KR101857647B1 - forming method of hybrid pattern by vacuum deposition, manufacturing method of sensor device and sensor device thereby - Google Patents

Abstract

The present invention provides a method for forming a metal nanostructure pattern using a vacuum deposition process, the method comprising: a first step of forming a mask pattern layer exposing a part of the upper surface of the substrate; A second step of setting a vacuum deposition condition that satisfies a minimum critical radius of the metal nanostructure necessary for growth of the metal nanostructure on the substrate; A fourth step of forming a metal nanostructure pattern on the substrate by forming a metal nanostructure on an exposed region of the substrate by removing the mask pattern layer and a fourth step of forming a metal nanostructure pattern on the substrate, And a fifth step of forming a hybrid pattern by wet-etching a part of the substrate using And a hybrid method of pattern formation according to a vacuum deposition, characterized by the technical gist. Accordingly, the present invention provides a method of forming a metal nanostructure pattern on a substrate using a vacuum deposition process by setting vacuum deposition conditions that satisfy a minimum critical radius of the metal nanostructure necessary for growth of the metal nanostructure, Wet etching to provide a hybrid pattern in a part of the substrate.

Description

[0001] The present invention relates to a method of forming a hybrid pattern by vacuum deposition, a method of manufacturing a sensor element using the same,

The present invention relates to a method of forming a hybrid pattern by using a vacuum deposition process, and more particularly, to a method of forming a hybrid pattern using a vacuum vapor deposition process by setting a vacuum deposition condition satisfying a minimum critical radius of a metal nanostructure necessary for growing a metal nanostructure, And a method of forming a hybrid pattern by wet etching a substrate using the metal nanostructure pattern, a method of manufacturing a sensor element using the same, and a sensor element manufactured thereby.

In recent years, studies on nanostructures and their fabrication methods have been actively pursued in accordance with the trend toward high integration and miniaturization of devices. In general, nanostructures exhibit different properties depending on the particle size, material, and shape.

Such nanostructures are utilized in various fields such as materials, electric and electronic fields as well as biotechnology, and are used in various fields such as display, sensor, laser, LED, solar cell, and capacitor by forming a specific pattern.

In a conventional method of forming a nanostructure, a chemical process (Korean Patent No. 10-1032791) in which a dispersion solvent containing nanoparticles is coated on a substrate and a solvent is removed through a sintering process (Korean Patent No. 10-1032791) It has been widely used because it can be mass-produced at a high cost.

However, this conventional chemical method has disadvantages in that uniform adsorption of nanoparticles on a large-sized substrate is not easy, and the size control of nanoparticles is not easy and the utilization thereof is low.

In addition, this method is not easy to form a pattern, has a high temperature and pressure in a sintering process, and has difficulty in a process. It is difficult to uniformly disperse nanoparticles in a solvent and to distribute the nanoparticles uniformly on a substrate , And does not contribute to improvement of efficiency using nanoparticles.

In particular, nanoparticles exhibit various properties depending on the size, shape, etc. of the pattern. In order to utilize these characteristics, it is very important to control the pattern using nanoparticles for each application field and to form a pattern having a uniform distribution of nanoparticles in a desired shape and size at appropriate positions.

Accordingly, a method of forming a nanopattern by various methods has been studied, and a hybrid pattern in which a nanopattern and a micropattern are combined is also being studied.

A conventional method for forming a nano-pattern is a process including a photolithography process or a process including nano-imprint lithography, or a process for forming a seed layer on a substrate to form nanoparticles on the seed layer (Korean Patent No. 1419531, Application No. 10-2015-0001430).

A method of forming a hybrid pattern in which a nano pattern and a micro pattern are combined is generally formed by repeating a nano and microlithography process and a dry etching process more than twice (Korean Patent No. 1357087).

However, in the above method, since a mask (or a mask layer) or an imprint stamp corresponding to the size and density of the nanopattern must be fabricated, the process is complicated and the formation of a single type of nanopattern corresponding to the mask or imprint stamp pattern The control of the nano pattern is not easy and the process of depositing and removing the seed layer is required and the process is complicated. In addition, a process for forming a hybrid pattern in which a nano pattern and a micro pattern are combined involves two or more lithography processes and an etching process, which is a very complicated disadvantage.

Particularly, in the case of forming a detection substance used for a sensor element, a photoresist pattern is formed on a substrate, and a dispersion solvent containing nanoparticles by the chemical method is dropped on the substrate on which the photoresist pattern is formed Dropping or spin-coating. However, it is not easy to uniformly form a nanostructure in the detection material forming region due to the agglomeration of nanoparticles as described above. Thus, a highly sensitive sensor element There have been difficulties.

In addition, in the sensor element, a detection substance formation region is formed between the source electrode and the drain electrode. However, the structure of the miniaturized and highly integrated device has a disadvantage in that the area of the detection substance formation region is small and the sensor sensitivity is low.

In addition, these processes must be accompanied by a heat treatment process at a high temperature of 500 ° C or more, such as forming a nanostructure by inducing de-wetting by a heat treatment process. Thus, the time required for the temperature increase The process takes a long time and the heat treatment is carried out at a temperature higher than 500 ° C, which makes it difficult to form a nanostructure on a flexible substrate such as a polymer substrate.

Further, diffusion and intermixing of the element material may occur due to the heat treatment process at a high temperature, or the shape and thickness of the nanostructure may be deformed, which may degrade the quality and characteristics of the device. do.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and it is an object of the present invention to provide a method of forming a metal nanostructure pattern on a substrate using a vacuum deposition process by setting a vacuum deposition condition satisfying a minimum critical radius of a metal nanostructure necessary for growth of the metal nanostructure And a method of forming a hybrid pattern by etching the substrate using the same, a method of manufacturing a sensor element using the same, and a sensor element manufactured by the method.

According to an aspect of the present invention, there is provided a method for fabricating a semiconductor device, comprising the steps of: forming a mask pattern layer exposing a part of an upper surface of a substrate; A second step of setting a vacuum deposition condition satisfying a minimum critical radius of the nanostructure; a third step of growing a metal nanostructure on the exposed region of the substrate and the mask pattern layer by a vacuum deposition process; A fourth step of forming a metal nanostructure pattern on the substrate by forming a metal nanostructure on an exposed region of the substrate by removing a mask pattern layer and a fourth step of forming a metal nanostructure pattern on the substrate using a wet etching And a fifth step of forming a hybrid pattern by a vacuum deposition process And a turn-forming method with the technical gist.

In order to achieve the above object, the present invention also provides a GaN-based buffer layer formed on a substrate, a GaN layer formed on the buffer layer, an Al _x Ga _{1 - x} N layer formed on the GaN layer, an InAlN layer and an InAlGaN layer Preparing a substrate including one layer selected from the group consisting of a source electrode and a drain electrode formed on the one layer and masking the source electrode and the drain electrode, (B) forming a mask pattern layer for exposing a surface of the substrate; (b) forming a mask pattern layer for exposing the mask pattern layer; (D) growing a metal nanostructure on the exposed region of the substrate and the mask pattern layer by a vacuum deposition process, (d) Forming a metal nanostructure pattern on the substrate by forming a metal nanostructure on an exposed region of the substrate by removing the pattern layer to form a metal nanostructure pattern on the substrate, (B) forming a hybrid pattern on the surface of the silicon substrate; and (c) forming a hybrid pattern on the silicon substrate.

The present invention relates to a method of forming a metal nanostructure pattern on a substrate using a vacuum deposition process by setting a vacuum deposition condition satisfying a minimum critical radius of the metal nanostructure necessary for growth of the metal nanostructure, As a method of forming a hybrid pattern, there is no need to manufacture a separate mask or imprint stamp or a seed layer for manufacturing a metal nanostructure pattern, simplifying the process and facilitating the formation of a hybrid pattern.

In addition, it is possible to easily and easily form various types of metal nanostructure patterns according to vacuum deposition conditions, basically to uniformly distribute metal nanostructures on a substrate, The shape of the metal nanostructure can be easily formed while having a uniform metal nanostructure distribution as a whole, and the shape of the hybrid pattern can be easily and variously formed. Is expected.

In addition, by setting special vacuum deposition conditions, the conventional heat treatment process becomes unnecessary, and the process time for warming and lowering the temperature to a high temperature heat treatment temperature is drastically shortened, which is economical and prevents problems such as diffusion and mixing of device materials And it is possible to provide a high-quality device by minimizing the shape and thickness deformation of the metal nanostructure.

Particularly, in the case of forming the detection region used for the sensor element, the detection substance is formed on the detection substance formation region by the vacuum deposition process according to the specially set vacuum deposition conditions, not by the conventional chemical method, It is easy to form a uniform detection region, and there is an effect that a sensor element with high sensitivity can be provided.

In addition, in the sensor element, a detection substance formation region is formed between the source electrode and the drain electrode. The hybridization pattern is formed in the detection substance formation region and the detection substance is formed to widen the area of the detection substance formation region, Various sensing materials can be easily formed, and sensing of various materials can be performed while enhancing the sensitivity of the sensor element.

1 and 2 are schematic diagrams of a hybrid pattern formation method by vacuum deposition according to the present invention.
3 is a schematic view of a method of manufacturing a sensor element using a hybrid pattern by vacuum deposition according to the present invention.
Figure 4 - is a schematic diagram of a process in which a substrate is tilted according to another embodiment of the present invention.
5 is a view showing a mechanism for setting a deposition rate and a deposition thickness range to satisfy a minimum critical radius of a metal nanostructure for growing a metal nanostructure according to the present invention.
FIG. 6 is a SEM (Scanning Electron Microscope) image of a Au metal nano structure shape according to the control of an Au deposition thickness by an E-beam evaporator; FIG.
Figure 7 - Diameter distribution of Au metal nanostructures during 0.75, 1.5 and 5 nm thick Au deposition by electron beam evaporator.
Pt, and Pd metal nano-structures and Au, Pt, and Pd metal nano-structures, respectively, after depositing 1.5 nm thick Au, 1.5 nm thick Pt and 1.5 nm thick Pd on a Si substrate separately using an electron beam evaporator. (SEM and optical microscope image) and Energy Dispersive X-ray analysis (EDX).
FIG. 9 - Plating of 1.5 nm thick Pt and 1.5 nm thick Pd on an Si substrate in an in-situ manner continuously using an electron beam evaporator and then patterning of Pt and Pd composite metal nanostructures and Pt and Pd composite metal nanostructure patterns (SEM and optical microscope image) and component analysis (EDX).
FIG. 10 - SEM and optical microscope images of the Au metal nanostructure and Au metal nanostructure patterns after sputtering on a Si substrate with 1.5 nm thick Au deposition, Diameter distribution of metal nanostructure.
FIG. 11 is a SEM image of the shape change of the lower substrate according to the wet etching time control using the Au metal nanostructure. FIG.
FIG. 12 is a SEM image of a patterned substrate under change in wet etching time using Au metal nanostructure; FIG.
Figure 13 shows SEM images of the results of the Au metal nanostructure pattern using the nano / microscale-based substrate and the selective wet etching results of the underlying nano / microscale patterned substrate using the patterned Au metal nanostructure Degree.
FIG. 14 Au films of 0.75 nm and 1.5 nm thickness were deposited on a PC (Polycarbonate) substrate using an electron beam evaporator, and then the surface plasmon resonance (SPR) was measured using a UV-Vis spectrophotometer Resonance) Fig.
Fig. 15 - Diagram showing surface plasmon resonance characteristics analysis data using ultraviolet-visible spectrophotometer by 1 step process (black graph) and 2 step process (red graph).
16 - PC substrate was subjected to hydrophobic surface treatment and hydrophobic surface treatment, and 1.5 nm thick Au was deposited on a PC substrate using an electron beam evaporator, and then a surface plasmon resonance characteristic was measured using an ultraviolet-visible light spectrophotometer Fig.
Fig. 17 is a SEM image of a Si nanostructure depending on whether a hydrophilic surface treatment is performed on a part of a substrate having a metal nanostructure pattern formed thereon; Fig.

The present invention relates to a method for forming a metal nanostructure pattern using a vacuum deposition process, and more particularly, to a method of forming a metal nanostructure pattern by a vacuum deposition process by setting a vacuum deposition condition satisfying a minimum critical radius of a metal nanostructure necessary for growing a metal nanostructure, A metal nanostructure pattern is formed on the substrate, and the substrate is wet-etched using the metal nanostructure pattern to form a hybrid pattern on a part of the substrate.

As a result, there is no need to produce a separate mask or imprint stamp or a seed layer for manufacturing the metal nanostructure pattern, and the process is simple. Depending on the vacuum deposition conditions, the size, shape And position control can be easily performed and can be basically evenly distributed on a base material. Thus, various types of metal nanostructure patterns can be easily formed, and hybrid patterns using the same can be easily formed The application field is expected to be more diversified.

In addition, by setting special vacuum deposition conditions, a conventional heat treatment process is not required, and the process time for temperature rise and temperature at a high temperature heat treatment temperature is drastically shortened, and problems such as diffusion and mixing of device materials can be prevented Therefore, it is possible to provide a high-quality device by minimizing the shape and thickness deformation of the metal nanostructure pattern and the hybrid pattern.

Particularly, in the case of forming the detection material region used in the sensor element, the metal nanostructure pattern is formed on the detection substance formation region by a vacuum deposition process according to specially set vacuum deposition conditions, instead of forming by the conventional chemical method It is easy to form a uniform detection region by forming a hybrid pattern on the hybrid pattern by wet etching using the same, and it is possible to provide a highly sensitive sensor element.

In addition, in the sensor element, a detection substance formation region is formed between the source electrode and the drain electrode. By forming a hybrid pattern in the detection substance formation region and forming a detection substance, the area of the detection substance region is widened, The sensing material can be easily formed, and sensing of various materials can be performed while increasing the sensitivity of the sensor element.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a schematic view showing a method of forming a hybrid pattern by vacuum deposition according to the present invention, FIG. 3 is a schematic view of a method of manufacturing a sensor element using a hybrid pattern by vacuum deposition according to the present invention, 4 is a schematic diagram of a case where a substrate is tilted according to another embodiment of the present invention.

First, as shown in FIGS. 1 and 2, a method of forming a hybrid pattern by vacuum deposition according to the present invention includes a first step of forming a mask pattern layer exposing a part of the upper surface of the substrate, A second step of setting a vacuum deposition condition that satisfies a minimum critical radius of the metal nanostructure necessary for growth of the metal nanostructure on the mask pattern layer and the exposed region of the substrate by a vacuum deposition process; A third step of growing a metal nanostructure on the mask pattern layer; and a fourth step of forming a metal nanostructure on the exposed region of the substrate by removing the mask pattern layer to form a metal nanostructure pattern on the substrate, And a fifth step of forming a hybrid pattern by etching a part of the substrate using the metal nanostructure, .

The present invention forms a metal nanostructure pattern on a substrate. The metal nanostructure refers to a metal nanostructure having a size of several nanometers to several hundreds of nanometers and is not limited in its shape and size such as a cylinder, a cone, a sphere, In the present invention, the metal nanostructure is formed in a predetermined pattern so as to be suitable for the application field.

Such a metal nanostructure pattern may be formed in a single pattern on various types of substrates (substrate or thin film, transistor structure in a sensor element), or may be formed by repeating a single pattern or a combination of various patterns And these patterns may be implemented regularly or irregularly. The metal nanostructure forming material for this purpose may be a homogeneous or heterogeneous material and may be variously implemented as a single layer or a plurality of layers.

As shown in FIG. 1, the method for forming a hybrid pattern by vacuum deposition according to the present invention firstly forms a mask pattern layer exposing a part of the upper surface of the substrate. (Step 1)

As described above, various types of metal nanostructure patterns may be used depending on the application of the metal nanostructure pattern, and the substrate may be a thin film, a transistor structure in a sensor device, or the like.

Specifically, the substrate (the substrate in the transistor structure) may be formed of at least one selected from the group consisting of Si, GaAs, GaP, GaAsP, MgO, sapphire, quartz, and glass can be used.

Here, the substrate may be formed to be inclined at a predetermined angle with respect to a transport path of a target material (metal nanostructure material) to be vacuum-deposited, and the distribution and concentration of the metal nanostructure may be adjusted on the substrate to grow , So that the hybrid pattern may control the shape. This will be described in detail later.

On this substrate, a mask layer made of a thermosetting resin or a photocurable resin, specifically, an imprint resin, a lithography resist, or the like may be formed, or a photosensitive film using DFR (Dry Film Resist) or the like, a SiO ₂ SiN _x and a Si ₃ N ₄ is formed and then patterned to form a mask pattern layer such that a part of the upper surface of the substrate is exposed.

Here, after hydrophobic surface treatment of the surface of the substrate, the mask pattern layer is formed, or the mask pattern layer is formed, the surface of the exposed part of the upper surface of the substrate may be subjected to hydrophobic surface treatment.

The hydrophobic surface treatment may be performed before or after the mask pattern layer is formed according to the type of the base material and the mask pattern layer, the hydrophobic surface treatment method, and the surface of a part of the substrate exposed by the mask pattern layer, Coating or plasma treatment.

The hydrophobic material may be coated on the surface of the substrate with an anti-sticking material. The anti-sticking material may include octadecyltrichlorosilane (OTS), 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (FDTS), tridecafluoro- Any one of 1,1,2,2-tetra-hydrocytyltrichlorosilane (FOTS), dichlorodimethylsilane (DDMS) and diamond-like carbon (DLC) may be used.

Hydrophobic surface treatment of the substrate surface minimizes adhesion on the surface of the metal nanostructure, thereby increasing the contact angle between the metal nanostructure and the substrate surface to uniformly induce the size of the metal nanostructure generating nuclei, Thereby facilitating the formation of the nanostructure.

On the other hand, as shown in FIG. 2, irregularities may be formed on the substrate of the first step, and a mask pattern layer may be formed to expose a part of the upper surface of the substrate on which the irregularities are formed.

The irregularities are formed by forming a nano- or micro-scale pattern on the substrate by a separate patterning and etching process and then forming the mask pattern layer in a required area, will be.

After the hydrophobic surface treatment of the substrate surface on which the irregularities have been formed, a mask pattern layer may be formed to expose a part of the upper surface of the substrate on which the irregularities are formed. Alternatively, as shown in FIG. 2, And a hydrophobic surface treatment may be performed on a part of the substrate exposed by the mask pattern layer.

Here, before forming the mask layer for forming the mask pattern layer, a polymer layer may be formed on the substrate, and a mask pattern layer may be formed on the polymer layer.

The polymer layer may be selectively formed depending on the kind of the substrate, the purpose of use, the kind of the mask layer formed on the substrate, or the like, and the coating property and the film property of the mask layer formed on the polymer layer And etching resistance in the dry etching process in the patterning process, contributing to the precise formation of the mask pattern layer.

The polymer layer is formed by dry-etching a part of the polymer layer using the mask pattern layer as a dry etching mask to expose a part of the lower substrate in a part of the polymer layer, As the nanostructure is formed, it contributes to the formation of a precise metal nanostructure pattern.

The polymer layer may be formed of a material selected from the group consisting of polyvinyl chloride (PVC), neoprene, polyvinyl alcohol (PVA), poly methyl methacrylate (PMMA), polybenzyl methacrylate (PBMA), polystyrene, spin on glass (SOG), polydimethylsiloxane , Polyvinyl formal (PVFM), parylene, polyester, epoxy, polyether, polyimide, and lift-off resist (LOR).

After the formation of a mask pattern layer for exposing a part of the substrate, an exposed region of the substrate and a mask pattern layer are formed on the mask pattern layer by vacuum evaporation, which satisfies a minimum critical radius of the metal nano- (Second step).

That is, after setting the vacuum deposition conditions to satisfy the minimum critical radius for growing the metal nanostructure as a metal nanostructure without growing the metal nanostructure, the exposed region of the substrate and the mask pattern layer And then growing the metal nanostructure on the upper part. (Step 3)

The vacuum deposition conditions are preferably set such that the deposition rate is in a range of 0.01 nm / second to 5 nm / second and a thickness of 30 nm or less.

This shows the mechanism for setting the deposition rate and the deposition thickness range to satisfy the minimum critical radius (r _crit in FIG. 5) of the metal nanostructure for metal nanostructure growth, as shown in FIG.

As shown in FIG. 5, when the radius of the metal nanostructure is r _crit or more, the metal nanostructure can be continuously grown to grow as a crystal nucleus and exist as a stable metal nanostructure. When the radius is less than r _crit , the thermodynamically stable state can not be maintained, and the nucleus does not grow and the unstable particle state is maintained.

The vacuum deposition condition according to the present invention is that the deposition rate is in the range of 0.01 nm / sec to 5 nm / sec, and the metal nanostructure is grown to a thickness of 30 nm or less. The condition is that the radius of the metal nanostructure is r _Crit is equal to or less than the minimum radius condition that can grow into crystal nuclei.

In other words, when the deposition rate is out of the range, the metal nanostructure can not grow as a crystal nucleus and grows as a thin film mainly due to cotton growth rather than volume growth. If the thickness is thicker than that, And the growth is made into a thin film that is not a metal nanostructure.

By growing the metal nanostructure by the vacuum deposition process as described above, the metal nanostructure can be uniformly distributed on the substrate, and the size and shape of the metal nanostructure pattern as well as the position control can be easily controlled, Structure distribution.

In addition, although the uniform distribution of the metal nanostructure on the substrate can be achieved as described above, if necessary, the substrate is formed to be inclined at a predetermined angle with respect to the transport path of the target material (metal nanostructure material) And the distribution and the concentration of the metal nanostructure may be differently grown on the substrate.

When the wet etching process using the metal nano structure having such uneven distribution and concentration is performed, various shapes of the hybrid pattern can be realized.

The effect of growing the metal nanostructure to have such uneven distribution and concentration can be maximized when the irregularities are formed in a part of the base material of the first step as shown in Fig. 2 .

That is, FIG. 4 shows the case where the substrate provided with irregularities is arranged perpendicularly to the conveying path of the target material (perpendicular vapor deposition) and inclinedly arranged (bellow deposition), and when the substrate is inclined, The distribution of the structure is not uniform, and thus various hybrid patterns can be realized for each concave-convex pattern in the wet etching process using the metal nanostructure.

In particular, the present invention can be applied to a case where the area or the distribution of the hybrid pattern is to be adjusted according to the application field. In particular, by controlling the area of the detection substance formation region in the sensor element or the like, And to increase sensitivity.

The irregularities are formed by forming a nano- or micro-scale pattern on the substrate by a separate patterning and etching process and then forming the mask pattern layer in a required area, will be.

Further, by growing the metal nanostructure by a vacuum deposition process, it is unnecessary to manufacture a separate mask or imprint stamp or a seed layer for manufacturing the metal nanostructure pattern, so that the process is simple, and according to the vacuum deposition condition The control of the pattern of the metal nanostructure can be easily performed and the formation of various types of metal nanostructure patterns can be easily and easily formed.

After the vacuum deposition conditions are set, the metal nanostructure is grown on the exposed region of the substrate and on the mask pattern layer by a vacuum evaporation process under a vacuum deposition condition satisfying a minimum critical radius of the metal nanostructure .

That is, the metal nanostructure is grown under the conditions of the minimum critical radius for the formation of the metal nanostructure using the set vacuum deposition conditions.

The metal nanostructure may be first grown by a vacuum deposition process under a vacuum deposition condition satisfying the minimum critical radius of the metal nanostructure, and then the first grown metal nanostructure may be subjected to plasma treatment or heat treatment , And the metal nanostructure is grown secondarily with a relatively high deposition rate as compared with the vacuum deposition conditions.

Namely, a metal nanostructure having a minimum critical radius necessary for the formation of a metal nanostructure is formed at a low rate so as to form a metal nanostructure having a minimum critical radius in the first step, In the second step, the nucleation is performed at a relatively high deposition rate as compared with the vacuum deposition conditions in the first step, and then, By forming the nanostructure, crystallinity is improved in a short period of time as a whole, and a uniform metal nanostructure can be formed.

The metal nanostructure may be first grown by a vacuum deposition process under a vacuum deposition condition that satisfies the minimum critical radius of the metal nanostructure and then the first nanostructure may be grown at a deposition rate different from the deposition rate in the vacuum deposition condition The metal nanostructures in growth and the same or different metal nanostructures can be grown continuously (1 + n) (n is 1,2,3 ,,, n is a natural number).

That is, for the purpose of realizing the growth of the metal nanostructure having various composition profiles or crystal structures while controlling the crystallinity of the metal nanostructure by the (1 + n) step method, the metal nanostructure A low rate of deposition rate is set to produce a metal nanostructure having a minimum critical radius required for formation to induce nucleation of uniform size and a different deposition rate than the first step such as a higher deposition rate or a lower deposition rate (1 + n) (n is a natural number of 1, 2, 3, ...) at a deposition rate in which high and low are alternately realized, and the metal nanostructure is successively grown a number of times.

Here, the metal nanostructures grown in each deposition step can be grown with different deposition rates in the same kind, and can be grown with different deposition rates in different kinds.

As a result, various composition profiles, crystal structures, surface states, and shapes according to the deposition rate can be realized while achieving uniform growth and crystallinity of the metal nanostructure, thereby making it possible to adapt to various application fields.

In addition, plasma treatment or heat treatment may be selectively performed on the metal nanostructure grown in the preliminary step before the growth of the metal nanostructure in the next step after the first metal nanostructure is grown, So that the characteristics of the device can be improved.

As described above, in the present invention, by setting special vacuum deposition conditions for growing the metal nanostructure, a conventional heat treatment process is not required, and the process time for heating and lowering the temperature to a high temperature heat treatment temperature is remarkably shortened, It can be applied to a flexible substrate such as a fragile polymer substrate.

In addition, it is unnecessary to carry out a heat treatment process at a high temperature, thereby preventing problems such as diffusion and mixing of device materials, and it is possible to provide a high quality device by minimizing the shape and thickness deformation of metal nanostructure patterns and hybrid patterns .

The metal nanostructure may be variously provided depending on the application field. In particular, in the case of a sensor device, a variety of materials can be deposited depending on a substance to be detected, and gold (Au), silver (Ag) (Pt), Cu, Pd, Ni, W, Fe, Co, Ti, Cr, The substrate is vacuum-deposited using at least one of Zn, Zr, Molybdenum (Mo), Ir (Ir), Ru (ruthenium), Ta (tantalum) And the upper part of the mask pattern layer.

The growth of the metal nanostructure can be carried out plural times or a plurality of times of different materials of the same kind under the same deposition condition or different deposition conditions as required for the application field and the necessity.

The growth of such a metal nanostructure can be achieved by a vacuum deposition process according to a predetermined vacuum deposition condition, and can be realized by at least one of an electron beam evaporator, a thermal evaporation deposition, a sputtering, and a chemical vapor deposition have. However, the present invention is not limited to such a vacuum deposition process and a variety of known vacuum deposition processes or methods may be used as needed.

Here, the diameter of the metal nanostructure and the interval between the metal nanostructures can be basically controlled according to the vacuum deposition conditions. In addition, after the growth of the metal nanostructure by the vacuum deposition process, a heat treatment process or a plasma treatment process is performed The diameter of the metal nanostructure and the distance between the metal nanostructures can be controlled.

Then, after the metal nanostructure is grown on the exposed region of the substrate and the mask pattern layer, the mask pattern layer is removed to form a metal nanostructure on the exposed region of the substrate, Thereby forming a nanostructure pattern. (Step 4)

That is, when the mask pattern layer is removed on the substrate, a metal nanostructure pattern having a pattern corresponding to the mask pattern layer on the substrate is formed.

The chemical solution to be used may be acetone, isopropyl alcohol, water (H ₂ O), KOH, NaOH, NH ₄ OH, H ₂ SO ₄ , HF, HCl, H ₃ PO ₄ , HNO ₃ , CH ₃ COOH, H ₂ O ₂ and BOE (Buffered Oxide Etchant), and uses dipping or sonication.

On the other hand, an additional mask pattern layer may be formed after the removal of the mask pattern layer in accordance with the application field or the intended use, and the metal nano structure pattern on the substrate may be formed on the same region or another region on the substrate, The metal nanostructure pattern may be formed continuously or discontinuously with the metal nanostructure pattern of the fourth step by additionally forming the same or different kinds of metal nanostructure as the structure.

After the metal nanostructure pattern is formed on the substrate, a portion of the substrate is wet-etched using the metal nanostructure to form a hybrid pattern. (Step 5)

Here, the fifth step of the wet etching process is characterized by using a solution containing at least one of acid, water (H ₂ O), and peroxide (H ₂ O ₂ ) the etching depth may be controlled by controlling the mixing ratio of acid and peroxide (H ₂ O ₂ ) or adjusting the time of wet etching.

Generally, the wet etching process using a metal nano structure (metal) is a chemical etching using a metal, unlike a general chemical wet etching, in which the metal acts as a catalyst in the chemical reaction of wet etching, It has a feature to implement a large nano structure, and it can control the etching depth by adjusting mixing ratio or time of etching solution, thereby enabling various hybrid patterns to be realized. Herein, after the wet etching is completed, the metal nanostructure may be partially or wholly removed, but the metal nanostructure may be completely removed, and in the case where the metal nanostructure is completely removed, It is also possible to carry out a plurality of homogeneous or heterogeneous materials.

FIG. 4 is a schematic view of a hybrid pattern in the case of vertical deposition and bump deposition on a substrate having unevenness as described above. In FIG. 4 (a), in the case of vertical deposition and bump deposition, FIG. 4 (b) shows the difference in the hybrid pattern when the wet etching using the metal nanostructure was performed, the vertical deposition and the bump deposition, and FIG. 4 (c) FIG. 4 (d) shows a case where wet etching is performed using other types of metal nanostructures in the state of FIG. 4 (c) .

As described above, according to the present invention, various types of hybrid patterns can be realized very easily according to the kind of the metal nanostructure, the mixing ratio of the etchant, and the wetting time according to the vertical deposition and the sputtering deposition.

In addition, a homogeneous or heterogeneous metal nanostructure may be additionally formed on the hybrid pattern of the fifth step so as to be utilized as a device having a metal nanostructure pattern formed thereon. In accordance with the shape of the hybrid pattern, A different kind of metal nanostructure may be further grown to allow the metal nanostructure to penetrate into the hybrid pattern.

In this case, the hydrophilic surface treatment is performed on a part of the substrate where the metal nanostructure pattern of the fourth step is formed, and the etching rate by the wet etching using the metal nanostructure is remarkably improved to improve the surface area of the hybrid pattern Thereby improving the sensitivity of the sensor when used in a sensor element.

In the hydrophilic surface treatment of the substrate, an oxide layer is coated on the substrate, oxygen plasma treatment or the like is performed to improve the wettability on the surface of the substrate, and the penetration of the etchant can be precisely performed.

In addition, although the uniform distribution of the metal nanostructure on the substrate can be achieved as described above, if necessary, the substrate is formed to be inclined at a predetermined angle with respect to the transport path of the target material (metal nanostructure material) And the distribution and the concentration of the metal nanostructure may be differently grown on the substrate.

When the wet etching process using the metal nano structure having such uneven distribution and concentration is performed, various shapes of the hybrid pattern can be realized.

The effect of growing the metal nanostructure to have such uneven distribution and concentration can be maximized when the irregularities are formed in a part of the base material of the first step as shown in Fig. 2 .

That is, FIG. 4 shows the case where the substrate provided with irregularities is arranged perpendicularly to the conveying path of the target material (perpendicular vapor deposition) and inclinedly arranged (bellow deposition), and when the substrate is inclined, The distribution of the structure is not uniform, and thus various hybrid patterns can be realized for each concave-convex pattern in the wet etching process using the metal nanostructure.

In particular, the present invention can be applied to a case where the area or the distribution of the hybrid pattern is to be adjusted according to the application field. In particular, by controlling the area of the detection substance formation region in the sensor element or the like, And to increase sensitivity.

FIG. 3 is a schematic view of a method of manufacturing a sensor element using a hybrid pattern by vacuum evaporation, which includes a GaN buffer layer formed on a substrate, a GaN layer formed on the buffer layer, an Al _x Ga _{1 -x} N layer, an InAlN layer, and an InAlGaN layer, and a source electrode and a drain electrode formed on the one layer, the method comprising the steps of: (a) (B) forming a mask pattern layer that exposes a part of the upper surface of the substrate while masking the drain electrode, and (b) forming a mask pattern layer on the exposed region of the substrate and a metal (C) setting a vacuum deposition condition satisfying a minimum critical radius of the nanostructure; and (c) (D) growing a metal nanostructure on the substrate; (d) removing the mask pattern layer to form a metal nanostructure on the exposed region of the substrate to form a metal nanostructure pattern on the substrate; And forming a hybrid pattern by wet-etching a portion of the substrate using the metal nanostructure.

The major structure (step (a)) of the above-described HEMT (High Electron Mobility Transistor) device is a well-known technique, which is a method of manufacturing a sensor having a high electron mobility transistor structure No. 10-2016-0036136), and a detailed description thereof will be omitted in the present invention.

A mask pattern layer is basically formed on a substrate and a metal nanostructure pattern is formed by a vacuum deposition process in a manner similar to that in the above-described hybrid pattern formation method by vacuum deposition, and a duplicate description will be omitted , described in this example is, as for application to the transistor structure, the sensor element (e.g., HEMT), Al _x formed on a buffer layer of GaN-based formed on the substrate, the GaN layer, the GaN layer formed on the buffer layer A Ga _{1 - x} N layer, an InAlN layer and an InAlGaN layer, and a source electrode and a drain electrode formed on the one layer.

A mask pattern layer for exposing a part of the upper surface of the substrate is formed while masking the source electrode and the drain electrode on the substrate.

The x value of the Al _x Ga _{1 - x} N layer is 0 <x? 1, and a GaN cap layer having a thickness of 10 nm or less may be additionally formed on the one layer.

After the mask pattern is masked with the source and drain electrodes and a mask pattern layer is formed to expose a part of the upper surface of the substrate (after the step (b)), a part of the one layer is etched Regions can be formed.

The recessed region is a part of the exposed upper part of the substrate, that is, a part of the area between the source electrode and the drain electrode. By etching the recessed area, the area of the sensing material forming area is widened to increase the sensor sensitivity.

The formation of the recessed region may be realized by dry or wet etching after masking an area other than the region where the recessed region is to be formed.

In this case, the metal nanostructure is grown by setting deposition conditions that satisfy the minimum critical radius condition for forming the metal nanostructure as described above on the exposed part of the substrate, thereby forming a metal nano structure corresponding to the mask pattern layer Thereby forming a structure pattern.

A part of the exposed upper part of the substrate on which the metal nanostructure is grown is a part of the region between the source electrode and the drain electrode, and a detection material layer of the sensor element is formed on this area. The metal nanostructure is grown as a detection substance for the metal nanostructure.

Here, the metal nanostructure for forming the detection material layer may be at least one selected from the group consisting of Au, Ag, Pt, Cu, Pd, Ni, (Fe), Co, Ti, Cr, Mn, Zn, Zr, Molybdenum, Ir, Ru), tantalum (Ta), and alloys thereof. The material is selected by reacting with a gas or a biochemical substance to be detected and capable of changing the potential of the HEMT active layer use.

For example, Pd, Pt or Pd and Pt are used as the detection substance of hydrogen gas, ZnO nanowire is used as a detection substance of Co gas, InZnO is used as detection substance of oxygen gas, Ag / AgCl electrode, ZnO nanorod as a detection substance of clucose or lactic acid, and thioglycolic acid / Au as a detection substance of water temperature ion.

As shown in FIG. 3, the metal nanostructure may be grown in the same or different materials a plurality of times as described above, depending on the substance or environment to be sensed, in addition to the above-exemplified detection substances, After the removal of the mask pattern layer, an additional mask pattern layer is formed, and on the same area or another area where the metal nanostructure pattern on the substrate is formed, a metal nanostructure homologous or heterogeneous to the metal nanostructure of step (D) The metal nanostructure pattern may be formed continuously or discontinuously with the metal nanostructure pattern of step (e).

The metal nanostructure is used to wet-etch a part of the substrate to form a hybrid pattern on the substrate of the sensor element. In this case, all or part of the remaining metal nanostructures function as a sensing material of the sensor element, and if necessary, the same or different metal nanostructures can be further formed on the hybrid pattern, The metal nanostructure formed additionally according to the shape of the pattern may be formed to penetrate into the inside of the hybrid pattern.

In this case, hydrophilic surface treatment is performed on a part of the base material on which the metal nanostructure pattern is formed, and the surface area of the hybrid pattern can be improved by significantly improving the etching rate by wet etching using the metal nanostructure, It is possible to improve the sensitivity of the sensor when used in the device.

In the hydrophilic surface treatment of the substrate, an oxide layer is coated on the substrate, oxygen plasma treatment or the like is performed to improve the wettability on the surface of the substrate, and the penetration of the etchant is efficiently performed. As a result, the formation of a large surface area of a hybrid pattern having a high aspect ratio can be easily realized, and the detection material area can be widened when used as a sensor element, thereby improving the efficiency and sensitivity of the sensor.

As described above, in the sensor element, the detection substance formation region is formed between the source electrode and the drain electrode. The hybridization pattern is formed in the detection substance formation region and the detection substance is formed, Various sensing materials can be easily formed, and sensing of various materials can be performed while increasing the sensitivity of the sensor element.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 6 is a SEM measurement result of the surface of Au deposited on an Si substrate at 0.75 nm, 1.5 nm, 5 nm, 10 nm, and 20 nm at a deposition rate of 0.025 nm / sec using an electron beam evaporator. Au metal nanostructures increased in size as the thickness of the Au deposition increased, and thinner as the Au thickness was larger than 20 nm. That is, when the Au thickness is 20 nm, it is confirmed that the size of the Au metal nanostructure can be controlled by controlling the thickness of the Au deposition.

FIG. 7 shows the size distribution of the Au metal nano-structure in the case where Au is deposited on Si substrates at 0.75 nm, 1.5 nm, and 5 nm at a deposition rate of 0.025 nm / sec using an electron beam evaporator, respectively. When the Au thicknesses were 0.75 nm, 1.5 nm, and 5 nm, respectively, the average diameter of the Au metal nanostructures was 4.6 nm, 8.3 nm, and 16.9 nm, respectively. It was confirmed that the diameter and diameter distribution of the Au metal nanostructure can be controlled by controlling the Au thickness.

After the rectangular regions (10 탆 by 75 탆 and 20 탆 by 80 탆) were opened with a photoresist on the top of the Si substrate, the thicknesses of Au, Pt and Pd were 1.5 nm 8 (a), (d) and (g), the pattern results of the metal nanostructures after the N ₂ blowing are shown in FIGS. 8 (a) Figs. 8 (b), 8 (e) and 8 (h) show the results of measuring the shape of the Au, Pt and Pd metal nanostructures. In addition, it is possible to form Au, Pt and Pd metal nanostructures and Au, Pt and Pd metal nanostructure patterns on the Si substrate through EDX component analysis (FIGS. 8 (c), (f) and (i) Respectively.

After opening the rectangular region (10 ㎛ by 75 ㎛ and 20 ㎛ by 80 ㎛) on the top of the Si substrate with a photoresist, the thickness of Pt and Pd was reduced to 1.5 nm at an evaporation rate of 0.025 nm / sec using an electron beam evaporator -Situ After continuous deposition, the pattern results of the composite metal nanostructure are shown in FIG. 9 (a), after dipping in acetone to remove the photoresist and ultrasonication for 10 minutes, and after N ₂ blowing, the shape of the composite metal nanostructure The measurement result is shown in Fig. 9 (b). In addition, it was confirmed through the EDX component analysis (Fig. 9 (c)) that formation of Pt and Pd composite metal nanostructures on the Si substrate and production of Pt and Pd composite metal nanostructure patterns were confirmed.

After opening only a rectangular area (10 μm by 75 μm and 20 μm by 80 μm) on the top of the Si substrate with a photoresist, Au was deposited to a thickness of 1.5 nm at a deposition rate of 0.25 nm / sec using sputtering, 10 (a) and 10 (b) show pattern results and shape measurement results of the Au metal nanostructure after Dipping in acetone and Ultrasonication for 10 minutes to remove the resist and N ₂ blowing. 10 (c)], it was confirmed that the Au metal nanostructure and the Au metal nanostructure pattern could be formed on the Si substrate, and the average diameter of the Au metal nanostructure was 16.2 nm 10 (d). From this result, it was possible to form an Au nanostructure having a metal nanostructure similar to an electron beam evaporator. 7 (b) and 10 (d), the deposition rate was 0.025 nm / sec (average diameter 8.3 nm) to 0.25 nm / sec (average diameter 16.2 nm], the average diameter of the Au metal nanostructures increased. From these results, it was confirmed that the deposition rate is a factor in controlling the size of the Au metal nanostructure.

Au was deposited to a thickness of 1.5 nm on the Si substrate at a deposition rate of 0.025 nm / sec using an electron beam evaporator. 18.2 ml of hydrofluoric acid (HF), 1.8 ml of hydrogen peroxide (H ₂ O ₂ ) and 80 ml of water (H ₂ O) The Au metal nanostructure formed on the Si substrate was immersed in the mixed solution for a predetermined period of time (0.5 minutes (FIG. 11B), 1.5 minutes (FIG. 11C), 3.0 minutes 11 (e)]), rinsed in deionized water, and then subjected to N ₂ blowing. 11 is a SEM measurement result of the surface change with the change of the wet etching time. It is confirmed that the wet etching of the lower substrate is possible by using the Au metal nanostructure formed by this method.

A resist pattern of 50 nm line and 50 nm space structure was formed on the upper surface of the Si substrate by electron beam lithography and then the resist pattern was used as an etching mask for dry etching the lower Si substrate to obtain a Si substrate having a 100 nm height and a 50 nm line pattern Respectively. Then, Au was deposited to a thickness of 1.5 nm at a deposition rate of 0.025 nm / sec using an electron beam evaporator on top of a Si substrate having a 50 nm line pattern, and 18.2 ml of hydrofluoric acid (HF), 1.8 ml of hydrogen peroxide (H ₂ O ₂ ) (H ₂ O) to Au metal nano-structure formed on a Si substrate in a solution mixture of 80ml predetermined time (0.5 min [Figure 12 (b)], 1.5 minutes [Fig. 12 (c)], 3.0 minutes [12 ( d)] and 5.0 minutes [Fig. 12 (e)]), rinsing with deionized water and N ₂ blowing. SEM measurement results of the surface change with the wet etching time are shown in FIG. The Au metal nanostructure can be formed on the lower substrate on which the pattern (concavity and convexity) is formed, and it is confirmed that the wet etching of the lower substrate having the pattern (concavity and convexity) is possible using the Au metal nano structure formed.

After forming 50nm line, 500nm line and 1μm line pattern on the top of Si substrate using electron beam lithography or photolithography, electron beam lithography or photolithography resist pattern is used as an etching mask for dry etching the lower Si substrate A Si substrate having a height of 200 nm, a 50 nm line, a 500 nm line and a 1 μm line pattern was manufactured.

950 PMMA A5 (Micro Chem Co., USA) was spin coated on the top of a Si substrate having a 50 nm line, a 500 nm line and a 1 μm line (nano or micro) structure at 2000 rpm and baked at 170 ° C. for 300 seconds to form a (PFPE) resin was dropped on the silicon master stamp (Si Stamp having a hole diameter of 300 nm) and the PET (polyethylene-terephthalate) substrate was squeezed. Then, ultraviolet rays were irradiated for 3 minutes To produce a pillar-patterned PFPE mold. The imprint resin was spin-coated on the top of the PMMA layer with NIP-SC28LV400 (Chem. Optics, Korea), and the pillar-patterned PFPE stamps were pressed, irradiated with ultraviolet rays for 2 minutes, An imprint pattern having a hole diameter was formed on top of a Si structure having a 50 nm line, a 500 nm line and a 1 탆 line pattern. The imprint remnant film was then removed and the PMMA layer under the 300 nm Hole was etched to expose the surface of the Si structure with 50 nm line, 500 nm line and 1 μm line pattern below the 300 nm diameter hole, 13 (a).

13 (b) shows the result of deposition of Au with a thickness of 1.5 nm at a deposition rate of 0.025 nm / sec using an electron beam evaporator on top of the fabricated nano / micropatterned Si substrate. As can be seen in FIG. 13 (b), it was confirmed that Au metal nanostructure was formed inside the hole.

13 (c) shows the result of N ₂ blowing after dipping in acetone for 10 minutes and ultrasound treatment for 10 minutes. Au metal nanostructures were formed on top of Si structures of 50 nm line, 500 nm line and 1 μm line (nano or micro) Was patterned in a hole region having a diameter of 300 nm.

The Au metal nanostructure pattern on the top of the 50 nm line, 500 nm line and 1 um line (nano or micro) Si structure was treated with 18.2 ml of HF, 1.8 ml of hydrogen peroxide (H ₂ O ₂ ) and 80 ml of water (H ₂ O) Fig. 13 (d) shows the result of immersing in the mixed solution for 1.5 minutes, rinsing in deionized water, and N ₂ blowing. Nano / nano / microscale hybrid patterns of three-dimensional shape were confirmed by selectively wet-etching the nano- or micro-scale Si structure underlying the Au metal nanostructure patterned in the hole.

FIG. 14 is a graph showing the relationship between the surface plasmon resonance and the surface plasmon resonance of the surface plasmon resonance spectroscopy (hereinafter, referred to as &quot; surface plasmon resonance &quot;) using an electron beam evaporator and depositing Au on the PC substrate with a thickness of 0.75 nm and 1.5 nm at a deposition rate of 0.025 nm / The results of the characteristics analysis. The maximum resonance absorption peak positions were 574 nm and 626 nm when Au of 0.75 nm thickness (average diameter of Au metal nanostructure: 4.6 nm) and 1.5 nm thickness (average diameter of Au metal nanostructure: 8.3 nm) were deposited, respectively. As a result, it was confirmed that the position of the peak of maximum resonance absorption shifted to a short wavelength (Blue Shift) as the average diameter of the Au metal nanostructure was reduced through the measurement of ultraviolet-visible light spectrophotometer. It can be confirmed that precise control of the diameter distribution is possible.

FIG. 15 shows the data of the surface plasmon resonance characterization using ultraviolet-visible light spectrophotometer by a 1 step process (black graph) and a 2 step process (red graph). It can be seen that the maximum absorption peak wavelength value is shifted to a short wavelength in the Au metal nano structure by the 2 step method compared to the one step and the full width at half maximum (FWHM) value of the Au metal nano structure by the 2 step method is It was confirmed that the value was smaller than that obtained by the 1 step method. That is, it can be seen that the diameter of the Au metal nanostructure by the 2-step method is smaller than that of the maximum absorption peak wavelength shifted to a shorter wavelength. From the point that the half width value of the peak is small, the Au metal nanostructure It was confirmed that the size distribution of the sample was narrower (Narrow). It can be confirmed from the present embodiment that the metal nanostructure can be formed even more uniformly by the 2 step method. In addition, the first step through the two-step method induces nucleation at a low deposition rate to induce nucleation of the nucleus by external energy, and then the second step rapidly deposits the Au metal nanostructure And the formation time can be shortened.

The hydrophobic surface treatment was performed by heating the PC substrate and the FOTS solution in a sealed space at 80 ^° C for 15 minutes using a vacuum oven. The FOTS solution was vaporized and bonded onto the PC substrate, The surface was subjected to a hydrophobic treatment. FIG. 16 is a graph showing the results obtained by depositing 1.5 nm thick Au on a hydrophobic surface treated PC substrate and a PC substrate not subjected to a hydrophobic surface treatment using an electron beam evaporator as described above, using an ultraviolet-visible light spectrophotometer Surface plasmon resonance characteristics. In the case of the sample subjected to the hydrophobic surface treatment on the PC substrate, it can be seen that the maximum absorption peak wavelength value of the Au metal nanostructure is shifted to a short wavelength as compared with the sample not subjected to the hydrophobic surface treatment. It was confirmed that the half width value of the structure was smaller than the half width value of the Au metal nanostructure of the sample not subjected to the hydrophobic surface treatment. That is, it can be seen that the diameter of the Au metal nanostructure of the sample subjected to the hydrophobic surface treatment is smaller than the point of the maximum absorption peak wavelength shifted to the shorter wavelength. From the point that the half width value of the peak is smaller, Au metal nanostructure size distribution was narrower. It was confirmed that the hydrophobic surface treatment of the substrate or the thin film can form a metal nanostructure having a uniform size of the metal nanostructure and a narrow size distribution as compared with the case where the surface treatment is not performed.

17 shows an electron microscope image of a Si nanostructure according to whether or not a hydrophilic surface treatment is performed on a part of a substrate having a metal nanostructure pattern formed thereon. FIG. 17 (a) shows a hydrophilic surface And Fig. 17 (b) shows a case where a hydrophilic surface treatment is performed on the Si substrate on which unevenness is formed by the oxygen plasma treatment.

Oxygen plasma treatment was carried out for 30 seconds under conditions of 2500 sccm of oxygen gas, 1000 W of power, and 1 Torr of pressure. As a result, it was confirmed that a wet etching was performed to easily form a large surface area of a hybrid pattern having a high aspect ratio on the Si substrate.

Claims (32)

A first step of forming a mask pattern layer exposing a part of the upper surface of the substrate;
A second step of setting a vacuum deposition condition that satisfies a minimum critical radius of the metal nanostructure necessary for growing the metal nanostructure on the exposed region of the substrate and the mask pattern layer;
A third step of growing the metal nanostructure on the exposed region of the substrate and the mask pattern layer by a vacuum deposition process;
A fourth step of removing the mask pattern layer to form a metal nanostructure on an exposed region of the substrate to form a metal nanostructure pattern on the substrate; And
And a fifth step of wet-etching a part of the substrate using the metal nanostructure to form a hybrid pattern,
The third step is a step of firstly growing the metal nanostructure by a vacuum deposition process under a vacuum deposition condition that satisfies a minimum critical radius of the metal nanostructure of the second step, The metal nanostructure and the same kind or different kind of metal nanostructure in the first growth are successively grown at (1 + n) (n is 1, 2, 3 ,, and n is a natural number) at different deposition rates Wherein the hybrid pattern is formed by vacuum deposition. 2. The method according to claim 1,
Wherein the metal nanostructure is grown by a vacuum deposition process under a vacuum deposition condition satisfying a minimum critical radius of the metal nanostructure of the second stage. 2. The method according to claim 1,
The metal nanostructure is first grown by a vacuum deposition process under a vacuum deposition condition satisfying a minimum critical radius of the metal nanostructure of the second stage,
The first grown metal nanostructure is subjected to plasma treatment or heat treatment,
Wherein the metal nanostructure is grown at a relatively higher deposition rate than the vacuum deposition conditions. delete 2. The method of claim 1, wherein after growing the first-order metal nanostructure,
Wherein the metal nanostructure grown in the previous step before the growth of the metal nanostructure is selectively subjected to plasma treatment or heat treatment. 2. The method according to claim 1,
Wherein the metal nanostructure is grown by inclining the substrate at a predetermined angle. The method according to claim 1, wherein the vacuum deposition conditions in the second step include:
Wherein the deposition rate is set to a thickness of 30 nm or less in a range of 0.01 nm / second to 5 nm / second. The hybrid pattern forming method according to claim 1, wherein the substrate of the first step is provided with concave and convex portions, and a mask pattern layer is formed to expose a part of the upper surface of the substrate on which the concavities and convexities are formed. The hybrid pattern forming method according to claim 1, wherein after the mask pattern layer of the first step is formed, a part of the exposed top of the substrate is subjected to hydrophobic surface treatment. 2. The method according to claim 1,
A polymer layer is formed on the substrate, a mask pattern layer is formed on the polymer layer,
Wherein the polymer layer
Polyvinyl Chloride (PVC), Neoprene, PVA (Polyvinyl Alcohol), PMMA (Poly Methyl Meta Acrylate), PBMA (Poly Benzyl Meta Acrylate), PolyStylene, SOG (Spin On Glass), PDMS (Polydimethylsiloxane) , Parylene, Polyester, Epoxy, Polyether, Polyimide, and Lift-Off Resist (LOR). The method of claim 1, wherein the metal nanostructure comprises:
A metal such as gold, gold, silver, platinum, copper, palladium, nickel, tungsten, iron, cobalt, titanium, And any one of chromium (Cr), manganese (Mn), zinc (Zn), zirconium (Zr), molybdenum (Mo), iridium (Ir), ruthenium (Ru), tantalum Or more of the above-mentioned material is used. 2. The method of claim 1, wherein the growth of the metal nanostructure in the third step comprises:
Wherein the vapor deposition is carried out plural times with a homogeneous material or a heterogeneous material. 2. The method of claim 1, wherein after growing the metal nanostructure in the third step,
Wherein a heat treatment process or a plasma treatment process is further implemented. The method as claimed in claim 1,
After the removal of the mask pattern layer, an additional mask pattern layer is formed,
The metal nanostructure of the third step is further formed with the same or different kind of metal nanostructure as the metal nanostructure of the third step on the same area or another area where the metal nanostructure pattern on the substrate is formed, Or a discontinuous metal nanostructure pattern is additionally formed on the surface of the substrate. The hybrid pattern forming method according to claim 1, wherein the metal nanostructure is further formed on the hybrid pattern of the fifth step or the metal nanostructure is penetrated into the hybrid pattern. 16. The method according to claim 15, wherein a hydrophilic surface treatment is performed on a part of the substrate on which the metal nanostructure pattern of the fourth step is formed. A GaN buffer layer formed on the substrate, a GaN layer formed on the buffer layer, an Al _x Ga _{1 - x} N layer formed on the GaN layer, an InAlN layer and an InAlGaN layer, (A) preparing a substrate comprising a source electrode and a drain electrode formed on a layer of species;
(B) forming a mask pattern layer for masking the source electrode and the drain electrode and exposing a part of the upper portion of the substrate;
(C) setting a vacuum deposition condition satisfying a minimum critical radius of the metal nanostructure necessary for growing the metal nanostructure on the exposed region of the substrate and the mask pattern layer;
(D) growing a metal nanostructure on the exposed region of the substrate and the mask pattern layer by a vacuum deposition process;
Removing the mask pattern layer to form a metal nanostructure on the exposed region of the substrate to form a metal nanostructure pattern on the substrate; And
And forming a hybrid pattern by wet-etching a portion of the substrate using the metal nanostructure. The method of manufacturing a sensor device using a hybrid pattern according to claim 1, 18. The method of claim 17, wherein the step (d)
Wherein the metal nanostructure is grown by a vacuum deposition process under a vacuum deposition condition satisfying the minimum critical radius of the metal nanostructure of the step (c). 18. The method of claim 17, wherein the step (d)
The metal nanostructure is first grown by a vacuum deposition process under a vacuum deposition condition satisfying the minimum critical radius of the metal nanostructure in the step (c)
The first grown metal nanostructure is subjected to plasma treatment or heat treatment,
Wherein the metal nanostructure is grown at a relatively higher deposition rate than that of the vacuum deposition condition by a secondary deposition. 18. The method of claim 17, wherein the step (d)
The metal nanostructure is first grown by a vacuum deposition process under a vacuum deposition condition satisfying the minimum critical radius of the metal nanostructure in the step (c)
(1 + n) (n = 1, 2, 3, ..., n) of the metal nanostructure and the same or different metal nanostructures in the first growth at a deposition rate different from the deposition rate in the vacuum deposition condition and n is a natural number). 2. A method of manufacturing a sensor element using a hybrid pattern by vacuum deposition. 21. The method according to claim 20, wherein after the primary metal nanostructure is grown,
Wherein the metal nanostructure grown in the previous step before the growth of the metal nanostructure is selectively subjected to plasma treatment or heat treatment. 18. The method of claim 17, wherein the step (d)
Wherein the metal nanostructure is grown by inclining the substrate at a predetermined angle. 2. The method of manufacturing a sensor element according to claim 1, 18. The method of claim 17, wherein the vacuum deposition conditions in step (c)
Wherein the deposition rate is set to a thickness of 30 nm or less in a range of 0.01 nm / second to 5 nm / second. The method according to claim 17, wherein after the mask pattern layer in the step (b) is formed, a part of the exposed upper surface of the substrate is subjected to hydrophobic surface treatment, and a method of manufacturing a sensor element using the hybrid pattern by vacuum deposition . 18. The method of claim 17, wherein step (b)
Forming a polymer layer on the substrate, forming a mask pattern layer on the polymer layer,
Wherein the polymer layer
Polyvinyl Chloride (PVC), Neoprene, PVA (Polyvinyl Alcohol), PMMA (Poly Methyl Meta Acrylate), PBMA (Poly Benzyl Meta Acrylate), PolyStylene, SOG (Spin On Glass), PDMS (Polydimethylsiloxane) , Parylene, Polyester, Epoxy, Polyether, Polyimide, and Lift-Off Resist (LOR). 2. A method of manufacturing a sensor element using a hybrid pattern by vacuum deposition. 18. The method of claim 17, wherein the metal nanostructure comprises:
A metal such as gold, gold, silver, platinum, copper, palladium, nickel, tungsten, iron, cobalt, titanium, And any one of chromium (Cr), manganese (Mn), zinc (Zn), zirconium (Zr), molybdenum (Mo), iridium (Ir), ruthenium (Ru), tantalum Wherein the vacuum deposition is performed using a vacuum deposition method using the above material. 18. The method of claim 17, wherein the growth of the metal nanostructure in step (d)
Wherein the vapor deposition is performed a plurality of times with the same material or different kinds of materials. 18. The method of claim 17, wherein after growing the metal nanostructure of step (d)
Wherein a heat treatment process or a plasma treatment process is further implemented. The method of manufacturing a sensor device using a hybrid pattern by vacuum deposition. 18. The method of claim 17, wherein the step (e)
After the removal of the mask pattern layer, an additional mask pattern layer is formed,
(D) additionally forming a metal nanostructure of the same or different kind as the metal nanostructure in step (d) on the same area or another area where the metal nanostructure pattern on the substrate is formed, And a continuous or discontinuous metallic nanostructure pattern is additionally formed on the surface of the substrate. 18. The method according to claim 17, wherein the metal nanostructure is further formed on the hybrid pattern of step (b), or the metal nanostructure is penetrated into the hybrid pattern. A method of manufacturing a sensor element. The method of manufacturing a sensor element according to claim 30, wherein a hydrophilic surface treatment is performed on a part of the base material on which the metal nanostructure pattern is formed in step (e). 32. A sensor element manufactured by the manufacturing method of any one of claims 17 to 31, wherein a sensor detecting material is penetrated into the hybrid pattern.

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