoethane, Chloroform, Dichloromethane, 1-Butylene, 2-Butylene, 1-Pentene, 2-Pentene, Isobutylene, Carbon tetrachloride, 1-Chlorobutane, , 1,2-dichloroethane, 1-nitroprpane, and nitromethane.

Preferably, the stabilizing agent may comprise a basic compound. More specifically, the basic compound may be any one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and aqueous ammonia.

Preferably, the mixing ratio of the metal precursor and the organic material may be 1: 3 to 1:12.

Preferably, the organic material may be an alkoxysilane compound or an alkylsilane compound having a functional group capable of binding to a metal atom.

The polymer solution according to an embodiment of the present invention includes metal atoms, and it is possible to form the in situ nanoparticles on the substrate after coating the polymer on the substrate.

Even though nanoparticle synthesis technology is highly developed and it is possible to synthesize extremely fine nanoparticles composed of tens to hundreds of atoms, thermodynamically, externally synthesized nanoparticles have only a certain distribution of nanoparticles of various sizes This is due to the fact that the larger the reaction field in the synthesis, the greater the intergranular size difference. Therefore, a known technique for attaching preformed nanoparticles on a substrate, rather than a substrate, has limitations in producing uniform nanoparticles. In addition, although the method of manufacturing nanoparticles by top-down etching by etching is highly developed to enable particles of 5 nm or less to be manufactured, the process requires expensive and complicated and precise control, There is a limit to mass production.

When the nanoparticles are prepared using the polymer solution according to the embodiment of the present invention, nanoparticles are directly produced in an extremely small reaction field corresponding to the surface area of the substrate, The particles can be formed at a high density. Further, since metal atoms are fixed on a substrate by a polymer coating containing only metal atoms and energy is applied to metal atoms to form nanoparticles, it is easy and easy to mass-produce nanoparticles at low cost in a short time There are advantages to be able to. Further, as the nucleation and growth (nanoparticle formation) are performed by the energy application while the metal atoms are fixed on the substrate, migration of the metal atoms is uniformly suppressed as a whole and more uniform and fine nanoparticles are formed . In detail, the supply of the metal required for nucleation and growth of the material for nanoparticle formation can be accomplished only by the metal atom bound to the organic material. That is, the supply of the material for nanoparticle formation occurs only by the movement of the metal atoms bonded with the organic material, and as the metal atoms move to a certain distance or more by joining with the organic material, it becomes difficult to participate in nucleation and growth , The reaction field of each nanoparticle can be confined to the periphery of the nucleus. As a result, nanoparticles of more uniform and fine size can be formed at high density on the substrate, and uniformly spaced nanoparticles can be formed. At this time, the distance between the metallic nanoparticles can correspond to the metal atom diffusion distance contributing to nucleation and growth of each nanoparticle.

It is possible to prepare nanoparticles through an in-situ process using a polymer according to an embodiment of the present invention. In addition, metal atoms are attached to the patterned silicon substrate, the flexible polymer film, and the transparent substrate through a direct coating process, and then the metal atoms are reduced and grown to produce patterned nanoparticles . Therefore, waste of manufacturing cost can be minimized, and mass production is possible in a short time.

1 is a process flow diagram illustrating a method of fabricating a nanostructure according to an embodiment of the present invention.
2 is a schematic diagram showing a step of preparing a polymer containing metal atoms.
3 is a cross-sectional view showing a nanoparticle layer formed on a substrate.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following drawings are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. Therefore, the present invention is not limited to the following drawings, but may be embodied in other forms, and the following drawings may be exaggerated in order to clarify the spirit of the present invention. Also, throughout the specification, like reference numerals designate like elements.

Hereinafter, the technical and scientific terms used herein will be understood by those skilled in the art without departing from the scope of the present invention. Descriptions of known functions and configurations that may be unnecessarily blurred are omitted.

1 is a process flow diagram illustrating a method of fabricating a nanostructure according to a first embodiment of the present invention.

Referring to FIG. 1, a method of fabricating a nanostructure according to a first embodiment of the present invention includes preparing a substrate (S120), preparing a polymer containing a plurality of metal atoms (S140) (S160) of attaching the metal atoms onto the substrate, and forming the metal atoms attached on the substrate to at least one metallic nanoparticle (S180).

Preparing a substrate (S120)

First, the step of preparing a substrate (S120) will be described in detail.

The substrate may be a semiconductor substrate, a transparent substrate, or a flexible substrate, and the material, structure, and shape may vary depending on the device to which the invention is applied. The substrate may also serve as a support for physically supporting the components of the device to which it is applied, or may be a raw material for the components.

As a non-limiting example, the flexible substrate may be made of a material selected from the group consisting of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetylcellulose (TAC) Sulfone (PES), polydimethylsiloxane (PDMS), or a mixture thereof.

In the case of a semiconductor substrate, the substrate may be materially an organic semiconductor, an inorganic semiconductor, or a laminate thereof.

As a non-limiting example of the inorganic semiconductor substrate, a quaternary semiconductor including silicon (Si), germanium (Ge), or silicon germanium (SiGe), gallium arsenide (GaAs), indium phosphide (InP), or gallium phosphide (GaP) Group semiconductors including cadmium sulphide (CdS) or zinc telluride (ZnTe), group 4-6 semiconductors including lead sulphide (PbS), or two or more materials selected therefrom And a laminated body formed by stacking the layers. Crystalline, the inorganic semiconductor substrate may be a monocrystalline, polycrystalline or amorphous, or a mixed phase in which a crystalline phase and an amorphous phase are mixed. When the inorganic semiconductor substrate is a laminate in which two or more layers are laminated, each layer may be monocrystalline, polycrystalline, amorphous or mixed phase, independently of each other.

As a specific example, the inorganic semiconductor substrate may be a semiconductor substrate (including a wafer) such as a silicon (Si) substrate, a semiconductor substrate formed with a surface oxide film, or a silicon on insulator (SOI) substrate (including a wafer).

When the semiconductor substrate is an organic semiconductor substrate, the organic semiconductor of the organic semiconductor substrate may be an n-type organic semiconductor or a p-type organic semiconductor, and may be an organic transistor, an organic solar cell or an n-type organic semiconductor conventionally used in the field of organic light- A p-type organic semiconductor can be used. As a non-limiting example, organic semiconductors include but are not limited to CuPc (Copper-Phthalocyanine), P3HT (poly-3-hexylthiophene), Pentacene, SubPc (Subphthalocyanines), C60 (Fulleren), PCBM (Fulleren-derivative), F4-TCNQ (tetrauorotetracyanoquinodimethane), and the like, which are included in the present invention, But is not limited to materials of semiconductors.

The substrate may comprise a surface layer. For example, the substrate may comprise a surface layer of silicon oxide (SiO ₂₎ formed on the silicon substrate.

Specifically, the surface layer of the substrate may be a single layer of a material selected from oxides, nitrides, oxynitrides, and silicates, or a laminated film in which each of two or more selected materials are laminated in a film. By way of non-limiting example, the surface layer of the substrate can be a silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, titanium oxide, tin oxide, A single film or two or more selected materials of a material selected from at least one of oxide, silicon nitride, silicon oxynitride, zirconium silicate, hafnium silicate, mixture thereof and a composite thereof is formed as a laminated film .

On the other hand, the surface layer of the substrate may be a thin metal film. At this time, the thickness of the metal thin film may be 100 nm or less, specifically 1 nm to 100 nm. If the thickness of the metal thin film is extremely thin, such as less than 1 nm, the uniformity of the thin film may be deteriorated. The metal thin film as the surface layer can be, by way of non-limiting example, a transition metal including a noble metal, a metal, or a mixture thereof. The transition metal may be at least one selected from the group consisting of Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Te, Re, Fe, Ru, Os, , Pd, Pt, Cu, Ag, Au or a mixture thereof, and the other metal may include Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, , Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi, Po or mixtures thereof.

The surface layer may be formed through a thermal oxidation process, physical vapor deposition or chemical vapor deposition, and physical vapor deposition or chemical vapor deposition may be performed by sputtering, magnetron-sputtering, E-beam evaporation, thermal evaporation, (L-MBE), Pulsed Laser Deposition (PLD), vacuum deposition, ALD (Atomic Layer Deposition), or plasma enhanced chemical vapor deposition (PECVD) Deposition), but is not limited thereto.

When a flexible substrate is used, the surface layer of the substrate may be an organic material having an -OH functional group.

On the other hand, as will be described later in detail, the surface of the substrate may be patterned in various shapes. Preferably, the surface of the substrate may be patterned with a plurality of guide grooves. The guide grooves can guide the metal atoms (atoms) to aggregate therein to hold the nanoparticles. Therefore, it is possible to easily arrange the nanoparticles using the guide grooves on the surface of the substrate.

Preparing a polymer containing a metal atom (S140)

2 is a schematic diagram showing a step of preparing a polymer 250 containing a metal atom. Referring to FIG. 2, the metal precursor 210 and the organic material 230 are mixed with a solvent to form a metal atom-containing polymer 250.

In the embodiment of FIG. 2, HAuCl ₄ is used as the metal precursor 210, but the metal precursor can be designed in consideration of the desired nanoparticle material. In one example, the metal of the metal precursor may be a transition metal, a metal selected from the group consisting of a transition metal and a metal, and a metal selected from two or more metals. As a non-limiting example, the transition metal precursor may be a transition metal salt. Specifically, the transition metal may be at least one selected from Au, Ag, Ru, Pd and Pt, and the transition metal salt may be a halide, a chalcogenide, a hydrochloride, a nitrate, a sulfate, an acetate or an ammonium salt . When the transition metal of the transition metal precursor two days Au, particularly the transition metal precursor is a non-limiting one _{example, HAuCl 4, AuCl, AuCl 3} , Au 4 Cl 8, KAuCl 4, NaAuCl 4, NaAuBr 4, AuBr 3, AuBr, AuF ₃ , AuF ₅ , AuI, AuI ₃ , KAu (CN) ₂ , Au ₂ O ₃ , Au ₂ S, Au ₂ S ₃ , AuSe and Au ₂ Se ₃ . .

2, 3-mercaptopropyl trimethoxysilane (3-MPTMS), which is one of silane compounds containing a sulfur functional group, is used as the organic material 230 , Other kinds of organic materials may be used.

For example, mercaptopropyl triethoxysilane, 11-mercaptoundecyl trimethoxysilane, mercaptomethyl methyl diethoxysilane, octyl trichlorosilane, Octyltrichlorosilane (OTS), hexamethyldisilazane (HMDS), octadecyltrichlorosilane (ODTS), (3-aminopropyl) trimethoxysilane (APS) (3-aminopropyl) triethoxysilane, N- (3-aminopropyl) -dimethyl-ethoxysilane (APDMES), perfluorodecyltrichlorosilane But are not limited to, perfluorodecyltrichlorosilane (PFS), mercaptopropyl trimethoxysilane (MPTMS), N- (2-aminoethyl) -3aminopropyltrimethoxysilane, (3-trimethoxysilylph Phil) diethylenetriamine ((3

Octadecyltrimethoxysilane (OTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane ((Heptadecafluoro-1,1,2,2- tetrahydrodecyl trichlorosilane (FDTS), dichlorodimethylsilane (DDMS), N- (trimethoxysilylpropyl) ethylenediamine triacetic acid, hexadecanethiol (HDT), and epoxy It may be one or more selected from hexyltriethoxysilane.

In terms of ensuring stable insulation between adjacent nanoparticles and between the nanoparticles and the substrate, the organic material may include an alkane chain group, specifically an alkane chain group of C3-C20, and further includes a moiety containing oxygen can do. An example of an oxygen-containing moieties, and ethylene glycol _{(-O-CH 2 -CH 2 -} ), carboxylic acid (-COOH), alcohol (-OH), ether (-O-), ester (-COO-), ketone ( -CO-), aldehyde (-COH) and / or amide (-NH-CO-).

The solvent used for mixing the metal precursor 210 and the organic material 230 may be hydrophilic or hydrophobic. A hydrophilic solvent may be used when the surface of the base material is hydrophilic, and a hydrophobic solvent may be used when the surface of the base material is hydrophobic. This is to increase the adhesion between the substrate surface and the polymer in the subsequent process.

As well known, examples of the hydrophilic solvent include alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-pentanol, 2-butoxyethanol and ethylene glycol. Acetone, 2-butanone and 4-methyl- Pranone, and may be an acid such as Acetic Acid.

Examples of the hydrophobic solvent include alkanes and cycloalkanes such as Pentanes, Hexane, Decane, Cyclohexane, Cyclopentane and 2,2,4-Trimethylpentane, and 1-butylene, 2-butylene, 1-Pentene and 2-Pentene And isobutylene and substituted alkanes such as carbon tetrachloride, 1-chlorobutane, 1-chloropentane, 2-chloropropane, 1-chloropropane, bromoethane, chloroform, dichloromethane, 1,2-dichloroethane, 1-nitroprpane, Can be.

As described above, the metal precursor and the organic material are mixed to form the metal atom-containing polymer 250. In FIG. 2, the gold-thiol polymer is shown. It can be seen that the polymer 250 is an organic chain having a plurality of metal atoms bonded thereto.

As will be described later in detail, the concentration of metal atoms in the polymer 250 can be controlled by controlling the mixing ratio of the metal precursor 210 and the organic material 230. This may be one of the important factors controlling the diameter of the nanoparticles formed in the subsequent process. In addition, the concentration of the polymer containing metal atoms may be one of the important factors controlling the density of nanoparticles formed on the substrate and the number of nanoparticles. For example, when the ratio of the metal precursor 210 to the organic material 230 is adjusted to 1: 3 to 1: 7, it is possible to manufacture fine nanoparticles having a diameter of 1.4 nm to 1.9 nm and the metal precursor 210 and the organic material 230, Can be formed of fine nanoparticle particles having a diameter of 1.0 nm to 1.3 nm when the ratio is 1: 8 to 1:12.

On the other hand, in a polymer solution containing metal ions, precipitation occurs after a certain period of time. Thus, a stabilizing agent for preventing precipitation can be added to the polymer solution. Preferably, the stabilizing agent may comprise a basic compound, and the basic compound may be any one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and aqueous ammonia.

The chemical reaction formula of FIG. 2 can be represented by the following formula (1).

[Chemical Formula 1]

MX ^Z (solvent) + FR _n ? (-M ^Y FR _n -) _m (polymer)

In the formula (1), MX ^Z is a metal precursor, M is a metal atom, and X is a ligand. The functional group F may be any one of a thiol group, an amine group, and a phosphine group. R is an insulator monomer. Wherein n is a natural number of 1 to 15 in the number of carbon atoms in the alkanes. M is a natural number of 5 to 10,000. Z and Y are oxidized.

Specifically, the metal atom M may be any one selected from the group consisting of Au, Ag, Ru, Pd, Pt, and Cu. The insulator monomer C may be organic or inorganic. And may be an alkoxysilane compound or an alkylsilane compound when it is an organic material.

Supplying the polymer onto the substrate (S160)

When the substrate and the polymer are ready, the polymer is supplied on the substrate to attach the metal atoms contained in the polymer to the substrate.

The method of supplying the polymer onto the substrate can be variously carried out. Preferably the polymer can be coated on the substrate by spin coating or dipping. By feeding the polymer onto the substrate, the metal atoms in the polymer are deposited on the substrate.

As will be described in detail later, it is possible to control the concentration of metal atoms by controlling the speed and time of spin coating. This can be one of the important ways to control the diameter of nanoparticles.

Forming metallic atoms into metallic nanoparticles (S180)

Metal atoms attached to a substrate are formed into metallic nanoparticles by reduction and growth, where the growth includes the meaning of nucleation and aggregation.

When energy is applied to a metal atom, the metal atoms are reduced and grown to be granulated. The energy applied for this may be one or more energy sources selected from heat, chemical, light, vibration, atomic beam, electron beam and radiation energy.

Specifically, the thermal energy may include joule heat. Thermal energy can be applied either directly or indirectly, where direct application may refer to the physical contact of the source with the substrate on which the metal atoms are immobilized, It may mean that the fixed semiconductor substrate is in a physically non-contact state. As a non-limiting example, a direct application is a method in which a heating element that generates a joule heat is placed in the lower part of a substrate, and heat energy is transferred to metal atoms through the substrate. As a non-limiting example, the indirect application includes a space in which a subject to be heat-treated such as a tube is located, a heat-resistant material to prevent heat loss by surrounding a space where the heat- And a method using a heat treatment furnace. As a non-limiting example, the indirect application is to place the heating element at a distance from the metal atom on the upper surface of the fixed metal substrate and to transfer heat energy to the metal atom through the fluid (including air) existing between the metal atom and the heating element And the like.

Specifically, the light energy may include extreme ultraviolet light or near-infrared light, and the application of light energy may include irradiation of light. As a non-limiting example, a light source may be positioned above the substrate on which the metal atoms are fixed so as to be spaced from the metal atoms by a certain distance, so that the metal atoms may be irradiated with light.

Specifically, the vibration energy may include microwaves and / or ultrasonic waves, and the application of the vibration energy may include irradiation of microwaves and / or ultrasonic waves. As a non-limiting example, a microwave and / or an ultrasonic wave generating source may be positioned at a distance above a metal atom on the fixed substrate so as to irradiate microwaves and / or ultrasonic waves to the metal atoms.

Specifically, the radiation energy may include one or more radiation selected from? Rays,? Rays and? Rays, and may be? Rays and / or? Rays in terms of reduction of metal atoms. As a non-limiting example, a radiation source may be located at a distance from a metal atom on a substrate on which a metal atom is fixed, so that the metal atom can be irradiated with the radiation.

In particular, the energy may be kinetic energy by the particle beam, and the particle beam may comprise an atomic beam and / or an electron beam. In terms of the reduction of the metal atom, the atom of the beam may be an atom having a negative charge. By way of non-limiting example, using an accelerating member that provides an electric field (electromagnetic field) that accelerates an atom or an electron toward a metal atom, with an atom or an electron source located at a distance from the metal atom, An atomic beam and / or an electron beam can be applied to the atom.

Specifically, the chemical energy may mean the Gibbs free energy difference before and after the reaction of the chemical reaction, and the chemical energy may include the reducing energy. In detail, the chemical energy may include a reduction reaction energy by a reducing agent, and may mean a reduction reaction energy in which a metal atom is reduced by a reducing agent. As a non-limiting example, the application of chemical energy may be a reduction reaction in which a metal atom is contacted with a fixed substrate and a reducing agent. At this time, it is needless to say that the reducing agent may be supplied in a liquid phase or in a vapor phase.

In the manufacturing method according to an embodiment of the present invention, the application of energy may include simultaneous or sequential application of two or more energy selected from heat, chemical, light, vibration, atomic beam, electron beam and radiation energy.

As a specific example of the simultaneous application, the application of the particle beam simultaneously with the application of the heat can be performed at the same time, and the particles of the particle beam can be heated by the thermal energy. As another concrete example of the simultaneous application, the application of the heat and the introduction of the reducing agent can be performed at the same time. As another specific example of simultaneous application, infrared rays may be applied simultaneously with the application of the particle beam, or the microwave may be applied together with the particle beam.

Sequential application may mean that one type of energy application is performed and then another kind of energy application is performed, which may mean that different kinds of energy are applied to the metal atoms continuously or discontinuously. It is preferable that the reduction of the metal atoms fixed to the substrate through the organic material be performed prior to the granulation. Therefore, as a specific example of sequential application, heat is applied after the reductant is charged, or heat is applied after the application of the negatively charged particle beam Can be applied.

For example, energy can be applied using a rapid thermal processing system (RTP) including a tungsten-halogen lamp, and the heating rate during the rapid thermal annealing is 50 To 150 < 0 > C / sec. During the heat treatment using the rapid thermal annealing apparatus, the annealing atmosphere may be a reducing atmosphere or an inert gas atmosphere.

As a non-limiting, practical example, the application of energy can be performed by contacting the metal atom with a reducing solution in which the reducing agent is dissolved in the solvent, followed by heat treatment using a rapid thermal processing apparatus. During the heat treatment using the rapid thermal annealing apparatus, the annealing atmosphere may be a reducing atmosphere or an inert gas atmosphere.

In a non-limiting, practical example, the application of energy can be performed by generating an electron beam from an electron beam generator in a vacuum chamber and accelerating it with metal atoms. At this time, the electron beam generating apparatus may be a square type or a linear gun type. The electron beam generating apparatus can generate an electron beam by generating electrons and extracting electrons by using a shielding film after generating the plasma. In addition, a heating member may be formed in the specimen holder for supporting the substrate in the vacuum chamber, and thermal energy may be applied to the substrate by the heating member before the electron beam application, during the electron beam application and / Of course.

When the desired nanoparticles are metal nanoparticles, the metal nanoparticles can be produced in situ by the application of the energy described above. In the case where metal compound particles other than metal nanoparticles are to be produced, The metal compound nanoparticles can be prepared by supplying a dissimilar element different from the metal atom after the application of the above-described energy. In detail, the metal compound nanoparticles may include metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles, or intermetallic compound nanoparticles. More specifically, the metal compound nanoparticles can be prepared by supplying the dissimilar element in a gas phase or a liquid phase upon the application of the energy described above. As a specific example, metal oxide nanoparticles other than metal nanoparticles can be prepared by supplying an oxygen source including oxygen gas upon application of energy, and by supplying a nitrogen source including nitrogen gas upon application of energy, Metal nitride nanoparticles can be produced. When applying energy, metal carbide nanoparticles can be prepared by supplying a carbon source including a hydrocarbon gas of C1-C10. In order to produce desired intermetallic compounds upon application of energy, Intermetallic compound nanoparticles can be prepared by supplying a heterogeneous element precursor gas to a source of a heterogeneous element. More specifically, intermetallic compound nano-particles can be produced by carbonizing, oxidizing, nitriding or alloying the metal nanoparticles produced by energy application after the above-described energy application.

The density of the nanoparticles, the size and distribution of the nanoparticles are controlled by one or more factors selected from the energy application conditions including the type of energy applied, the amount of energy applied, the time of application of energy, and the temperature .

On the other hand, by changing the metal nanoparticles to metal compound nanoparticles by supplying a source of different kinds of atoms at the time of energy application or energy application, metal nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles, Compound nanoparticles can be prepared.

Meanwhile, in the production method according to an embodiment of the present invention, i) a surfactant organic substance which is bonded or adsorbed to a metal atom before energy application, and then energy can be applied to adjust the size of nanoparticles, ii) During the application of energy, surfactant organics can be supplied to control the size of nanoparticles during growth. The supply of such surfactant organics may be optional during the manufacturing process. The surfactant organic material supplied before or during the application of energy may be a discontinuous organic material and may be a plurality of different organic materials.

In order to more effectively inhibit the mass transfer of the metal, the surfactant organics may use different species of first and second organics.

The first organic material may be nitrogen or a sulfur-containing organic material, for example, the sulfur-containing organic material may include a linear or branched hydrocarbon compound whose one end group is a thiol group. Specific examples of the sulfur-containing organic materials include HS-C _n -CH ₃ (n is an integer of 2 to 20), n-dodecyl mercaptan, methyl mercaptan, ethyl mercaptan, butyl mercaptan, One or more selected materials selected from mercaptans, isooctyl mercaptan, tert-dodecyl mercaptan, thioglycol acetic acid, mercaptopropionic acid, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptohexanol and octylthioglycolate .

The second organic material may be an organic material based on a phase-transfer catalyst, and may be quaternary ammonium or phosphonium salts. More specifically, the second organic material is selected from the group consisting of Tetraocylyammonium bromide, tetraethylammonium, Tetra-n-butylammonium bromide, Tetramethylammonium chloride. And may be one or more selected from tetrabutylammonium fluoride.

These surfactant organics inhibit mass transfer of metals during energy application, allowing for the formation of more uniform and finer nanoparticles. The metal atom binds to the surfactant organic substance, so that a higher activation energy is required for diffusion to participate in nucleation or growth, or physically migration is inhibited by the organic material, whereby the diffusion of the metal (atom) And the number of metals (atoms) contributing to the growth of the nuclei can be reduced.

Meanwhile, in the manufacturing method according to the embodiment of the present invention, energy may be simultaneously applied to all the regions of the metal atoms, or energy may be applied to some regions of the metal atoms. When energy is applied to some regions, energy can be applied (irradiated) as spots, lines, or facets of a predetermined shape. As a non-limiting example, the energy may be applied (irradiated) in such a way that the spot is irradiated with energy and scanned over the entire area of the metal atom. In this case, the application of energy to a part of the metal atom bonding region means that energy is applied to a spot, a line or a surface and energy is applied only to a part of the metal atom bonding region as well as when the entire region of the metal atom bonding region is scanned Investigation) may also be included. In this manner, a pattern of nanoparticles can be formed by partially applying energy. That is, partial energy application (irradiation) can enable patterning of nanoparticles by energy application (irradiation).

3 is a cross-sectional view showing a nanoparticle layer formed on a substrate.

As shown in FIG. 3, a plurality of metallic nanoparticles 330 are separated from each other on the substrate 310 to form a nanoparticle layer 300. The nanoparticle layer 300 may be a one-nanoparticle-thick layer and may be a monolayer of a two-dimensional array. And may be a multi-layer of a three-dimensional array.

Each nanoparticle may have a particle diameter of 0.5 nm to 3 nm.

The diameter of the nanoparticles 330 can be determined by the concentration of metal atoms contained in the polymer used during the manufacturing process. That is, when the polymer is prepared by mixing the metal precursor and the organic material, the diameter of the nanoparticles can be controlled by adjusting the mixing ratio thereof. For example, when the ratio of the metal precursor to the organic material is adjusted to 1: 3 to 1: 7, it is possible to prepare fine nanoparticles having a diameter of 1.4 nm to 1.9 nm, and the ratio of the metal precursor to the organic material is 1: 8 to 1:12 It is possible to form fine nanoparticle particles having a diameter of from 1.0 nm to 1.3 nm.

Further, when the polymer is spin-coated on a substrate, the diameter and density of the nanoparticles can be controlled by adjusting the spin rate and time. In addition, when the energy for reducing and growing metal atoms is applied, the diameter of the nanoparticles can be controlled by controlling the conditions.

As described above, the nanoparticle layer 300 can be formed as a monolayer or a multilayer. The nanoparticle layer 300 can be formed by adjusting the concentration of metal atoms (ions) in the polymer, adjusting the conditions of metal atoms or spin coating, Can be formed.

Referring again to FIG. 3, the nanoparticle layer 300 may include an insulator 350 covering the nanoparticles 330.

After formation of the nanoparticles 300, organic or surfactant organics in the polymer may remain around the nanoparticles 330 and may be removed. A protective layer may be formed to fix and protect the nanoparticles 330 in a state in which the organic material remains or in the state in which the organic material is removed, and the protective layer may be an inorganic material.

Thus, the insulator 350 may be an organic matter in the polymer, a surfactant organics, or an inorganic matter such as an oxide or a nitride.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Those skilled in the art will recognize that many modifications and variations are possible in light of the above teachings. Accordingly, the spirit of the present invention should not be construed as being limited to the embodiments described, and all of the equivalents or equivalents of the claims, as well as the following claims, belong to the scope of the present invention .

Claims (11)

Mixing a metal precursor and an organic material into a solvent; And
Adding a stabilizing agent to the solvent to prevent precipitation
A method for producing a metal atom containing polymer solution.
The method according to claim 1,
The metal precursor may be any one selected from the group consisting of a halide, a chalcogenide, a hydrochloride, a nitrate, a sulfate, an acetate, and an ammonium salt of a transition metal
A method for producing a metal atom containing polymer solution.
The method according to claim 1,
The metal precursor,
_{HAuCl 4, AuCl, AuCl 3,} Au 4 Cl 8, KAuCl 4, NaAuCl 4, NaAuBr 4, AuBr 3, AuBr, AuF 3, AuF 5, AuI, AuI 3, KAu (CN) 2, Au 2 O 3, Au ₂ S, Au ₂ S ₃ , AuSe and Au ₂ Se ₃ ,
A method for producing a metal atom containing polymer solution. The method according to claim 1,
Wherein the organic material includes a functional group capable of binding to the metal atom
A method for producing a metal atom containing polymer solution.
The method of claim 3,
Preferably,
But are not limited to, mercaptopropyl trimethoxysilane (3-MPTMS), mercaptopropyl triethoxysilane, 11-mercaptoundecyl trimethoxysilane, Mercaptomethyl methyl diethoxysilane octyltrichlorosilane (OTS), hexamethyldisilazane (HMDS), octadecyltrichlorosilane (ODTS), (3-aminopropyl) trimethoxysilane Aminopropyl) trimethoxysilane (APS), (3-aminopropyl) triethoxysilane, N- (3-aminopropyl) -dimethyl-ethoxysilane (N- 3-aminopropyl) -dimethyl-ethoxysilane (APDMES) Perfluorodecyltrichlorosilane (PFS), mercaptopropyl trimethoxysilane (MPTMS), N- Trimethoxysilane ( N- (2-aminoethyl) -3aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine ((3-
Octadecyltrimethoxysilane (OTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane ((Heptadecafluoro-1,1,2,2- tetrahydrodecyl trichlorosilane (FDTS), dichlorodimethylsilane (DDMS), N- (trimethoxysilylpropyl) ethylenediamine triacetic acid, hexadecanethiol (HDT), and epoxy And any one selected from the group of < RTI ID = 0.0 > hexyltriethoxysilane &
A method for producing a metal atom containing polymer solution.
5. The method of claim 4,
The functional group is any one of a thiol group, an amine group, and a phosphine group
A method for producing a metal atom containing polymer solution.
The method according to claim 1,
The solvent may be,
Methanol, Ethanol, 1-Propanol, 2-Propanol, 1-Pentanol, 2-Butoxyethanol, Ethylene glycol, Acetone, 2-Butanone, 4-Methyl-2-Pranone, Acetic Acid, Pentanes, Hexane, Decane, Cyclohexane, 1-Chloropropane, 2-Chloropropane, 1-Chloropropane, Bromoethane, Chloroform, Dichloromethane, 1-Butylene, 2-Butylene, 1-Pentene, 2-Pentene, Isobutylene, Carbon tetrachloride, 1-Chlorobutane, , 1,2-Dichloroethane, 1-Nitroprpane, and Nitromethane.
A method for producing a metal atom containing polymer solution.
The method according to claim 1,
The stabilizing agent comprises a basic compound
A method for producing a metal atom containing polymer solution.
9. The method of claim 8,
The basic compound is any one selected from the group of sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water
A method for producing a metal atom containing polymer solution.
The method according to claim 6,
Wherein the mixing ratio of the metal precursor to the organic material is 1: 3 to 1:12.
The method according to claim 1,
The organic material is an alkoxysilane compound or an alkylsilane compound having a functional group capable of binding to a metal atom
A method for producing a metal atom containing polymer solution.

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