WO2012144728A2 - Procédé de fabrication d'un réseau de nanoparticules dont la taille est ajustable, réseau de nanoparticules ainsi fabriqué et ses utilisations - Google Patents

Procédé de fabrication d'un réseau de nanoparticules dont la taille est ajustable, réseau de nanoparticules ainsi fabriqué et ses utilisations Download PDF

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WO2012144728A2
WO2012144728A2 PCT/KR2012/001216 KR2012001216W WO2012144728A2 WO 2012144728 A2 WO2012144728 A2 WO 2012144728A2 KR 2012001216 W KR2012001216 W KR 2012001216W WO 2012144728 A2 WO2012144728 A2 WO 2012144728A2
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block copolymer
metal ion
metal
polymer
array
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PCT/KR2012/001216
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Korean (ko)
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WO2012144728A3 (fr
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김상욱
신동옥
문정호
박수진
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한국과학기술원
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Priority claimed from KR1020120005867A external-priority patent/KR20120123184A/ko
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material

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  • the present invention relates to a method for manufacturing a nanoparticle array which can be adjusted in size, and to a nanoparticle array prepared by the present invention and its application, and more particularly, the nanoparticle size can be easily controlled by the loading time of the metal ion, such as a catalyst and the like.
  • the present invention relates to a method for manufacturing a scalable nanoparticle array, which can be effectively applied to various applications of the nanoparticle array and its application.
  • Nanoscale particles have a large surface area resulting from nanoscale quantum confinement effects and small sizes, from which they exhibit size-dependent electrical, magnetic, chemical, optical, and catalytic properties. Patterning nanoparticles into two-dimensional (2D) arrays is already under considerable research due to their potential applications in sensors, magnetic data reservoirs, flash memories, and catalysts. However, despite active research in nanoparticle synthesis, the technique of precisely positioning, aligning and immobilizing nanoparticles on a desired substrate remains a technical challenge. In addition, it is very important to arrange nanopatterned particles on a desired substrate in a controlled manner. If the accuracy of the technique of locating and arranging nanoparticles is high, a nanoparticle array with controlled size can be applied to the various applications described above.
  • Block copolymer lithography is evolving into lithography technology to overcome the inherent resolution limitations of conventional photolithography processes.
  • the horizontal self-assembly technique of the separated block copolymer nanodomains of the microphase allows the fabrication of nanolithography masks that repeat at a size of 30 nm or less on any large area.
  • recent self-assembly and orientation techniques using external electric field application, chemical or topography prepattern methods have achieved nano-patterns arranged horizontally over large areas.
  • the inherent polydispersity of self-assembled nanoregions remains a technical challenge for producing nanopatterned morphologies with monodispersity.
  • scaled pattern transfer techniques have not been achieved on a block copolymer lithography basis to date.
  • the problem to be solved by the present invention is to provide a method for producing a nanoparticle array having a monodisperse property and controllable in size on a substrate and a nanoparticle array produced thereby.
  • a nanoparticle array of monodisperse properties are provided on a substrate and a nanoparticle array produced thereby.
  • the present invention provides a nanoparticle array comprising contacting a metal ion solution with a charged polymer that electrostatically bonds with the metal ion in the solution, thereby binding the metal ion to the polymer.
  • a nanoparticle array comprising contacting a metal ion solution with a charged polymer that electrostatically bonds with the metal ion in the solution, thereby binding the metal ion to the polymer.
  • monodisperse nanoparticle arrays can be deposited by block copolymer lithography.
  • the nanoparticle size can be easily controlled by the loading time of the metal ion, it can be effectively applied to various applications such as a catalyst.
  • metals having different physical properties may be deposited on a substrate in an array of lines and dots.
  • it is possible to freely determine the type of metal array and the type of metal through the selective electrostatic bonding of the block copolymer of self-assembly and the specific polymer of the block copolymer with the metal ion, and also there is no limitation on the substrate area.
  • an alloy array due to the simultaneous bonding of dissimilar metal ions can also be easily manufactured.
  • FIG. 1 is a process schematic diagram according to an embodiment of the present invention.
  • FIG. 2 is a process schematic diagram according to another embodiment of the present invention.
  • PS-b-P4VP thin film SEM images (FIG. 1B) after spin on a silicon substrate
  • PS-b-P4VP thin film images (FIG. 1C, 1D) after solvent-annealing.
  • 6 to 8 are SEM images of Fe 2 O 3 nanoparticle arrays prepared by immersing a spincast-solvent annealed block copolymer template in an aqueous solution containing a metal ion complex for 1 minute.
  • 9-11 are statistical distributions of Fe 2 O 3 nanoparticle diameters.
  • FIG. 12 is an SEM image showing the growth of an array of nanoparticles obtained from a solvent annealed template for 5 hours with time the template was immersed (loaded) in a metal complex ion solution.
  • FIG. 13 is a graph illustrating change in diameter of nanoparticles according to metal ion loading time.
  • 15 is a cross-sectional SEM image of vertically grown carbon nanotubes.
  • FIG. 16 is an SEM image of the lower portion of the carbon nanotube at high magnification.
  • 17 and 18 are SEM images of carbon nanotubes grown from double-walled and triple-walled nanoparticle catalysts.
  • FIG. 19 is a graph of statistically comparing the number of carbon walls prepared from the block copolymer template in the spin state with the block copolymer template after annealing for 5 hours.
  • FIG. 20 shows single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), triple-walled carbon nanotubes (TWNTs), and four-walled multi-walled carbon nanotubes (MWNTs) prepared from a 5-hour annealed block copolymer template. The relative fractions of) are analyzed according to the loading time of the complex complex.
  • SWNTs single-walled carbon nanotubes
  • DWNTs double-walled carbon nanotubes
  • TWNTs triple-walled carbon nanotubes
  • MWNTs four-walled multi-walled carbon nanotubes
  • FIG. 21 is a schematic diagram of hierarchical patterning of nanoparticle arrays and corresponding carbon nanotube growth.
  • FIG. 26 is a photograph after formation of a Pt line (34 nm period, 10 nm wide) according to the first block copolymer lithography prepared according to the present invention.
  • FIG. 27 is a photograph showing that the P4VP cylinder structure protruding in a plane at the 34 nm period and the 10 nm diameter was correctly formed between Pt lines.
  • FIG. 28 is a photograph showing that a 10 nm diameter Pd nanopoint is formed at a position of the P4VP cylinder nanodomain of FIG. 27.
  • FIG. 29 shows an array of nanoparticles formed in the form of an intersection of a Pt line and a Pd line
  • FIG. 30 is a dot-dot form
  • FIGS. 31 and 32 are EDS mapping images of the Pt line and the Pd dot array.
  • 33 to 37 are images of Pt line-Co point, Pt line-Au point, Pd line-Fe 2 O 3 point, Pt point-Fe 2 O 3 point, and Pd line-Pd line, respectively.
  • 39 to 41 are SEM images and size distribution graphs, FePt alloy nanodot arrays and size distribution graphs, TEM images and high temperature heat treatment graphs of self-assembled cylinder block copolymers, respectively.
  • the present invention provides a method for achieving monodisperse nanoparticle arrays that can be scaled to sub-nanometer levels directly from block copolymer lithography in order to solve the above problems.
  • the present invention produces monodisperse nanoparticle arrays on a substrate, in particular by inducing an electrostatic interaction between a polymer and a metal ion of any of the self-assembled block copolymers.
  • the interaction of block copolymers with metal ions in the present invention has a very high specificity (because electrostatic interactions only occur for certain block polymers of limited size) and are oriented in a specific direction with metal deposition.
  • Monodispersed nanoparticle arrays can be deposited to a desired size, depending on the uniformity of the block copolymer morphology of the structure.
  • the method for producing a nanoparticle array according to the present invention produces a nanoparticle array using a block copolymer comprising at least two different types of polymers, namely, a first polymer and a second polymer, as described above.
  • the copolymer is self-assembled to prepare a block copolymer template having a specific structure, and the metal ions of the specific polymer (first polymer) in the self-assembled block copolymer template and the nanoparticles to be prepared are subjected to electrostatic interaction. Selectively bind and remove the block copolymer again.
  • the block copolymer is used as a template for preparing nanoparticle arrays, and in particular, the present invention specifically binds the self-assembled first polymer and precursor solution ions of nanoparticles (metal nanoparticles).
  • the selective bonding between the base metal ion and the first polymer proceeds in such a way that the self-assembled block copolymer is immersed in the solution containing the metal ion.
  • the metal ion is in the form of an anionic metal complex and the first polymer bears a cation in the aqueous solution.
  • a polymer having a cation-containing nitrogen-containing group for example, pyridine
  • a metal such as Fe
  • FIG. 1 is an overall schematic diagram of a process according to an embodiment of the present invention.
  • the amphiphilic poly (styrene-block-4-vinylpyridine) (PS-b-P4VP) on any substrate PS block (second polymer) is 24.0 kg / mol
  • P4VP block ( 1 polymer) was mixed with a 9.5 kg / mol) block copolymer thin film in a toluene: tetrahydrofuran (THF) mixed solution, spin-cast and immediately self-assembled to form a P4VP nanocylinder array perpendicular to the PS matrix.
  • THF tetrahydrofuran
  • the size of the self-assembled cylinder region structure was fairly uniform.
  • a horizontally-arranged hexagonal cylinder array with a very narrow size distribution was produced.
  • the block copolymer thin film having a high order, horizontally arranged nanoarea structure, and deposited on the substrate was immersed in a 1 mM K 3 [Fe (CN) 6 ]: 0.1% HCl aqueous solution.
  • the anionic metal complex of Fe (CN) 6-3 binds to the quantized pyridine nitrogen (cationic) of the P4VP cylinder nanodomain, which is the first polymer.
  • the nanoparticle size can be controlled to be less than nanometers.
  • the Fe 2 O 3 nanoparticle array prepared according to the present invention may function as a catalytic functional material for carbon nanotube (CNT) growth.
  • CNT carbon nanotube
  • K 3 [Fe (CN) 6 ] any other ionic metal complex ion can be used to fabricate and fix various types of metal nanoparticle arrays on any substrate.
  • the following examples of the present invention used one kind of metal ion complex, but when two or more ion complexes are mixed and used, heterogeneous metal nanoparticle arrays are also possible.
  • a specific block copolymer (P4VP in one embodiment of the present invention) that is protonated in an acidic solution is immersed in an acidic solution, and the specific block is formed by electrostatic action with a metal anion.
  • P4VP polyvinyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-styrene-styrene-styrene-styl-styl-styl-styl-styrene-styrene-styrene-styrene-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-N-phenyl-
  • FIG. 2 is a process schematic diagram of a metal layer manufacturing method according to the embodiment of the present invention.
  • a P4VP polymer substrate deposited on a silicon substrate is immersed in an acid solution containing metal anion (M ⁇ ) to electrostatically bond a metal anion to the polymer substrate charged with a cation, thereby providing the metal Anions are deposited on the polymer substrate. Thereafter, the polymer substrate is removed to prepare a metal layer deposited in a form corresponding to the polymer substrate.
  • M ⁇ metal anion
  • Polystyrene-block-poly (4-vinylpyridine) PS-b-P4VP, molecular weight: 24 kg mol-1 PS, 9.5 kg mol-1 P4VP), asymmetric block copolymer, potassium hexacyanoate (III) (Potassium ferricyanide), pure ammonia and acetylene gas were prepared.
  • the silicon wafer was immersed in a piranha solution ((7: 3 H 2 SO 4: H 2 O 2) for 1 hour at 110 ° C. and washed several times with deionized water.
  • Ps-b-P4VP block copolymer (0.5 wt%) was added to the toluene / THF mixture.
  • a 25 nm thick PS-b_P4VP thin film from 0.5 wt% toluene was dissolved and spincoated onto the washed silicon
  • the spinned film was solvent annealed in a small sealed container, first toluene and THF (toluene: THF).
  • the solvent annealed sample was immersed in a 1 mM K 3 [Fe (CN) 6]: 0.1% HCl aqueous solution for a given time (loading time) After metal ion bonding (loading), the sample was washed several times with deionized water, The metal ions were removed, and then dried with nitrogen, and then subjected to oxygen plasma treatment to remove the polymer template to prepare an array of Fe 2 O 3 nanoparticles of iron oxide on a silicon substrate.
  • the present invention selected the catalyst as one of the applications of the prepared nanoparticle array.
  • the carbon nanotubes were grown by PECVD using the nanoparticle array according to the present invention as a catalyst.
  • the substrate on which the Fe 2 O 3 nanoparticle array was prepared was first heated to 600 ° C. while flowing hydrogen and ammonia mixed gas.
  • the hydrogen and ammonia content was 80: 20% by volume and the total mixed gas flow rate was maintained at 100 sccm.
  • the substrate temperature reached 600 ° C. the substrate was annealed (usually less than 2 minutes) and the Fe 2 O 3 nanoparticles were reduced to Fe metal particles.
  • the chamber pressure was increased to 5 torr, and the direct current plasma proceeded according to the application of the cathode DC voltage of 470V.
  • acetylene gas was slowly flowed at a flow rate of 5 sccm for 1 to 2 minutes to prepare carbon nanotubes grown densely and vertically.
  • FIG. 3 to 5 are PS-b-P4VP thin film SEM images (FIG. 1B) after spin on a silicon substrate, and PS-b-P4VP thin film images (FIG. 1C, 1D) after solvent-annealing.
  • FIG. 1B PS-b-P4VP thin film SEM images
  • FIG. 1C, 1D PS-b-P4VP thin film images
  • the nanocylinders of the P4VP blockpolymer are oriented vertically, which is due to the high directional vapors generated during the spin-cast process.
  • the arrangement density in the horizontal direction of the cylinder is not uniform and the size distribution is also wide (see Fig. 3).
  • the horizontal orientation and size uniformity of the cylinder is greatly improved after solvent annealing at room temperature in toluene: THF (20:80 v: v).
  • Samples annealed for 2 hours are orderly ordered in a hexagon and exhibit a relatively small grain size (see FIG. 4).
  • FFT Fast Fourier transform
  • 6 to 8 are SEM images of Fe 2 O 3 nanoparticle arrays prepared by immersing a spincast-solvent annealed block copolymer template in an aqueous solution containing a metal ion complex for 1 minute.
  • the anionic metal complex easily binds to the quantized pyridine group even in mildly acidic conditions.
  • the resulting Fe2O3 nanoparticle array accurately replicates the morphology of the block copolymer template.
  • the particles obtained after the spin, or from an insufficiently annealed block copolymer template have a large particle diameter and a wide size distribution (10.84 nm 2.98 nm after spin, 8.40 nm 1.79 nm after 2 hours annealing).
  • nanoparticles obtained from well grown molds have a cylinder structure of small size and narrow size distribution (6.03 nm to 1.0 nm).
  • 9-11 are statistical distributions of Fe 2 O 3 nanoparticle diameters.
  • Table 1 summarizes the nanosize characteristics of the block copolymer nano template and the obtained nanoparticle array of FIG. 1.
  • the average diameter of the nanoparticles is somewhat smaller than the block copolymer cylinder diameter, due to the particle density that occurs when the block copolymer is removed by plasma treatment.
  • FIG. 12 is an SEM image showing the growth of an array of nanoparticles obtained from a solvent annealed template for 5 hours with time the template was immersed (loaded) in a metal complex ion solution.
  • the size of monodispersed nanoparticles gradually increases with loading time. Precise control of particle size down to nanometer-sized sizes is possible at relatively low concentrations of aqueous metal complex ions (1 mM K3 [Fe (CN) 6]).
  • the difference in average diameter and height is graphed according to loading time, which is shown in FIG. 13.
  • the growth rate was fast at short loading times but gradually slowed down.
  • the growth behavior may correspond to a typical power law curve, At ⁇ . According to the least square fit, an index ⁇ of 0.16 in diameter and 0.39 in height is obtained.
  • the PS matrix functions as a barrier to diffusion of metal ions around the P4VP cylinder structure, but the nanoparticles are adsorbed as the loading time gradually increases.
  • 14 is an XPS spectrum of an Fe 2 O 3 nanoparticle array obtained after oxygen plasma treatment. Referring to Figure 14 results, Fe-2p3 / 1 peak of 710.5eV proves that the Fe 2 O 3 Fe state exists.
  • the catalytic functionality of monodisperse nanoparticle arrays was analyzed through catalyst-based carbon nanotube growth experiments.
  • plasma vapor deposition (PECVD) was used to induce vertically oriented carbon nanotube growth.
  • PECVD enables low temperature growth at temperatures below 600 ° C., which is one of the important conditions for device integration.
  • the Fe 2 O 3 particle array prepared in the present invention is converted into Fe particles by thermal reduction before carbon nanotube growth. That is, vertically oriented carbon nanotubes were prepared with high yield by slowly adding nitrogen, ammonia, and acetylene mixed gas (FIG. 15).
  • Such high yield growth of carbon nanotubes proves the high purity and high functionality of the monodisperse nanoparticle array prepared according to the present invention.
  • FIG. 16 is an SEM image of the lower portion of the carbon nanotube at high magnification.
  • FIG. The carbon nanotube diameter is 5.3 nm, which corresponds to 2/3 of the diameter of the catalyst particles of 8.6 nm.
  • 17 and 18 are high-resolution TEM images of carbon nanotubes grown from monodisperse catalyst particles prepared according to the present invention. When the images are analyzed, average diameters of 5.8 and 9.9 nm appear. The narrow distribution of carbon nanotube diameters and the number of carbon walls in the graphite structure is due to the monodisperse nature of the catalyst particles.
  • FIG. 18 is a statistical comparison of the number of carbon walls prepared from the block copolymer template in the spin state with the block copolymer template after annealing for 5 hours. The loading of the complex ion was maintained at 5 minutes. Since spinned nanoparticle arrays have a wide size distribution, carbon nanotubes grown from them also exhibit a wide carbon wall number distribution. In contrast, the carbon wall numbers of the carbon nanotubes obtained from the blow copolymer templates annealed for 5 hours showed a much narrower distribution.
  • FIG. 19 shows single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), triple-walled carbon nanotubes (TWNTs) and four-walled multi-walled carbon nanotubes (MWNTs) prepared from a block copolymer template annealed for 5 hours.
  • the relative fractions of) were analyzed according to the ion complex loading time.
  • the relative fraction of each carbon wall number varied with catalyst size as a function of loading time.
  • the growth of single-walled carbon nanotubes was suppressed, which is thought to be due to the nitrogen doping effect.
  • FIG. 21 illustrates a process of growing carbon nanotubes in a desired substrate region through selective deposition of block copolymers.
  • the monodisperse nanoparticle array deposition method according to the present invention can be controlled in size, which can be achieved by block copolymer lithography.
  • Vertically aligned cylindrical block copolymer nanoregions are prepared by a solvent annealed PS-b-P4VP block copolymer thin film, which is immersed in a water soluble ion metal complex solution, whereby the anionic metal complex is transferred to the P4VP cylinder core. Diffusion, which is achieved by very specific electrostatic interactions.
  • the specific dispersion of metal ions in nanoscale confined spaces enables the production of monodisperse nanoparticle arrays arranged sideways at sub-nanometer levels to the desired size.
  • the catalytic functionality of monodisperse nanoparticle arrays was demonstrated through carbon nanotubes grown vertically by catalytic PECVD.
  • the present invention which controls the catalyst particle size to a size less than nanometers, enables the growth of carbon nanotubes in a vertical orientation, in particular where the number of carbon walls can be selectively determined. It is also possible to align nanoparticle arrays within the trenches through graphoepitaxy. That is, in the case of Graphoepitaxy, since the block copolymer is aligned in the trench formed in the substrate, it is possible to form a nanostructure having a single domain, and to form a single or dissimilar metal array according to various methods described below. Can be formed in the desired trench structure.
  • another heterogeneous metal is deposited on the metal nanoparticle array (first metal array) manufactured according to the present invention to an area other than the first metal array formation region by electrostatic interaction.
  • a block copolymer is raised, followed by solvent annealing or heat treatment to form nanolines parallel to the substrate. After applying the block copolymer again on the formed nano-line again, to form a nano dot by the method according to the invention. As a result, nanodots are located between the spaces of the pre-formed nanoline.
  • alloy nanopoints of dissimilar metal on a substrate using two kinds of metal precursor solutions together. Even in this case, the dissimilar metal precursor solution must be selectively electrostatically bonded to the self-assembled block copolymer. That is, when loading a metal anion, alloy nanoparticles can be obtained by using a heterogeneous sample, and the properties of the alloy nanoparticles can be observed by heat treatment and recrystallization thereof.
  • FIG. 25 illustrates a process of depositing nanoparticles of a so-called core-shell structure on a substrate, in which a plurality of nanopoint deposition processes according to the present invention are sequentially performed, in which a second nanopoint is sequentially stacked on a first nanopoint.
  • the method is shown.
  • Yet another embodiment of the present invention provides a method of manufacturing a dissimilar metal array according to such an electrostatic loading method.
  • PS-b-P4VP poly (styrene-block-4-vinylpyridine)
  • THF tetrahydrofuran
  • a homogeneous toluene: tetrahydrofuran mixture (760/30 v / v or 80/20 v / v) is injected into the annealed vessel to form a cylinder array.
  • In-plane structures and planar protrusion structures of are derived, respectively.
  • a 59 kg / mol PS-b-P4VP block copolymer thin film was treated with THF vapor to assemble into a cylinder array of planar protrusion structures. The vessel was saturated with solvent vapor which spontaneously evaporated at room temperature for several minutes.
  • the spin-coated thin film was then annealed for 1 to 5 hours to form orderly arranged cylindrical nanodomains.
  • the solvent annealed sample was immersed in an aqueous HCl solution containing metal ions to load the metal ions into the thin film.
  • the first metal ion-containing solution was 2 mM Na 2 PdCl 4 / 0.1% HCl solution
  • another second metal ion-containing solution was 1 mM Na 2 PtCl 4 / 0.1% HCl.
  • the sample was washed several times with deionized water, excess metal ions were removed, and the thin film was dried again with nitrogen. Thereafter, an oxygen plasma treatment was performed on the entire area to remove the block polymer template. Thereafter, for the second block copolymer lithography process, a 33.5 kg / mol PS-b-P4VP block copolymer thin film was spin-coated to a thickness of 30 nm on the substrate on which the metal nanopattern was formed. Subsequent solvent annealing was performed to form a cylindrical array included in the planar layer, or to form an array of cylindrical structures projecting from the planar layer.
  • the manufactured assembly pattern may be in the form of a dot-point, a line-line, a dot-line, as shown in FIG. 1, and various types of metals are formed in a desired shape on a large-area substrate by repeating the above steps. You can.
  • FIG. 26 is a photograph after the Pt line (34 nm period, 10 nm width) is formed according to the first block copolymer lithography prepared according to the present invention, and FIG. 27 is protruded in plane at the 34 nm period and 10 nm diameter. Photograph showing that the P4VP cylinder structure was correctly formed between Pt lines. FIG. 28 is a photograph showing that 10 nm diameter Pd nanopoints are formed at the position of the P4VP cylinder nanodomain of FIG. 27.
  • FIG. 29 shows an array of nanoparticles formed in the form of an intersection of a Pt line and a Pd line
  • FIG. 30 is a dot-dot form
  • FIGS. 31 and 32 are EDS mapping images of the Pt line and the Pd dot array.
  • 33 to 37 show various heterogeneous metal arrays fabricated on a substrate in an electrostatic manner according to the present invention, wherein Pt line-Co point, Pt line-Au point, Pd line-Fe 2 O 3 point, Pt point, respectively -Images of Fe 2 O 3 point and Pd line-Pd line.
  • the present invention can form metal arrays of various shapes and components on a substrate through electrostatic coupling between block copolymer lithography and polymer-metal ions.
  • Another embodiment of the present invention is not a multi-step process to configure the first metal array and the second metal array in different positions, but rather a block copolymer mold according to the present invention in a solution containing two or more metal ions. Is immersed to form a composite metal array.
  • a block copolymer prepared according to the present invention is immersed in a mixed solution of Fe (CN) 6-3 and PtCl4-2, and the two kinds of metal ions are protonated polymers in the block copolymer.
  • a FePt alloy pattern is formed on the substrate.
  • the alloy pattern corresponds to the electrostatically coupled polymer pattern, when the polymer pattern is in the form of dots, the alloy pattern may be in the form of dots. Alternatively, when the polymer pattern is in the form of a line, the alloy pattern may be in the form of a line.
  • a FePt alloy nanoarray is formed through heat treatment.
  • a vertical cylinder PS-b-P4VP thin film formed on a substrate is immersed in an aqueous hydrochloric acid solution in which ferricyanide and chloroplatinate anions are dissolved.
  • metal complex anions are located by electrostatic attraction. If this is removed and only the polymer is removed by oxygen plasma, the metal sample remaining in the cylinder block remains in the form of nanoparticles.
  • the specimen is flowed a little hydrogen and heat treated at an appropriate high temperature, the specimen is aggregated to form an array of single crystal nanopoints.
  • the polymer pattern is in the form of a line, an array of alloys in the form of a line may be formed on a substrate by the same method as described above.
  • 39 to 41 are SEM images and size distribution graphs, FePt alloy nanodot arrays and size distribution graphs, TEM images and high temperature heat treatment graphs of self-assembled cylinder block copolymers, respectively.
  • a metal nanostructure array of about 8 nanometers can be obtained from a cylinder block of about 11 to 12 nanometers, and the nano-structure having a narrow size distribution of about 4.5 nanometers is subjected to heat treatment. You will get an array of points.
  • a specific block copolymer (P4VP in one embodiment of the present invention) that is protonated in an acidic solution is immersed in an acidic solution, and the specific block is formed by electrostatic action with a metal anion. Precipitates by bonding a metal to it.
  • various metal layers may be formed according to the form of the substrate. For example, when the copolymer substrate is in the form of a brush, a metal may be bonded to the surface of the brush and a rod-shaped metal layer may grow. In contrast, in the case of a thin film form, since the metal is electrostatically coupled to the entire thin film, the metal array may be aggregated and converted into a film form.
  • a P4VP polymer substrate deposited on a substrate is immersed in an acidic solution containing metal anion (M-). Contact in such a way. This causes the cation-charged polymer substrate and the metal anion to electrostatically interact and bind, thereby depositing the metal anion on the polymer substrate to form a metal thin film. Thereafter, the polymer substrate is removed to prepare a metal thin film deposited in a form corresponding to the polymer substrate.
  • the polymer may be in the form of a thin film, or a polymer in which an anion is charged electrostatically may include a brush.
  • Nanoparticle array according to the present invention has the industrial applicability to produce a catalyst, using nanoparticle growth.

Abstract

La présente invention concerne un procédé de fabrication d'un réseau de nanoparticules monodispersées, dont la taille est ajustable, un réseau de nanoparticules ainsi fabriqué et ses utilisations. Selon la présente invention, le procédé de fabrication d'un réseau de nanoparticules dont la taille est ajustable, se caractérise en ce qu'il comprend les étapes suivantes : auto-assemblage de copolymères séquencés ; liaison sélective, par interaction électrostatique, d'un premier polymère des copolymères séquencés auto-assemblés à des ions métalliques des nanoparticules à déposer ; et retrait des copolymères. Selon la présente invention, les réseaux de nanoparticules monodispersées peuvent être déposés par un procédé lithographique à copolymères séquencés. En outre, la taille des nanoparticules pouvant être simplement régulée au moyen de l'ajustement du temps de charge des ions métalliques, la présente invention peut être efficacement utilisée pour divers éléments appliqués comme des catalyseurs.
PCT/KR2012/001216 2011-04-19 2012-02-17 Procédé de fabrication d'un réseau de nanoparticules dont la taille est ajustable, réseau de nanoparticules ainsi fabriqué et ses utilisations WO2012144728A2 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2011-0036039 2011-04-19
KR20110036039 2011-04-19
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