KR20200034641A - Sensor including nanostructures and method for manufacturing the same - Google Patents

Abstract

The present invention relates to a sensor including a nanostructure and a manufacturing method thereof. The sensor includes the arrangement of at least one nanostructure containing a sensing material. The manufacturing method of the sensor comprises the steps of: (a) depositing a sensing material on a substrate on which a first prepattern is formed; (b) forming a first nano pattern; and (c) removing the first prepattern.

Description

A sensor comprising a nanostructure and a manufacturing method therefor {SENSOR INCLUDING NANOSTRUCTURES AND METHOD FOR MANUFACTURING THE SAME}

The present application relates to a sensor comprising a nanostructure and a method for manufacturing the sensor comprising the nanostructure.

Multimetallic nanomaterials, including bimetallic precious metals, have attracted attention due to their excellent properties such as excellent plasmon effect, improved stability, and synergistic catalysis. In particular, the nanomaterials can be used as a variety of heterogeneous catalysts such as hydrogen generation, carbon dioxide conversion, oxygen reduction, and methanol oxidation because they can exhibit high reactivity and high sensitivity to surrounding materials due to their large surface area when used as a catalyst. In addition, the shape, combination, and composition of the nanostructures of the nanomaterial significantly affects catalyst performance. For example, the porous Cu / Ti film exhibited very improved catalytic performance in hydrogen generation at a constant Ti composition due to its large surface area and optimal binding energy to protons. There are also several approaches, such as solvothermal synthesis, electrochemical methods (galvanic reaction), and multiple depositions, to increase controllability of nanomaterials. However, the above methods still have problems that are difficult to control because they require different experimental conditions in the solvent heat synthesis method for each metal, and it is difficult to independently control the shape and composition. Therefore, as a method for an improved catalyst, it is important to develop a process for manufacturing a polymetallic nanomaterial that is easy to control.

In the case of a hydrogen gas sensor, fast response time is essential because hydrogen must be detected before the concentration increases by more than 4%. The United States Department of Energy (DOE) defined management performance for hydrogen gas sensors, and among the above factors, targeted to respond and recover 1% hydrogen within 60 seconds of response time and recovery time. To meet the target performance, there have been several approaches using palladium (Pd) or platinum (Pt), which are mainly used for hydrogen sensing. Among them, Pd nanowires and Pt nanowires have been reported as channel materials for improving response time, but do not meet the standards of DOE. In addition, the Pd @ Pt core-shell nanowires exhibited a very fast response and recovery rate compared to previous studies, but the slow response to 1% hydrogen at room temperature remains a problem.

Republic of Korea Patent Publication No. 2018-0071991

The present application is intended to provide a sensor comprising an arrangement of one or more nanostructures containing a sensing material.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application relates to a sensor, comprising an arrangement of one or more nanostructures containing a sensing material.

In the second aspect of the present application, (a) a sensing material is deposited on a substrate on which a first pre-pattern is formed, and (b) the first nano-pattern is obtained by re-depositing the sensing material on the side of the first pre-pattern through an ion etching process. And removing the first pre-pattern through the ion etching process (c).

In the third aspect of the present application, (a) one side of the pre-pattern formed on the substrate is asymmetrically etched at an angle of 30 ° to 50 ° for 1 minute to 30 minutes to adjust the inclination angle of the pre-pattern, and (b) the pre-pattern The unformed portion is removed to expose the substrate, (c) a sensing material is deposited on the prepattern with the inclination angle adjusted, and (d) the prepattern is removed to incline 30 ° to 90 ° with respect to the substrate. It relates to a method of manufacturing a sensor, comprising obtaining a nanopattern.

In the fourth aspect of the present application, (a) one side of the pre-pattern formed on the substrate is asymmetrically etched at an angle of 50 ° to 80 ° for 1 minute to 30 minutes to adjust the inclination angle of the pre-pattern, and (b) the pre-pattern The unformed portion is removed to expose the substrate, (c) a sensing material is deposited on the pre-pattern with the inclination angle adjusted, and (d) the pre-pattern is removed, so that the upper part of the substrate is 30 ° to 90 ° It relates to a method of manufacturing a sensor, comprising obtaining a folded nano-pattern.

The nanostructure according to the embodiments of the present application is manufactured by a simple process and low cost by applying an ion impact phenomenon through physical ion etching, and has various line widths and shapes, and at the same time, ultra-fine nano particles having a line width of up to 10 nm. Since it is a structure, it can be usefully used for sensors that require excellent sensitivity.

The sensor including the nanostructure according to the embodiments of the present application may use a single component, a binary component, and / or a ternary substance as a sensing material, and may vary the aspect ratio, resolution, and grain size of the nanostructure. By controlling it, there is an advantage that it can be usefully applied to sensors requiring high sensitivity and fast response / recovery speed.

A method of manufacturing a sensor including a nanostructure according to embodiments of the present application, in the deposition of a sensing material, controls the order of deposition, the deposition thickness or the number of depositions, the angle of the ion etching process after deposition, or the ion etching process Since it is possible to change the composition, content ratio, or form of the redeposited sensing material by a simple process change through time control of, it is possible to easily manufacture a nanostructure for a sensor exhibiting high sensitivity and fast response / recovery speed.

1 shows, in one embodiment of the present application, a schematic diagram of a manufacturing process of a line-type nanostructure including a binary metal: (a) a manufacturing process using a secondary sputtering phenomenon, (b) a manufactured high resolution (15 nm to 20 nm) and high aspect ratio (15 to 20) enlarged nanostructures, (c) TEM-EDS mapping of each binary metal material, (d) composition ratio of Pt or Au in metal deposition.
2 is a schematic diagram showing a process for manufacturing a lattice-type nanostructure in one embodiment of the present application.
3 is, in one embodiment of the present application, a schematic view showing a manufacturing method of a nanostructure having an angle with respect to a substrate or a nanostructure having an upper part having an angle.
4 is a schematic diagram showing a process for manufacturing a lamella-shaped nanostructure in one embodiment of the present application.
5 is, in one embodiment of the present application, an enlarged view of a nanoporous cylinder-shaped nanostructure.
FIG. 6 shows, in one embodiment of the present application, (a) layered nanostructures, (b) mixed nanostructures and (c) core-shell structured EDS mapping, line profiles, and TEM It is a picture and graph representing an image.
7 is, in one embodiment of the present application, a schematic diagram (a) of Pd _0.66 Pt _0.33 nanostructures according to precursor deposition of various times, and their real-time response behavior (b), response amplitude (ΔR / R _a ) ( %) And recovery time (c).
8 is, in one embodiment of the present application, a graph showing EDS mapping of multi-element line nanopatterns: (a) various combinations of binary metal nanostructures, (b) EDS mapping, and (c) six-membered metal Spectra of line-type nanostructures.
9 is, in one embodiment of the present application, Pd film, Pd nanostructure, and Pd _{0 . 5} Pt _{0 .5} H ₂ is a graph showing the detection performance of a sensor including a nanostructure.
10 is, in one embodiment of the present application, is a graph showing the H ₂ detection performance of a sensor comprising a nanostructure containing Pd / Pt binary metal: (a) various composition ratios (Pd, Pd _0.66 Pt _0.33 , peak response amplitude of the H ₂ gas for the Pd _{0. 5} Pt _{0 .5,} and Pt) in response behavior of the Pd / Pt 2 won metal nanostructure having, (b) a wide range of concentrations (10 ppm to 10,000 ppm) [( ΔR / R _a ) _max (%)]. (c) Response / recovery time for 1% H ₂ of each sensor (τ _90% , time to reach 90% of the minimum / maximum resistance level). (d) Pd _{0 . 5} Pt _{0 .5} H ₂ and repeatable response behavior of pure Pd nanostructure.
Figure 11, in one embodiment of the present application, comprises a (a) Pd / Pt and (b) Pd / Au nanostructures having various binary metal composition ratios at a wide range of concentrations of H ₂ (10 ppm to 10,000 ppm). It is a graph showing the real-time detection performance of the sensor.
Figure 12, Pd / Au is a graph showing the H ₂ sensor for detecting the performance of the 2 source comprises the nanostructure containing the _metal:.. (A) various composition ratios _{(Pd, Pd 0 83 Au 0} .16, Pd 0 66 Pt _{0 .33,} and _{Pd 0.5 Pt 0.5) Pd / Au} 2 gas response behavior of the original metal nanostructure having, (b) the maximum response amplitude of the H ₂ gas over a wide range of concentrations (10 ppm to about 10,000 ppm) (ΔR / R _a ) _max (%), (c) Response / recovery time for 1% H ₂ of each sensor, (d) Pd _{0 . 5} Au _{0 .5} and the pure Pd repetitive H ₂ response behavior of the nano-pattern sensor.
13 is, in one embodiment of the present application, is a view showing the synergistic effect in the sensing performance of a nanostructure containing a Pd / Pt and Pd / Au binary metal: (a) various binary metal composition ratio ( pure _{Pd, Pd 0. 66 X 0} .33, and _{Pd 0. 5 X 0. 5} ) to the Pd / Pt and sensitivity, and (b) the response time of the Pd / Au nanostructures having, (c), (d) Schematic diagram of a mechanism for improving the sensitivity and response time of H ₂ detection of the Pd / Pt and Pd / Au nanostructures.
Figure 14, in one embodiment of the present application, shows the H ₂ adsorption / dissociation energy density function theory (DEF) simulation on the surface of a nanostructure containing Pd / Pt and Pd / Au binary metals. It is a drawing.
15 is, in one embodiment of the present application, Pt / Pd / Au according to precursor deposition of various times It is a graph showing the real-time response behavior, response amplitude (ΔR / R _a ,%) (a) and recovery time (b) of the nanostructure.

Throughout this specification, when a part is “connected” to another part, this includes not only “directly connected” but also “electrically connected” with another element in between. do.

Throughout this specification, when a member is said to be “on” another member, this includes not only the case where one member abuts another member, but also the case where another member exists between the two members.

Throughout this specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless specifically stated to the contrary. The terms “about”, “substantially”, etc., used to the extent of the present specification are used in or at a value close to the value when manufacturing and substance tolerances unique to the stated meaning are given, and the To aid, accurate or absolute figures are used to prevent unconscionable abusers from unduly using the disclosed disclosure.

The term “~ (steps)” or “steps of” of the degree used throughout this specification does not mean “steps for ~”.

Throughout the present specification, the term “combination (s)” included in the expression of the marki form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the marki form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, the description of “A and / or B” means “A or B, or A and B”.

At the amplitude (ΔR / R _a ) of the gas response, R _a and ΔR represent the baseline resistance (in air) of each sensor and the magnitude of resistance change after exposure to the sensing object.

Hereinafter, embodiments and examples of the present application will be described in detail. However, the present application may not be limited to these embodiments and examples.

A first aspect of the present application provides a sensor, comprising an arrangement of one or more nanostructures containing a sensing material.

In one embodiment of the present application, the nanostructure is manufactured using an ion bombardment phenomenon in which particles of a target material physically impacted are separated and bounced off, and the particles of the sensing material are attached to the outer circumferential surface. After having a patterned pre-pattern to be made, particles of the sensing material detached from the sensing material layer due to the ion bombardment phenomenon are attached to the outer peripheral surface of the pre-pattern to remove only the pre-pattern from the sensing material-pre-pattern composite structure A large-scale nanostructure having high aspect ratio and uniformity is manufactured.

In one embodiment of the present application, the shape of the nanostructure is in the group consisting of a line pattern, a lattice shape, a curved shape, a cylindrical shape, a square pillar shape, an inverted cone shape, a rectangular parallelepiped shape, a top shape, a cup shape and a U shape It may be selected, but is not limited thereto.

In one embodiment of the present application, the nanostructure may be inclined to about 30 ° to about 90 ° with respect to the substrate, or may be arranged such that the upper part of the substrate is folded to about 30 ° to about 90 ° with respect to the substrate. The substrate may be used as a flat plate as long as it is a material that does not physically deform by temperature and pressure of the lithography process, and may be specifically selected from the group consisting of silicon, silicon oxide, quartz, glass, and mixtures thereof. It is not limited.

In one embodiment of the present application, the shape of the nanostructure may be a lamellar shape or a nanoporous cylinder shape, but is not limited thereto.

In one embodiment of the present application, the grain size of the sensing material may be about 100 nm or less, but is not limited thereto. Specifically, the grain size of the sensing material may be about 100 nm or less, about 80 nm or less, about 60 nm or less, about 40 nm or less, about 20 nm or less, about 10 nm or less, or about 5 nm or less, but is not limited thereto. It does not work. If the grain size of the sensing material is 100 nm or less, it can effectively operate as a sensing material. In particular, in the case of sensing, if the grain size is adjusted to 5 nm or less, the ratio of the sensing target material can be adsorbed. Since the surface area is increased, the detection performance is significantly improved. In addition, when a binary component or a ternary component is used as a sensing material, when the grain size is 5 nm or less, the specific surface area of the interface between components increases significantly, which leads to an increase in the adsorption site of the sensing target material. Therefore, it has the effect of improving the detection ability.

In one embodiment of the present application, the sensing material refers to a material constituting a nanostructure which is a final product, and refers to a material that may be released in various directions by applying an ion bombardment phenomenon through physical ion etching. .

In one embodiment of the present application, the sensing material may include one selected from the group consisting of metal, metal oxide, metal sulfide, and polymer, but is not limited thereto. Specifically, the sensing material is selected from the group consisting of Au, Ag, Cu, Al, Ni, Pt, Pd, Sn, Mo, Ti, Cr, Mn, Fe, Co, Zn, In, W, Ir and Si It may be one or more metals, but is not limited thereto. More specifically, the sensing material is Au-Cu, Au-Pt, Au-Ni, Au-Ag, Au-Pd, Pd-Ag, Ni-Sn, Mo-Ni, Au-Al, Au-Sn, Au- Mo, Au-Ti, Au-Cr, Au-Mn, Au-Fe, Au-Co, Au-Zn, Au-In, Au-W, Au-Ir, Au-Si, Ag-Cu, Ag-Al, Ag-Ni, Ag-Pt, Ag-Pd, Ag-Sn, Ag-Mo, Ag-Ti, Ag-Cr, Ag-Mn, Ag-Fe, Ag-Zn, Ag-In, Ag-W, Ag- Bi-component (bimetallic) materials selected from the group consisting of Ir and Ag-Si or Au-Ag-Cu, Au-Cu-Pt, Au-Ag-Pt, Au-Ag-Pd, Au-Cu-Pd, Au -Pd-Pt, Ag-Cu-Pt and Ag-Cu-Pd, but may include a Samsung ternary (ternary metal) material selected from the group consisting of, but is not limited thereto.

In one embodiment of the present application, the sensing material is _a binary component of Pd _(1-a) / Au _a , Pd _(1-a) / Pt _a or Pd _(1-bc) / Au _b / Ni _c , Pt _(1-bc) / Pd _b / Au _c containing a ternary substance, 0≤a≤0.5, 0≤b + c <1, 0≤b≤0.5, 0≤c≤0.5.

In one embodiment of the present application, the sensing material is a _binary component of SnO _{2 (1-d)} / WO _3d , SnO _{2 (1-d)} / CuO _d or SnO _{2 (1-ef)} / WO _3e / Au _f , SnO _{2 (1-ef)} / WO _3e / Pt _f , including those of the ternary substance, 0≤d≤0.5, 0≤e + f <1, 0≤e≤0.5, 0≤f≤ 0.5.

Referring to FIG. 1, after depositing a multi-component sensing material on a substrate, a nanostructure including the multi-components can be obtained by re-depositing the sensing material on the outer circumferential surface of the prepattern through an ion etching process. As an example, when Pt and Pd are used as a sensing material, the size of the response amplitude (ΔR / R _a ) is increased in the nanostructures containing Pt / Pd binary components compared to the nanostructures of Pt or Pd single components. , Response time and recovery time are significantly improved. In particular, the nanostructures containing Pt / Pd bi-component materials showed the best effect in the molar ratio Pt 0.66: Pd 0.33.

In one embodiment of the present application, the sensing material may be to sense a gas or liquid (sensing). Specifically, the sensing material may be to detect that it is selected from the group consisting of H ₂ , CO, CO ₂ , water vapor, O ₂ , N ₂ , aromatic compounds (non-limiting examples: benzene, toluene, etc.) and VOC. , But is not limited thereto. In addition, the sensing material may be to detect blood, biomolecules, bacteria, acetone or alcohols, but is not limited thereto.

In one embodiment of the present application, the size of the sensing material grain is about 100 nm or less, the grain interface gap is about 50 nm or less, the aspect ratio of the nanostructure is about 1 or more, and the line width is about 50 nm. It may be the following, but is not limited thereto. Specifically, the size of the sensing material grain may be about 100 nm or less, about 80 nm or less, about 60 nm or less, about 40 nm or less, about 20 nm or less, about 10 nm or less, or about 5 nm or less, and the grain interface The gap may be about 50 nm or less, about 40 nm or less, about 30 nm or less, about 20 nm or less, about 10 nm or less, about 5 nm or less, or about 2.5 nm or less, and the aspect ratio of the nanostructure is about 1 or more, about 5 or more, about 10 or more, about 15 or more, about 20 or more, about 25 or more, or about 30 or more, and the line width is about 50 nm or less, about 40 nm or less, about 30 nm or less, about 20 nm or less or about 10 nm or less, but is not limited thereto.

In one embodiment of the present application, when the nanostructure is hydrogen gas or hydrogen sulfide gas, ΔR / R _a is greater than or equal to about 1%, response time is less than about 100 seconds, and recovery time ) May be less than about 200 seconds, but is not limited thereto. Specifically, ΔR / R _a may be greater than or equal to about 1%, greater than or equal to about 2%, greater than or equal to about 3%, greater than or equal to about 4%, or greater than or equal to about 5% when detecting a hydrogen gas or hydrogen sulfide gas, and the response The time can be less than about 100 seconds, less than about 120 seconds, less than about 140 seconds or less than about 150 seconds, wherein the recovery time is less than about 200 seconds, less than about 210 seconds, less than about 220 seconds, less than about 230 seconds, or about 240 It may be less than a second, but is not limited thereto. Among the various H ₂ detection performances, fast response speed is an important factor in H ₂ detection because H ₂ gas must be quickly detected before the concentration of H ₂ gas becomes higher than 4%, but most of the conventional H ₂ sensors Strict H ₂ detection rate requirements cannot be achieved with a low limit of detection (LOD), but the sensor according to the present application has a ΔR / R _a of about 1% or more even when the concentration of H ₂ gas is 1% or less. , Response time is less than about 100 seconds, and recovery time can be detected as less than about 200 seconds.

In one embodiment of the present application, the one or more nanostructures may have a line width of about 5 nm to about 100 μm and a height of about 10 nm to about 1000 μm, but are not limited thereto. In addition, the nanostructure is a large area of the nano-channel having a height of about 10 nm to about 1000 μm and a width of about 5 nm to about 100 μm by ion-etching a layer of a sensing material having a small thickness ranging from about 5 nm to about 50 nm. As it can be manufactured uniformly, it is possible to increase the surface area and easily adjust the height through additional etching.

In the second aspect of the present application, (a) a sensing material is deposited on a substrate on which a first pre-pattern is formed, and (b) the first nano-pattern is obtained by re-depositing the sensing material on the side of the first pre-pattern through an ion etching process. And removing the first prepattern through (c) an ion etching process.

In one embodiment of the present application, after the step (c), (d) a second prepattern is formed on the substrate on which the first nanopattern is formed at a different angle from the first nanopattern, and then on the substrate Depositing a sensing material on, (e) re-depositing the sensing material on the side of the second pre-pattern through an ion etching process to form a second nano-pattern, and (f) removing the second pre-pattern through ion etching It may include.

In one embodiment of the present application, the second pre-pattern has an angle of about 70 ° to about 90 ° with the first pre-pattern, specifically about 80 ° to about 90 °, more specifically about 85 ° to It may have an angle of about 90 °.

Referring to FIG. 2, a first prepattern 1 is fabricated on a substrate coated with a sacrificial layer 2 by a lithography process. The photolithography process uses a general photolithography process as a process for forming a prepattern by placing a photomask on a substrate on which the prepattern material is formed and selectively removing the deposited prepattern material by applying UV. After the sensing material is deposited (3) on the substrate having the first pre-pattern formed as described above, the sensing material is re-deposited (4) on the side of the first pre-pattern through an ion etching process. After removing the pre-pattern, a line-type first nano pattern 5 having a high aspect ratio and high resolution is formed. For fabrication of a mesh-shaped nanostructure, the prepattern 6 can be formed on the line-shaped first nanopattern by rotating it in a 90 degree direction using a photolithography process. After the sensing material 7 is deposited on the substrate on which the second pre-pattern is formed, the sensing material is re-deposited (8) on the side of the second pre-pattern through an ion etching process. After removing the pre-pattern, a lattice-like nanostructure 9 having a high aspect ratio and high resolution is formed.

The third aspect of the present application, (a) to adjust the inclination angle of the pre-pattern by asymmetrically etching the side surface of the pre-pattern formed on the substrate at an angle of about 1 minute to about 30 minutes, about 30 ° to about 50 °, (b ) Remove the portion where the pre-pattern is not formed to expose the substrate, (c) deposit a sensing material on the pre-pattern with the tilt angle adjusted, and (d) remove the pre-pattern, about 30 ° to the substrate It provides a method for producing a sensor, comprising obtaining a nanostructure tilted to about 90 °.

In the fourth aspect of the present application, (a) one side of the prepattern transferred to the substrate is asymmetrically etched at an angle of about 50 minutes to about 80 degrees for about 1 minute to about 30 minutes to adjust the inclination angle of the prepattern, ( b) removing the portion where the pre-pattern has not been transferred to expose the substrate, (c) depositing a sensing material on the pre-pattern with the inclined angle adjusted, (d) removing the pre-pattern, and partially above the substrate It provides a method of manufacturing a sensor, comprising obtaining a nanostructure folded from about 30 ° to about 90 °.

Referring to FIG. 3, a method of manufacturing the sensors of the third side and the fourth side is described, and a polystyrene prepattern is transferred to the ITO substrate by using a polydimethylsiloxane (PDMS) mold having a line pattern. Thereafter, the prepattern is etched asymmetrically using ion milling, and then the polymer is vertically etched using a RIE process to reveal the ITO substrate at the bottom. At this time, the inclined line pattern (b in FIG. 3) and the bent line pattern (c in FIG. 3) can be obtained by setting the angle of the asymmetric etching to 40 degrees and 60 degrees. Afterwards, the substrate is tilted about 16 degrees so that the ITO at the bottom is splashed through the ion etching process so that it is attached only to one side of the pre-etched asymmetrically etched pattern. At this time, the angle of the ion etching process can be adjusted at each angle to adjust the angle of the last line-type nanopattern. Finally, the pre-pattern polystyrene is removed through the RIE process to obtain a slanted or curved line-type nanostructure.

In the first to fourth aspects, contents that may be common to each other may be applied even if the description is omitted.

In one embodiment of the present application, the ion etching process for generating an ion bombardment phenomenon, as a physical method, is performed by ion milling. When performing ion bombardment by applying high energy to light ions, the ion milling reduces the wide angular distribution in the polycrystalline direction, so that the angle of separation and bounce is small, making it difficult to attach the sensing material particles to the outer circumferential surface of the pre-pattern. Preferably, a plasma is formed using a medium gas such as argon gas under a process pressure of about 0.001 mTorr to about 700 Torr, and then the plasma is accelerated to about 100V to about 2,000V to perform a physical ion etching process. If, in the physical ion etching process, the ion etching is performed by accelerating with a plasma exceeding 2,000 V, the angle at which the sensing material is released from the sensing material layer and bounces out is bounced perpendicularly to the direction in which the ions are incident, and the pre-pattern When the amount of adhesion to the outer circumferential surface is small and the ion etching is performed by accelerating with a plasma of less than 100 V, the etching rate of the sensing material layer is slow, which may cause a problem of reduced work efficiency.

In one embodiment of the present application, deposition of the sensing material is generally performed by chemical vapor deposition (CVD), atomic layer deposition, sputtering, laser ablation, or electrical discharge. Method (arc-discharge), plasma deposition, thermochemical vapor deposition and electron beam vapor deposition may be performed by a method selected from the group consisting of, but is not limited thereto.

In one embodiment of the present application, the prepattern may be formed as a polymer, and any polymer that can be used in a lithography process may be used without limitation, specifically polystyrene, chitosan, polyvinylalcohol, polymethylmetha Acrylate (PMMA), polyvinyl pyrrolidone (polyvinyl pyrrolidone), photoresist (PR) and may be selected from the group consisting of mixtures thereof, but is not limited thereto. The pre-pattern may be formed by spin coating or spray coating, but is not limited thereto. At this time, since the shape of the formed prepattern determines the shape of the nanostructure, it is possible to easily manufacture nanostructures of various shapes and sizes by adjusting the shape of the prepattern through various lithography processes. As the lithography process, a conventional lithography process may be used, and specifically, it may be performed by at least one method selected from the group consisting of nanoimprint, soft lithography, block copolymer lithography, optical lithography, and capillary lithography. In particular, the prepattern patterned using a lithography process may be further adjusted to various shapes and sizes according to reactive ion etching (RIE) conditions and the polymer layer around the prepattern. For example, the reactive ion etching under a high vacuum of 0.1 mTorr to 0.001 mTorr is anisotropic, that is, only etching of the lower part is possible, but the reactive ion etching under a low vacuum of 0.01 Torr to 0.1 Torr is isotropic, i.e., etching is performed in all directions, so it is free. When the pattern is additionally ion-etched under low vacuum, the overall height and diameter of the prepattern is reduced. Accordingly, all the polymer layers around the prepattern are removed and only the prepattern remains. In addition, the size of the patterned polymer structure can be controlled by the thickness of the polymer layer coated on the substrate. If the thickness of the polymer layer is thin, the polymer layer disappears during the short reactive ion etching time and only the prepattern remains, forming a cup-shaped polymer structure pattern in a short time, but in the case of the thick polymer layer, the reactive ion etching is performed for a long time. By performing, the pre-pattern is etched as a whole, and the overall size of the pre-pattern is also reduced, so that a pattern with a small diameter of the pre-pattern is produced.

Specifically, the removal of the prepattern is to obtain a nanostructure by removing only the polymer prepattern by dry or wet etching. The dry or wet etching may be performed by a conventional etching method capable of removing polymers.

In one embodiment of the present application, the line width and height of the prepattern may be from about 1 nm to about 100 μm and from about 10 nm to about 1000 μm, respectively, specifically, the line width and height are from about 1 nm to about 10 μm, respectively. About 10 nm to about 100 μm, more specifically, the line width and height may be about 1 nm to about 100 nm and about 200 nm to about 800 nm, respectively.

In one embodiment of the present application, the first prepattern may be formed by forming a block copolymer pattern on a substrate and then removing some polymers of the block copolymer through an ion etching process.

In one embodiment of the present application, the block copolymer is PS-b-PMMA, the PS-b-PMMA block copolymer is from about 270 kg / mol to about 280 kg / mol, and the first prepattern is lamellar Shape, the PS-b-PMMA block copolymer is about 65 kg / mol to about 140 kg / mol, and the first prepattern may be a nanoporous cylinder shape, but is not limited thereto.

4 and 5, when a block copolymer is used as a component of the prepattern, a lamellar shape and a nanoporous cylinder shape that cannot be prepared from a prepattern formed of a single polymer can be prepared. Specifically, PS-b-PMMA is used as a block copolymer, but the amount thereof is adjusted to 270 kg / mol to 280 kg / mol to prepare a prepattern in a lamella shape, and 65 kg / mol to 140 kg / The pre-pattern can be manufactured in a nanoporous cylinder shape by controlling with mol. Through this, the nanostructure may also be manufactured in a lamella shape or a nanoporous cylinder shape.

In one embodiment of the present application, the sensing material may be selected from the group consisting of metal, metal oxide, metal sulfide and polymer, but is not limited thereto. Specifically, the sensing material is selected from the group consisting of Au, Ag, Cu, Al, Ni, Pt, Pd, Sn, Mo, Ti, Cr, Mn, Fe, Co, Zn, In, W, Ir and Si It may be one or more metals, but is not limited thereto. Specifically, in the case of a multi-component nanostructure, catalytic properties may be exhibited differently than in the case of a conventional single component, and the manufacturing method of the present application maintains the uniformity, resolution, and aspect ratio at the same level as the conventional structure, and the internal structure is layered. It can be controlled by mixed structure, core-shell structure, etc. In addition, the catalytic properties coming from the multi-component system are significantly improved compared to the existing single-component nanostructures.

In one embodiment of the present application, the sensing material is at least one selected from the group consisting of Pd, Pt, Au, and Ni, and at least one selected from the group consisting of Pd, Pt, Au, and Ni. In turn, it may be to deposit on the substrate and redeposit each layer of the deposited sensing material through the ion etching process on the side surface of the first pre-pattern. Specifically, the redeposited sensing material is Pd _(1-a) / Au _a , Pd _(1-a) / Pt _a binary material or Pd _(1-bc) / Au _b / Ni _c , Pt _{( 1-bc)} / Pd _b / Au _c containing a ternary substance, 0≤a≤0.5, 0≤b + c <1, 0≤b≤0.5, 0≤c≤0.5, but It is not limited.

In one embodiment of the present application, the sensing material is at least one selected from the group consisting of Sn, W, Cu, and Au, and at least one selected from the group consisting of Sn, W, Cu, and Au. Subsequently, the first prepattern is formed by depositing on the substrate in turn and redepositing each layer of the deposited sensing material on the side surface of the first prepattern through an ion etching process, and through the ion etching process. It may be removed, and may include annealing the first nano-pattern. Specifically, the sensing material prepared through the annealing is a binary component of SnO _{2 (1-d)} / WO _3d , SnO _{2 (1-d)} / CuO _d or SnO _{2 (1-ef)} / WO _3e / Au _f , SnO _{2 (1-ef)} / WO _3e / Pt _f containing the ternary substance, 0≤d≤0.5, 0≤e + f <1, 0≤e≤0.5, 0≤f≤ 0.5, but is not limited thereto.

In one embodiment of the present application, in the deposition of the sensing material, the deposition order, the thickness of the deposition or the number of deposition is adjusted, or the time of the ion etching process or the time of the ion etching process after deposition is redeposited. It may be possible to change the composition, content ratio or form of the sensing material. Specifically, the sensing materials are Pd / Au / Ni and Pt / Pd / Au, and are deposited on the substrate in the order of Au-Ni-Pd, Pt-Pd-Au, but the deposition thickness is about 5 nm to about 20 nm. By adjusting, it may be to form a first nano-pattern including a layered structure ternary material. Alternatively, the sensing materials are Pd / Au / Ni and Pt / Pd / Au, and are deposited on the substrate in the order of Au-Ni-Pd, Pt-Pd-Au, by uniformly adjusting the deposition thickness to less than 5 nm, It may be to form a first nano-pattern comprising a mixed-shaped ternary material. Alternatively, the sensing materials are Pd / Au / Ni and Pt / Pd / Au, and are deposited on a substrate in the order of Au-Ni-Pd-Ni-Au, Pt-Pd-Au-Pt-Pd-Au, but the deposition thickness By adjusting the to 5 nm to 10 nm, it may be to form a first nano-pattern comprising a core-shell shaped ternary material.

Referring to FIG. 6, a of FIG. 6 is layered with a total thickness of 30 nm formed after secondary sputtering for deposition of Au (bottom, 10 nm), Ni (middle, 10 nm) and Pd (top, 10 nm) This indicates that the first nanopattern containing the ternary material of the structure was produced. The line profile indicates that the sequence layer from left to right is Pd-Ni-Au, which is identical to the top-middle-bottom sequence of the deposited layers. These results indicate that Ar ⁺ ion bombardment does not allow penetration to a thickness greater than 10 nm, leading to retention of layered structures after ion bombardment.

Referring to b of FIG. 6, since Ar ⁺ ion bombardment can allow intrusion into the metal layer, uniformly mixed internal structures can be obtained when depositing the metal deposition into a thinner layer with a thickness of less than 5 nm. You can confirm that there is.

Referring to c of FIG. 6, ternary metal core-shell internal structures having various metal deposition sequences may be manufactured, and specifically after deposition of five Au-Ni-Pd-Ni-Au metal layers on a substrate , The line pattern produced by redeposition showed core-shell structures with the same order of deposited metal layers. In the TEM image, Au portions of the outer shell represent darker portions than Pd and Ni inside the nanostructures.

Referring to FIG. 7, when a Pt / Pd binary component material is used as a sensing material, the Pt / Pd component ratio of the nanostructure manufactured according to the deposition thickness and the number of depositions of Pt and Pd on the substrate is different, thereby detecting performance It also changes. As an example, (i) when preparing a nanostructure after depositing with Pd 20 nm and Pt 10 nm on a substrate, (ii) when preparing a nanostructure after depositing twice with Pd 10 nm and Pt 5 nm on a substrate , (Ⅲ) When preparing nanostructures after depositing 4 times with Pd 5 nm and Pt 2.5 nm on a substrate, comparing the sensing capabilities, the magnitude of the response amplitude increases from (ⅰ) to (ⅲ) (ΔR / R _It was confirmed that _a ) increases and the response time decreases. It is confirmed that this is because the interface between Pd / Pt increases in the nanostructure being manufactured as the deposition thickness of the sensing material is thinned and deposited several times as shown in (i).

Referring to a of FIG. 8, a 13 nm thick line-type binary metal nanostructure having various binary metal combinations can be implemented, which is Ag / Pt, Ag / Pd, Au / Mo, Au / Pt, Au / Pd, Sn / Pd, and Cu / Pt combinations. EDS image analysis shows that all binary metal combinations are well mixed on the nanoscale with no significant difference in element distribution. In the Au-Pt binary metal nanostructure, the ratio of Au to Pt during redeposition is determined from the ratio of deposited Au-Pt binary metal. Since each metal exhibits a different etch rate for Ar ⁺ ion bombardment, the etch time for each composition-controlled Au-Pt bilayer can be calculated. The Au / Pt bilayer exhibited a higher etching rate (0.25 nm / sec) in Au than Pt (0.125 nm / sec). Au can be etched more than Pt during Ar ⁺ ion bombardment, leading to a lower Au / Pt ratio of the bimetallic nanostructures compared to the deposited bilayer.

Referring to b of FIG. 8, a nanostructure in which three or more metals are mixed can be achieved through simple deposition of additional metal layers on a substrate. A nanostructure comprising six components (Au, Cu, Pd, Ag, Pt, and Sn, respectively) of a nanoscale metal mixture obtained by simple deposition of six thin metal layers on a substrate and then redeposition It can be prepared, it can be seen through the b of Figure 8 that the six metal components are well mixed. In addition, it can be confirmed through the EDS spectrum of FIG. 8C that 6 elements are included in the line-type nanostructure: 26 at% Au, 12.9 at% Cu, 17.4 at% Pd, 13.1 at% Ag, 25.3 at% Pt, and 5.3 at% Sn.

Referring to a and b of FIG. 15, when a Pt / Pd / Au ternary material is used as a sensing material, Pt / Pd / of the nanostructure manufactured according to the deposition thickness and the number of depositions of Pt, Pd and Au on the substrate The Au component ratio is different, and thus the sensing ability is also changed. As an example, (i) depositing Pt 10 nm, Pd 10 nm and Au 10 nm on a substrate to prepare a nanostructure, (ii) depositing twice on a substrate with Pt 5 nm, Pd 5 nm and Au 5 nm In the case of manufacturing a nanostructure after (i) depositing Pt 5 nm, Pd 20 nm, and Au 5 nm on a substrate, and comparing the respective sensing capabilities when manufacturing the nanostructure, (ⅰ) to (ⅲ) As it goes to, the magnitude of the response amplitude (ΔR / R _a ) increases and the response time and recovery time decrease. Specifically, (ⅰ) ΔR / R _a ~ -1% and response time (Response time, τ90%,) 170 seconds, (ii) ΔR / R _a ~ -2% and response time 75 seconds, (ⅲ) ΔR / R _a to -3% and response time of 25 seconds were shown. As a result, it was confirmed that the reactivity increases and the reaction rate increases as the interface between the materials increases, even with the same composition, and it is confirmed that not only the binary component material but also the Samsung component material can be usefully used as a sensing material.

In one embodiment of the present application, the sensing material may be selected to be selected from the group consisting of H ₂ , CO, CO ₂ , water vapor, O ₂ , N ₂ , aromatic compounds, and VOC, but is not limited thereto. .

Hereinafter, the present application will be described in more detail by using examples, but the following examples are only illustrative to aid understanding of the present application, and the contents of the present application are not limited to the following examples.

[ Example ]

<Bicomponent system ( Binary metal ) Containing substances Sensing material  Manufacturing of Including Sensors>

Example  One

A prepattern of polystyrene (PS) components was formed on a SiO ₂ / Si wafer using capillary force lithography. Binary metals (Pd / Pt and Pd / Au) of sensing materials having different compositions were sequentially deposited on the prepattern. Next, etching was performed using Ar ion bombardment on the deposited metals to redeposit the metal on the sidewalls of the polystyrene prepattern. Finally, by removing the polystyrene prepattern through an ion etching process, 15 nm to 20 nm thick and ~ 230 nm high line-shaped nanostructures were obtained (a in FIG. 1 and b in FIG. 1).

The result of TEM-EDS mapping of the line-type nanostructures of Pd / Pt and Pd / Au showing the obtained binary metal nanopattern is as shown in FIG. 1C. In c of FIG. 1, orange represents Pd, green represents Pt, and yellow represents Au. It was confirmed that, over the entire area, a line-type nanostructure formed of binary metals in which each component was well mixed was obtained. In addition, each metal of the obtained line-type nanostructure exhibited a grain size of 5 nm or less, which formed large interfaces between binary metals. The content ratio of the constituent metal component of the nanostructure is as shown in d of FIG. 1.

Experimental Example  One

Hydrogen gas detection: response amplitude check ( ΔR / R _a )

To detect hydrogen gas at room temperature, the dynamic sensing response of the sensors comprising the line-type nanostructures containing the binary metal was tested under air. A constant bias was applied to the 2-probe resistance type sensor (Au / Ti electrode), and the electrical resistance change of the sensor was monitored in response to exposure to hydrogen gas, and a detection signal was recorded. The samples were loaded into the gas sensing chamber simultaneously, and the sensing signals of each nanostructure were measured using multi-channel sensing systems.

30 nm thick Pd film for 1% H ₂ gas, Pd nanostructures and Pd _{0 . 5} Pt _{0 . 5} The real-time gas response (%) of a nanostructure containing a binary metal material is shown in FIG. 9 a. As shown in FIG. 1, the line-type Pd nanostructures are due to the high surface-to-volume ratio of the line-type nanostructures, the high resolution of the Pd grain size (~ 5 nm), and the ultra-thin (~ 15 nm) Pd film ( ΔR / R ~ _a + 10 times or more than 0.2% larger) gas response of _{ΔR / R a ~ -2% (} Pd nanostructures) and _{ΔR / R a ~ -4% (} Pd 0. 5 Pt 0 .5 nanostructure ). That is, as a result of analyzing the amplitude (ΔR / R _a ) of the gas response, the Pd film sensed that the resistance increased by 0.2%, while the line-type Pd nanostructure sensed that the resistance decreased by 2%, Pd _{0 . 0 .5 5} Pt nanostructures in the hydrogen gas leak detection by the sense that the resistance is reduced 4%, it was confirmed that gas Sensing at least 10 times superior in the sensor including a nanostructure of the present application. In addition, the reduced resistance of the sensor of the present application, as hydrogen gas exposure, hydrogen atoms in the lattice in PdH _X not only disturb the electron flow, but also expand the volume of Pd, resulting in a very small interparticle gap in the Pd grain-Pd grain contact. The reason is that it became narrower and led to a decrease in resistance.

Binary metal  Synergy Check

Pd / Pt Binary metal  Nanostructures containing substances

In order to precisely investigate the synergistic effect of the Pd / Pt binary metal material on the hydrogen gas sensing ability of Pd, sensors (Pd, Pd) including nanostructures containing Pd / Pt binary metal material having various composition ratios _{0. 66 0 .33} Pt, Pd _{0. 5} Pt ₀ of _0.5, and Pt) were confirmed at the same time the gas response behavior (Fig. 10). A of Fig. 10 with respect to the hydrogen gas shows that exposure to 1% Pt is the amplitude of the response increased significantly as the mix with _{Pd (Pd, Pt, Pd 0} . 66 Pt 0 .33, Pd 0. 5 Pt 0 .5 , respectively For ΔR / Ra to 1.2%, 2.5%, 3%, 4%). In addition, both pure Pd and Pt showed lower hydrogen gas detection performance than Pd / Pt binary metal materials in terms of sensitivity and response / recovery time.

In addition, by measuring the maximum response amplitude [(ΔR / R _a ) max (%)] for hydrogen gas at a wide range of concentrations (10 ppm to 10,000 ppm), Pd / Pt binary metal nanostructures and pure Pd nanostructures and Pt The sensitivity and limit of detection (LOD) of the nanostructures were investigated (Fig. 10b). Pd _{0 . 66} Pt _{0 .33} only can detect the hydrogen gas of 10 ppm to 1% ΔR / R _a or more, which was not possible by the pure Pd and Pt nanostructures. In all hydrogen gas concentration ranges, the Pd / Pt binary metal nanostructure sensor exhibited higher response amplitudes than the pure Pd nanostructure sensor and the Pt nanostructure sensor. The real-time gas response data or resistance change is shown in Fig. 11A. To determine the improved adsorption / desorption rates of the bimetallic nanostructure, the response / recovery time of each sensor for 1% hydrogen gas (τ90%, time taken to reach 90% of the minimum / maximum resistance level) It was measured (c in Fig. 10). 5/188 seconds in the second 145/235 (pure _{Pd) (Pd 0. 66 Pt} 0. 33) in accordance with Pt was added to the can clearly see that the response / recovery time is significantly improved, which is weaker than that of pure Pd and Pt It is 30 times / 1.25 times faster. In addition, Pd _{0 . 5} Pt _{0 .5} and the pure iterative hydrogen gas detection response behavior of the Pd nanostructure were measured to confirm the stability of the base line and the amplitude response (Fig. 10 d). Pd _{0 . 5} Pt _{0 .5} nanostructure sensors exhibit a rapid recovery to a few seconds of fast response to all the hydrogen gas exposure and the original baseline, in contrast, pure Pd nanostructure is slow response time and low recovery to the original baseline It was shown. In addition, pure Pd nanostructures exhibited significant baseline drift, but Pd _{0 . 5} Pt _{0 .5} nanostructure showed a complete recovery to the original baseline, without any movement. The detailed sensing mechanism of the Pd / Pt binary metal nanopattern is described in the parts of FIG. 13.

Pd / Au Binary metal  Nanostructures containing substances

Using a variety of composition ratios _{(Pd, Pd 0. 83 Au} 0 .16, Pd 0. 66 Au 0 .33, and _{Pd 0. 5 Au 0. 5} ) was investigated. 2 won metal synergy of Pd / Au nanostructures (Figure 12). As shown in Figure 12 a, Pd / Au on the nanostructure was the response amplitude for a 1% hydrogen gas decreases with the increase in Au ratio _{(Pd, Pd 0. 83 Au} 0 .16, Pd 0. 66 Au 0 _{.33, Pd 0. 5 Au ΔR} / Ra ~ 1.7% for _{0, 0.5,} respectively 1.6%, 1.5%, 1%), which is opposite to the trend of the Pd / Pt effect. Since pure Au does not have the ability to form hydride surfaces with hydrogen gas, the sensitivity of the Pd / Au sensor decreases as the Au composition ratio increases, and eventually, pure Au nanostructures are exposed to repeated 1% hydrogen gas exposure. No resistance change was seen.

The sensitivity and LOD of the Pd / Au binary metal nanostructures were investigated by measuring the maximum response amplitude to hydrogen gas at a wide range of concentrations (10 ppm to 10,000 ppm) (FIG. 12B). All the sensors exhibited a similar response amplitude for the low concentration of the hydrogen gas (10 ppm) regardless of the Au content. However, above the 100 ppm range, the response amplitude was reduced by about 4 times by the addition of Au (Pd _0.5 Au _0.5 ). Real-time gas response data for various concentrations of hydrogen gas are shown in FIG. 11B. The response / recovery time of each sensor for 1% hydrogen gas was measured (c in FIG. 12). By adding only a small amount of Au (Pd _0.83 Au _0.16 ), the response time of the binary metal nanostructure was significantly improved from ~ 150 seconds to ~ 30 seconds. Pd / Au nanostructures _{(Pd 0. 5 Au 0.} 5) is a minimum of 2 seconds response time of less than, by a content of Au was observed, this is more than 75 times as fast as pure Pd. As far as the inventors know, ultrafast response times of less than 2 seconds at 1% H2 of a Pd based hydrogen gas sensor at 10 ppm LOD are reported first. In terms of recovery time, Pd / Au binary metal nanostructures did not show an improved recovery rate over pure Pd until Au was added at a high composition ratio. However, the fastest Pd / Au channel having a response time by the best composition ratio of _{(Pd 0. 5 Au 0.} 5), the recovery time was reduced to 30 seconds abruptly at to 200 sec. FIG. 12 d shows the above Pd ₀ for repeated 1% hydrogen gas exposure _{. 0} Au ₅ shows a response behavior of the sensor _0.5 and the pure water to Pd includes a nanostructure. Pd _0.5 Au _0.5 exhibited an ultra-fast response to all repetitive hydrogen gas exposures and completely restored to the original baseline, without any migration and unstable reaction, which contained pure Pd nanostructures as shown in Figure 10d. It cannot be achieved with sensors.

To accurately compare the binary metal synergistic effects of Au and Pt for the Pd sensor, the maximum response amplitudes of the sensors for 1% hydrogen gas exposure [(ΔR / R _a ) max (%)] and response time were varied. It was plotted in the same graph according to the binary metal composition ratio (a in Fig. 13 and b in Fig. 13). For the response amplitude, the sensitivity improved sharply by 4 times as the Pt ratio increased from 0 to 0.5. In contrast, the sensitivity of the Pd / Au sensor decreased as the Au composition ratio increased from 0.33 to 0.5. For the response time, both the Pd / Pt and Pd / Au binary metal nanostructures exhibited significantly improved rates of 35 and 75, respectively. Schematic diagrams of the structure between Pd / Pt and Pd / Au binary metal grains can demonstrate an improved hydrogen gas sensing mechanism (c in FIG. 13 and d in FIG. 13). In the case of the Pd / Pt binary metal nanostructure, most of the adsorbed hydrogen atoms are located in the vicinity of the interface region between the Pd core and the Pt shell of the Pd / Pt nanoparticles, which means that the interface boundary is the Pd / Pt nano It shows that it plays an important role in the formation of the hydride phase of the particles. Therefore, since more Pd / Pt grain interfaces are formed in the nanostructure, the hydrogen gas adsorption capacity of the Pd / Pt nanostructure increases rapidly as the Pt composition ratio increases from 0 to 0.5 (Fig. 13c) Top). The large amount of hydrogen gas adsorption sites in the Pd / Pt binary metal nanostructures means that the gas response of the sensors is amplified as observed in this example. In this regard, the nanostructures of the present application based on the secondary sputtering phenomenon have a large amount of Pd / in the channel of the nanostructures because the secondary sputtered Pd and Pt are uniformly formed with very small (<5 nm) grain size. Pt grain interfaces are easily formed.

Example  2

In order to confirm that the amount of the Pd / Pt interface for the adsorption site of hydrogen gas can effectively control the composition ratio of the metal to be redeposited, a nanostructure was prepared in the same manner as in Example 1, but a binary metal material A nanostructure was prepared by controlling the number of depositions of (FIG. 7). Figure 7 a is used to deposit a different number represents a schematic diagram of a lamination structure of Pd / Pt precursor having the composition ratio of the same two-won metal material _{(Pd 0. 55 Pt 0.} 33). While maintaining the total precursor thickness of Pd 20 nm / Pt 10 nm, the number of depositions was controlled (i) 1 time, (ii) 2 times, and (iii) 4 times. As shown in the schematic diagram, as the number of depositions increased, the interface of the Pd / Pt grain after the patterning process of ion bombardment increased. Therefore, it was confirmed that the amount of Pd / Pt interfaces is increased by the deposition of the metal material multiple times. Looking at the sensing performance of (i), (ii), and (iii) above, it was confirmed that the response amplitude improved from (i) to (iii) due to the increased hydrogen gas adsorption capacity from the Pd / Pt interfaces. (Fig. 7b and Fig. 7c). However, due to the strong capture of hydrogen gas molecules due to the excessively increased Pd / Pt interfaces, the desorption process was delayed to increase recovery time. This means that very large amounts of Pd / Pt interfaces may not be good for sensor applications due to the slow desorption process, but good for hydrogen gas storage applications. Therefore, it is important to control the composition ratio of Pd / Pt binary metal.

In the case of the Pd / Au binary metal structure, the hydrogen adsorption capacity decreases as the Au composition increases in Pd / Au because Au does not have the ability to form a hydride surface. Therefore, as the Au composition increased from 0.33 to 0.5, the sensitivity of the Pd / Au nanostructure decreased, and there was no response in the case of the pure Au line (bottom of c in FIG. 13). On the other hand, in terms of response time, both the Pd / Pt and Pd / Au significantly improved response speed as the binary metal composition ratio increased from 0 to 0.5 due to the ultra-fast dissociation process of hydrogen at the Pd / Pt and Pd / Au interfaces. It was shown (d in Fig. 13). This is due to the formation of heteroatom bonds between Pd / Au and Pd / Pt, where the fast dissociation process of adsorbed hydrogen creates additional degrees of freedom, and the adsorbed hydrogen dissociates rapidly within a few seconds of response time to form Pd-H hydride. can do.

The enhanced adsorption / dissociation energy of hydrogen gas on the surface of Pd / Pt and Pd / Au binary metal nanostructures was theoretically calculated using density functional theory (DFT) simulations (FIG. 14). 14C and 14D, respectively, show cluster models of H ₂ molecules and adsorption / desorption energy on the surfaces of the Pd / Au and Pd / Pt binary metal structures. The calculated adsorption / desorption energy of H ₂ decreases from the Pd surface (-12.73 / -42.50 eV) to Pd / Pt (-52.93 / -141.52 eV) and Pd / Au (-36.10 / -82.70 eV), which is approximately It is a 4x lower energy barrier. Thus, excellent catalytic properties of the Pd / Pt and Pd / Au binary metal interfaces for fast and sensitive H ₂ detection are clearly demonstrated through theoretical DFT simulations. Summarizing the above simulations, a remarkably improved H ₂ LOD (~ 1 ppm) and detection rate (fastest H ₂ detection rate of the previously reported Pd sensor) was achieved by the excellent synergistic effect of Pt and Au metals on Pd. can do. The above effects are related to the new morphological characteristics of the bimetallic nanopattern produced by low energy plasma impact, and the nanostructure technology using multimetal has high-performance optoelectronic applications due to the possibility of circuit integration, device configuration, and large area manufacturing process. It was confirmed that it is very suitable for the fields.

The above description of the present application is for illustrative purposes, and those skilled in the art to which the present application pertains will understand that it is possible to easily modify to other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined form.

The scope of the present application is indicated by the claims, which will be described later, rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts should be interpreted to be included in the scope of the present application.

Claims (32)

Arrangement of one or more nanostructures containing sensing material
Including, sensor.
According to claim 1,
The shape of the nanostructure is selected from the group consisting of a line pattern, a lattice shape, a curved shape, a cylindrical shape, a square pillar shape, an inverted cone shape, a cuboid shape, a top shape, a cup shape, and a U shape.
According to claim 1,
The nanostructure, the sensor is inclined to 30 ° to 90 ° with respect to the substrate, or is arranged so that the upper part of the substrate folded to 30 ° to 90 °.
According to claim 1,
The shape of the nanostructure is a lamella (lamella) shape or a nanoporous cylinder shape.
According to claim 1,
The sensor, the grain size (grain size) of the sensing material is less than 100 nm.
According to claim 1,
The sensing material is one that is selected from the group consisting of metal, metal oxide, metal sulfide and polymer, the sensor.
The method of claim 5,
The sensing material is at least one selected from the group consisting of Au, Ag, Cu, Al, Ni, Pt, Pd, Sn, Mo, Ti, Cr, Mn, Fe, Co, Zn, In, W, Ir and Si A sensor comprising metal.
The method of claim 5,
The sensing material is Au-Cu, Au-Pt, Au-Ni, Au-Ag, Au-Pd, Pd-Ag, Ni-Sn, Mo-Ni, Au-Al, Au-Sn, Au-Mo, Au- Ti, Au-Cr, Au-Mn, Au-Fe, Au-Co, Au-Zn, Au-In, Au-W, Au-Ir, Au-Si, Ag-Cu, Ag-Al, Ag-Ni, Ag-Pt, Ag-Pd, Ag-Sn, Ag-Mo, Ag-Ti, Ag-Cr, Ag-Mn, Ag-Fe, Ag-Zn, Ag-In, Ag-W, Ag-Ir and Ag- Bimetallic material selected from the group consisting of Si or Au-Ag-Cu, Au-Cu-Pt, Au-Ag-Pt, Au-Ag-Pd, Au-Cu-Pd, Ag-Cu-Pt and Ag-Cu Sensor comprising a ternary metal material selected from the group consisting of -Pd.
According to claim 1,
The sensing material includes _a binary metal material of Pd _(1-a) / Au _a , Pd _(1-a) / Pt _a or a ternary metal material of Pd _(1-bc) / Au _b / Ni _c ,
The sensor wherein 0≤a≤0.5, 0≤b + c <1, 0≤b≤0.5, 0≤c≤0.5.
According to claim 1,
The sensing material is a _binary component of SnO _{2 (1-d)} / WO _3d , SnO _{2 (1-d)} / CuO _d or SnO _{2 (1-ef)} / WO _3e / Au _f , SnO _{2 (1-ef )} / WO _3e / Pt _f containing the substance of the Samsung-based,
A sensor wherein 0≤d≤0.5, 0≤e + f <1, 0≤e≤0.5, 0≤f≤0.5.
According to claim 1,
The sensing material is a sensor for sensing a gas or a liquid.
According to claim 1,
The sensing material is to detect that selected from the group consisting of H ₂ , CO, CO ₂ , water vapor, O ₂ , N ₂ , aromatic compounds and VOC, the sensor.
According to claim 1,
The sensing material is to detect blood, biomolecules, bacteria, acetone or alcohols.
According to claim 1,
The size of the sensing material grain is 100 nm or less, and the grain interface gap is 50 nm or less,
The aspect ratio of the nanostructure is 1 or more, the line width is 50 nm or less, the sensor.
According to claim 1,
In the nanostructure, when sensing hydrogen gas or hydrogen sulfide gas, ΔR / R _a is 1% or more, a response time is less than 100 seconds, and a recovery time is less than 200 seconds.
(a) depositing a sensing material on the substrate on which the first pre-pattern is formed,
(b) re-depositing the sensing material on the side surface of the first pre-pattern through an ion etching process to form a first nano-pattern,
(c) removing the first prepattern through an ion etching process
A method of manufacturing a sensor comprising a.
The method of claim 16,
(d) After (c), a second prepattern is formed on the substrate on which the first nanopattern is formed at a different angle from the first nanopattern, and then a sensing material is deposited on the substrate,
(e) re-depositing the sensing material on the side surface of the second pre-pattern through an ion etching process to form a second nano-pattern,
(f) removing the second pre-pattern through ion etching.
(a) adjusting the inclination angle of the prepattern by asymmetrically etching one side surface of the prepattern formed on the substrate at an angle of 30 ° to 50 ° for 1 minute to 30 minutes,
(b) removing the portion where the pre-pattern is not formed to expose the substrate,
(c) depositing a sensing material on the pre-pattern in which the inclination angle is adjusted,
(d) removing the pre-pattern to obtain a nanostructure inclined 30 ° to 90 ° with respect to the substrate
A method of manufacturing a sensor comprising a.
(a) adjusting the inclination angle of the prepattern by asymmetrically etching one side of the prepattern formed on the substrate at an angle of 50 ° to 80 ° for 1 minute to 30 minutes,
(b) removing the portion where the pre-pattern is not formed to expose the substrate,
(c) depositing a sensing material on the pre-pattern in which the inclination angle is adjusted,
(d) removing the pre-pattern, thereby obtaining a nanostructure in which an upper part of the substrate is folded at 30 ° to 90 °
A method of manufacturing a sensor comprising a.
The method of claim 16,
The first pre-pattern is formed by removing a part of the polymer of the block copolymer through an ion etching process after forming a block copolymer pattern on the substrate, the method of manufacturing the sensor.
The method of claim 20,
The block copolymer is PS-b-PMMA,
The PS-b-PMMA block copolymer is 270 kg / mol to 280 kg / mol, and the first prepattern is in a lamellar shape,
The PS-b-PMMA block copolymer is 65 kg / mol to 140 kg / mol, and the first pre-pattern is a nanoporous cylinder shape.
The method according to any one of claims 16 to 19,
The sensing material is selected from the group consisting of metal, metal oxide, metal sulfide and polymer, the method of manufacturing the sensor.
The method according to any one of claims 16 to 19,
The sensing material is selected from the group consisting of Au, Ag, Cu, Al, Ni, Pt, Pd, Sn, Mo, Ti, Cr, Mn, Fe, Co, Zn, In, W, Ir and Si. A method of manufacturing a sensor comprising metal.
The method according to any one of claims 16 to 19,
The sensing material is at least one selected from the group consisting of Pd, Pt Au, and Ni,
One or more selected from the group consisting of the Pd, Pt Au, and Ni are sequentially deposited on a substrate,
A method of manufacturing a sensor, wherein each layer of the deposited sensing material is redeposited on a side surface of the first prepattern through an ion etching process.
The method according to any one of claims 16 to 19,
The sensing material includes _a binary component of Pd _(1-a) / Au _a , Pd _(1-a) / Pt _a or a ternary material of Pd _(1-bc) / Au _b / Ni _c ,
0≤a≤0.5, 0≤b + c <1, 0≤b≤0.5, 0≤c≤0.5, the manufacturing method of the sensor.
The method according to any one of claims 16 to 19,
The sensing material is one or more selected from the group consisting of Sn, W Cu, and Au,
One or more selected from the group consisting of the Sn, W Cu, and Au are sequentially deposited on a substrate,
Each layer of the deposited sensing material is redeposited on the side surface of the first pre-pattern through an ion etching process to form the first nano-pattern,
And removing the first pre-pattern through an ion etching process and annealing the first nano-pattern.
The method according to any one of claims 16 to 19,
The sensing material is a _binary component of SnO _{2 (1-d)} / WO _3d , SnO _{2 (1-d)} / CuO _d or SnO _{2 (1-ef)} / WO _3e / Au _f , SnO _{2 (1-ef )} / WO _3e / Pt _f contains the ternary substance,
0≤d≤0.5, 0≤e + f <1, 0≤e≤0.5, 0≤f≤0.5, the manufacturing method of the sensor.
The method of any one of claims 24 to 27,
In the deposition of the sensing material, the order of deposition, the deposition thickness or the number of deposition is controlled,
A method of manufacturing a sensor that can change a component, a content ratio, or a form of a sensing material to be redeposited by adjusting an angle of an ion etching process after deposition or time of an ion etching process.
The method of claim 28,
The sensing material is Pd / Au / Ni,
A method of manufacturing a sensor, which deposits on a substrate in the order of Au-Ni-Pd, and forms the first nanopattern containing a ternary structured ternary material by adjusting the deposition thickness to 5 nm to 10 nm.
The method of claim 28,
The sensing material is Pd / Au / Ni,
A method of manufacturing a sensor, which deposits on a substrate in the order of Au-Ni-Pd, and controls the deposition thickness to less than 5 nm to form a first nanopattern containing a ternary material of uniformly mixed shape.
The method of claim 28,
The sensing material is Pd / Au / Ni,
Depositing on the substrate in the order of Au-Ni-Pd-Ni-Au, by adjusting the deposition thickness to 5 nm to 10 nm, to form a first nano-pattern containing a core-shell-shaped ternary material, Method of manufacturing the sensor.
The method according to any one of claims 16 to 31,
The sensing material is to detect what is selected from the group consisting of H ₂ , CO, CO ₂ , water vapor, O ₂ , N ₂ , aromatic compounds and VOC, the method of manufacturing the sensor.

Images