Nanostructure-based high-performance radical and cation measurement device and method for manufacturing same

Abstract

A nanostructure-based high-performance radical and cation measurement device of the present invention is for measuring radicals and cations, and comprises: a sensing electrode which is formed on a substrate; a nanostructure sensing layer which is formed on the substrate having formed thereon the sensing electrode and senses radicals and cations with an electrical signal due to adsorption and desorption of the radicals and cations; and a packaging which has at least one through hole formed therein and is formed to surround the substrate having formed thereon the sensing electrode and the nanostructure sensing layer.

Description

Nanostructure-based high-performance radical and cation measuring device and method for manufacturing the same

[0001] The present invention relates to a nanostructure-based high-performance radical and cation measuring device with enhanced selective reactivity to radicals and cations, and a method for manufacturing the same.

[0002] When a gas is converted into plasma, a large amount of electrons and positive ions are generated, along with atoms that have broken away from molecular bonds. The phenomenon of molecules separating from their bonds upon receiving energy is called 'dissociation,' and the electrons, positive ions, and radicals generated by this dissociation are all referred to as plasma. Radicals are also formed when electrons frequently combine with positive ions.

[0003] In plasma, primary electrons that have received energy escape from the outermost shell of neutral atoms and collide with other atoms; the collision energy generates secondary and tertiary electrons and other positive ions at high densities. Under conditions where energy exceeding a certain level is applied, electrons, positive ions, and radicals are continuously generated while simultaneously annihilating each other through mutual bonding. As energy increases, dissociation becomes more frequent, while at lower energy, bonding forces become dominant.

[0004] Plasma is utilized in various fields such as semiconductor and display manufacturing, aircraft propulsion, gas and contaminated water purification, catalysts, and surface modification; however, plasma measurement methods are highly diverse and complex in principle, depending on the target variable and domain, including methods like ultra-high frequency cutoff diagnosis and laser scattering diagnosis. Furthermore, measurement results often exhibit significant variability depending on the user's expertise.

[0005] Therefore, research is needed on radical and cation measurement devices and methods to maximize the utilization of plasma performance in order to solve the aforementioned problems.

[0006] [Prior Art Literature]

[0007] [Patent Literature]

[0008] 1. Korean Registered Patent No. 10-2340564

[0009] 2. Korean Published Patent No. 10-2024-0070268

[0010] The objective of the present invention is to provide a nanostructure-based high-performance radical and cation measuring device capable of measuring radicals and cations in various environments, such as plasma processes, atmospheric monitoring, and chemical reaction processes, by enhancing selective reactivity toward radicals and cations, and a method for manufacturing the same.

[0011] A nanostructure-based high-performance radical and cation measuring device according to one embodiment of the present invention may include a sensing electrode formed on a substrate, a nanostructure sensing layer formed on the substrate on which the sensing electrode is formed to detect radicals and cations by an electrical signal resulting from the adsorption and desorption of the radicals and cations, and a packaging formed to surround the substrate on which the sensing electrode and the nanostructure sensing layer are formed, with at least one through hole formed therein.

[0012] In addition, a heater formed on the lower part of the substrate according to one embodiment of the present invention to supply heat to the nanostructure sensing layer may be further included.

[0013] In addition, the present invention further includes a feedthrough for transmitting real-time electrical signals of the radicals and cations according to one embodiment of the present invention to a measuring unit, wherein the measuring unit can analyze the electrical signals of the radicals and cations and convert them into digital signals.

[0014] In addition, the sensing electrode according to one embodiment of the present invention may include at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO₂, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide), and AZO (aluminum-doped zinc oxide).

[0015] In addition, the sensing electrode according to one embodiment of the present invention may be formed by arranging 2 to 40 finger electrodes with a spacing of 1 to 2000 μm on the substrate in an interdigitated structure.

[0016] In addition, the nanostructure sensing layer according to one embodiment of the present invention may include at least one selected from p-type metal oxide, n-type metal oxide, carbon allotrope, transition metal dichalcogenides (TMDs), MXene, metal nitride, and metal carbide.

[0017] In addition, the nanostructure sensing layer according to one embodiment of the present invention may be formed with at least one structure selected from nano thin films, nanorods, nanowires, nanoblades, nanotubes, nano trees, zigzag nanocolumns, nano springs, nano islands, nano flowers, nanowalls, nanoporous structures, nanocoils, nanobelts, and multilayer nanostructures.

[0018] In addition, the packaging according to one embodiment of the present invention may include at least one selected from SiC, Al₂O₃, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone).

[0019] In addition, the nanostructure sensing layer formed thereon according to one embodiment of the present invention may further include a catalyst layer.

[0020] In addition, the catalyst layer according to one embodiment of the present invention may include at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al.

[0021] A method for manufacturing a nanostructure-based high-performance radical and cation measuring device according to one embodiment of the present invention may include the steps of forming a sensing electrode on a substrate, forming a nanostructure sensing layer on the substrate on which the sensing electrode is formed, and packaging the substrate on which the sensing electrode and the nanostructure sensing layer are formed.

[0022] In addition, the step of forming the sensing electrode according to one embodiment of the present invention may involve patterning one surface of the substrate by a photolithography process and then electron beam depositing at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO2, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide), and AZO (aluminum-doped zinc oxide).

[0023] In addition, the step of forming the nanostructure sensing layer according to one embodiment of the present invention may be formed by at least one method selected from electron beam evaporation, oblique angle deposition (OAD), sputtering, chemical vapor deposition (CVD), pulsed laser deposition (PLD), electroplating, spray coating, hydrothermal synthesis, sol-gel method, electrospinning, spin coating, and inkjet printing.

[0024] In addition, the packaging step according to one embodiment of the present invention may enclose the substrate on which the sensing electrode and the nanostructure sensing layer are formed with a packaging comprising at least one selected from SiC, Al2O3, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone) and having at least one through hole formed therein.

[0025] In addition, the method may further include the step of forming a catalyst layer on the nanostructure sensing layer according to one embodiment of the present invention.

[0026] In addition, the step of forming the catalyst layer according to one embodiment of the present invention may be performed by electron beam deposition of at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al at the end of the nanostructure sensing layer.

[0027] The nanostructure-based high-performance radical and cation measuring device and the method for manufacturing the same according to the present invention enhance selective reactivity toward radicals and cations, thereby enabling the measurement of radicals and cations in various environments such as plasma processes, atmospheric monitoring, and chemical reaction processes.

[0028] FIG. 1 is a configuration diagram of a sensing unit of a radical and cation measuring device according to one embodiment of the present invention.

[0029] FIG. 2 is a conceptual diagram of a sensing unit of a radical and cation measuring device according to one embodiment of the present invention.

[0030] FIG. 3 is a configuration diagram of a radical and cation measuring device according to one embodiment of the present invention.

[0031] FIG. 4 is a conceptual diagram of a radical and cation measuring device according to one embodiment of the present invention.

[0032] Specific embodiments of the present invention will be described in detail below with reference to the drawings. However, the concept of the present invention is not limited to the presented embodiments. Those skilled in the art who understand the concept of the present invention may easily propose other inventions that are inferior or other embodiments included within the scope of the concept of the present invention by adding, changing, or deleting other components within the same scope of the concept, and such are also to be considered to be included within the scope of the concept of the present invention.

[0033] Additionally, components with the same function within the scope of the same concept appearing in the drawings of each embodiment are described using the same reference numeral.

[0034] FIG. 1 is a configuration diagram of a sensing unit (110) of a radical and cation measuring device (100) according to one embodiment of the present invention, and FIG. 2 is a conceptual diagram of a sensing unit (110) of a radical and cation measuring device (100) according to one embodiment of the present invention.

[0035] As shown in FIG. 1, a nanostructure-based high-performance radical and cation measuring device (100) according to the present invention includes a sensing electrode (112), a nanostructure sensing layer (111), and a packaging (114). The sensing electrode (112), the nanostructure sensing layer (111), and the packaging (114) serve as the sensing unit (110) of the radical and cation measuring device and detect radicals and cations generated inside vacuum plasma equipment used in semiconductor manufacturing processes in real time. This measuring device (100) can be utilized for optimizing process conditions and monitoring plasma states.

[0036] The sensing electrode (112) may be formed by arranging 2 to 40 finger electrodes with a spacing of 1 to 2000 μm on the substrate in an interdigitated structure. If the spacing of the finger electrodes is less than 1 μm, there is a risk of short circuit, and if it exceeds 2000 μm, the sensing performance may decrease. Additionally, while a larger number of finger electrodes may provide superior sensing performance, the number can be optimized according to the size and power consumption of the measuring device (100).

[0037] In particular, the sensing electrode (112) may include at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO₂, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide) and AZO (aluminum-doped zinc oxide) and can operate stably even in a high temperature environment of up to 1000°C.

[0038] The nanostructure sensing layer (111) is formed on a substrate on which the sensing electrode (112) is formed, and can detect radicals and cations through electrical signals resulting from the adsorption and desorption of radicals and cations. The nanostructure sensing layer (111) may be formed over the entire substrate on which the sensing electrode (112) is formed, or may be formed between the finger electrodes of the sensing electrode (112).

[0039] When radicals and cations generated by plasma generation are adsorbed onto the surface of the nanostructure sensing layer (111), they affect the charge density and conductivity of the surface, causing changes in electrical properties (resistance, voltage, current). These changes in electrical properties are quantitatively measured through electrical properties, and through this, the state of the plasma can be confirmed by detecting the presence of radicals and cations in real time. In particular, multiple radicals (H, O, OH, N, NO, CF, CO2, CH3, etc.) and cations can be detected simultaneously to detect and analyze their presence and concentration in real time.

[0040] That is, the measurement is made by the change in electrical characteristics that occurs as radicals and cations are adsorbed on the surface of the nanostructure sensing layer (111). At this time, the high specific surface area of ​​the nanostructure increases the portion capable of reacting with radicals and cations, thereby enabling the realization of a high-performance radical and cation measuring device.

[0041] Therefore, the radical and cation measuring device including the nanostructure sensing layer (111) can be used to monitor or optimize plasma process conditions by distinguishing the characteristics and reactivity of various radicals and cations.

[0042] In particular, when the nanostructure sensing layer (111) is a p-type semiconductor material, when oxidizing radicals are adsorbed, the concentration of holes increases due to the consumption of surface electrons, thereby decreasing the resistance. On the other hand, when reducing radicals are adsorbed, electrons are supplied to the surface, causing the concentration of holes to decrease, thereby increasing the resistance.

[0043] On the other hand, in the case of n-type semiconductor materials, resistance increases when oxidizing radicals are adsorbed, as surface electrons are consumed and the concentration of conduction electrons decreases. Conversely, when reducing radicals are adsorbed, resistance decreases as electrons are supplied to the surface, increasing the concentration of conduction electrons.

[0044] In the case of p-type semiconductor materials, resistance decreases as surface electrons are consumed due to the adsorption of cations, which increases the concentration of holes. Conversely, resistance increases as cations supply electrons to the surface, which decreases the concentration of holes.

[0045] In the case of n-type semiconductor materials, when surface electrons are consumed upon adsorption of cations, the concentration of conduction electrons decreases, leading to an increase in resistance. Conversely, when cations supply electrons to the surface, the concentration of conduction electrons increases, resulting in a decrease in resistance.

[0046] This detection principle depends on the types of radicals and cations, specifically oxidative radicals such as O·, OH·, and O2 - It can distinguish and detect the characteristics of ·, HO2·, NO·, Cl·, or reducing radicals such as H·, CH3·, NH2·, C2H5·, and SiH3·, and oxidizing cations such as Fe 3+ , Cu 2+ , Cr 6+ , Mn 7+ , Sn 4+ , Ti 4+ , Ce 4+ , Hg 2+ , Ag + or Na, a reducing cation + , K + , Ca + , Ba + , Fe 2+ , Co 2+ , Pb 2+ , Sn 2+It is possible to distinguish and detect the characteristics of radicals and cations. Through this, it is possible to analyze radicals and cations in real time. In addition, the detection principle of the present invention can be applied to monitor the generation status of radicals and cations or to optimize process conditions in various plasma processes.

[0047] In particular, the nanostructure sensing layer may include at least one selected from p-type metal oxide, n-type metal oxide, carbon allotrope, transition metal dichalcogenides (TMDs), MXene, nitride, and carbide.

[0048] The above p-type metal oxide may include at least one selected from nickel oxide (NiO), cobalt oxide (Co3O4), manganese oxide (Mn3O4), copper oxide (II) (CuO), chromium oxide (Cr2O3), selenium oxide (SeO2), tellurium oxide (TeO2), gallium oxide (Ga2O3), bismuth oxide (Bi2O3), antimony oxide (Sb2O3), scandium oxide (Sc2O3), and strontium oxide (SrO2).

[0049] The above n-type metal oxides are silica (SiO2), copper oxide (I) (Cu2O), tin oxide (SnO2), tungsten oxide (WO3), zinc oxide (ZnO), iron oxide (III) (Fe2O3), iron oxide (II,III) (Fe3O4), titanium oxide (TiO2), cobalt oxide (Co3O4), nickel cobalt oxide (NiCo2O4), cerium oxide (CeO2), lanthanum cobalt oxide (LaCoO3), calcium manganese oxide (Ca2Mn3O8), manganese oxide (MnO2), manganese oxide (Mn2O3), aluminum oxide (Al2O3), zinc tin oxide (Zn2SnO4), fluorine-doped tin oxide (FTO), aluminum zinc oxide (AZO), indium oxide (In2O3), indium tin oxide (ITO), indium tantalum oxide (InTaO4), zirconium oxide (ZrO2), vanadium oxide (V2O5), Niobium oxide (Nb2O5), silver vanadium oxide (Ag2V4O) 11 It may include at least one selected from silver oxide (Ag2O), palladium oxide (PdO) and lanthanum oxide (La2O3).

[0050] The above carbon allotrope may include at least one selected from carbon nanotubes (CNT), fullerene, activated carbon, and carbon nanofoam.

[0051] The above transition metal dichalcogenides (TMDs) may include at least one selected from molybdenum disulfide (MoS2), tungsten disulfide (WS2), tungsten selenide (WSe2), molybdenum selenide (MoSe2), niobium selenide (NbSe2), molybdenum telluride (MoTe2), tantalum disulfide (TaS2), titanium disulfide (TiS2), zirconium disulfide (ZrS2), hafnium disulfide (HfS2), rhenium disulfide (ReS2), and tin disulfide (SnS2).

[0052] The above MXene is trititanium dicarbide (Ti3C2T x ), titanium carbide (Ti2Cx T x ), Titanium trinitride (Ti4N3T x ), trititanium carbonitride (Ti3CN x T x ), vanadium carbide (V2C x T x ), savannadium tricarbide (V4C3T x ), iniobium carbide (Nb2C x T x ), Saniobium tricarbide (Nb4C3T x ), imolybdenum carbide (Mo2C x T x ), mixed molybdenum-titanium carbide (Mo 1.3 Ti 0.7 C2T x ), trizirconium dicarbide (Zr3C2T x ), zirconium carbide (Zr2C x T x ), trihafnium dicarbide (Hf3C2T x ), Iphanium carbide (Hf2C x T x ), chromium carbide (Cr2C x T x ) and chromium tricarbide (Cr3C2T x It may include at least one selected from ).

[0053] The above metal nitride may include at least one selected from titanium nitride (TiN), zirconium nitride (ZrN), hafnium nitride (HfN), vanadium nitride (VN), niobium nitride (NbN), tantalum nitride (TaN), chromium nitride (CrN), molybdenum nitride (Mo2N), tungsten nitride (WN), boron nitride (BN), silicon nitride (Si3N4), boron carbon nitride (BCN), lithium nitride (Li3N), magnesium nitride (Mg3N2), calcium nitride (Ca3N2), two-dimensional boron nitride (h-BN), 2D tantalum nitride (Ta2N), aluminum-titanium nitride (TiAlN), silicon-aluminum nitride (SiAlN), gallium nitride (GaN), indium nitride (InN), and aluminum nitride (AlN).

[0054] The above metal carbides are titanium carbide (TiC), zirconium carbide (ZrC), hafnium carbide (HfC), vanadium carbide (VC), niobium carbide (NbC), tantalum carbide (TaC), chromium carbide (Cr3C2), molybdenum carbide (Mo2C), tungsten carbide (WC), boron carbide (B4C), silicon carbide (SiC), germanium carbide (GeC), and trititanium dicarbide (Ti3C2T x ), imolybdenum carbide (Mo2C x T x ), tantalum-tantanium carbide (Ta x Nb 1-x C), chromium-tungsten carbide (Cr x WC 1-x It may include at least one selected from aluminum carbide (Al4C3), magnesium carbide (Mg2C3) and lithium carbide (Li2C2).

[0055] As described above, changes in electrical properties occur on the surface of the nanostructure sensing layer (111) according to the oxidative and reducing properties of radicals and cations, and can react with radicals and cations in a temperature range from room temperature to 700°C, and the surface area can be increased to increase the sensing performance.

[0056] The nanostructure sensing layer (111) can be formed with at least one structure selected from nano thin films, nanorods, nanowires, nanoblades, nanotubes, nano trees, zigzag nanocolumns, nano springs, nano islands, nano flowers, nanowalls, nanoporous structures, nanocoils, nanobelts, and multilayer nanostructures.

[0057] The above nanostructure sensing layer (111) can be implemented as various nanostructures of one, two, and three dimensions. Each provides specific physical and chemical properties, contributing to the improvement and optimization of the performance of the radical and cation measuring device.

[0058] For example, nanorods and nanowires provide a high specific surface area to maximize interactions between the sensing material and radicals and cations, while nanotubes utilize both their inner and outer surfaces to increase the adsorption efficiency of radicals and cations. Nanoblades and nanoflowers are structures with specific orientations that can enhance the detection response by maximizing active sites.

[0059] Nanosprings and zigzag nanocolumns can enhance detection speed by optimizing the diffusion pathways of gas molecules while providing structural stability. Nanowalls and nanoporous structures provide porous surfaces to facilitate the diffusion and adsorption of gas molecules. Multilayer nanostructures can realize complex sensing functions through interlayer interactions.

[0060] The above packaging (114) may be formed to surround a substrate having at least one through hole formed therein and having the sensing electrode (112) and the nanostructure sensing layer (111) formed therein. The packaging may include at least one selected from SiC, Al2O3, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone).

[0061] The gaseous environment for measuring radicals and cations is a corrosive environment caused by plasma, so the substrate, sensing electrode (112), nanostructure sensing layer (111), etc. of the radical and cation measuring device are susceptible to damage from oxidation or corrosion.

[0062] The above packaging (114) has at least one through hole formed therein to detect radicals and cations through electrical signals resulting from the adsorption and desorption of radicals and cations in the nanostructure sensing layer (111), and at the same time, the packaging (114) is formed to surround the substrate on which the sensing electrode (112) and the nanostructure sensing layer (111) are formed, except for the portion where the through hole is formed, so as to protect against physical damage and chemical corrosion caused by plasma.

[0063] In addition, the above packaging (114) modularizes the substrate on which the sensing electrode (112) and the nanostructure sensing layer (111) are formed, so that the measuring device is compatible with various plasma generation equipment and can be used in various application environments such as plasma processes, atmospheric monitoring, and chemical reaction processes.

[0064] In particular, the nanostructure-based high-performance radical and cation measuring device (100) of the present invention may include a plurality of modularized sensing units (110) formed to surround a substrate on which the sensing electrode (112) and the nanostructure sensing layer (111) are formed by the packaging (114). The nanostructure sensing layer (111) may have selective reactivity to specific radicals and cations depending on the material and structure of the nanostructure sensing layer (111). Therefore, by measuring multiple electrical signals through a plurality of sensing units (110) with different materials or structures of the nanostructure sensing layer (111), measurement efficiency and accuracy can be increased.

[0065] The nanostructure sensing layer (111) may further include a catalyst layer formed thereon, which may be formed by doping or coating the nanostructure sensing layer. In particular, the catalyst layer may include at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al. The catalyst layer may be doped or coated onto the nanostructure sensing layer to enhance selective reactivity to radicals and cations.

[0066] In addition, the nanostructure-based high-performance radical and cation measuring device (100) according to the present invention may further include a heater (113). The heater is formed on the lower part of the substrate and can supply heat to the nanostructure sensing layer (111) and the sensing electrode (112). As a device for promoting the reaction of the nanostructure sensing layer (111) based on a semiconductor material, the temperature can be controlled from room temperature to 700°C depending on the applied voltage.

[0067] FIG. 3 is a configuration diagram of a radical and cation measuring device (100) according to one embodiment of the present invention, and FIG. 4 is a conceptual diagram of a radical and cation measuring device (100) according to one embodiment of the present invention. The nanostructure-based high-performance radical and cation measuring device (100) according to the present invention may further include a feedthrough (120) and a measuring unit (130).

[0068] The above feedthrough (120) transmits the real-time electrical signals of the radicals and cations to the measuring unit (130), and the measuring unit (130) can analyze the electrical signals of the radicals and cations and convert them into digital signals. The above feedthrough (120) is a device for transmitting real-time electrical signal changes obtained inside equipment such as a vacuum to the outside, and the electrical signal changes through the detection of radicals and cations can be monitored in real-time at the measuring unit (130) outside the equipment.

[0069] In addition, when a plurality of sensing units (110) are included, electrical signals measured through a plurality of feedthroughs (120) are each transmitted to a measuring unit (130), and interference of the measured electrical signals can be prevented.

[0070] A method for manufacturing a nanostructure-based high-performance radical and cation measuring device according to the present invention comprises a step of forming a sensing electrode, a step of forming a nanostructure sensing layer, and a packaging step.

[0071] The step of forming the sensing electrode described above is a step of forming a sensing electrode on a substrate, and the electrode can be formed using processes such as photolithography or etching. After patterning one surface of the substrate using a photolithography process, the process can be performed by electron beam deposition of at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO₂, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide), and AZO (aluminum-doped zinc oxide).

[0072] In particular, the sensing electrode may be formed by arranging 2 to 40 finger electrodes with a spacing of 1 to 2000 μm on the substrate in an interdigitated structure.

[0073] The step of forming the nanostructure sensing layer is a step of forming a nanostructure sensing layer on a substrate on which the sensing electrode is formed, and can be formed by at least one selected from p-type metal oxide, n-type metal oxide, carbon allotrope, transition metal dichalcogenides (TMDs), MXene, metal nitride and metal carbide using at least one method selected from electron beam evaporation, oblique angle deposition (OAD), sputtering, chemical vapor deposition (CVD), pulsed laser deposition (PLD), electroplating, spray coating, hydrothermal synthesis, sol-gel method, electrospinning, spin coating and inkjet printing.

[0074] The electron beam evaporation method described above is used to manufacture the nanostructure sensing layer and has the advantage of being able to form a very high-purity thin film. This process is carried out in a high vacuum environment, so it contains almost no impurities, and the deposition thickness and speed can be precisely controlled. Through this, a high-quality thin film can be formed on the surface of a substrate, and nanostructures can be fabricated based on this thin film in a subsequent process. For example, nanowires or nanorods can be formed through an etching process after applying a thin film pattern.

[0075] The above-mentioned oblique angle deposition (OAD) method is used to fabricate unique nanostructures by adjusting the angle of the substrate to impart specific orientation during deposition. This method can fabricate three-dimensional structures such as nanoblades, zigzag nanocolumns, and nanosprings by controlling the incident angle. These structures provide a high specific surface area and can contribute to improving the sensitivity of sensors.

[0076] The sputtering described above is a process capable of depositing a uniform thin film on a large-area substrate and is particularly suitable for commercial mass production processes. The uniform thin film formed by sputtering can be utilized as a base layer for nucleation of nanostructures. When fabricating nanostructures, the sputtered thin film can be heat-treated under specific conditions to create nano-islands or nano-pillars.

[0077] The aforementioned Chemical Vapor Deposition (CVD) is widely used for the formation of uniform thin films and is suitable for fabricating films with high crystallinity. Additionally, precise nanostructures such as nanowires and nanorods can be fabricated through a specific modified process called Vapor-Liquid-Solid (VLS). In this process, metal catalysts can be utilized to control the growth direction and structure.

[0078] The above-mentioned pulsed laser deposition (PLD) is a process that uses a laser to deposit thin films while maintaining the compositional ratio of the material precisely. This method is suitable for the high-quality synthesis of multi-component materials and can form homogeneous nano-sized thin films while maintaining a uniform compositional ratio. This enables the fabrication of composite nanostructures and can be utilized, for example, for the formation of multilayer structures.

[0079] The aforementioned electroplating is advantageous for the low-temperature deposition of metals and metal oxides, and allows for the easy fabrication of complex structures through an economical process. This method can form nanowires, nanorods, or nanopatterns by applying a specific voltage to electrodes to deposit metal ions. It is suitable for heat-sensitive substrates as it can operate in low-temperature environments.

[0080] The spray coating described above is a process that can form a uniform thin film using simple equipment and is suitable for mass production and low-cost manufacturing. Spray coating can be utilized to form a thin film by spraying a solution containing nanoparticles onto a substrate, or to form a three-dimensional nanostructure under specific conditions.

[0081] The hydrothermal synthesis method described above is used to form complex three-dimensional nanostructures through chemical reactions in a high-temperature and high-pressure environment. This method allows for precise structural control and is suitable for fabricating nano trees, nano springs, or porous nanostructures. Hydrothermal synthesis can be primarily utilized to fabricate nanostructures with high crystallinity and unique shapes.

[0082] The aforementioned Sol-Gel Method is a process capable of forming uniform thin films and nanostructures at low temperatures, and it is easy to process and economical. This method allows for the formation of nanoparticles in a solution phase, followed by coating them onto a substrate or fabricating structures containing nanopores through heat treatment. The Sol-Gel Method can be utilized for the fabrication of nanoblades and porous thin films.

[0083] The aforementioned electrospinning is a process that uses high voltage to fabricate a solution or melt into a nanofiber form. This method is suitable for fabricating nanofiber-based sensor materials and can significantly improve sensing efficiency due to its unique structure and high specific surface area.

[0084] The spin coating described above is used to form a uniform coating layer on the surface of a substrate, enabling the formation of thin films through a fast and simple process. Furthermore, this process allows for the formation of a coating layer of uniform thickness on the substrate surface. Spin coating can also be utilized in conjunction with the transfer printing process to fabricate complex nanopatterns.

[0085] The above inkjet printing is a technology that can deposit sensing materials in a desired pattern through digital control, enabling the fabrication of high-resolution nanopatterns and the precise placement of specific nanostructures.

[0086] The above packaging step is a step of packaging the substrate on which the sensing electrode and the nanostructure sensing layer are formed, and the substrate on which the sensing electrode and the nanostructure sensing layer are formed can be wrapped with a packaging that includes at least one selected from SiC, Al2O3, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone) and has at least one through hole formed therein.

[0087] Prior to the above packaging step, the method may further include a step of forming a catalyst layer by doping or coating the nanostructure sensing layer. In particular, this can be performed by electron beam deposition of at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al on the ends of the nanostructure sensing layer.

[0088] As described above, the nanostructure-based high-performance radical and cation measuring device of the present invention enhances selective reactivity toward radicals and cations, enabling the measurement of radicals and cations in various environments such as plasma processes, atmospheric monitoring, and chemical reaction processes.

[0089] The following describes manufacturing examples and experimental examples of the present invention. However, it is specified that these manufacturing examples and experimental examples are intended to explain the composition and effects of the present invention more specifically, and that the scope of the present invention is not limited thereto.

[0090]

[0091] <Fabrication of the Detector for Radical and Cation Measurement Devices>

[0092] [n-type metal oxide (SnO₂) nanorods containing a Ti catalyst layer]

[0093] Cr / Au (thickness 20 nm / 80 nm) interdigitated electrodes (IDEs) were deposited on an 8 mm × 8 mm SiO2 / Si substrate. The spacing of the fabricated IDEs was 5 μm, and a photolithography process was used. Subsequently, ultrasonically cleaned in CH3COCH3, C2H5OH, and DI water for 5 minutes each, and the areas excluding the selective regions where the IDE electrodes were interlocked were masked using tape to deposit the sensing material only on these selective regions.

[0094] SnO2 was deposited on the prepared electrode using an electronic-beam evaporator. The oblique angle deposition method (GLAD) was used, and the GLAD technique is a method for fabricating nanostructures based on the shadowing effect that occurs when an angle is formed between the incident material and the substrate.

[0095] The deposition conditions are 5 × 10 -5NRs were fabricated at a vacuum of less than torr with a substrate angle of 80°, a deposition rate of 3 A / s, and a substrate rotation speed of 10 rpm. Subsequently, for crystallization and surface activation, the materials were heat-treated at 500°C for 1 hour in an air atmosphere at atmospheric pressure with a heating rate of 5°C per minute, followed by air cooling to room temperature. Next, to decorate the SnO2NRs with a Ti catalyst, the materials were deposited with thicknesses of 1, 2, and 3 nm, respectively, at a substrate angle of 0° and a deposition rate of 3 Å / s without substrate rotation. The Ti was then converted to TiO2 by heat-treating at 500°C for 1 hour in an air atmosphere at atmospheric pressure with a heating rate of 5°C per minute, followed by air cooling to room temperature.

[0096]

[0097] [n-type metal oxide (In2O3) nanorods containing a NiO catalyst layer]

[0098] Interdigitated electrodes (IDEs) were fabricated using a lift-off-based photolithography process. First, a SiO2 / Si substrate was ultrasonically cleaned in CH3COCH3, C2H5OH, and DI water for 5 minutes each, and a photoresist was spin-coated on top at 3,000 rpm for 30 seconds. For soft-bake, the substrate was heated at 190°C for 5 minutes, then a heterogeneous photoresist was spin-coated at 3,000 rpm, and heated at 150°C for 1 minute. After patterning the IDEs with a sensing area spacing of 5 μm between 20 electrodes using a micro-pattern alignment exposure machine, Au / Pt / Cr (100 nm / 70 nm / 30 nm) was deposited using an E-beam evaporator to form the electrode material.

[0099] Vertically aligned NiO-decorated In2O3NRs were fabricated using an E-beam evaporator-based GLAD technique. The GLAD technique enables the fabrication of various one-dimensional metal oxide nanostructures through the self-shadowing effect that occurs depending on the incident angle of the vapor flux during initial nucleation. Based on this, to fabricate vertically aligned In2O3NRs, 99.99% pure In2O3 and NiO granules (iTASCO) were used, 5 × 10 -5 In2O3NRs were deposited at a deposition rate of 1 A / s on a substrate rotating at 3.3 rpm with an 80° tilt angle under a vacuum of less than torr. To form a pn junction, NiO was decorated on the surface of the In2O3NRs at a rate of 0.1 A / s without a tilt angle to thicknesses of 1, 2, and 3 nm. The deposition rate and thickness were measured using a Quartz Crystal Microbalance (QCM) mounted inside an E-beam evaporator, and the vacuum level was measured using a Bayard-Alpert ion gauge. For the crystallization of the NiO-decorated In2O3NRs, the temperature was increased in an electric furnace to 500°C at a rate of 5°C per minute, maintained for 1 hour, and then air-cooled to room temperature.

[0100]

[0101] [n-type metal oxide (SnO2) zigzag nanocolumns (ZZNCs) containing Au and Pd catalyst layers]

[0102] Gold IDEs were fabricated using photolithography and electron beam deposition technologies. The SiO₂ / Si substrate was sequentially cleaned with acetone, isopropanol, and deionized water for 5 minutes each using an ultrasonic cleaner. A uniform layer of photoresist (LOR 5 A, MicroChem Corporation) was spin-coated onto the SiO₂ / Si substrate at 3000 rpm for 30 seconds, followed by baking at 190°C for 5 minutes. Subsequently, a second layer of photoresist (AZ GXR 601, AZ Electronic Materials) was coated under the same spin-coating conditions. After baking at 150°C for 1 minute, an IDE pattern was formed using a mask aligner system (MDA-400S, MIDAS System). The patterned photoresist was developed using AZ 300MIF (MicroChemicals) and then washed with deionized water.

[0103] After photolithography, an Au / Pt / Cr (100 nm / 70 nm / 30 nm) layer was deposited on a patterned SiO₂ / Si substrate using an electron beam deposition machine (EBX-1000, ULVAC). To form the Au / Pt / Cr layer into an IDE pattern, the remaining photoresist was removed using mr-Rem 700 (Micro Resist Technology), and the substrate was washed with ethanol and deionized water. The IDE consists of 12 fingers, with a spacing of 20 μm between the fingers.

[0104] After loading an Au-IDEs patterned SiO2 / Si substrate into an electron beam evaporator (Korea Vacuum), multiple deposition steps were performed to control the number of SnO2 (99.99%, Taewon Scientific Co.) ZZNC layers. First, a SnO2 tilted nanocolumn was deposited on the substrate at an angle of 80° (Step 1). Subsequently, the substrate was rotated 180° to perform a second deposition in the opposite direction (Step 2). Steps 1 and 2 were repeated sequentially to fabricate 3-layered SnO2 ZZNCs, 5-layered SnO2 ZZNCs, and 7-layered SnO2 ZZNCs (Step 3).

[0105] For the decoration of Au (99.99%, Taewon Scientific Co.) and Pd (99.98%, Taewon Scientific Co.) NPs, 1 nm thick Au and Pd films were deposited with the substrate set to an initial position (0°). Additionally, SnO2 thin films were fabricated on the substrate at the same initial angle (0°). All samples were finally annealed in an air atmosphere at 500°C for 1 hour, converting the metal films into Au-SnO2ZZNCs and Pd-SnO2ZZNCs nanoparticles.

[0106]

[0107] <Packaging and Testing of Radical and Cation Measurement Device Detector Units>

[0108] After mounting a heater on the bottom of each substrate having a sensing electrode and a nanostructure sensing layer formed as described above, the substrates were housed in a package with an outer surface made of SiC and having through holes formed therein. Subsequently, voltage was applied to the heater to conduct an environmental test of the measuring device at operating temperatures ranging from room temperature to 700°C, and it was confirmed that the sensing unit operated stably in a high-temperature environment up to 700°C.

[0109] As described above, the nanostructure-based high-performance radical and cation measuring device of the present invention enhances selective reactivity toward radicals and cations, enabling the measurement of radicals and cations in various environments such as plasma processes, atmospheric monitoring, and chemical reaction processes.

Claims

1. In a device for measuring radicals and cations, A sensing electrode formed on a substrate; A nanostructured sensing layer formed on a substrate having the above-mentioned sensing electrode, which detects radicals and cations by an electrical signal resulting from the adsorption and desorption of the radicals and cations; and A nanostructure-based high-performance radical and cation measuring device characterized by including a packaging formed to surround a substrate having at least one through hole and having the sensing electrode and the nanostructure sensing layer formed thereon.

2. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized by further including a heater formed on the lower part of the substrate to supply heat to the nanostructure sensing layer.

3. In Paragraph 1, It further includes a feedthrough that transmits real-time electrical signals of the above radicals and cations to a measuring unit, A nanostructure-based high-performance radical and cation measuring device characterized by the above measuring unit analyzing the electrical signals of the radicals and cations and converting them into digital signals.

4. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized in that the sensing electrode comprises at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO₂, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide), and AZO (aluminum-doped zinc oxide).

5. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized in that the sensing electrode is formed by arranging 2 to 40 finger electrodes with a spacing of 1 to 2000 μm on the substrate in an interdigitated structure.

6. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized by the above nanostructure sensing layer comprising at least one selected from p-type metal oxide, n-type metal oxide, carbon allotrope, transition metal dichalcogenides (TMDs), MXene, metal nitride, and metal carbide.

7. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized in that the nanostructure sensing layer is formed of at least one structure selected from nano thin films, nanorods, nanowires, nanoblades, nanotubes, nano trees, zigzag nanocolumns, nano springs, nano islands, nano flowers, nanowalls, nanoporous structures, nanocoils, nanobelts, and multilayer nanostructures.

8. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized by the above packaging comprising at least one selected from SiC, Al2O3, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone).

9. In Paragraph 1, A nanostructure-based high-performance radical and cation measuring device characterized by further including a catalyst layer formed in the nanostructure sensing layer.

10. In Paragraph 9, A nanostructure-based high-performance radical and cation measuring device characterized by the catalyst layer comprising at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al.

11. A step of forming a sensing electrode on a substrate; A step of forming a nanostructure sensing layer on a substrate having the above-mentioned sensing electrode formed thereon; and A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized by including the step of packaging a substrate on which the sensing electrode and the nanostructure sensing layer are formed.

12. In Paragraph 11, A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized in that the step of forming the sensing electrode comprises patterning one surface of the substrate by a photolithography process and then electron beam depositing at least one selected from Au, Ag, Pt, Ir, W, Mo, Ta, TiN, Ni, Sn, Pd, Ru, RuO₂, ITO (Indium tin oxide), FTO (fluorine-doped tin oxide), and AZO (aluminum-doped zinc oxide).

13. In Paragraph 11, A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized in that the step of forming the nanostructure sensing layer comprises forming at least one selected from p-type metal oxide, n-type metal oxide, carbon allotrope, transition metal dichalcogenides (TMDs), MXene, metal nitride, and metal carbide using at least one method selected from electron beam evaporation, oblique angle deposition (OAD), sputtering, chemical vapor deposition (CVD), pulsed laser deposition (PLD), electroplating, spray coating, hydrothermal synthesis, sol-gel method, electrospinning, spin coating, and inkjet printing.

14. In Paragraph 11, A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized in that the above packaging step comprises wrapping a substrate having the sensing electrode and the nanostructure sensing layer formed thereon with a packaging that includes at least one selected from SiC, Al2O3, BN, DLC (Diamond-Like Carbon), PTFE (Polytetrafluoroethylene), and PEEK (Polyetheretherketone) and has at least one through hole formed therein.

15. In Paragraph 11, A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized by further including the step of forming a catalyst layer on the nanostructure sensing layer.

16. In Paragraph 15, A method for manufacturing a nanostructure-based high-performance radical and cation measuring device, characterized in that the step of forming the catalyst layer is performed by electron beam deposition of at least one selected from Pt, Pd, Au, Ru, Rh, Ir, TiN, ZrN, Ag, N, Cu, Fe, Co, Mn, Sn, Ce, La, Y, and Al at the end of the nanostructure sensing layer.

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