KR102467610B1 - Forming method of surface control 3D nano-structure, Surface control 3D nano-structure and Photoelectronic device Thereby - Google Patents

Abstract

The present invention relates to a surface-controlled three-dimensional nanostructure, comprising the steps of forming a plurality of surface control layers having different etch resistance on top of a substrate, and by an exposure process, each of the surface control layers has different sizes according to the etch resistance. Forming another control pattern, but forming an extension-cut on the lower control pattern compared to the upper control pattern to secure a surface control area on the substrate, and masking the plurality of surface control layers on which the control pattern is formed. A method for forming a surface-controlled three-dimensional nanostructure comprising the steps of forming a first nanostructure in the surface control region and removing the surface control layer, and the surface-controlled three-dimensional nanostructure formed thereby And the photoelectric device using this is the technical point. Accordingly, a surface-controlled 3D nanostructure is provided on the substrate to improve its properties by controlling the surface of the substrate (surface area expansion, surface shape control, surface property control, etc.) by forming a surface-controlled 3D nanostructure on the substrate. A photoelectric device with maximized light extraction efficiency is provided.

Description

Forming method of surface control 3D nano-structure, Surface control 3D nano-structure and Photoelectronic device Thereby

The present invention relates to a surface-controlled three-dimensional nanostructure, and a method for forming a surface-controlled three-dimensional nanostructure for improving its properties by controlling the surface of a substrate by forming a surface-controlled three-dimensional nanostructure on a substrate and controlling the surface formed thereby It is about 3D nanostructures and optoelectronic devices.

Photoelectronic devices are devices that convert light energy into electrical energy, such as Light Emitting Diodes (LEDs), Micro-LEDs, Solar cells, and Laser Diodes. LD), photo diode (PD), avalanche photo diode (APD), and the like.

Such optoelectronic devices are applied to various electrical and electronic products, and research is focused on performance improvement for high integration and high efficiency according to the trend of miniaturization and high performance of electrical and electronic products.

Recently, attempts have been made to form a nano or micro structure suitable for high efficiency by improving the surface area of a component that absorbs or emits light in the structure of an optoelectronic device.

Among these photoelectric devices, light emitting diodes have a long lifespan, reduce power consumption and maintenance costs, and are used in various fields such as displays, semiconductors, solar cells, lighting devices, bio, optical communication, and optical sensors. Researchers are trying various methods to realize this.

In general, a light emitting diode includes an n-type semiconductor layer, an active layer, and a p-type semiconductor layer, and when current flows in the forward direction through the n-type semiconductor layer and the p-type semiconductor layer, electrons and holes injected into the active layer recombine to emit light. will cause

Efficiency, that is, light efficiency, in these light emitting diodes is determined by internal quantum efficiency and light extraction efficiency (external quantum efficiency), but unlike internal quantum efficiency, light extraction efficiency is significantly reduced by scattering or total reflection in the internal structure of the light emitting diode. This reduces the overall light efficiency of the light emitting diode.

That is, in order to improve light extraction efficiency in the light emitting diode, the internal structure of the light emitting diode needs to be improved. It is mainly implemented by forming a concavo-convex pattern on the surface of the n-type semiconductor layer or p-type semiconductor layer, which is the uppermost layer of the light emitting diode. have.

In the prior art, a wet etching process was mainly performed to form such a concavo-convex pattern, but in this process, the distribution and shape of the concavo-convex pattern are non-uniform, so light scattering or light reflection is frequent, resulting in low light extraction efficiency, and having the same light extraction efficiency It is difficult to produce products.

In addition, when light is emitted from the active layer, light reflection or scattering occurs according to a difference in refractive index between the semiconductor layer and the air, further reducing the light extraction efficiency.

Attempts have been made to add a dry etching process or an imprinting process to the wet etching process to impart directionality to the concavo-convex pattern and to form a more uniform concavo-convex pattern, but it is still insufficient to improve light extraction efficiency.

Meanwhile, recently, micro-light emitting diodes (Micro-LED) having a size of several μm to several tens of μm are being used in various fields. Due to the characteristic that the luminous efficiency of these micro light emitting diodes rapidly decreases as the size of the chip decreases, high output with maximized light extraction efficiency is required for all of the blue, green, and red micro light emitting diodes.

For example, compared to a 1,000×1,000㎛ ² high power light emitting diode light source, the luminous efficacy of a 50×50㎛ ² micro light emitting diode light source rapidly decreases to 30% or less in the same area, and a micro light emitting diode chip of 100 ㎛ or less In the case of the light emitting diode chip, the sidewall area is rapidly increased compared to the existing light emitting diode chip (FIG. 1), so structural improvement for maximizing light extraction efficiency is inevitably required.

The present invention was devised in response to the above needs, and a method for forming a surface-controlled 3D nanostructure for improving the properties of a substrate by controlling the surface of a substrate by forming a surface-controlled 3D nanostructure on a substrate, and a surface-controlled 3D nanostructure formed thereby. It aims to provide a structure and an optoelectronic device.

The present invention for achieving the above object is to form a plurality of surface control layers having different etch resistance on top of a substrate, and to form control patterns having different sizes according to the etch resistance on each of the surface control layers by an exposure process. Forming, but forming an extension-cut for the lower control pattern compared to the upper control pattern to secure a surface control area on the substrate, and using a plurality of surface control layers formed with the control pattern as a mask to form an extension-cut on the surface Forming a first nanostructure in a control region, and removing the surface control layer A method for forming a surface-controlled three-dimensional nanostructure, a surface-controlled three-dimensional nanostructure thereby, and an optoelectronic device using the same as the technical point.

In addition, the first nanostructure is formed on the substrate by removing all of the surface control layer, or the first nanostructure is formed on a portion of the substrate using the remaining surface control layer as a mask while sequentially removing the surface control layer. It is preferable to overlap a nanostructure different from the above.

In addition, the surface-controlled three-dimensional nanostructure formation method includes a first step of forming a first surface control layer on a substrate, and a relatively high etch resistance to the first surface control layer on the first surface control layer. A second step of forming a second surface control layer having, a third step of forming a first control pattern on the second surface control layer by an exposure process, and a first control pattern of the second surface control layer. A fourth step of forming a second control pattern continuously or sequentially formed on the first surface control layer and forming an extension-cut with respect to the first control pattern; A fifth step of securing a surface control area on the substrate by two control patterns, and using the second surface control layer formed with the first control pattern and the first surface control layer formed with the second control pattern as a mask, A sixth step of forming a first nanostructure in a surface control region, and removing the second surface control layer and the first surface control layer to form a first nanostructure on the substrate or the second surface control layer. is removed, and a second nanostructure is formed in the surface control region using the first surface control layer having the second control pattern as a mask, and the first surface control layer having the second control pattern is removed to obtain the substrate It is preferable to include a seventh step of forming a composite nanostructure composed of the first nanostructure and the second nanostructure on the surface.

In addition, the etching resistance ratio of the first surface control layer and the second surface control layer is preferably 1:1.1 to 10.

In the fourth step, it is preferable to form the second control pattern by performing a developing process according to the exposure process of the third step, and continuously or sequentially additional developing processes.

In the fourth step, after the developing process or the additional developing process, it is preferable to dry-etch or wet-etch the first surface control layer to further expand the extended cut to form a second control pattern.

In addition, the arrangement of the second control pattern of the first surface control layer is determined according to the arrangement of the first control patterns of the second surface control layer, or between the first control patterns of the second surface control layer. It is preferable that the shape of the pattern is controlled by the distance.

In the fifth step, it is preferable that the size of the surface control region is adjusted by changing the area of the second control pattern constituting the extended cut of the fourth step.

In addition, the first nanostructure may be a chemically synthesized single metal nanostructure, two or more chemically synthesized metal nanostructures, or a nanostructure formed by forming a single or multilayer property control thin film layer having a surface property different from that of the substrate. It is desirable to be

In addition, the composite nanostructure has a surface characteristic different from that of the substrate in the surface control region by using the second surface control layer formed with the first control pattern and the first surface control layer formed with the second control pattern as a mask. The first nano structure and the second surface control layer are removed by using another characteristic control thin film layer as a single layer or multiple layers, and using the first surface control layer formed with the second control pattern as a mask, the first nanostructure is formed in the surface control region. It is preferably made of a second nanostructure made of a metal nanostructure overlapped with the structure.

In addition, after the fifth step, an etching pattern is additionally applied to the surface control region by using the second surface control layer formed with the first control pattern and the first surface control layer formed with the second control pattern as an etching mask. It is desirable to form

In addition, the first nanostructure and the composite nanostructure are preferably formed to correspond to the etching pattern.

In addition, the etching pattern is formed by a single etching process such as a dry etching process or a wet etching process, or a complex etching process such as a wet etching process after a dry etching process or a dry etching process after a wet etching process. Formed by any one of it is desirable to be

In addition, the substrate is preferably an n-type semiconductor layer or a p-type semiconductor layer formed on the uppermost layer of the photoelectric device.

In addition, the photoelectric device includes a light emitting diode (LED), a micro-light emitting diode (Micro-LED), a solar cell, a laser diode (LD), and a photo diode (PD). , an avalanche photo diode (APD).

The present invention relates to a method for forming a structure having a controlled surface, and is intended to improve the properties of a substrate by forming a surface-controlled three-dimensional nanostructure on a substrate to control the surface of the substrate (surface area expansion, surface shape control, surface property control, etc.) It has the effect of providing a surface-controlled three-dimensional nanostructure for

In addition, the present invention forms a plurality of surface control layers on the substrate to increase the precision and freedom of surface area control of the substrate, so that surface control is easy and a structure of various materials can be formed to increase its applicability.

In addition, the present invention makes it easy to secure a surface control region on the substrate by forming an extended cut in the first surface control layer by excessively performing the developing process, thereby forming an etching pattern on the surface of the substrate, A nanostructure is formed here to form a three-dimensional nanostructure having a complex pattern, so that the expansion and control of the surface area and the control of physical properties are facilitated.

In addition, the present invention has an effect of providing an optoelectronic device that maximizes light extraction efficiency by forming a surface-controlled three-dimensional nanostructure on the uppermost layer of the optoelectronic device to expand the surface area of the uppermost layer and control its shape.

In addition, the present invention is easy to control the refractive index of the substrate by forming a single layer or multi-layer property control thin film layer having a different refractive index from the substrate, and forming a metal nanostructure overlapping thereon, so that the refractive index of the substrate can be easily controlled. There is an effect of further improving the light extraction efficiency.

1 - A diagram showing the ratio of the top area to the side area according to the size of a conventional light emitting diode.
2 to 6 - schematic diagrams of methods for forming surface-controlled three-dimensional nanostructures according to various embodiments of the present invention.
Figure 7 (a) - SEM (Scanning Electron Microscope, Scanning Electron Microscope) and optical images of the conventional second surface control layer on which the first control pattern is formed and the first surface control layer on which the second control pattern (undercut) is formed shown figure.
7(b), 7(c), and 7(d) - a second surface control layer formed with a first control pattern and a first surface formed with a second control pattern (extended cut) according to an embodiment of the present invention. A diagram showing data obtained by measuring SEM and optical images of the surface control layer.
Figure 8 (a), (c) and (e) - the second surface control layer formed with the first control pattern according to the conventional development time (20 seconds) and the first surface control formed with the second control pattern (undercut) An optical image of the layer is shown.
8 (b), (d) and (f) - a second surface control layer formed with a first control pattern according to an embodiment of the present invention and a second control pattern (extended cut) formed according to an embodiment of the present invention. 1 A diagram showing an optical image of the surface control layer.
Figure 9 - Drying conditions (temperature and time) of the first surface control layer according to an embodiment of the present invention (Fig. 9 (a), (b) and (c)) and Post Exposure Bake (PEB) after UV irradiation Optical images showing the area control of the extended cut through the implementation of various second control patterns of the first surface control layer according to conditions (temperature and time) control [Fig. 9 (d), (e) and (f)] do.
Figure 10 - Figure 10 (a), (b) and (c) showing the results of measuring the metal-organic photolysis reaction according to the change in ultraviolet irradiation time according to an embodiment of the present invention, according to the change in ultraviolet irradiation time A diagram showing the color change of the metal-organic solution [FIG. 10 (d), (e) and (f)], and a diagram showing the diameter distribution of metal nanostructures according to the change in UV irradiation time [FIG. 10 (g), (h) and (i)].
11 - A photolysis mechanism in which metal nanostructures are formed when a sample having an extended cut is immersed in a photosensitive metal-organic solution according to an embodiment of the present invention and then irradiated with ultraviolet rays, and a photodegradation mechanism according to various embodiments of the extended cut A diagram showing an image of an optical image and an SEM measurement result of a metal nanostructure.
12 - A diagram showing a result of measuring PL (Photoluminescence) and a PL increase rate when the substrate is a semiconductor laminate of light emitting diodes according to an embodiment of the present invention.

The present invention relates to a surface-controlled nanostructure, in which a surface-controlled three-dimensional nanostructure is formed on a substrate to control the surface of the substrate (surface area expansion, surface shape control, surface property control, etc.) to improve its properties Surface control 3 It is to provide a dimensional nanostructure.

In particular, the present invention is to form a plurality of surface control layers on top of a substrate to increase the precision and freedom of surface area control of the substrate, thereby forming a material that is easy to control the surface and has various physical properties, thereby broadening its application field.

In addition, the present invention is to provide a photoelectric device that maximizes light extraction efficiency by forming a surface-controlled three-dimensional nanostructure on the top layer of the photoelectric device to expand the surface area of the top layer and control physical properties.

A method of forming a surface-controlled three-dimensional nanostructure according to the present invention includes forming a plurality of surface control layers having different etch resistance on top of a substrate, and each surface control layer having a size according to the etch resistance by an exposure process. Forming different control patterns, but forming an extension-cut in the lower control pattern compared to the upper control pattern to secure a surface control area on the substrate, and a plurality of surface control layers on which the control pattern is formed forming a first nanostructure in the surface control region using as a mask, and removing the surface control layer, forming a nanostructure in the surface control region to provide a surface control three-dimensional nanostructure It is characterized by doing.

First, in the present invention, a plurality of surface control layers having different etch resistances are formed on a substrate.

The present invention can be applied when improving performance or expressing new characteristics by controlling the surface in various ways, such as surface area expansion, surface shape change, surface refractive index control, surface property control, etc. It can be applied to any material if it conforms to .

Specifically, the substrate may be an inorganic substrate, an organic substrate or a thin film, a semiconductor device, in particular, an uppermost layer of an optoelectronic device, etc. A surface-controlled three-dimensional nanostructure is formed.

For the surface control layer, an appropriate material is selected and used according to the type, use, and purpose of the substrate, and the type of other surface control layers to be laminated adjacently. In particular, the coating and coating properties between the adjacent surface control layers are improved. Use the materials you are told to do.

In particular, the surface control layer in the present invention is formed in plurality on the substrate, but is formed of materials having different etching resistance, so that the shape, size, and arrangement of the control patterns formed on each surface control layer are formed differently so that they are mutually Even if overlapped, the shape of each control pattern is reflected.

Preferably, the surface control layer formed relatively far from the substrate is formed of a material with higher etching resistance relative to the surface control layer formed closer to the substrate, so that the size of the control pattern formed on the surface control layer is relatively closer to the uppermost layer. formed small. The meaning of etching in the present invention includes all physical and chemical etching processes, and particularly includes etching according to the developing process.

Depending on the type, thickness, and etch resistance of the surface control layer and exposure process conditions in the exposure process (surface control layer thickness, energy irradiation time, developing time, developing temperature, curing temperature and time, etc.), each surface control layer The shape and size of the control pattern formed can be formed in various ways, and the size ratio between adjacent control patterns can be adjusted to form an optimal surface-controlled three-dimensional nanostructure.

In particular, in the case of the surface control layer formed close to the substrate, since it is involved in securing the surface control region of the substrate, an appropriate kind of material is taken into account in consideration of the area of the surface control region of the substrate and the etch resistance according to the exposure process and the etching process. to an appropriate thickness.

In addition, control patterns having different sizes according to the etching resistance are formed on each of the surface control layers by an exposure process, and the lower control patterns are extended-cut compared to the upper control patterns.

The exposure process in the present invention refers to a process of selectively irradiating energy including the uppermost surface control layer in consideration of the position or size of the control pattern to be formed on the surface control layer, curing it to an appropriate hardness, and developing process. By proceeding, a control pattern is formed on each surface control layer.

Here, the shape and size of the control pattern formed on the surface control layer according to the development process are controlled according to the etching resistance of the surface control layer.

As described above, when the etch resistance of the surface control layer close to the substrate is relatively low, the width of the control pattern is formed larger as it is closer to the substrate, which becomes a surface control region above the substrate described later.

According to the developing process according to the general exposure process, since the control pattern of the upper layer is formed to an under-cut shape compared to the control pattern of the lower layer, it is difficult to implement the surface control area according to the present invention.

In the present invention, the development process in the exposure process is performed additionally and excessively while making a difference in etching resistance, so that a control pattern forming a more extended extension-cut is formed in the undercut.

The additional developing process may be realized by further extending the developing time, increasing the concentration or developing temperature of the developing solution, or changing the type of the developing solution during the developing process.

Therefore, a partial area of the substrate exposed by each control pattern is secured as a surface control area.

That is, by adjusting the extent of the extended cut, the area of the surface control region of the substrate is adjusted, which leads to surface control (surface area expansion, surface shape control, surface property control, etc.) of the substrate.

Meanwhile, after the developing process or the additional developing process, the surface control layer may be dry-etched or wet-etched to further expand the extended cut. This is a process that can be usefully used when adjusting the area of the surface control region of the substrate according to the purpose of use.

The area of the control pattern formed on the surface control layer may be controlled according to exposure process conditions (thickness of the surface control layer, energy irradiation time, developing time, developing temperature, curing temperature and time, etc.).

For example, if the curing degree of the surface control layer is high, the area of the surface control region of the substrate can be secured relatively small, and if the curing degree is low, the area of the surface control region of the substrate can be secured relatively large. Control of the surface area of the substrate can be achieved very easily.

In this way, the formation of the extended cut according to the control pattern to secure the surface control area of the substrate according to the present invention, the size and shape of the control pattern according to the exposure process conditions, the degree of curing of the surface control layer, and the development process conditions or It is controlled according to etching process conditions and the like.

In addition, a first nanostructure is formed in the surface control region using the plurality of surface control layers on which the control pattern is formed as a mask.

The first nanostructure is formed in the surface control region secured by the surface control layer by coating or depositing a material having characteristics different from those of the substrate in order to control or express the surface characteristics of the substrate.

In one embodiment of the present invention, the first nanostructure is a chemically synthesized single metal nanostructure or two or more chemically synthesized metal nanostructures, or a property control thin film layer having a different surface property from that of the substrate is formed as a single layer or a chemically synthesized metal nanostructure. It may be a nanostructure formed in multiple layers. It may also be a composite nanostructure of these.

The metal nanostructure is formed by a photolysis reaction, and may be a nanostructure containing one or more nanoparticles, nanorods, nanowires, nanotube metals, etc., such as silver, gold, platinum, copper, palladium, A metal nanoparticle made of any one of nickel, silicon, iron, and cobalt, or a combination of two or more thereof.

In the case of the property control thin film layer, a material having different electrical or optical properties from that of the substrate, for example, a material having a different refractive index may be formed by depositing a single layer or multiple layers. In particular, when deposited in multiple layers, a material having a high refractive index to a material having a low refractive index may be deposited from the substrate, or a material having a low refractive index may be deposited from the substrate to a material having a high refractive index, among metals, metal oxides, fluorides, phosphides, nitrides, and sulfides. Any one or more may be selected and deposited as a thin film.

And, by removing the surface control layer, only the first nanostructure is formed in the surface control region on the substrate. Depending on the type of the first nanostructure and the size of the pattern, it is possible to control the surface properties of the substrate or to develop specific surface properties.

In addition, without removing the surface control layer at once, the first nanostructure is formed in the surface control region of the substrate, and the surface control layer is sequentially removed from the uppermost layer, while using the remaining surface control layer as a mask to form the surface of the substrate A composite nanostructure may be formed in the control region by overlapping a nanostructure other than the first nanostructure.

In other words, by repeating this process, each nanostructure is formed of different materials or has a different shape (nanoparticle, nanorod, nanowire, nanotube metal, thin film, etc.) and surface control secured by a plurality of surface control layers. formed in the area.

In particular, as described above, the plurality of surface control layers according to the present invention have a control pattern etched more, that is, a control pattern forming an extended cut, as the surface control layer is closer to the substrate, and thereby secured in the surface control region of the present invention. Accordingly, a nanostructure is formed.

Here, in the surface control region of the substrate, an etching pattern may be further formed by using the surface control layer formed with the control pattern as an etching mask, and the above-described nanostructure is formed on the etching pattern to obtain various forms of surface area expansion. A nanostructure having a three-dimensional pattern can be implemented.

The etching pattern is formed by a single etching process such as a dry etching process or a wet etching process using the plurality of surface control layers as an etch mask, or a wet etching process after a dry etching process or a dry etching process after a wet etching process. It can be formed by an etching process.

That is, according to the depth, width, arrangement, etc. of the etching pattern, the surface area of the substrate may be expanded, the surface formation of the substrate may be changed, and a single nanostructure or composite nanostructure may be formed in this area.

As a result, a substrate having a surface-controlled three-dimensional nanostructure suitable for the purpose is provided, and by forming a plurality of surface control layers, the precision and freedom of surface control of the substrate surface are increased to facilitate surface control and to express various surface characteristics. and to increase its applicability.

Hereinafter, as a preferred embodiment of the present invention, a case in which the surface control layer is formed of two layers will be described in detail with reference to the accompanying drawings.

2 to 6 show a schematic view of a method for forming a surface-controlled three-dimensional nanostructure according to various embodiments of the present invention in which the surface control layer is made of two layers. 7(a) is a view showing SEM and optical images of a conventional second surface control layer formed with a first control pattern and a first surface control layer formed with a second control pattern (undercut), FIG. 7(b), 7(c) and 7(d) are SEMs of a second surface control layer formed with a first control pattern and a first surface control layer formed with a second control pattern (extended cut) according to an embodiment of the present invention. and optical image measurement data, and FIG. 8 (a), (c) and (e) show the second surface control layer and the second surface control layer formed with the first control pattern according to the conventional development time (20 seconds). 2 is a diagram showing optical images of the first surface control layer on which the control pattern (undercut) is formed, and FIG. 9 is a view showing an optical image of a second surface control layer having a first control pattern formed thereon and a first surface control layer having a second control pattern (extended cut) formed thereon, and FIG. Drying conditions (temperature and time) of the layer [Fig. 9 (a), (b) and (c)] and Post Exposure Bake (PEB) conditions (temperature and time) after UV irradiation are adjusted [Fig. 9 (d), (e) and (f)] is a view showing an optical image related to the area control of the extended cut through the implementation of various second control patterns of the first surface control layer, and FIG. 10 is a diagram showing an optical image according to one embodiment of the present invention A diagram showing the measurement results of the metal-organic photolysis reaction according to the change in irradiation time [Fig. 10 (a), (b) and (c)], a diagram showing the color change of the metal-organic solution according to the change in ultraviolet irradiation time [diagram 10 (d), (e) and (f)], a diagram showing the diameter distribution of metal nanostructures according to changes in ultraviolet irradiation time [Fig. 10 (g), (h) and (i)], and Fig. 11 A photolysis mechanism in which metal nanostructures are formed when a sample having an extended cut is immersed in a photosensitive metal-organic solution according to an embodiment of the present invention and then irradiated with ultraviolet rays, and an optical image of the extended cut according to various embodiments And a diagram showing an image of an SEM measurement result of a metal nanostructure, 12 is a diagram showing a result of measuring PL (Photoluminescence) and a PL increase rate when the substrate is a semiconductor laminate of light emitting diodes according to an embodiment of the present invention.

As shown, the method of forming the surface-controlled three-dimensional nanostructure 400 according to an embodiment of the present invention includes the first step of forming the first surface control layer 200 on the substrate 100, and the first A second step of forming a second surface control layer 300 having a relatively high etching resistance with respect to the first surface control layer 200 on the surface control layer 200, and an exposure process on the second surface The third step of forming the first control pattern 310 on the control layer 300, and the first control pattern 310 of the second surface control layer 300 continuously or sequentially on the first surface control layer ( 200), a fourth step of forming a second control pattern 210 forming an extension-cut with respect to the first control pattern 310, and A fifth step of securing the surface control area 110 on the base material 100 by the second control pattern 210, the second surface control layer 300 having the first control pattern 310, and the 2 A sixth step of forming a first nanostructure 410 in the surface control region 110 using the first surface control layer 200 having the control pattern 210 as a mask, and the second surface control layer 300 and the first surface control layer 200 are removed to form the first nanostructure 410 on the substrate 100, or the second surface control layer 300 is removed and the second control layer 300 is removed. A second nanostructure 420 is formed in the surface control region 110 using the first surface control layer 200 having the pattern 210 as a mask, and the second control pattern 210 is formed on the first surface control layer 200 . It is characterized in that it comprises a seventh step of forming a composite nanostructure consisting of the first nanostructure 410 and the second nanostructure 420 on the substrate 100 by removing the surface control layer 200.

First, in the present invention, the first surface control layer 200 is formed on the substrate 100 (first step).

The substrate 100 according to the present invention may be an inorganic substrate, an organic substrate or a thin film, a semiconductor device, in particular, an uppermost layer of an optoelectronic device, etc. A surface-controlled three-dimensional nanostructure 400 is formed on the surface of (100).

Specifically, the substrate 100 is silicon (Si), gallium arsenic (GaAs), gallium phosphide (GaP), gallium arsenic phosphide (GaAsP), boron nitride (BN), SiC, GaN, ZnO, MgO, InP , Ge, InAs, GaSb, sapphire, quartz, and any one inorganic substrate of glass may be used.

Or, depending on the application, polycarbonate (PC), polyethylene naphthalate (PEN), polynorbornene (PN), polyacrylate, polyvinyl alcohol (PVA), Polyimide (PI), polyethylene terephthalate (PET), polyethersulfone (PES), polystyrene (PS), polypropylene (PP), polyethylene (PE), Any one of polyvinylchloride (PVC), polyamide (PA), polybutyleneterephthalate (PBT), polymethyl methacrylate (PMMA), and polydimethylsiloxane (PDMS) A polymer substrate of can be used.

In one embodiment of the present invention, the substrate 100 may be a semiconductor laminate having an n-type semiconductor layer or a p-type semiconductor layer as an uppermost layer, and the surface-controlled three-dimensional nanostructure 400 according to the present invention is formed on the uppermost layer. is to form

For the first surface control layer 200, an appropriate material is selected and used according to the type, use and purpose of the substrate 100, and the type of the second surface control layer 300 to be described later. In particular, the second surface control layer 200 is used. The layer 300 has improved coating and film properties, and a polymer material having lower etch resistance than the second surface control layer 300 is used.

In addition, since the first surface control layer 200 is formed on the substrate 100 and is involved in securing the surface control area 110 of the substrate 100, the surface control area 110 of the substrate 100 ), an appropriate type of material with an appropriate thickness is formed on the substrate 100 in consideration of the etching resistance according to the development process and the etching process in consideration of the area of ).

The first surface control layer 200 is made of PVC (Polyvinyl Chloride), Neoprene, PVA (Polyvinyl Alcohol), PMMA (Poly Methyl Meta Acrylate), PBMA (Poly Benzyl Meta Acrylate), PolyStylene, SOG (Spin On Glass) , PDMS (Polydimethylsiloxane), PVFM (Poly Vinyl formal), Parylene, Polyester, Epoxy, Polyether, Polyimide, and LOR (Lift-Off Resist).

The first surface control layer 200 is formed on the substrate 100 by a method such as spin coating, dip coating, or spray coating, and at a temperature of 50° C. to 300° C. It is formed with a thickness of about 50 μm or less by heat treatment for 15 seconds to 10 minutes.

Alternatively, depending on the type and thickness of the first surface control layer 200, deposition or coating conditions may be set differently, and the deposition or coating of the first surface control layer 200 may be performed in various ways.

Next, a second surface control layer 300 having relatively high etching resistance with respect to the first surface control layer 200 is formed on the first surface control layer 200 (second step).

Here, when the first surface control layer 200 and the second surface control layer 300 are simultaneously etched, the etch resistance is higher than that of the second surface control layer 300. This means that the etching rate of The meaning of etching in the present invention includes all physical and chemical etching processes, and particularly includes etching according to the developing process.

Preferably, the etch resistance ratio of the first surface control layer 200 and the second surface control layer 300 is 1: 1.1 to 10, which is the surface control area ( 110) As an optimal condition for securing, if the etching rate of the first surface control layer 200 is higher than this, the barrier rib made of the first surface control layer 200 collapses and the pattern according to the surface control region 110 is not formed or adjacent However, if the etching rate is lower than this, the effectiveness of the surface control region 110 is reduced.

The second surface control layer 300 may use a photoresist or a photosensitive metal-organic precursor material having relatively high etching resistance with respect to the first surface control layer 200 .

Here, the photoresist may include a positive-type photoresist and a negative-type photoresist, and may include an electron beam resist, a KrF resist, an ArF resist, and the like. In addition, in order to control the etching resistance, silicon or metal oxide nanoparticles may be included in the photoresist, and the etching resistance of the first surface control layer 200 is higher. use the material

The photosensitive metal-organic precursor may be synthesized by mixing a metal-organic precursor and an organic solvent, and various metals such as a photosensitive Zn-organic precursor, a photosensitive Sn-organic precursor, and a photosensitive Ti-organic precursor may be added to the photosensitive metal-organic precursor. It is included so that the etch resistance of the first surface control layer 200 is higher.

The photoresist and the photosensitive metal organic precursor are coated on the first surface control layer 200 by a method such as spin coating, dip coating, or spray coating and then cured. , The degree of curing (heat, light, or heat and light) is adjusted in consideration of the area of the surface control region 110 .

Then, the first control pattern 310 is formed on the second surface control layer 300 by an exposure process (third step).

In the exposure process, the shape, size, and arrangement of the first control pattern 310 are designed in consideration of the area of the surface control region 110, and accordingly, the upper side of the second surface control layer 300 is selectively exposed [ Heat or light (ultraviolet rays, extreme ultraviolet rays, electron beams, X-rays, etc.)] or placing a designed mask on the upper side of the second surface control layer 300, exposing, and then going through a developing process, A first control pattern 310 is formed on the second surface control layer 300 .

Here, the curing degree of the second surface control layer 300 may be adjusted by irradiating appropriate energy, thereby adjusting the size of the first control pattern 310 .

In addition, the developing process is performed by adjusting the developing process conditions, such as the type and concentration of the developing solution, the developing time, and the developing temperature, in consideration of the area of the surface control region 110 .

In addition, it is continuously or sequentially formed on the first control pattern 310 of the second surface control layer 300, and the extended cut ( A second control pattern 210 constituting an extension-cut is formed (fourth step). Then, the surface control area 110 is secured on the substrate 100 by the second control pattern 210 of the first surface control layer 200 (step 5).

In the fifth step, the size of the surface control region 110 may be adjusted by changing the area of the second control pattern 210 forming the extended cut of the fourth step.

According to a general development process, the second control pattern 210 is formed under the first control pattern 310 to an undercut shape of the first surface control layer 200, and according to the present invention It is difficult to implement the surface control area 110 according to the present invention.

In the present invention, an additional excessive developing process is performed following the development process in the exposure process of the third step to form the second control pattern 210 forming a further extended cut from the undercut.

In the additional developing process, the developing time is further increased, the concentration of the developing solution or the developing temperature is further increased, or the developer used when forming the first control pattern 310 is used when forming the second control pattern 210. It can be realized by changing the type of developing solution to be used.

Therefore, the second control pattern 210 formed as an extended cut is formed under the first control pattern 310 of the second surface control layer 300, and a part of the substrate 100 exposed by this is the surface It is secured as the control area 110 .

That is, by adjusting the extent of the extended cut (area of the second control pattern 210), the area of the surface control region 110 of the substrate 100 is adjusted, which means that the surface control of the substrate 100 ( This leads to surface area expansion, surface shape control, surface property control, etc.).

Meanwhile, after the developing process or the additional developing process, the first surface control layer 200 may be dry-etched or wet-etched to form the second control pattern 210 by further extending the extended cut. This is a process that can be usefully used when adjusting the area of the surface control region 110 of the substrate 100 according to the purpose of use.

The area of the second control pattern 210 of the first surface control layer 200 is determined by the curing degree of the first surface control layer 200 as well as the development time and development temperature as described above during the development process. can be controlled

That is, when the curing degree of the first surface control layer 200 is high, the area of the surface control region 110 of the base material 100 can be secured relatively small, and when the curing degree is low, the base material 100 It is possible to secure a large area of the surface control region 110, so that the surface area control of the substrate 100 can be achieved very easily.

In this way, the formation of the extended cut of the first surface control layer 200 to secure the surface control region 110 of the substrate 100 according to the present invention is the first control pattern of the second surface control layer 300 ( 310), the shape, size and arrangement of the second control pattern 210 of the first surface control layer 200, the first surface control layer 200 and the second surface control layer 300 ) is controlled according to the degree of curing, and development process conditions or etching process conditions.

In addition, the second control pattern 210 may be continuously formed with extended cuts in the process of forming the first control pattern 310, and after the first control pattern 310 is formed, other cuts may be sequentially formed. An extended cut may be formed by performing an exposure process under different conditions, a development process under different conditions, or a dry or wet etching process.

As a result, the substrate 100 having the surface control area 110 secured is provided, and as the number of surface control layers increases, the precision and freedom of surface area control of the surface of the substrate 100 are increased, so that the surface area control is easy and the applicability thereof is increased. can be increased, and the nanostructure according to the present invention is additionally formed in the surface control region 110.

Then, the surface control region 110 is formed using the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed as masks. ) to form the first nanostructure 410 (step 6).

The sixth step is to form a nanostructure in the surface control region 110 secured by a plurality of surface control layers, and any material suitable for improving the surface characteristics of the substrate 100 and expressing specific surface characteristics can be used. And, as a preferred embodiment of the present invention, metal nanostructures and the like can be applied.

Conventional metal nanostructures have various shapes aligned in a specific direction. It can be manufactured to have size and patterning, and in particular, metal nanostructures have excellent directionality and can be suitable for high efficiency in optoelectronic devices, and can be used in various electronic devices such as electrodes and sensors.

According to the present invention, single or composite nanostructures are formed on the surface control region 110 in various ways, thereby diversifying the application fields and increasing applicability.

In one embodiment of the present invention, the first nanostructure 410 is a chemically synthesized single metal nanostructure or two or more chemically synthesized metal nanostructures, or has different surface properties from those of the substrate 100. It may be a nanostructure in which the control thin film layer is formed as a single layer or multiple layers. It may also be a composite nanostructure of these.

The metal nanostructure is formed by a photolysis reaction, and may be a nanostructure containing one or more nanoparticles, nanorods, nanowires, nanotube metals, etc., such as silver, gold, platinum, copper, palladium, A metal nanoparticle made of any one of nickel, silicon, iron, and cobalt, or a combination of two or more thereof.

In the case of the property control thin film layer, a material having electrical or optical properties different from that of the substrate 100, for example, a material having a different refractive index may be formed by depositing a single layer or multiple layers. In particular, when deposited in multiple layers, a material having a high refractive index to a material having a low refractive index may be deposited from the substrate 100, or a material having a low refractive index may be deposited from a material having a high refractive index from the substrate 100, such as metal, metal oxide, fluoride, Any one or more of phosphide, nitride and sulfide may be selected and deposited as a thin film.

Then, the second surface control layer 300 and the first surface control layer 200 are removed to form the first nanostructure 410 on the substrate 100, or the second surface control layer 300 ) is removed and the second nanostructure 420 is formed in the surface control region 110 using the first surface control layer 200 on which the second control pattern 210 is formed as a mask, and the second control The first surface control layer 200 on which the pattern 210 is formed is removed to form a composite nanostructure composed of the first nanostructure 410 and the second nanostructure 420 on the substrate 100 ( Step 7).

That is, in order to form only the single first nanostructure 410, both the second surface control layer 300 and the first surface control layer 200 are removed, and the type and pattern of the first nanostructure 410 Depending on the size of the substrate 100, it is possible to control the surface properties or express specific surface properties.

In addition, the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed are removed without removing the surface control layer at once. Using a mask, the first nanostructure 410 is formed on the surface control region 110 (step 6), the second surface control layer 300 is removed, and the second control pattern 210 is formed. Using the first surface control layer 200 as a mask, a second nanostructure 420 is formed in the surface control region 110, and the first surface control layer 200 having the second control pattern 210 formed thereon is removed to form a composite nanostructure composed of the first nanostructure 410 and the second nanostructure 420 on the substrate 100 (step 7).

That is, a composite nanostructure may be formed in which a nanostructure other than the first nanostructure 410 is overlapped on the surface control region 110 of the substrate 100, and by repeating this process, each nanostructure is They are formed of different materials or in different shapes (nanoparticles, nanorods, nanowires, nanotube metals, thin films, etc.) in the surface control region 110 secured by a plurality of surface control layers.

In one embodiment of the present invention, the composite nanostructure includes the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed. ) as a mask, the first nanostructure 410 and the second surface control layer 300 are formed in a single layer or multi-layer with a property control thin film layer having a surface property different from that of the substrate 100 in the surface control region 110 is removed and the first surface control layer 200 on which the second control pattern 210 is formed is used as a mask to form a metal nanostructure overlapping the first nanostructure 410 in the surface control region 110. It may be made of the second nanostructure 420 .

As described above, the plurality of surface control layers according to the present invention have a control pattern etched more, that is, a control pattern forming an extended cut, as the surface control layer is closer to the substrate 100, thereby securing the surface control area 110 ), the nanostructure according to the present invention is formed.

The solvent for removing the first surface control layer 200 and the second surface control layer 300 is acetone, isopropyl alcohol, hydrofluoric acid (HF), phosphoric acid (H ₃ PO ₄ ), hydrochloric acid (HCl) , Nitric acid (HNO ₃ ), Acetic acid (CH ₃ COOH), Sulfuric acid (H ₂ SO ₄ ), Dihydrogen dioxide(H ₂ O ₂ ), Potassium hydroxide(KOH), 4-Methyl-2-pentanone, Ketone, MIBK(Methyl Iso Butyl Ketone), Methyl Ethyl Ketone, Water(H ₂ O), Methanol(CH ₃ OH) , Ethanol (C ₂ H ₅ OH), Propanol, Isopropanol, Butanol, Pentanol, Hexanol, DMSO (Dimethyl sulfoxide), DMF (Dimethylformamide), NMP (N-Methyl Pyrrolidone), 1-Methyl-2-pyrrolidone, 1-Methyl At least one selected from the group consisting of -3-pyrrolidone, dimethylacetamide, acetonitrile, THF (Tetrahydrofuran), Nonane (C ₉ H ₂ 0), Octane, Heptane, Pentane, and 2-Methoxyethanol is used.

Here, in the surface control region 110 of the substrate 100, the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer on which the second control pattern 210 is formed An etching pattern 430 may be further formed on the surface control region 110 using (200) as an etching mask, and the above-described nanostructure is formed on the etching pattern 430 to form the first nanostructure ( 410) and composite nanostructures are formed correspondingly according to the etching pattern 430, and nanostructures having various three-dimensional patterns can be implemented.

The etching pattern 430 is formed by a single etching process such as a dry etching process or a wet etching process using the plurality of surface control layers as an etching mask, or a wet etching process after a dry etching process or a dry etching process after a wet etching process. It can be formed by a complex etching process such as.

That is, the expansion of the surface area of the substrate 100, the change of the surface shape of the substrate 100, etc. may be induced according to the depth, width, arrangement, etc. of the etching pattern 430, and a single nanostructure or composite nanostructure may be formed in this area. will be formed

As a result, the substrate 100 having the surface-controlled three-dimensional nanostructures 400 suitable for the purpose is provided, and by forming a plurality of surface control layers, the precision and freedom of surface control of the surface of the substrate 100 are increased to control the surface. Its applicability is increased by making it easy to use and expressing various surface characteristics.

Accordingly, the present invention provides a substrate 100 having a surface control region 110 secured by a plurality of surface control layers having control patterns formed thereon, and a plurality of surface control layers having the control patterns formed thereon as a mask. A surface-controlled three-dimensional nanostructure 400 comprising a nanostructure formed in the surface-controlled region 110 on the surface is provided.

In one embodiment of the present invention, when two surface control layers are formed, the second control pattern 210 of the first surface control layer 200 is the first control pattern 310 of the second surface control layer 300. ), the pattern size, the distance between patterns, and the shape of the pattern. That is, the extended cut area is adjusted according to the first control pattern 310 of the second surface control layer 300 .

For example, the arrangement of the second control pattern 210 of the first surface control layer 200 is determined according to the arrangement of the first control pattern 310 of the second surface control layer 300, or The shape of the pattern may be adjusted by the distance between the first control patterns 310 of the second surface control layer 300 .

According to one embodiment of the present invention, when the arrangement form of the first control pattern 310 of the second surface control layer 300 is a square array (hexagonal array) under a specific extended cut formation condition, the first surface control layer The arrangement of the second control patterns 210 of (200) is also a square array (hexagonal array), and the distance between the first control patterns 310 of the second surface control layer 300 under a specific extended cut formation condition. If is the same, the second control patterns 210 of the first surface control layer 200 can be connected, and if the distance between the patterns is different, the patterns can be separated.

In addition, the etch pattern 430 may form a secondary etch pattern, a tertiary etch pattern, and the like while removing the surface control layer. The third etch pattern is formed to overlap the first etch pattern and the second etch pattern.

In addition, according to the number of surface control layers, the dry or wet etching process may be performed multiple times in a direction in which the surface area is expanded or in a direction in which the surface shape is changed to form nth etch patterns in an overlapping manner, such a surface control region ( 110), the nanostructure 400 according to the present invention is formed.

As described above, the first nanostructure 410, the second nanostructure 420, and the etch pattern 430 form the number and thickness of the surface control layer or the first control pattern 310 and the extended cut. It depends organically and complexly on the size of the second control pattern 210 .

That is, by adjusting the size of the first control pattern 310 and the second control pattern 210, the surface state of the substrate 100 can be changed, for example, the shape and degree of expansion of the surface area can be adjusted. The surface-controlled 3D nanostructure 400 may be formed on the surface of the substrate 100 in various ways.

As described above, the surface-controlled three-dimensional nanostructure 400 is a single metal nanostructure or two or more types of metal nanostructures, or a nanostructure in which a single-layer or multi-layered property-controlled thin film layer having surface properties different from those of the substrate 100 is formed. It can be a struct. Also, as described above, these nanostructures may be formed in a complex manner.

Such a nanostructure improves the intrinsic properties of the substrate 100 or expresses specific properties. For example, a material having a different refractive index from that of the substrate 100 is deposited on the surface control region 110 or ), it is possible to implement a property-controlled thin film layer having various properties according to the necessary purpose, such as having a different hydrophilicity or hydrophobicity, or having a different electrical or chemical property from that of the substrate 100.

In one embodiment of the present invention, a refractive index control layer may be formed with the characteristic control thin film layer, and a material having a refractive index different from that of the substrate 100 is deposited in a single layer or multiple layers to control the refractive index.

According to an embodiment of the present invention, a dry etching process or a wet etching process is performed on the surface control region 110 formed by the extended cut of the first surface control layer 200, or a dry etching process and a wet etching process or A refractive index control layer is formed by depositing a material having a different refractive index from that of the substrate 100 on the etching pattern 430 formed by performing the wet etching process and the dry etching process, thereby controlling the refractive index of the substrate 100.

When the refractive index control layer is deposited in multiple layers, a material having a high refractive index to a material having a low refractive index may be deposited from the substrate 100, or a material having a low refractive index may be deposited from a material having a high refractive index from the substrate 100.

Here, in a state where the refractive index control layer is formed on the surface control region 110, a metal nanostructure may be further formed.

Depending on the use of the substrate 100, light path control is facilitated by a combination of a characteristic control thin film layer (refractive index control layer) and a metal nanostructure to improve light extraction efficiency or, if necessary, to induce diffuse reflection or total reflection of light. may also be used for In addition, the detector can be properly configured according to the sensor's purpose, and it can be used in various electronic devices by enabling the modulation of emitted light.

In one embodiment of the present invention, the substrate 100 may be an uppermost layer of an optoelectronic device.

The photoelectric device includes a light emitting diode (LED), a micro-LED, a solar cell, a laser diode (LD), a photo diode (PD), and an avalanche. It may be any one of an Avalanche Photo Diode (APD).

In the case of a light emitting diode among the optoelectronic devices, in the case of an n-type semiconductor layer or a p-type semiconductor layer formed on the uppermost layer, the refractive index control layer has a lower refractive index than the substrate 100 or a higher refractive index from the substrate 100 It is deposited from a material to a low material to improve the light extraction efficiency of the light emitting diode by reducing the difference in refractive index between the substrate 100 and the air.

The refractive index control layer may be deposited as a thin film by selecting one or more of metal, metal oxide, fluoride, phosphide, nitride, and sulfide according to the purpose of the substrate 100 .

2 to 6 show the formation of nanostructures in the surface control region 110 on the substrate 100 when two surface control layers are formed according to an embodiment of the present invention.

Referring to the embodiment according to FIG. 2, the first surface control layer 200 is formed on the substrate 100, and the first surface control layer 200 is formed on the first surface control layer 200. A second surface control layer 300 having relatively high etching resistance is formed (a).

In addition, a first control pattern 310 is formed on the second surface control layer 300 by an exposure process, and the first control pattern 310 of the second surface control layer 300 is continuously or sequentially applied to the first control pattern 310 . A second control pattern 210 formed on the first surface control layer 200 and forming an extension-cut with respect to the first control pattern 310 is formed, and the first surface control layer 200 The surface control area 110 is secured on the substrate 100 by the second control pattern 210 of [(b), (c)].

The second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed are used as a mask to cover the surface control region 110. The first nanostructure 410 is formed [when the first nanostructure 410 made of a single type of metal is formed (d), when the second nanostructure 420 made of two or more types of metal is formed ( f)].

Then, by removing all of the surface control layer, the first nanostructure 410 is formed in the surface control region 110 of the substrate 100 [(e), (g)].

Referring to the embodiment according to FIG. 3, the first surface control layer 200 is formed on the substrate 100, and the first surface control layer 200 is formed on the first surface control layer 200. A second surface control layer 300 having relatively high etching resistance is formed (a).

In addition, a first control pattern 310 is formed on the second surface control layer 300 by an exposure process, and the first control pattern 310 of the second surface control layer 300 is continuously or sequentially applied to the first control pattern 310 . A second control pattern 210 formed on the first surface control layer 200 and forming an extension-cut with respect to the first control pattern 310 is formed, and the first surface control layer 200 The surface control area 110 is secured on the substrate 100 by the second control pattern 210 of [(b), (c)].

And the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed are used as etching masks to An etching pattern 430 is formed on the surface control region 110 (d).

Then, the etching pattern 430 is formed by using the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed as a mask. A first nanostructure 410 is formed in the surface control region 110 including a [in the case where the first nanostructure 410 is formed of a single type of metal (e), a second nanostructure made of two or more types of metal is formed. When the nanostructure 420 is formed (g)].

Then, the surface control layer is completely removed to form the first nanostructure 410 in the surface control region 110 of the substrate 100 [(h), (f)].

Referring to the embodiment according to FIG. 4, the first surface control layer 200 is formed on the substrate 100, and the first surface control layer 200 is formed on the first surface control layer 200. A second surface control layer 300 having relatively high etching resistance is formed (a).

In addition, a first control pattern 310 is formed on the second surface control layer 300 by an exposure process, and the first control pattern 310 of the second surface control layer 300 is continuously or sequentially applied to the first control pattern 310 . A second control pattern 210 formed on the first surface control layer 200 and forming an extension-cut with respect to the first control pattern 310 is formed, and the first surface control layer 200 The surface control area 110 is secured on the substrate 100 by the second control pattern 210 of [(b), (c)].

The surface control region 110 is formed by using the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed as masks. In the multi-layer (first nanostructure), a characteristic-controlled thin film layer is formed (d).

Then, the second surface control layer 300 on which the first control pattern 310 is formed is removed (e), and the first surface control layer 200 on which the second control pattern 210 is formed is used as a mask. The second nanostructure 420 is formed to overlap with the property control thin film layer of the surface control region 110 [(f), (h)].

Then, by removing the first surface control layer 200 on which the second control pattern 210 is formed, the first nanostructure 410 and the second nanostructure ( 420) is formed [(g), (i)]. [In the case of forming the second nanostructure 420 made of a single type of metal (g), a second nanostructure made of two or more types of metal When the 2-nano structure 420 is formed (i)].

Referring to the embodiment according to FIG. 5 , the first surface control layer 200 is formed on the substrate 100, and the first surface control layer 200 is formed on the first surface control layer 200. A second surface control layer 300 having relatively high etching resistance is formed (a).

In addition, a first control pattern 310 is formed on the second surface control layer 300 by an exposure process, and the first control pattern 310 of the second surface control layer 300 is continuously or sequentially applied to the first control pattern 310 . A second control pattern 210 formed on the first surface control layer 200 and forming an extension-cut with respect to the first control pattern 310 is formed, and the first surface control layer 200 The surface control area 110 is secured on the substrate 100 by the second control pattern 210 of [(b), (c)].

And the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed are used as etching masks to An etching pattern 430 is formed on the surface control region 110 (d).

The surface control region 110 is formed by using the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed as masks. A multi-layer (first nanostructure) of a characteristic control thin film layer is formed on the etching pattern 430 of (e).

Then, the second surface control layer 300 on which the first control pattern 310 is formed is removed (f), and the first surface control layer 200 on which the second control pattern 210 is formed is used as a mask. The second nanostructure 420 is formed to overlap the characteristic control thin film layer of the surface control region 110 including the etch pattern 430 [(g), (i)].

Then, by removing the first surface control layer 200 on which the second control pattern 210 is formed, the first nanostructure ( 410) and the second nanostructure 420 to form a composite nanostructure [(h), (j)]. [In the case of forming the second nanostructure 420 made of a single type of metal (h) , When the second nanostructure 420 made of two or more metals is formed (j)].

Referring to the embodiment according to FIG. 6, the first surface control layer 200 is formed on the substrate 100, and the first surface control layer 200 is formed on the first surface control layer 200. A second surface control layer 300 having relatively high etching resistance is formed (a).

In addition, a first control pattern 310 is formed on the second surface control layer 300 by an exposure process, and the first control pattern 310 of the second surface control layer 300 is continuously or sequentially applied to the first control pattern 310 . A second control pattern 210 formed on the first surface control layer 200 and forming an extension-cut with respect to the first control pattern 310 is formed, and the first surface control layer 200 The surface control area 110 is secured on the substrate 100 by the second control pattern 210 of [(b), (c)].

And the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed are used as etching masks to An etching pattern 430 is formed on the surface control region 110 (d).

The surface control region 110 is formed by using the second surface control layer 300 on which the first control pattern 310 is formed and the first surface control layer 200 on which the second control pattern 210 is formed as masks. A characteristic control thin film layer (first nanostructure) is formed on the etching pattern 430 of (e). Here, the characteristic control thin film layer is formed with an inclination within the etching pattern 430 by utilizing a tilt evaporation process.

Then, the second surface control layer 300 on which the first control pattern 310 is formed is removed (f), and the first surface control layer 200 on which the second control pattern 210 is formed is used as a mask. The second nanostructure 420 is formed to overlap the characteristic control thin film layer of the surface control region 110 including the etch pattern 430 [(g), (i)].

Then, by removing the first surface control layer 200 on which the second control pattern 210 is formed, the first nanostructure ( 410) and the second nanostructure 420 to form a composite nanostructure [(h), (j)]. [In the case of forming the second nanostructure 420 made of a single type of metal (h) , When the second nanostructure 420 made of two or more metals is formed (j)].

Hereinafter, the process result data of the present invention will be described with reference to the accompanying drawings.

According to an embodiment of the present invention, when the substrate is a semiconductor laminate of light emitting diodes, the substrate is a Red LED epi-wafer (p-AlGaInP/u-AlGaInP/MQW(AlGaInP/InGaP)/u-AlGaInP/n+GaAs /n-AlGaInP/GaAs substrate) was used. The second surface control layer (AZ GXR-601 resist) on which the first control pattern is formed on the Red LED epi-wafer and the first surface control layer (LOR [Lift-Off Resist]) on which the second control pattern (extension cut) is formed ) was formed.

More specifically, Hexamethyldisilazane (HMDS) [AZ AD Promoter-K, AZ Electronic Materials, Luxembourg] was spin-coated on a Red LED epi-wafer at 2000 rpm for 40 seconds, and then dried at 100 ° C for 120 seconds, and LOR 20B [MicroChem Corp. ., Japan] was spin-coated at 4000 rpm for 40 seconds and then dried at 170° C. for 300 seconds to form a first surface control layer having a thickness of 2 μm. AZ GXR-601 resist was spin-coated on the first surface control layer at 4500 rpm for 40 seconds and dried at 90° C. for 90 seconds to form a 2 μm-thick AZ GXR-601 resist layer as a second surface control layer.

After locally irradiating UV rays of 60mJ/cm ² using a photomask, dry at 110℃ for 90 seconds in the Post Exposure Bake (PEB) process, and then apply AZ 300 MIF [AZ Electronic Materials, Luxembourg] as a developer for 20 seconds. The results of N ₂ blowing after soaking and rinsing in deionized (DI) water are shown in FIG. 7 (a).

And, in the case of FIGS. 7(b), 7(c), and 7(d), as a result of excessively performing the developing process, after immersing in the developer for 40 seconds, 50 seconds, and 60 seconds, respectively, rinsing in DI water and blowing N ₂ is a result

That is, FIG. 7 (a) shows the optical and SEM analysis results of the conventional second surface control layer formed with the first control pattern and the first surface control layer formed with the second control pattern (undercut), and FIG. 7 ( b), 7(c) and 7(d) are for the second surface control layer on which the first control pattern is formed and the first surface control layer on which the second control pattern (extended cut) is formed according to an embodiment of the present invention. Optical and SEM pictures are shown.

As shown in FIGS. 7(b), 7(c) and 7(d), the second control pattern of the first surface control layer corresponds to the first control pattern of the second surface control layer. It was confirmed that extended cuts having various shapes and areas were formed on the surface control layer, which acted as the surface control region 110 on the substrate.

The process was performed in the same manner as in the detailed embodiment described in FIG. 7, and in the case of (a), (c) and (e) of FIG. 8, the development time was 20 seconds, and in (b) and (d) of FIG. And in the case of (f), the developing time was set for 50 seconds to form an extended cut.

When forming the extended cut, it is possible to form a new pattern (second control pattern) in the first surface control layer by the first control pattern of the second surface control layer, and also adjust the arrangement of the first control pattern of the second surface control layer. Through this, it was confirmed that the arrangement of the second control pattern of the newly formed first surface control layer was possible.

That is, in the case of FIG. 8 (a), they are arranged in a square array (a square array in which holes form four sides), and the arrangement of the second control pattern of the first surface control layer newly formed when the extended cut is formed is also arranged in a square array (new It is characterized in that the pattern of the shape is arranged in a square arrangement (FIG. 8(b)) constituting four sides.

In addition, in the case of FIG. 8(c), they are arranged in a hexagonal array (a hexagonal array with six holes), and when an extended cut is formed, the array of the second control pattern of the first surface control layer newly formed is also arranged in a hexagonal array ( It is characterized by the fact that the pattern of the new shape is arranged in a hexagonal arrangement (FIG. 8(d)) constituting six sides.

That is, the second control pattern of the first surface control layer newly formed according to the method of arranging the first control pattern of the second surface control layer according to the present embodiment is characterized in that the pattern is formed in an arrangement having the same shape. have.

Another characteristic factor is that, as shown in FIG. 8(e), if the lengths of A and B are the same as those of B and C, it is possible to connect patterns [Fig. 8(f)] when forming an extended cut, and the lengths of B and C are possible. When is the same and the lengths of C and D are different, the space of C and D is separated, that is, separation between patterns [FIG. 8(f)] is possible.

9 is an extension through the realization of various patterns of the first surface control layer newly formed according to the adjustment of the drying conditions (temperature and time) of the first surface control layer and Post Exposure Bake (PEB) conditions (temperature and time) after UV irradiation. An example of adjusting the area of the cut is shown.

The process was performed in the same manner as in the detailed embodiment described in FIG. 7 (development time was fixed at 50 seconds), and in the case of (a), (b) and (c) of FIG. 9, the drying conditions of the first surface control layer ( temperature and time), and in the case of (d), (e) and (f) of FIG. 9, the results are shown according to PEB (temperature and time) control.

When comparing the results of FIG. 9, it was confirmed that the second control pattern of the newly formed first surface control layer changed according to the change in the drying time and drying temperature of the first surface control layer, and also the PEB temperature and PEB time. It was confirmed that the pattern of the first surface control layer was changed according to the change. It was confirmed that the control of the drying condition of the first surface control layer had a greater effect on the control of the area of the extended cut than the change of the PEB condition.

That is, the process variables capable of implementing various second control patterns of the newly formed first surface control layer are the thickness of the first surface control layer, the thickness of the second surface control layer, locally irradiated energy, developing time, soft baking Temperature and time, PEB (Post-exposure baking) temperature and time, the range for each process variable is 25 nm to 50㎛ for the thickness of the first surface control layer and the second surface control layer, and the locally irradiated ultraviolet energy 1mJ/cm ² ~ 10J/cm ² , electron beam energy 1μC/cm ² ~5mC/cm ² , development time 10 seconds ~ 5 minutes, Soft-baking and PEB temperature and time range from 50 ℃ ~ 300 ℃ 15 seconds ~ 10 minutes .

Figure 10 is a diagram showing the results of measuring the metal-organic photolysis reaction according to the change in ultraviolet irradiation time according to an embodiment of the present invention [Fig. 10 (a), (b) and (c)], according to the change in ultraviolet irradiation time A diagram showing the color change of the metal-organic solution [FIG. 10 (d), (e) and (f)], and a diagram showing the diameter distribution of metal nanostructures according to the change in UV irradiation time [FIG. 10 (g), (h) and (i)].

After putting the light-sensitive metal (silver [Ag], gold [Au], and platinum [Pt])-organic solution in the vial bottle, it was confirmed that metal (silver, gold, and platinum) nanostructures were created according to the UV irradiation time control. In addition, UV-vis. Measurement results [Fig. 10 (a), (b) and (c)], color change of metal-organic solution [Fig. 10 (d), (e) and (f)] and diameter distribution of metal nanostructures [Fig. 10 Through the analysis of (g), (h) and (i)], it was confirmed that the diameter size and distribution of the metal nanostructures can be controlled by adjusting the UV time.

11(a) is a photolysis in which metal nanostructures are formed when a sample having an extended cut is immersed in a photosensitive metal [M (Metal)]-organic solution in which the location, area, and shape are controlled, and then irradiated with ultraviolet rays. As an illustration of the reaction mechanism, it is shown that sodium citrate (dihydrate), one of the photo-initiators, induces a photolysis reaction to form metal nanostructures on the extended cut.

In addition, it is possible to control the size distribution of the metal nanostructure by adjusting the UV irradiation time during the photolysis reaction, and the metal constituting the metal nanostructure is silver, gold, platinum, copper, palladium, nickel, silicon, iron, cobalt Any one or a combination of two or more of them, and the shape of the nanostructure is a mixture of any one or two or more shapes of nanoparticles, nanorods, nanowires, and nanotubes.

11(b) is an optical microscope measurement result of an extended cut formed by performing the process in the same order as the detailed embodiment described in FIG. 7 and developing the development time at 40 seconds, and FIG. 11(c) is silver nitrate (AgNO ₃ ) After preparing a photosensitive Ag-organic solution by mixing a certain amount of sodium citrate (dihydrate) [Sodium citrate tribasic dihydrate] and water and removing the second surface control layer from the sample shown in FIG. 11 (b) It was immersed in a photosensitive Ag-organic solution.

FIG. 11(c) shows the SEM measurement results observed after irradiation with ultraviolet rays for 7 minutes thereafter. The diameter of the nanostructures formed on the extended cut was approximately 20 nm, and it was observed that some of the nanostructures were also formed on the side of the first surface control layer. In addition, it was confirmed that the nanostructure formed using energy dispersive spectrometry (EDS) was silver (Ag).

11(d) is an SEM measurement result of an extended cut formed after processing in the same order as in the detailed embodiment described in FIG. 7, developing for 50 seconds, and removing the second surface control layer. After immersing the sample in the described photosensitive Ag-organic solution and then irradiating with ultraviolet rays for 15 minutes, the first surface control layer was removed and the SEM results measured are shown in FIG. 11(e).

It was confirmed that silver (Ag) nanostructures were formed in the extended cut region where the position was controlled, and it was confirmed that the size of the silver (Ag) nanostructures was approximately 40 to 50 nm. From this result, it was confirmed that the distribution of the diameter of the silver (Ag) nanostructure can be controlled by adjusting the UV irradiation time.

The organic matter in the metal-organic solution is sodium citrate (dihydrate), ethyl hexanonate, dialkyl isocarbamate, carboxyl acid, carboxylate, pyridine, diamine, aracin, diaracin, phosphine, diphosphine , arenes, chloride, acetate, acetylacetonate, carbonyl, carbonate, hydrate, hydroxide, nitrate, oxalate, and at least one of the group consisting of mixtures thereof, and the solvent is water, methanol, At least one of the group consisting of ethanol, propanol, isopropanol, butanol, pentanol, hexanol, DMSO, DMF, N-methyl pyrrolidone, acetone, acetonitrile, THF, tecan, nonane, octane, heptane, hexane and pentane can

In addition, the energy source for inducing the decomposition reaction of the metal-organic solution may be heat, microwave or laser as well as ultraviolet rays.

12 is a diagram in which the substrate is a semiconductor laminate of light emitting diodes according to an embodiment of the present invention, the substrate is a Blue LED epi-wafer [p-GaN//MQW (InGaN/GaN)/n-GaN/un-GaN /sapphire substrate) was used. A second surface control layer (AZ GXR-601 resist) having a first control pattern formed on the Blue LED epi-wafer and a first surface control layer (LOR [Lift-Off Resist]) having a second control pattern (extension cut) formed thereon ) was formed.

More specifically, Hexamethyldisilazane (HMDS) [AZ AD Promoter-K, AZ Electronic Materials, Luxembourg] was spin-coated on a Blue LED epi-wafer at 2000 rpm for 40 seconds, and then dried at 100 ° C for 120 seconds, and LOR 20B [MicroChem Corp. ., Japan] was spin-coated at 4000 rpm for 40 seconds and then dried at 170° C. for 300 seconds to form a first surface control layer having a thickness of 2 μm.

AZ GXR-601 resist was spin-coated on the first surface control layer at 4500 rpm for 40 seconds and dried at 90° C. for 90 seconds to form a 2 μm thick AZ GXR-601 resist layer as a second surface control layer. 60 mJ/cm ² using a photomask ([Fig. 12(a), Hole diameter 4㎛, Pitch 16㎛ and Square array] and [Fig. 12(c), Hole diameter 4㎛, Pitch 12㎛ and Hexagonal array]) After locally irradiating ultraviolet rays, drying at 110 ℃ for 90 seconds in the Post Exposure Bake (PEB) process, AZ 300 MIF [AZ Electronic Materials, Luxembourg] as a developer for 40 seconds, respectively [Fig. 12 (a)] and After soaking for 60 seconds [FIG. 12(c)], rinsing in deionized (DI) water and N ₂ blowing.

After forming the extended cut, dry etching is performed with an ICP etcher [Multiplex ICP, STS, America] for 30 seconds using the patterned second surface control layer and the first surface control layer as a dry etching mask, and then the patterned second surface control layer is used as a dry etching mask. 12(a) and 12(c) show the results of observing the three-dimensional structure with an optical microscope after removing only the surface control layer and performing dry etching for 30 seconds additionally with an ICP etcher and then removing the first surface control layer. to be.

12(b) and 12(d) show ICP etcher [Multiplex ICP, STS, America] using the patterned second surface control layer and the first surface control layer as dry etching masks after forming the extended cut. After performing dry etching for 30 seconds, only the patterned second surface control layer is removed, dry etching is additionally performed for 30 seconds with an ICP etcher, and after immersion in the photosensitive Ag-organic solution described in FIG. 12(b) and 12(d) show measurement results observed with an optical microscope after irradiation for 10 minutes and removal of the first surface control layer.

As shown in FIGS. 12(b) and 12(d), it was confirmed that the local formation of Ag nanostructures was possible in the region where the position was controlled.

12(e) shows Ag on a flat surface substrate that is not roughened, a substrate roughened into various 3D shapes (3D A and B structures [FIGS. 12(a) and 12(c)]) and a 3D structure. This is a result of measuring PL (Photoluminescence) of a substrate on which nanostructures are locally formed in a controlled area (FIGS. 12(b) and 12(d)).

In the case of FIG. 12(f), this is a table showing the increase rate of PL intensity compared to a substrate with a flat surface. It was shown that the PL intensity increased by 130.73 and 239.03% as Ag nanostructures were formed locally in the regions where the positions of the structures A and B were controlled.

From the above results, it was experimentally confirmed that the PL intensity increased as the three-dimensional structure was formed on the flat surface substrate, and that a greater increase in the PL intensity was possible by additionally forming Ag nanostructures in the region where the location was controlled.

This causes a resonance phenomenon by the surface plasmon of the Ag nanostructure, and a strong enhancement of local electromagnetic fields around the Ag nanostructure, resulting in light absorption by the locally strongly formed electric field around the Ag nanostructure. It was confirmed that the excitation enhancement by the increase became possible and the PL intensity increased.

That is, in controlling the light extraction efficiency, it was confirmed that controlling the diameter, pitch size, arrangement type, and degree of compactness of the surface-controlled 3D nanostructure according to the present invention is an important factor in improving the light extraction efficiency.

100: substrate 110: surface control area
200: first surface control layer 210: second control pattern
300: second surface control layer 310: first control pattern
400: surface control 3-dimensional nanostructure 410: first nanostructure
420: second nanostructure 430: etching pattern

Claims (25)

Forming a plurality of surface control layers having different etch resistances on top of a substrate;
Through an exposure process, control patterns having different sizes according to the etching resistance are formed on each of the surface control layers, and an extension-cut is formed in the lower control pattern compared to the upper control pattern to form a surface control region on the substrate. securing;
forming a first nanostructure in the surface control region using the plurality of surface control layers on which the control pattern is formed as a mask;
Including; removing the surface control layer;
The first nanostructure is formed on the substrate by removing all of the surface control layer, or the first nanostructure is formed on a portion of the substrate by using the remaining surface control layer as a mask while sequentially removing the surface control layer. Overlapping other nanostructures,
The plurality of surface control layers formed on the upper part of the substrate are formed of a material having higher etching resistance of the surface control layer formed farther from the substrate than the surface control layer formed close to the substrate, and the lowest layer of the plurality of surface control layers The rest of the surface control layer other than the surface control layer is made of photoresist or photosensitive metal-organic precursor,
Performing a developing process according to the exposure process,
An additional developing process is continuously or sequentially performed, and after the developing process or the additional developing process, the surface control layer is dry-etched or wet-etched to further expand the extended cut,
The method of forming a surface-controlled three-dimensional nanostructure, characterized in that by adjusting the degree of curing of the surface control layer to control the area of the surface control region. delete The method of claim 1, wherein the method of forming the surface-controlled three-dimensional nanostructure,
A first step of forming a first surface control layer on a substrate;
a second step of forming a second surface control layer having a relatively high etching resistance with respect to the first surface control layer on the first surface control layer;
a third step of forming a first control pattern on the second surface control layer by an exposure process;
A second control pattern formed on the first surface control layer in succession or sequentially to the first control pattern of the second surface control layer and forming an extension-cut with respect to the first control pattern. Step 4;
a fifth step of securing a surface control area on the base material by means of a second control pattern of the first surface control layer;
a sixth step of forming a first nanostructure in the surface control region using the second surface control layer on which the first control pattern is formed and the first surface control layer on which the second control pattern is formed as a mask;
The second surface control layer and the first surface control layer are removed to form a first nanostructure on the substrate, or the second surface control layer is removed and the first surface control layer on which the second control pattern is formed is formed. A composite nanostructure composed of the first nanostructure and the second nanostructure is formed on the substrate by forming a second nanostructure in the surface control region as a mask and removing the first surface control layer on which the second control pattern is formed. A method for forming a surface-controlled three-dimensional nanostructure comprising a; seventh step of forming a. The method of claim 3, wherein the etching resistance ratio of the first surface control layer and the second surface control layer is 1: 1.1 to 10. The method of claim 3, wherein the fourth step,
A method for forming a surface-controlled three-dimensional nanostructure, characterized in that the second control pattern is formed by performing a developing process according to the exposure process of the third step and performing an additional developing process continuously or sequentially. The method of claim 5, wherein the fourth step,
After the developing process or after the additional developing process, the first surface control layer is dry-etched or wet-etched to form a second control pattern further expanding the extended cut. Method for forming a surface-controlled three-dimensional nanostructure. The method of claim 3, wherein the second control pattern of the first surface control layer,
The arrangement form is determined according to the arrangement form of the first control pattern of the second surface control layer;
Alternatively, the surface-controlled three-dimensional nanostructure formation method, characterized in that the shape of the pattern is adjusted by the distance between the first control patterns of the second surface control layer. The method of claim 3, wherein the fifth step,
The method of forming a surface-controlled three-dimensional nanostructure, characterized in that the size of the surface control region is adjusted by changing the area of the second control pattern constituting the extended cut of the fourth step. The method of claim 3, wherein the first nanostructure,
A chemically synthesized single metal nanostructure or two or more chemically synthesized metal nanostructures,
Or a method of forming a surface-controlled three-dimensional nanostructure, characterized in that a nanostructure formed by forming a single or multi-layered property-controlled thin film layer having a surface property different from that of the substrate. The method of claim 3, wherein the composite nanostructure,
Using the second surface control layer having the first control pattern and the first surface control layer having the second control pattern as a mask, a single or multi-layer property control thin film layer having a surface property different from that of the substrate is placed in the surface control region With the first nanostructure,
A second nanostructure composed of a metal nanostructure overlapped with the first nanostructure in the surface control region by removing the second surface control layer and using the first surface control layer formed with the second control pattern as a mask. A method for forming a surface-controlled three-dimensional nanostructure, characterized in that. The method of claim 3, after the fifth step,
Surface control 3, characterized in that an etching pattern is additionally formed in the surface control region by using the second surface control layer on which the first control pattern is formed and the first surface control layer on which the second control pattern is formed as an etching mask Method for forming dimensional nanostructures. The method of claim 11, wherein the first nanostructure and the composite nanostructure,
A method for forming a surface-controlled three-dimensional nanostructure, characterized in that formed in response to the etching pattern. The method of claim 11, wherein the etching pattern,
formed by a single etching process such as a dry etching process or a wet etching process;
A method for forming a surface-controlled three-dimensional nanostructure, characterized in that it is formed by any one of a complex etching process such as a wet etching process after a dry etching process or a dry etching process after a wet etching process. The method of claim 3, wherein the substrate,
A surface-controlled three-dimensional nanostructure formation method, characterized in that the n-type semiconductor layer or p-type semiconductor layer formed on the uppermost layer of the photoelectric device. delete delete delete delete delete delete delete delete delete delete delete

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