KR20150072306A - Nano structures - Google Patents

Abstract

The present invention relates to a nanostructure, a manufacturing method thereof, and an applied device. According to an embodiment of the present invention, the nanostructure comprises: a substrate; an insulating material particle support formed on the substrate and combined with a linker on surfaces; metallic nanoparticles growing from metal ion combined on the linker; and surfactant organic matters combined on the metal ion or the growing nanoparticle. The average diameter of the nanoparticles may be 1.3 to 1.9 nm.

Description

[0001] NANO STRUCTURES WITH INSULATOR PARTICLE SUPPORT [0002]

In this patent document, a nanostructure, a manufacturing method thereof, and an application device are described.

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. Vapor-liquid-solid growth method and liquid-phase growth method are proposed as a bottom up method. The vapor-phase growth method may be a thermal chemical vapor deposition (CVD) method, a metal-organic chemical vapor deposition (MOCVD) method, a pulsed laser deposition (PLD) And a catalytic reaction such as 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 limitation in reducing the size of the nanoparticles, and moreover, because the size distribution of the nanoparticles is large, the reproducibility and the reliability of the memory are deteriorated. That is, the method of forming a nanostructure by simply attaching already prepared nanoparticles can not improve the memory performance 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.

The first problem to be solved by the embodiments of the present invention is to provide a nanostructure capable of mass production in a short time by a commercially available low-cost method and a method of manufacturing the same.

A second problem to be solved by the embodiments of the present invention is to provide a nanostructure that can control a desired fine particle size and a method of manufacturing the same.

A third problem to be solved by the embodiments of the present invention is to provide a nanostructure capable of securing operation stability, reproducibility and reliability of an application device even at the time of scaling.

A fourth problem to be solved by the embodiments of the present invention is to provide a device having a nanostructure excellent in operational stability, reproducibility and reliability.

A nanostructure according to an embodiment of the present invention includes a substrate, an insulator particle support formed on the substrate and having a linker bonded to its surface, metallic nanoparticles grown from the metal ions bonded to the linker, Or a surfactant organics bound to the nanoparticles being grown. The nanostructure may further include an insulating organic substance bonded to the surface of the metallic nanoparticle.

Preferably, the substrate may comprise a surface layer having a functional group capable of bonding to the linker. The surface layer may comprise an oxide layer.

The linker may be an organic monomolecular molecule that is bonded to the substrate surface by self-assembly.

A linker layer can be composed of a plurality of linkers bonded on a substrate. The linker layer may be an organic monomolecular film formed by magnetic coupling. Further, the linker layer may be a silane compound layer formed on the substrate and having any one functional group selected from an amine group, a carboxyl group and a thiol group.

The metallic nanoparticles may be any one selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles and intermetallic compound nanoparticles.

The size of the metallic nanoparticles can be controlled according to energy application conditions at the time of growth. In addition, the nanoparticle size can be adjusted depending on whether the surfactant organic material is supplied before or during the application of energy to grow the particles. As the surfactant, a single type or plural types of surfactants can be used. The surfactant organics may comprise a first organic material and a second organic material of different species, the first organic material may be nitrogen or a sulfur-containing organic material, and the second organic material may be a phase-transfer catalyst- Organic material.

Surfactant organics may remain on the surface of the grown nanoparticles. Preferably, when the surfactant is not used, the metallic nanoparticles may have a diameter of 2.0 nm to 3.0 nm. If any one type of surfactant is used, the metallic nanoparticles may have a diameter of 1.3 nm to 1.6 nm. When a plurality of different kinds of surfactants are used, the metallic nanoparticles may have a diameter of 0.5 nm to 1.2 nm.

The insulating organic material may be bonded to the surface of the grown metallic nanoparticles. The insulating organic material more reliably prevents conduction between the metallic nanoparticles. The insulating organic material may be coated on the surface of the nanoparticles, and may exist in a form filling the space between the nanoparticles spaced apart from each other.

When the surfactant is supplied before or during the growth of the nanoparticles, the surface of the metallic nanoparticles may contain a component of the surfactant. Since a surfactant can also use an insulating organic material, formation of an insulating organic material formed in a state in which the nanoparticles are completely grown can be omitted if insulation between the arranged nanoparticles is possible using only the surfactant remaining after growth.

The nanostructure according to embodiments of the present invention is extremely fine, uniform in size, and can be manufactured with high density. Further, since the nanoparticles are fixed by the insulating linker, the physical stability is excellent. Therefore, a device using the device can perform device scaling for low power consumption, and has excellent operation stability, reproducibility and reliability even when scaling.

The nanostructure according to embodiments of the present invention can be manufactured through an in-situ process. Therefore, waste of manufacturing cost can be minimized, and mass production is possible in a short time.

The nanostructure according to the embodiment of the present invention and the method of manufacturing the nanostructure can control the fine particle size through a simple process of introducing and reacting the surfactant when growing nanoparticles. That is, nanoparticles can be produced with particles of desired size, and characteristics of application devices can be secured.

1A to 1E are schematic views illustrating a method of fabricating a nanostructure according to a first embodiment of the present invention.
2A to 2E are schematic views illustrating a method of fabricating a nanostructure according to a second embodiment of the present invention.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a nanostructure of the present invention, a method of manufacturing the nanostructure, and an application device 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.

[NANO STRUCTURE OF THE FIRST EMBODIMENT OF THE PRESENT INVENTION AND METHOD FOR PRODUCING THE SAME]

1A to 1E are schematic views for explaining a nanostructure according to a first embodiment of the present invention and a method of manufacturing the same.

A method of fabricating a nanostructure according to a first embodiment of the present invention includes the steps of preparing a substrate 110 (FIG. 1A); Coupling the linker 120A onto the substrate 110 (Figure IB); Binding metal ion 130 to linker 120A (Figure 1C); And applying energy to form the metal ions 130 into the metallic nanoparticles 140 (FIG. 1D). In addition, the method may further include the step of supplying the insulating organic material 150 onto the structure having the metallic nanoparticles 140 (FIG. 1E). Further, the method may further include supplying the surfactant organics to the endogenous or plural species before or during the application of the energy.

Figure 1A shows a prepared substrate 110. Referring to FIG. 1A, the substrate 110 may have a surface layer 114 having a functional group capable of bonding with a linker. For example, the substrate 110 may be a silicon substrate 112 having silicon oxide as the surface layer 114.

The substrate 110 may be a semiconductor substrate and may further include a support substrate that physically supports the semiconductor substrate or may serve as a support for physically supporting each component of the memory element. Furthermore, the semiconductor substrate plays a role of providing a channel and can be used as a raw material in manufacturing a single component of a memory device. As a non-limiting example of a semiconductor substrate used as a raw material, formation of a passivation film by oxidation and / or nitridation of a semiconductor substrate, formation of a source or drain through impurity doping or alloying (e.g., silicidation) Channel formation, and the like.

In a macroscopic configuration, the semiconductor substrate may be in the form of a wafer, a film, or a thin film, and the surface of the semiconductor substrate may be nanopatterned (structured) in consideration of the physical shape of the memory device designed such as a recessed or three- .

As a physical property, the substrate 110 may be a rigid substrate or a flexible substrate.

The substrate 110 may comprise a flexible substrate or a transparent substrate. Non-limiting examples of the flexible substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetylcellulose (TAC) A flexible polymer substrate containing sulfone (PES), polydimethylsiloxane (PDMS), or a mixture thereof. Non-limiting examples of the transparent support include a glass substrate, a transparent plastic substrate, and the like. When the substrate 110 is a flexible substrate, the surface layer 114 of the substrate may be an organic material having a functional group (e.g., -OH functional group) capable of bonding with a linker.

Materially, the substrate 110 may be 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 includes a semiconductor substrate (including a wafer) having a semiconductor oxide layer such as a silicon (Si) substrate 112, a silicon substrate having a surface oxide film formed thereon, or a SOI (Silicon on Insulator) (Including a wafer), a metal thin film, and a silicon (Si) semiconductor substrate having a surface oxide film formed thereon.

The inorganic semiconductor substrate may be a planar substrate having a flat active area, or a structured substrate having a pin-shaped protruding active area. In detail, the semiconductor substrate may be a substrate on which an active region, which is a region where an element is formed in a semiconductor substrate by isolation such as a trench or a field oxide (LOCOS), is defined, One or more active regions may be defined substrates. The active region, which is one region of the substrate defined by normal isolation, may include a channel region forming a channel, source and drain regions facing each other with a channel region therebetween.

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, It is needless to say that it can not be limited by the material of the semiconductor.

When the semiconductor substrate is an organic semiconductor substrate, the channel region of the active region may be an organic semiconductor layer, and may include a substrate having a source and a drain disposed opposite to each other at both ends of the organic semiconductor layer. At this time, the semiconductor substrate may include a supporting substrate supporting the organic semiconductor layer, the source and the drain, and the supporting substrate may include a rigid substrate or a flexible substrate.

The semiconductor substrate may be a planar substrate that provides flat planar channels or may be a structured substrate that provides two or more planar channels that are not coplanar, depending on the physical configuration of the channel region, Shaped substrate having a shape.

The source and drain can function to form an electric field in a direction parallel to the channel, and the channel length can be determined by the distance between the source and the drain which are mutually opposed to each other. The spacing distance may be appropriately designed according to the design of the memory, but the distance between the source and the drain (i.e., the channel length) may be 5 nm to 200 nm.

The surface layer 114 of the substrate 110 is applicable as long as it has a functional group capable of binding to a linker. For example, the film may be a single film or a laminated film in which films of different materials are laminated, and in the case of a laminated film, the dielectric constant of each film may be different from each other. Specifically, the surface layer 114 of the substrate 110 may be a single film of one or more selected materials from oxides, nitrides, oxynitrides, and silicates, or a laminated film in which each of two or more selected materials are laminated in a film. As a non-limiting example, the surface layer 114 of the substrate 110 may be formed of a material selected from the group consisting of silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, A single film or a combination of two or more selected materials of one or more materials selected from oxides, barium-zirconium complex oxides, silicon nitrides, silicon oxynitrides, zirconium silicates, hafnium silicates, mixtures thereof, Layered laminated film. In addition, the surface layer 114 of the substrate 110 may be an oxide of one or more selected elements from metals, transition metals, post-transition metals and metalloids. The metal may include lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium and barium, and the transition metal may be a transition metal, The metal is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, And the metal may include aluminum, gallium, indium, tin, thallium, lead, and bismuth, and the submetal may include boron, silicon, tin, Germanium, arsenic, antimony, tellurium, and polonium.

When the surface layer 114 functions as a tunnel insulating film of, for example, a flash memory, its surface layer has a thickness of 0.1 to 20 nm, specifically, a thickness of 0.5 to 10 nm, more specifically, a thickness of 0.8 to 5 nm based on EOT (Equivalent Oxide Thickness) But is not limited thereto.

The surface layer 114 may be formed by 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 ), Laser molecular beam epitaxy (L-MBE), pulsed laser deposition (PLD), vacuum deposition, atomic layer deposition (ALD), or plasma assisted chemical vapor deposition (PECVD) Enhanced Chemical Vapor Deposition).

1B shows a state in which a linker layer 120 is formed on a substrate 110. FIG. The linker layer 120 may be composed of a plurality of linkers 120A and the linker layer 120 may be a self-assembled monolayer film self-assembled to the surface of the substrate 110. [

The linker 120A may be an organic linker chemically bonded to or adsorbed on the surface of the substrate 110, and capable of chemically bonding with metal ions. Specifically, the linker 120A may be an organic linker having both functional groups 122 that chemically bond or adsorb to the surface layer 114 of the substrate and functional groups 126 that chemically associate with the metal ions (formed subsequently). Here, the chemical bond may include a covalent bond, an ionic bond, or a coordination bond. As a specific example, the bond between the metal ion and the linker is a bond between a metal ion having a positive charge (or negative charge) and a linker having a negative charge (or positive charge) by at least one terminal group Lt; / RTI > As a specific example, the bond between the surface layer of the substrate 110 and the linker may be a bond by self-assembly, and may be a spontaneous chemical bond between the other terminal end of the linker and the surface atom of the substrate.

More specifically, linker 120A can be an organic monomolecular molecule that forms a self-assembled monolayer. That is, the linker 120A may be an organic single molecule having a functional group 122 self-assembled to the surface layer 114 and a functional group 126 capable of binding metal ions. The linker 120A may also include a chain 124 connecting the functional groups 122 and the functional groups 126 and enabling the formation of a monolayer aligned by van der Waals interactions.

Self-assembly may be accomplished by appropriately designing the surface material of the substrate and the first functional group 122 of the organic monomolecules, and may utilize a commonly known set of end groups per self-assembled material.

In a specific and non-limiting example, when the surface layer 114 of the substrate 110 is an oxide, a nitride, an oxynitride, or a silicate, the organic monomolecule which is a linker may be a material satisfying the following formula (1).

(Formula 1)

R1-C-R2

In the general formula (1), 'R1' denotes a functional group which binds to a substrate, 'C' denotes a chain group, and R2 denotes a functional group which binds to a metal ion. R1 represents at least one functional group selected from the group consisting of an acetyl group, an acetic acid group, a phosphine group, a phosphonic acid group, an alcohol group, a vinyl group, an amide group, a phenyl group, an amine group, an acryl group, a silane group, . 'C' is a C1-20 linear or branched carbon chain. 'R2' may be at least one functional group selected from the group consisting of a carboxylic acid group, a carboxyl group, an amine group, a phosphine group, a phosphonic acid group and a thiol group.

As a non-limiting example, the organic monomers that are linker 120A can be selected from the group consisting of octyltrichlorosilane (OTS), hexamethyldisilazane (HMDS), octadecyltrichlorosilane (ODTS) Aminopropyl) trimethoxysilane (APS), (3-aminopropyl) triethoxysilane, N- (3-aminopropyl) -dimethyl-ethoxysilane (3-aminopropyl) -dimethyl-ethoxysilane (APDMES) Perfluorodecyltrichlorosilane (PFS), mercaptopropyltrimethoxysilane (MPTMS), 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 It may be one or more selected from hexyltriethoxysilane.

In terms of ensuring stable insulation between the nanoparticles and the substrate, the organic monomolecule as a linker may include an alkane chain group, specifically, an alkane chain group of C3-C20, and may further include a moiety containing oxygen . 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-).

Attachment of the linker 120A can be performed by the linker 120A contacting the substrate 110 with the linker solution dissolved in the solvent. The solvent of the linker solution can be any organic solvent that dissolves the linker and is easily removable by volatilization. Also, as is known, when the linker comprises a silane group, water may be added to the linker solution to promote the hydrolysis reaction. The contact between the substrate and the linker solution can of course be carried out by any known method of forming a self-assembled monolayer on a substrate. As a non-limiting example, the contact between the linker solution and the substrate may be performed by dipping, micro contact printing, spin-coating, roll coating, screen coating, Spray coating, spin casting, flow coating, screen printing, ink jet coating, or a drop casting method. .

When the metal ion is fixed to the substrate by using the linker 120A, damage of the surface layer 114 of the substrate can be prevented, and particularly, it is possible to form a metal ion membrane in which metal ions are uniformly distributed by self- The nanoparticles formed by energy application can also be stably fixed.

On the other hand, the linker may be a functional group itself which chemically bonds with a metal ion. Specifically, after the surface of the substrate 110 is modified to form a functional group (linker), a metal precursor may be supplied to the surface-modified substrate so that the metal ion binds to the functional group. Here, the functional group may be at least one functional group selected from the group consisting of a carboxylic acid group, a carboxyl group, an amine group, a phosphine group, a phosphonic acid group, and a thiol group. Any method may be used for forming the functional group on the surface of the substrate 110. As a specific example, plasma modification, chemical modification, and evaporation (application) of a compound having a functional group can be exemplified. Through the deposition (application) of a compound having a functional group in terms of introduction of impurities into the film, deterioration of the film quality, The reforming can be performed.

In a specific, non-limiting example, when the surface material of the substrate 110 is an oxide, a nitride, an oxynitride, or a silicate, a functional group (linker) can be formed by forming a silane compound layer on the substrate 110.

Specifically, the silane compound layer may be an alkoxysilane compound having at least one functional group selected from a carboxylic acid group, a carboxyl group, an amine group, a phosphine group, a phosphonic acid group and a thiol group.

More specifically, the silane compound may be represented by the following formula (2).

(2)

R ¹ _n (R ² O) _{3- n} Si-R

In Formula 2, R < ¹ > is hydrogen; A carboxylic acid group; A carboxyl group; An amine group; Phosphine; Phosphonic acid group; Thiol group; Or a linear or branched, - a (C1 C10) alkyl group, R ² is linear or branched, - a (C1 C10) alkyl group, R is as defined in R alkyl (C1-C10) alkyl, linear or branched are carboxylic Unsaturated acid group; A carboxyl group; An amine group; Phosphine; Phosphonic acid group; Or a thiol group; the alkyl group of R ^{1 and} the alkyl group of R ² are independently of each other halogen; A carboxylic acid group; A carboxyl group; An amine group; Phosphine; Phosphonic acid group; And a thiol group; and n is 0, 1, or 2.

More specifically, the silane compound may be represented by the following formulas (3) to (5).

(Formula 3)

(R ³ ) ₃ Si-R ⁴ -SH

(Formula 4)

(R ³ ) ₃ Si-R ⁴ -COOH

(Formula 5)

(R ³ ) ₃ Si-R ⁴ -NH ₂

In Formula (3), Formula (4) or Formula (5), R ³ is independently alkoxy or alkyl, at least one R ³ group is an alkoxy group, and R ⁴ is a divalent hydrocarbon group of (C 1 -C 10). Specifically, in the formulas (3), (4), and (5), R ³ is the same or different and is composed of alkoxy or alkyl of methoxy, ethoxy or propoxy, R ⁴ is -CH ² -, -CH ₂ -CH _{2 -, -CH 2 -CH 2 -CH} 2 -, -CH 2 -CH (CH 3) -CH 2 - or _{-CH 2 -CH 2 -CH (CH 3} ) - 2 is C1-C20, such as hydrocarbons, Group.

As a non-limiting example, the carboxysilane compound may be selected from the group consisting of methyldiacetoxysilane, 1,3-dimethyl-1,3-diacetoxydisiloxane, 1,2- Dimethyl-1,3-dipropionoside silyl methane or 1,3-diethyl-1,3-diacetoxydisilyl methane. By way of non-limiting example, the aminosilane compound can be selected from the group consisting of N- (2-aminoethyl) aminopropyltriethoxysilane, N- (2-aminoethyl) aminopropyltriethoxy silane, N- (Methoxy) silane, 3-aminopropyltriethoxy (methoxy) silane, N- (2-aminoethyl) Silane, 3-aminopropylmethyl di (methoxy) silane or 3-aminopropylmethyl di (ethoxy) silane. As a non-limiting example, the mercaptosilane compound may include mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, or mercaptoethyltriethoxysilane.

The functional group (functional group by the silane compound layer) can be formed by coating or vapor-depositing the above-mentioned silane compound on the surface of the substrate 110. In detail, a method in which a solution in which the silane compound is dissolved is applied and dried to form a silane compound layer, or a gaseous silane compound is supplied to the substrate surface to deposit a silane compound.

At this time, it is more preferable that the functional group of the silane compound reacts with the metal precursor to be subsequently supplied so that the metal ion can be fixed on the substrate to form a uniform film, and the functional group forms a silane compound layer evenly exposed to the surface thereof. In this respect, the silane compound layer can be formed using an atomic layer deposition (ALD) method.

The above-mentioned functional group-containing silane compounds, specifically the silane compounds of the general formula (2), more specifically the silane compounds of the general formulas (3) to (4), can also belong to the above-mentioned self assembled monomers. In detail, (R ³ ) ₃ Si may correspond to a functional group bonded to the surface of the substrate, R ⁴ may correspond to a chain group, R such as -SH, -COOH or -NH ₂ ) May correspond to a functional group binding to a metal ion. The silane compound layer may be a monomolecular film of a silane compound.

1C shows a state in which the metal ion 130 is bonded to the linker 120A. The metal ion 130 may be coupled to the functional group 126 of the linker 120A.

The metal ions 130 may be formed by supplying a metal precursor to a substrate (a substrate on which a linker is formed). That is, this can be achieved by applying a solution in which the metal precursor is dissolved to the substrate, or supplying a gaseous metal precursor onto the substrate.

The metal precursor can be designed considering the material of the desired nanoparticles. In one example, the metal of the metal precursor may be a transition metal, a precursor of a metal selected from one or more metals in the pre-metal and sub-metal groups. The transition metal is selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, And the metal may include aluminum, gallium, indium, tin, thallium, lead, and bismuth, and the sub-metals may be selected from the group consisting of boron, silicon , Germanium, arsenic, antimony, tellurium, and polonium.

That is, the metal ions 130 bonded to (attached to) the substrate through the linker 120A may be one or more metal (element) ions selected from transition metals, transition metal and metalloid groups. The metal ion 130 may be a metal ion itself or a monomolecular ion including the metal described above depending on the kind of the metal precursor. The metal ion itself binds to the functional group 126 of the organic single linker (linker) (See Fig. 1 (C)), or the second functional group 126 of the organic monomolecule is bound to a monomolecular ion containing a metal (see Fig. 1 (b)). At this time, the monomolecular ion containing a metal may be an ion generated from a metal precursor (caused by reaction with a functional group of an organic monomolecule).

The metal precursor may be any metal precursor capable of reacting with the functional group of the organic monomolecular molecule, which is the linker 120A. As a non-limiting example, the metal precursor may be a metal salt. Specifically, the metal salt may be a halide, a chalcogenide, a hydrochloride, a nitrate, a sulfate, an acetate, or an ammonium salt of a metal selected from the group consisting of a transition metal, a metal after the transition, and a metalloid group. When the metal of the metal precursor is Au, a specific and non-limiting example is 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, Au 2 include the Se _3, but can not be the present invention is defined by the type of transition metal precursor Of course.

FIG. 1D shows a state in which the metal nanoparticles 140 are formed by applying the energy to grow the metal ions 130 at the same time as the reduction. Metallic nanoparticles 140 may be formed on the substrate 110 via the linker 120A.

Although the 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 a certain distribution in particle size, The larger the reaction field of the city, the greater the difference in particle size. In addition, the method of manufacturing nanoparticles in a top-down manner by etching has a problem in that although the lithography technique is highly developed and it becomes possible to manufacture particles with a diameter of 20 nm or less, the process is complicated, strict and precise control is required, There are many.

However, in the manufacturing method according to the first embodiment of the present invention, nanoparticles are directly produced in an extremely small reaction field corresponding to the surface area of the substrate, and extremely uniform and finely controlled nanoparticles having a high density are formed can do. In addition, since metal ions are fixed on a substrate through a linker only and energy is applied to metal ions to form nanoparticles, it is possible to produce nanoparticles in a simple and easy manner at a low cost in a short time. Further, as the nucleation and growth (nanoparticle formation) are carried out by the energy application while the metal atoms (ions) are fixed on the substrate through the linker, the movement of the metal atoms (ions) And more uniform and fine nanoparticles can be formed. In detail, the material supply of the metal required for the nucleation and growth of the material for nanoparticle formation can be made only by metal atoms (ions) bonded to the linker. That is, the supply of the material for nanoparticle formation occurs only by the movement of metal atoms (ions) bonded to the linker, and the metal atoms (ions) move by a certain distance or more by nucleus formation and growth As participation becomes more difficult, 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 metallic nanoparticles remain bonded with the linker, so that the nanoparticles can be physically and stably fixed via the linker. The distance between the nanoparticles is determined by the diffusion distance of metal atoms .

The energy applied for nanoparticle formation can be one or more energy sources selected from heat, chemical, light, vibration, ion 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 ion is immobilized, It may mean that the semiconductor substrate to which the ions are fixed is physically in a non-contact state. As a non-limiting example, a direct application may be a method of transferring thermal energy to a metal ion through a substrate, in which a heating element generating a juxtaposition is positioned under the substrate by a current flow. 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 certain distance from the metal ion on top of the substrate where the metal ion is immobilized, so that the metal ion is transferred through the fluid (including air) existing between the metal ion and the heating element And a method of transferring heat energy.

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 on the substrate on which the metal ions are fixed, so that the light source is spaced apart from the metal ions by a certain distance.

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 above the substrate on which the metal ions are fixed so as to be spaced apart from the metal ions by a certain distance, so that the metal ions may be irradiated with microwaves and / or ultrasonic waves.

Specifically, the radiation energy may include one or more radiation selected from alpha rays, beta rays and gamma rays, and may be beta rays and / or gamma rays in terms of reduction of metal ions. As a non-limiting example, a radiation source may be positioned above the substrate on which the metal ions are immobilized so as to be spaced from the metal ions by a certain distance so that the metal ions may be irradiated with the radiation.

Specifically, the energy may be kinetic energy by the particle beam, and the particle beam may comprise an ion beam and / or an electron beam. In terms of the reduction of the metal ion, the ion of the beam may be an ion having a negative charge. By way of non-limiting example, an accelerating member is provided which provides an electric field (electromagnetic field) in which an ion or electron source is located at a certain distance from the metal ion above the substrate on which the metal ion is immobilized and accelerates the ion or electron toward the metal ion , And ion beams and / or electron beams can be applied to metal ions.

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 metal ions are reduced by a reducing agent. As a non-limiting example, the application of chemical energy may be a reduction reaction in which the metal ion is contacted with the substrate to which the metal ions are fixed and the 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, application of energy may include simultaneous or sequential application of two or more energy selected from heat, chemical, light, vibration, ion 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 kind of energy application is performed and then another kind of energy application is performed, which may mean that different kinds of energy are continuously or discontinuously applied to metal ions. Since it is preferable that the metal ions fixed on the substrate via the linker are formed before the granulation, as a specific example of the sequential application, heat is applied after the reductant is charged, or after application of the negatively charged particle beam Heat 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 may be performed by contacting the metal ions with a reducing solution in which the reducing agent is dissolved in the solvent, and then heat-treating the substrate with 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.

As 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 ions. 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 ion 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 . Specifically, nanoparticles having an average particle size of 0.5 to 3 nm can be produced by the application of energy, and extremely uniform nanoparticles having a standard deviation of the particle radius of 20% or less can be formed, and nanoparticles Density nanoparticles having a density of 10 < ¹³ > to 10 < ¹⁵ > / cm < ² >

As a specific example, when the energy applied is an electron beam, the electron beam irradiation amount may be 0.1 KGy to 100 KGy. Ultrafine nanoparticles having an average particle diameter of 2 to 3 nm can be formed by such an electron beam irradiation amount, and extremely uniform nanoparticles having a standard deviation of the particle radius of 20% or less can be formed, Nanoparticles having a density of 10 < ¹³ > to 10 < ¹⁵ > / cm < ² >, and substantially 0.1x10 ¹⁴ to 10x10 ¹⁴ / cm < ² >

In a specific example, when the energy applied is an electron beam, an electron beam irradiation dose is 100 μGy to 50 KGy. With such an electron beam irradiation dose, extremely fine nano particles having an average particle diameter of 1.3 to 1.9 nm can be formed, a standard deviation of 10 ¹³ to 10 ^15, the number density of nanoparticles of the nanoparticle may be ± 20% or less is extremely uniform nanoparticles formed per unit area dog / cm ^2, substantially 0.2x10 ¹⁴ to 20x10 ¹⁴ pieces / cm ² In nanoparticles can be formed.

In a specific example, when the energy applied is an electron beam, an electron beam irradiation dose is 1 μGy to 10 KGy. With such an electron beam irradiation dose, extremely fine nanoparticles having an average particle diameter of 0.5 to 1.2 nm can be formed, a standard deviation of 10 ¹³ to 10 ^15, the number density of nanoparticles of the nanoparticle may be ± 20% or less is extremely uniform nanoparticles formed per unit area dog / cm ^2, substantially 0.2x10 ¹⁴ to 30x10 ¹⁴ pieces / cm ² In nanoparticles can be formed.

As a specific example, when the applied energy is thermal energy, a heat treatment is performed in a reducing atmosphere at a temperature of 300 to 500 DEG C for 0.5 to 2 hours, or a reducing agent is supplied to metal ions fixedly bonded via a linker, To 400 ° C for 0.5 hours to 2 hours to form extremely fine nanoparticles having an average particle diameter of 2 to 3 nm and extremely uniform nanoparticles having a standard deviation of the particle radius of 20% It may be, and the number density per unit area of the nanoparticles nanoparticles may be formed of 10 ¹³ to 10 ¹⁵ / cm ^2, 0.1x10 ¹⁴ to 10x10 ¹⁴ gae / cm ² nanoparticles.

Specifically, when the applied energy is thermal energy, heat treatment is performed in a reducing atmosphere at a temperature of 200 to 400 ° C for 0.5 hours to 2 hours, or a reducing agent is supplied to metal ions fixedly bonded via a linker, and 100 To 300 < 0 > C for 0.5 hours to 2 hours, extremely fine nanoparticles having an average particle diameter of 1.3 to 1.9 nm can be formed, and extremely uniform nanoparticles having a standard deviation of the particle radius of 20% It can be formed, and the density of the number of nanoparticles per unit area, nano-particles may be formed of 10 ¹³ to 10 ¹⁵ / cm ^2, 0.2x10 ¹⁴ to 20x10 ¹⁴ gae / cm ² nanoparticles.

As a specific example, when the applied energy is thermal energy, heat treatment is performed in a reducing atmosphere at a temperature of 200 to 400 ° C for 0.2 hour to 1 hour, or a reducing agent is supplied to metal ions fixedly connected via a linker, To 300 < 0 > C for 0.2 hour to 1 hour, extremely fine nanoparticles having an average particle diameter of 0.5 to 1.2 nm can be formed, and extremely uniform nanoparticles having a standard deviation of the particle radius of 20% It can be formed, and the density of the number of nanoparticles per unit area, nano-particles may be formed of 10 ¹³ to 10 ¹⁵ / cm ^2, 0.2x10 ¹⁴ to 30x10 ¹⁴ gae / cm ² nanoparticles.

As a specific example, when the applied energy is chemical energy, extremely fine nanoparticles having an average particle diameter of 2 to 3 nm can be formed by chemical reaction at a reaction temperature of 20 to 40 캜 by a reducing agent for 0.5 to 2 hours and, and the standard deviation of the particle radius a can be formed with extremely uniform nanoparticles less than ± 20%, the number density per unit area of the nanoparticles 10, the nanoparticles ¹³ to 10 ¹⁵ / cm ^2, 0.1x10 ¹⁴ to 10x10 ¹⁴ gae / cm < ² > can be formed.

Specifically, when the applied energy is chemical energy, extremely fine nanoparticles having an average particle diameter of 1.3 to 1.9 nm are formed by chemical reaction at a reaction temperature of -25 to 5 DEG C for 0.5 to 2 hours by a reducing agent may be, and the standard deviation of the particle radius is ± 20% or less is extremely uniform nanoparticles can be formed, and the unit is the number density of the nanoparticles 10, the nanoparticles ¹³ to 10 per area of ¹⁵ / cm ^2, 0.2x10 ¹⁴ to 20x10 Nanoparticles of ¹⁴ / cm < ² > can be formed.

Specifically, when the applied energy is chemical energy, extremely fine nanoparticles having an average particle diameter of 0.5 to 1.2 nm are formed by chemical reaction at a reaction temperature of -25 to 5 캜 by a reducing agent for 0.2 to 1 hour Extremely uniform nanoparticles having a standard deviation of the particle radius of 20% or less can be formed, and the nanoparticle density per unit area, which is the number of nanoparticles, is 10 ¹³ to 10 ¹⁵ / cm ² , 0.2 × 10 ¹⁴ to 30 × ¹⁰ Nanoparticles of ¹⁴ / cm < ² > can be formed.

As described above, when thermal energy is applied, thermal energy is applied in a reducing atmosphere, or chemical energy and thermal energy are applied sequentially or chemical energy is applied. When thermal energy is applied in a reducing atmosphere, the reducing atmosphere is hydrogen And a specific example is a reducing gas atmosphere which is an inert gas containing 1 to 5% of hydrogen. In addition, thermal energy may be applied in an atmosphere in which a reducing gas flows in terms of providing a uniform reducing power, and a specific example may be an atmosphere in which a reducing gas flows at 10 to 100 cc / min. When chemical energy and thermal energy are applied sequentially, thermal energy may be applied in an inert atmosphere after the reducing agent is brought into contact with the metal ion associated with the linker. The reducing agent can be used if it is a substance that reduces metal ions. When the chemical energy is applied by the introduction of the reducing agent, the granulation can be achieved by the reduction reaction. In the case of particle formation during the reduction reaction, the reduction reaction must be performed very quickly and homogeneously in the whole channel region, so that nanoparticles of uniform size can be formed. In this respect, a reducing agent having a strong reducing power can be used. As a typical example, the reducing agent can be NaBH ₄ , KBH ₄ , N ₂ H ₄ H ₂ O, N ₂ H ₄ , LiAlH ₄ , HCHO, CH ₃ CHO, . In addition, when the reducing agent having a strong reducing power as described above is used when chemical energy is applied, the nanoparticle size can be controlled by adjusting the nucleation rate and the growth rate of the nanoparticles by controlling the chemical reaction temperature. The contact of the reducing agent with the metal ion bonded to the linker can be performed by applying a solvent in which the reducing agent is dissolved to the metal ion attachment region, impregnating the substrate with the solvent in which the reducing agent is dissolved, or supplying the reducing agent in the vapor phase. As a specific, non-limiting example, the contact between the reducing agent and the metal ion may occur at room temperature and may be for 1 to 12 hours.

As described above, the nucleation and growth of nanoparticles can be controlled using one or more factors selected from the type of energy applied, the size of energy applied, the time and temperature of application of energy, Metal nanoparticles, metal carbide nanoparticles, or intermetallic compound nanoparticles as well as metal nanoparticles, as well as metal nanoparticles, by supplying a different source of nitrogen to the metal nanoparticles, Can be manufactured.

Meanwhile, in the production method according to an embodiment of the present invention, i) the surfactant organic substance bound or adsorbed to the metal ion before the application of the energy can be supplied and then the energy can be applied to adjust the size of the nanoparticle, ii) The size of the nanoparticles can be regulated by supplying a surfactant organics that bind or adsorb to metal ions during the application of energy. The supply of such surfactant organics may be optional during the manufacturing process. The surfactant organic substance supplied before or during the application of energy may be a discontinuous organic substance or a plurality of different organic substances.

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.

The surfactant organics supplied during the energization or energization can bind or adsorb to the metal ion or the metal ion associated with the linker, and the nucleation and growth of the nanoparticles due to the supplied energy can be combined with the metal ion Can be controlled by the surfactant organics that adsorb to metal ions. These surfactant organics inhibit mass transfer of metals during energy application, allowing for the formation of more uniform and finer nanoparticles. The metal ion binds with the surfactant organic substance, so that a higher activation energy is required for diffusion to participate in nucleation or growth, or physical movement is inhibited by organic matter, The diffusion becomes slow and the number of metals (ions) contributing to the growth of the nuclei can be reduced.

The configuration for applying the energy in the presence of the surfactant organic substance specifically includes a step in which the solution in which the organic substance is dissolved is introduced into the metal ion binding region (i.e., the substrate surface to which the metal ion is bonded via the linker) Or applying an organic substance in a gaseous state. Alternatively, it may be a method in which a solution in which an organic matter is dissolved together with energy application is applied to a metal ion binding region, or a gaseous organic matter is supplied to adsorb or bind an organic substance to a metal nucleus. Alternatively, a solution in which organic matter is dissolved during the application of energy may be applied to the metal ion-binding region, or a gaseous organic matter may be supplied to adsorb or bind the organic matter to the metal nucleus. Alternatively, after the energy is applied for a predetermined period of time, the application of the energy is stopped, the solution in which the organic matter is dissolved is applied to the metal ion binding region, or the gaseous organic matter is supplied to adsorb or bind the organic matter to the metal nucleus, Lt; / RTI >

In the manufacturing method according to the first embodiment of the present invention, energy may be applied to the entire region of the metal ion-binding region at the same time or energy may be applied to a portion of the metal ion-binding region. When energy is applied to a part, energy can be applied (irradiated) as a spot, a line, or a surface of a predetermined shape. As a non-limiting example, energy can be applied (irradiated) in such a way that energy is irradiated to the spot and the entire region of the metal ion binding region is scanned. In this case, energy is applied to a part of the metal ion-binding region, energy is applied to a spot, a line, or a surface, and not only when a whole region of the metal ion-binding region is scanned, Investigation) may also be included.

FIG. 1E shows a state where the insulating organic material 150 is bonded to the metallic nanoparticles 140 grown by energy application. The insulating organic material 150 may be coated on the surface of the metallic nanoparticles 140 or may fill the void space between the metallic nanoparticles 140. The insulating organic material 150 may isolate the nanoparticles 140 from each other to more reliably prevent conduction between neighboring nanoparticles.

On the other hand, if the surfactant organic material is sufficiently supplied in the previous step, that is, the surfactant organic material supplied before or during the energy application remains on the surface of the grown nanoparticles, if the insulation between the grown nanoparticles is sufficient, It is not necessary to further form the insulating organic material 150 on the surface of the insulating layer 150. That is, depending on the size of the desired nanoparticles, the presence or absence (or supply amount, type, etc.) of the organic material supplied before or during the energy application is determined. Therefore, the formation of the insulating organic material 150 is optional.

The supply of the insulating organic material 150 may be performed by applying a solution in which the insulating organic material is dissolved to a nanoparticle layer produced by energy application, and then drying to fill the void space between the nanoparticles with the insulating organic material. Thus, it is possible to have a structure in which nanoparticles are embedded in an insulating matrix made of an insulating organic material. The insulating organic material can be used as long as it is a typical insulating organic material used for forming an insulating film in a conventional organic-based electronic device. As a specific example, the insulating organic material may be at least one selected from the group consisting of BCB (Benzocyclobutene), an acrylic material, polyimide, polymethylmethacrylate (PMMA), polypropylene, fluorine-based material (CYTOPTM), polyvinyl alcohol, polyvinyl phenol, polyethylene terephthalate Poly-p-xylylene, CYMM (cyanopulluane), or polymethylstyrene. However, the present invention is not limited thereto.

The insulating organic material 150 may be a material that spontaneously bonds with the metal. That is, after the particleization by energy application is performed, an insulating organic solution spontaneously bonding with a metal ion metal attached to the base material is applied to the channel region through the linker, or an insulating organic material is vapor- (A metal ion metal attached to the semiconductor substrate through the linker) and the insulating organic material to form a composite particle of the core-shell structure of the shell of the nanoparticle core-insulating organic material. This method can form an insulating film extremely uniformly on fine nanoparticles and can secure more stable insulating property between nanoparticles.

The insulating organic material 150 can be used as long as it is an organic material having a functional group that binds to the metal contained in the nanoparticles and is insulating. As a specific example, the insulating organic material that spontaneously binds to the metal contained in the nanoparticles may be spontaneously reacted with the metal contained in the nanoparticles such as a thiol group (-SH) carboxyl group (-COOH) and / or an amine group (-NH ₂ ) A chemically bondable monofunctional group, such as a methyl group, and other functional groups that do not react with the metal contained in the nanoparticles, and a trunk portion of the alkane chain that enables the formation of a regular insulating film. At this time, the thickness of the insulating film (shell) may be controlled by the carbon number of the alkane chain, and the insulating organic material may be an organic material of C3-C20 alkane chain structure.

When the layer comprising the metallic nanoparticles 140 and the insulating organic material 150 is applied to, for example, a floating gate of a flash memory cell, the weight ratio of the nanoparticles and the insulating organic material of the floating gate may be 1: 0.5 to 10. The weight ratio of the nanoparticles and the insulating organic material is a weight ratio that can stably prevent the conduction between the nanoparticles and the physical stability of the floating gate. The weight ratio of the nanoparticles and the insulating organic material can be controlled through the amount of the insulating organic material charged into the substrate on which the nanoparticles are formed. In addition, when an insulating organic material that spontaneously binds to a metal contained in the nanoparticles is used, the weight ratio of the nanoparticles and the insulating organic material can be controlled by the carbon number of the above-described alkane chain of the insulating organic material.

Referring to FIG. 1E, the nanostructure formed by the manufacturing method according to the first embodiment of the present invention will be described in more detail.

1E, the nanostructure according to the first embodiment of the present invention includes a substrate 110, a linker 120A formed on the substrate, and metal nanoparticles (not shown) grown from the metal ions bonded to the linker 120A 140). The nanostructure may further include an insulating organic material 150 having a functional group bonded to the surface of the metallic nanoparticles.

The substrate 110 may include a surface layer 114 having a functional group capable of bonding with the linker 120A. The surface layer 114 may comprise an oxide layer. More specifically, the surface layer may be formed of at least one of silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, titanium oxide, tin oxide, barium- Silicon oxide, silicon oxynitride, zirconium silicate, hafnium silicate, and the like.

The substrate 110 may be a flexible substrate, and the flexible substrate may comprise a surface layer having a hydroxyl group (-OH) functionality. 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), polyether sulfone Dimethylsiloxane (PDMS), or a mixture thereof.

The linker 120A may be an organic single molecule that is bonded to the surface of the substrate 110 by self-assembly. The nanostructure may include a linker layer 120 consisting of a plurality of linkers 120A coupled onto a substrate 110. [ The linker layer 120 may be a self-assembled monolayer formed by the organic monomers being magnetically bonded on the substrate 110. Further, the linker layer 120 may be a silane compound layer formed on the substrate 110 and having any one functional group selected from an amine group, a carboxyl group and a thiol group. The linker 120A may include any one functional group selected from an amine group, a carboxyl group, and a thiol group. The linker 120A comprises a first functional group (122 of FIG. 1B) coupled to the surface of the substrate 110, a second functional group (126 of FIG. 1B) that couples to the metal ion, and a second functional group (124 in FIG. 1B).

The metallic nanoparticles 140 may be any one selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles, and intermetallic compound nanoparticles. The metallic nanoparticles 140 are particles produced by binding a metal ion to the linker 120A and growing the metal ion.

The size of the metallic nanoparticles 140 can be controlled according to energy application conditions at the time of growth. In addition, the nanoparticle size can be adjusted depending on whether the surfactant is supplied before or during the application of energy to grow the particles. The surfactant may be organic and may remain on the surface of the grown nanoparticles 140. Preferably, when the surfactant is not used, the metallic nanoparticles 140 may have a diameter of 2.0 nm to 3.0 nm. Preferably, when using any one type of surfactant, the metallic nanoparticles 140 may have a diameter of 1.3 nm to 1.6 nm. Preferably, when using a plurality of different kinds of surfactants, the metallic nanoparticles 140 may have a diameter of 0.5 nm to 1.2 nm.

The insulating organic material 150 may be bonded to the surface of the grown metallic nanoparticles 140. The insulating organic material 150 prevents conduction between the metallic nanoparticles 140. The insulating organic material 150 may be coated on the surface of the nanoparticles 140 and may exist in the form of filling a space between the nanoparticles 140 spaced apart from each other. When the surfactant is supplied to the metal ion or the growing nanoparticles before growth into the nanoparticles, the surfactant component may remain on the surface of the metallic nanoparticles 140. Since a surfactant can also use an insulating organic material, formation of an insulating organic material formed in a state in which the nanoparticles are completely grown can be omitted if insulation between the arranged nanoparticles is possible using only the surfactant remaining after growth.

Further, although not shown in the figure, additional insulating material may be additionally formed between the metallic nanoparticles 140 coated with the insulating organic material 150. That is, a plurality of metallic nanoparticles 140 may be arranged on the linker layer 120 to form a monolayer nanoparticle layer. The nanoparticle layer may comprise a surfactant organics bound to or coated on the surface of the metallic nanoparticles and / or an insulating organic material, and may further include an insulating material filling between the coated metallic nanoparticles.

The nanostructure according to the first embodiment of the present invention may have a vertical multi-stack structure. That is, the linker layer 120 and the nanoparticle layer can be alternately repeatedly laminated. At this time, the lower nano particle layer and the upper linker layer may further include an insulating layer capable of bonding with the linker of the upper linker layer. If the insulating organic material (or the surfactant organic material constituting the lower nanoparticle layer, or the insulating material filling the empty spaces between particles) has a functional group capable of binding with the linker of the upper linker layer, the insulating material between the lower nanoparticle layer and the upper linker layer Formation of the layer can be omitted. That is, depending on the type of the insulating organic material 150, whether or not the insulating layer between the lower nano particle layer and the upper linker layer is formed can be determined.

[NANO STRUCTURE AND METHOD FOR MANUFACTURING THE SAME]

2A to 2E are schematic views for explaining a nanostructure according to a second embodiment of the present invention and a method of manufacturing the same.

The method of manufacturing a nanostructure according to a second embodiment of the present invention includes the steps of preparing a substrate 210 (FIG. 2A), a step of forming an insulating particle support 222 (FIG. 2B) forming the metal nanoparticles 240 (FIG. 2B), coupling the metal ions 230 to the linker 224 (FIG. 2C) . Further, the method may further include the step of supplying an insulating organic material (FIG. 2E) onto the structure having the metallic nanoparticles formed thereon. Further, the method may further include supplying the surfactant organics to the endogenous or plural species before or during the application of the energy.

Figure 2A shows a prepared substrate 210. Referring to FIG. 2A, the substrate 210 may have a surface layer 214. For example, the substrate 210 may be a silicon substrate 212 having an oxide layer as the surface layer 214.

The substrate 210 may comprise a flexible substrate or a transparent substrate. When the flexible substrate 210 is used, the surface layer 214 may be an organic material having a hydroxyl group (-OH) functional group.

Non-limiting examples of the flexible substrate include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene (PP), triacetylcellulose (TAC) A flexible polymer substrate containing sulfone (PES), polydimethylsiloxane (PDMS), or a mixture thereof. Non-limiting examples of the transparent support include a glass substrate, a transparent plastic substrate, and the like.

The substrate 210 may be a preformed structure in which some or all of the components of the application device are formed. The substrate 210 may be in the form of a wafer, a film, or a thin film. The surface 210 may be formed into a nanopatterned structure (structure) in consideration of the physical shape of an application device designed such as a recessed or three- .

In the second embodiment of the present invention, the substrate 210 may have the materials and structure described in the first embodiment of the present invention, and redundant description will be omitted for the sake of understanding of the invention.

2B shows a state in which an insulator particle support 222 having a linker 224 coupled thereto is formed on a base material 210. Fig. A plurality of insulator particle supports 222 combined with the linkers 224 are formed on a substrate to constitute a support layer 220.

The method for forming the support layer 220 having the linker bonded on the base material 210 includes the steps of mixing the insulator particle powder with the linker solution in which the linker is dissolved in the solvent to produce the support layer raw material, Lt; RTI ID = 0.0 > and / or < / RTI > In this case, the coating method may be a method of spin-coating the support layer raw material on the substrate, and the vapor deposition method may be a liquid deposition method in which the substrate is immersed in a solution in which the support layer raw material is dissolved.

The insulator particle support 222 may comprise an oxide having at least one element selected from the group consisting of metals, transition metals, transition metals and metalloids. The dielectric particle support 222 may be formed of a material selected from the group consisting of silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, titanium oxide, tin oxide, , Silicon nitride, silicon oxynitride, zirconium silicate, hafnium silicate, and a polymer.

The linker 224 may be an organic monomolecular molecule chemically bonded to or adsorbed on the surface of the insulator particle support 222 and chemically bonded to the metal ion. Specifically, the linker 224 may be an organic monomolecular molecule having both a first functional group that chemically bonds or adsorbs with the surface of the insulator particle support 222 and a second functional group that chemically bonds with the metal ion (subsequently formed) . The linker 224 may also include a chain 124 connecting the first and second functionalities. The linker 224 may include any one functional group selected from an amine group, a carboxyl group and a thiol group capable of binding with a metal ion. The linker 224 may be applied to the methods or materials of the various embodiments described through the first embodiment of the present invention in the same or similar manner.

2C shows a state in which the metal ion 230 is bonded to the linker 224. FIG. Metal ions 230 may be coupled to the functional groups of linker 224. The metal ions 230 can be formed by supplying a metal precursor to a substrate (a substrate on which a linker is formed). That is, this can be achieved by applying a solution in which the metal precursor is dissolved to the substrate, or supplying a gaseous metal precursor onto the substrate. The method for bonding metal ions 230 to the linker 224 in the second embodiment of the present invention and the materials used in the method can be variously performed as in the first embodiment of the present invention.

2D shows a state in which metal nanoparticles 240 are formed by growing metal ions 230 by applying energy. The energy applied for nanoparticle formation may be one or more energy sources selected from heat, chemical, light, vibration, ion beam, electron beam and radiation energy, and the various embodiments may be the same or similar to the first embodiment .

Meanwhile, in the production method according to the second embodiment of the present invention, i) a surfactant organic substance which is bound or adsorbed to metal ions before the application of energy can be supplied and energy can be applied to control the size of nanoparticles, And ii) by supplying a surfactant organics that bind or adsorb to metal ions during the application of energy, the size of nanoparticles can be controlled 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 or 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.

FIG. 2E shows a state where the insulating organic material 250 is bonded to the metallic nanoparticles 240 grown by energy application. The insulating organic material 250 may be coated on the surface of the metallic nanoparticles 240 or may fill the void space between the metallic nanoparticles 240. The insulating organic material 250 can isolate the nanoparticles 240 from each other to more reliably prevent conduction between neighboring nanoparticles.

If the surfactant organic material is sufficiently supplied in the previous step, that is, the surfactant organic material supplied before or during the energy application remains on the surface of the grown nanoparticles, if the insulation between the grown nanoparticles is sufficient, It is not necessary to further form the insulating organic material 250 on the insulating layer 250. That is, depending on the size of the desired nanoparticles, the presence or absence (or supply amount, type, etc.) of the surfactant organic material is determined, so that formation of the insulating organic material 250 is optional.

The method of forming the insulating organic material 250 and the material thereof are the same as or similar to the first embodiment described above.

Referring to FIG. 2E, the nanostructure formed by the manufacturing method according to the second embodiment of the present invention will be described in more detail.

2E, a nanostructure according to a second embodiment of the present invention includes a substrate 210, an insulator particle support 222 formed on the substrate 210 and coupled with a linker 224, a linker 224 ). ≪ / RTI > The nanostructure may further include an insulating organic material 250 having a functional group bonded to the surface of the metallic nanoparticles 240.

The substrate 210 may comprise a surface layer 224. The surface layer 114 may comprise an oxide layer. More specifically, the surface layer may be formed of at least one of silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, titanium oxide, tin oxide, barium- Silicon oxide, silicon oxynitride, zirconium silicate, hafnium silicate, and the like.

The substrate 210 can be a flexible substrate, and the flexible substrate can include a surface layer 224 having a hydroxyl group (-OH) functionality. 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), polyether sulfone Dimethylsiloxane (PDMS), or a mixture thereof.

The insulator particle support 222 may be an oxide particle having at least one element selected from the group consisting of metals, transition metals, transition metals and metalloids. The insulator particle support 222 may be particles having a diameter of 10 nm to 20 nm. The insulator particle support 222 may be formed as a monolayer or a multi-molecular layer on the substrate 210.

The insulator particle support 222 may be any one of silicon oxide, hafnium oxide, aluminum oxide, zirconium oxide, barium-titanium composite oxide, yttrium oxide, tungsten oxide, tantalum oxide, zinc oxide, titanium oxide, tin oxide, barium- A nitride, a silicon oxynitride, a zirconium silicate, a hafnium silicate, and a polymer.

Linker 224 may be an organic monomolecular molecule. The nanostructure may comprise a linker layer consisting of a plurality of linkers 224 coupled onto a substrate 210. The linker layer may be a self-assembled monolayer formed by self-bonding of an organic monomolecular layer on an insulator particle support layer. Also, the linker 224 may include any one functional group selected from an amine group, a carboxyl group, and a thiol group. The linker 224 may include a first functional group that binds to the surface of the insulator particle support 222, a second functional group that binds to the metal ion, and a chain group that connects the first functional group and the second functional group.

The metallic nanoparticles 240 may be any one selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles, and intermetallic compound nanoparticles. The metallic nanoparticles 240 are particles produced by binding a metal ion to the linker 224 and growing the metal ion.

The size of the metallic nanoparticles 240 can be controlled according to energy application conditions at the time of growth. In addition, the nanoparticle size can be adjusted depending on whether the surfactant is supplied before or during the application of energy to grow the particles. The surfactant may be organic and may remain on the surface of the grown nanoparticles 240. Preferably, when the surfactant is not used, the metallic nanoparticles 240 may have a diameter of 2.0 nm to 3.0 nm. Preferably, when using any one type of surfactant, the metallic nanoparticles 240 may have a diameter of 1.3 nm to 1.6 nm. Preferably, when using a plurality of different types of surfactants, the metallic nanoparticles 240 may have a diameter of 0.5 nm to 1.2 nm.

The insulating organic material 250 may be bonded to the surface of the grown metallic nanoparticles 240. The insulating organic material 250 prevents conduction between the metallic nanoparticles 240. The insulating organic material 250 may be coated on the surface of the nanoparticles 240 and may exist in a form filling a space between the nanoparticles 240 spaced apart from each other. When the surface active agent is supplied to the metal ion or the growing nanoparticles before growth into the nanoparticles, the surfactant component may remain on the surface of the metallic nanoparticles 240. Since the surfactant can also use an insulating organic material, formation of the insulating organic material 250 can be omitted if the surfactant organic material can sufficiently insulate the grown nanoparticles. Although not shown in the drawing, if the insulating organic material 250 is coated on the surface of the nanoparticles, additional insulating material may be additionally formed between the coated metallic nanoparticles 240.

On the other hand, a plurality of metallic nanoparticles 240 may be spaced apart to form a nanoparticle layer, and the nanoparticle layer may be a monolayer. The nanoparticle layer may include an insulating organic material (or an organic material for a surfactant) bonded or coated on the surface of the metallic nanoparticle, and may further include an insulating material filling between the coated metallic nanoparticles.

The nanostructure according to the second embodiment of the present invention may have a vertical multi-stack structure. That is, the insulator particle support layer and the nanoparticle layer, to which the linker is bonded, may be alternately repeatedly laminated. At this time, the lower nano particle layer and the upper support layer may further include an insulating layer having a functional group capable of binding with a support (a support to which a linker is coupled). If the insulating organic material 250 constituting the lower nano particle layer has a functional group capable of binding with the upper support layer, the formation of the insulating layer may be omitted. That is, depending on the type of the insulating organic material 250, the formation of the insulating layer may be determined.

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 (15)

materials;
An insulator particle support formed on the substrate and having a linker bonded to its surface;
Metallic nanoparticles grown from metal ions bound to the linker; And
Wherein the metal ions or the surfactant organics bound to the growing nanoparticles
Nanostructures.
The method according to claim 1,
And an insulating organic material bonded to the surface of the grown metallic nanoparticles.
The method according to claim 1,
Wherein the surfactant organics are nitrogen or sulfur containing organics.
The method according to claim 1,
Wherein the metallic nanoparticles have a diameter of 1.3 nm to 1.9 nm.
The method according to claim 1,
The substrate has an oxide layer on its surface.
The method according to claim 1,
The insulator particles
A silicon oxide, a hafnium oxide, an aluminum oxide, a zirconium oxide, a barium-titanium composite oxide, a yttrium oxide, a tungsten oxide, a tantalum oxide, a zinc oxide, a titanium oxide, a tin oxide, a barium-zirconium composite oxide, a silicon nitride, a silicon oxynitride, Wherein the nanostructure comprises particles of at least one material selected from the group consisting of zirconium silicate, hafnium silicate, and polymer.
The method according to claim 1,
Wherein the linker comprises an organic monomolecular molecule bound to the surface of the insulator particle. The method according to claim 1,
Wherein the linker comprises a first reactor for binding with the surface of the insulator particles, a second reactor for coupling with the metal ions, and a chain group for connecting the first reactor and the second reactor.
3. The method of claim 2,
Wherein the linker comprises any one selected from an amine group, a carboxyl group, and a thiol group bonded to the metal ion.
The method according to claim 1,
Wherein the metallic nanoparticles are any one selected from the group consisting of metal nanoparticles, metal oxide nanoparticles, metal nitride nanoparticles, metal carbide nanoparticles, and intermetallic compound nanoparticles.
The method according to claim 1,
Wherein a plurality of insulator particle supports to which the linkers are bonded are arranged on the substrate to constitute a support layer of a monomolecular layer or a multi-molecular layer.
12. The method of claim 11,
A nanoparticle layer on said support layer,
Wherein the nanoparticle layer comprises:
A plurality of the metallic nanoparticles spaced apart from each other; And
And an insulating organic material bonded to the surface of the metallic nanoparticles.
Nanostructures.
12. The method of claim 11,
A nanoparticle layer on said support layer,
Wherein the nanoparticle layer comprises:
A plurality of the metallic nanoparticles spaced apart from each other;
An insulating organic material coated on the surface of the metallic nanoparticles; And
And an insulating material filling between the coated metallic nanoparticles
Nanostructures.
13. The method of claim 12,
Wherein the support layer and the nanoparticle layer are alternately repeatedly laminated to form a vertical multi-stack structure.
15. The method of claim 14,
And an oxide layer formed between the nanoparticle layer and the support layer of the vertical multi-stack structure.

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