KR20180000612A - three-dimentional composite structure, manufacturing method thereof and SERS substrate comprising thereof - Google Patents

Abstract

According to the present invention, it is very difficult to achieve a hierarchical three-dimensional structure formed of multiple components that are formed in one-dimensional structure although it is general to design and manufacture a two-dimensional array formed of such a single component. In order to solve this problem, a three-dimensional composite structure of the present invention includes a new wire-on-pillar structure formed by vertically growing a gold nanowire in a radial shape from a side surface portion of a silicon micro pillar. The present invention has obtained a new three-dimensional composite structure which is called as a three-dimensional wire-on-pillar that is different from a zero dimensional dot shaped, one-dimensional linear, or two-dimensional planar gold structure. Such an Au composite structure provides abundant hotspot between neighboring Au nanowires, and a very high surface-enhanced Raman scattering (SERS) signal can be obtained accordingly.

Description

Dimensional composite structure, a method of manufacturing the SUS substrate, and a SERS substrate including the SUS substrate, including a three-dimensional composite structure, a manufacturing method thereof and a SERS substrate,

The present invention relates to a three-dimensional complex structure, and more particularly, to a complex structure having a three-dimensional structure including a micro-column and a nanowire formed on a side of the column, in which a large amount of hot spots are formed, .

Various types of micro- and nanostructures have various advantages and characteristics and have been widely used for many years by many researchers.

In particular, the one-dimensional structure is highly likely to be used for various applications such as solar cells, charge storage devices, transistors, drug delivery devices, and sensors. The one-dimensional structure can be roughly classified into a micro-nano-sized wire and a micro-nano-sized pillar.

In the case of a silicon micropillar, the surface capacitance is relatively higher than that of a conventional flat structure having the same area and is widely used in many fields.

In addition to the silicon micro pillars, various types of one-dimensional structures exist. For example, various types of structures are known, such as a metal coating or a hollow shape.

While there are advantages to these various applications, there are structural and component limitations in manufacturing a majority of one-dimensional structures.

In other words, since the one-dimensional structure is specified only by a simple orientation such as the y direction (e.g., vertical direction) or the xy plane (e.g., the horizontal direction) There are some difficulties in manufacturing a structure composed of a three-dimensional shape including a multi-directionality and a variety of materials different from each other through a manufacturing method.

In order to overcome the above-mentioned problems, it is known to produce a large-area controllable three-dimensional microstructure by adjusting the width, surface, height, and arrangement of the micropillar array, which is a combination of top- And suggests alternatives to existing manufacturing methods. This means that the one-dimensional structure has been developed into a complex structure, but there is still a limitation that the structure is composed of only a single component.

The present inventors have made efforts to produce a structure made of a three-dimensional composite material while retaining excellent advantages and advantages of the one-dimensional microstructure and the one-dimensional nanostructure. As a result, We realized the three-dimensional complex structure which was manufactured so as to realize the direction of using the structure as a building block and to have different directions through it.

Patent Document 1: Korean Patent Laid-Open Publication No. 10-2015-0097039

SUMMARY OF THE INVENTION It is an object of the present invention to provide a three-dimensional composite structure of a new structure made of different materials.

Another object of the present invention is to provide a method for mass-producing the three-dimensional complex structure.

Still another object of the present invention is to provide an SRES substrate which can be applied to various fields including the three-dimensional complex structure and its use.

In order to achieve the above object,

Board;

A micro pillars spaced apart from one another on the substrate;

A metal nanowire growing and arranged in a vertical direction from a side portion of the micropillar; And

And a nanogap is formed between the metal nanowires of the micropillar.

The average height of the micro pillars may be 1 to 5 mu m.

The micropillar may be divided into a side upper end portion and a side lower end portion of the micropillar based on an average height of 20 to 70%.

The nanogap may be formed on a side upper end portion of the micropillar.

The distance between the micro pillars may be 0.1 to 1 占 퐉.

The length of the metal nanowire may be 10 to 600 nm.

The upper end of the micropillar may be a smoother surface than the side surface of the micropillar.

The angle between the micropillar and the metal nanowire or network structure may be in the range of 80 to 100 degrees.

According to another aspect of the present invention, there is provided a method of manufacturing a three-dimensional complex structure including the steps of:

(I) oxygen plasma treatment of the surface of a substrate having micro pillars spaced apart from each other;

(II) contacting the pretreated substrate with a first solution in which a coupling agent is mixed with a solvent;

III) fixing the metal nanoparticles on the surface of the substrate prepared in the step II); And

And (iv) growing a metal nanowire by treating a second solution for growing the metal nanoparticles on a substrate on which the metal nanoparticles are immobilized.

The average height of the micro pillars may be 1 to 5 mu m.

The distance between the micro pillars may be 0.1 to 1 占 퐉.

The length of the metal nanowire may be 10 to 600 nm.

The upper end of the micropillar may be a relatively smooth surface than the side surface of the micropillar.

The coupling agent may be at least one aminoalkylsilane selected from the group consisting of 3-aminopropyltriethoxysilane (APTES), 4-aminopropyltrimethoxysilane and 4-aminobutyltrimethoxysilane.

The solvent may be any one selected from the group consisting of C _{1 -6} alcohols, water, and mixed solvents thereof.

The mixing volume ratio of the coupling agent and the solvent may be 1: 700-1300.

The second solution comprises a ligand, a reducing agent and a metal precursor, and the content of the ligand in the second solution may be 100 to 300 [mu] M.

The ligand may be 4-mercaptobenzoic acid, 4-mercapto-2-methoxy-benzoic acid and 3-mercaptopropionic acid. ≪ / RTI >

The reducing agent may be at least one selected from the group consisting of borohydride, hydrazine, citric acid or a salt thereof, and reducing sugar of L-ascorbic acid, alkali metal or alkaline earth metal.

The metal precursor may be at least one selected from the group consisting of AgNO ₃ , AgCl, AgNO ₃ , HAuClO ₄ , HAuCl _{4 ,} H ₂ PtCl ₆ and H ₂ Pt (OH) ₆ .

The immersing time in the second solution of the step IV) may be carried out for 60 to 120 minutes.

According to another aspect of the present invention, there is provided a surface enhanced Raman spectroscopy plate including the three-dimensional complex structure.

The present invention provides the use of the surface enhanced Raman spectroscopy plate, which can be used as a biosensor or a microelectrode array by including the surface enhanced Raman spectroscopy plate.

The three-dimensional complex structure according to the present invention provides a new structure of a three-dimensional structure as a different material. Such a structure can be manufactured easily and easily at low cost by using chemical methods using a metal seed and a ligand.

Specifically, the three-dimensional complex structure according to the present invention provides a new structure of a metal wire (hereinafter, also referred to as a wire-on-pillar) formed on a non-metallic micro-pillar, (Nanogaps) to form a high-density hot spot. These high-density hotspots enable the SERS signal to be maximized, creating more hotspots than conventional 1, 2 or 3-dimensional structures.

A three-dimensional composite structure according to the present invention, due to the above-described structural characteristics may enhance the SERS signal of R6G probe molecules and, more specifically silicon pillar nothing is processed (pillar) in 520 ㎝ ^-1 peak array than 8.6 X 10 ⁶ times It is possible to improve the SERS signal as well as to present the direction of a new manufacturing method capable of manufacturing the structure and to improve the merits of existing structures and to achieve a more complex and hierarchical structure .

1 is a cross-sectional view schematically showing a structure of a three-dimensional complex structure according to an embodiment of the present invention.
FIG. 2 is a schematic view showing an overall process of growing gold nanowires on a silicon substrate according to embodiments 1 to 4 of the present invention.
3 is a schematic view showing the structure of the three-dimensional complex structure produced from Examples 1 to 4. FIG.
4 is a SEM photograph of the three-dimensional composite structures manufactured in Examples 1 to 4; Where a is the three-dimensional composite structure prepared in Example 1, b is the three-dimensional composite structure prepared in Example 2, c is the three-dimensional composite structure prepared in Example 3, d is the three- Structure.
5 is a SEM image at a low magnification of the three-dimensional composite structure produced from Example 1. Fig.
6 is a SEM image at a low magnification of the three-dimensional composite structure produced from Example 2. Fig.
7 is an SEM image at a low magnification of the three-dimensional composite structure produced from Example 3. Fig.
8 is an SEM image at a low magnification of the three-dimensional composite structure produced from Example 4. Fig.
9 is a SEM image (a) taken from above and a SEM image (b) taken from a side direction (60 ° slope) of the silicon micropillar manufactured in the step 2) of Example 5 described above.
FIG. 10 is an image of each of the three-dimensional composite structures manufactured in Examples 5 to 8 taken by SEM. The SEM images (a, b, c, and d) , b ', c', d ').
11 is a SEM image (b) of the three-dimensional composite structure manufactured in Example 8 taken in the lateral direction (60 ° tilt).
12 shows SERS spectra (a, b, c, and d) and SEM images (a ', b', c ', and d) of the three-dimensional complex structure prepared from Comparative Example for R6G, Examples 2, ')to be.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.

In general, the three-dimensional structure can be applied as a three-dimensional plasmonic hotspot matrix, which leads to a significant improvement in the SERS signal. In the studies related to the SERS hotspot, most of them are due to the zero-dimensional point shape, the one-dimensional linear shape, the two-dimensional plate shape, and the density of the hotspots is not more than a certain value due to the fundamental limit of the zero-dimensional, one-dimensional or two- .

Further, in order to overcome the above-mentioned problem, the present invention provides a new three-dimensional composite structure called a "wire-on-pillar" by growing nanowires radially from the side of a silicon micropillar (hereinafter also referred to as a micropillar) .

An aspect of the present invention provides a semiconductor device comprising: a substrate; At least one micro pillar 120 spaced apart from one another on the substrate 110; At least one metal nanowire (130) grown and grown in a vertical direction from a side surface of the micropillar (120); And a nanogap 140a are formed between the metal nanowires 130 and 130 'of the micro pillars 120 and 120'. FIG. 1 shows the structure of the three-dimensional complex structure.

The three-dimensional complex structure 100 of the present invention having the above-described structure provides a new type of structure in which a three-dimensional structure is manufactured using different materials. In addition, by introducing the structure 140 of the metal nanowires 130 and 130 'including a plurality of nano gaps 140a between the micro pillars 120 and 120', the SERS signal can be maximized, The distance was minimized to enhance the SERS signal.

Due to the plurality of nano gaps 140a formed between the metal nanowires 130 and 130 ', a high-density hot spot can be provided to further increase the SERS signal, and the uniformity of the SERS signal size Lt; / RTI >

The substrate 110 may be any one of non-metallic materials selected from the group consisting of silicon (Si), gallium arsenide (GaAs), glass, quartz, and polymer.

The metal may be any one selected from the group consisting of gold (Au), platinum (Pt), silver (Ag), copper (Cu), aluminum (Al), and alloys thereof.

The average height of the micro pillars 120 may be 1 to 5 占 퐉. If the average height of the micro pillars exceeds 5 占 퐉, the material to be targeted may extend to the side lower ends 120c of the micro pillars 120 ) Can not sufficiently infiltrate into the water.

The micro pillars 120 may be divided into an upper portion 120a of the micro pillars and side portions 120b and 120c of the micro pillars. The side portions 120b and 120c of the micro pillars may be divided into a plurality of A portion distant from the substrate with respect to an average height of 20 to 70% is referred to as a side upper end portion 120b of the micropillar and a portion near the substrate side is referred to as a side lower end portion 120c of the micropillar.

If the average height of the micro pillars 120 is 2.5 to 5 占 퐉, the nanogap 140a may be formed only on the side upper end 120b of the micro pillars, The nano gap 140a may be formed over the micro column side upper end portion 120b and the side lower end portion 120c.

The spacing between the micro pillars 120 may be determined according to the length of the metal nanowires 130. The length of the metal nanowires 130 is at least 10 nm and at most 600 nm, The distance between the micro pillars may be 0.1 to 1 占 퐉.

If the length of the metal nanowires 130 is less than 10 nm, the minimum level for achieving the three-dimensional nanogaps can not be achieved. If the length of the metal nanowires grown on the side surfaces of the micropillar is controlled to be less than 10 nm Is difficult. When the length of the metal nanowires 130 is greater than 600 nm, the metal nanowires 120 may not be vertically grown, but may be bent or laid to grow, so that the metal nanowires 130 ') And the network structure.

Preferably, the distance between the micro pillars 120 is 0.1 to 1 占 퐉, because the nanowires 130 and 130 'of the adjacent micro pillars 120 and 120' are spaced apart from each other with the nanogap 140a therebetween In other words, the nanowires 130 and 130 'of the micro pillars 120 and 120' adjacent to each other within a distance between the micro pillars 120 and 120 'overlap with each other to form the network structure 140 The distance between the micro pillars 120 and 120 'may be determined within a range of twice the length of the nanowire 130. [

The upper end 120a of the micropillar 120 may be a smoother surface than the side surfaces 120b and 120c of the micropillar 120. Specifically, The roughness may be 1.5 to 3 times larger than the roughness of the surface of the upper end 120a of the micropillar 120. [

If the roughness of the upper surface 120a of the micropillar 120 and the surfaces of the side surfaces 120b and 120c of the micropillar 120 are similar to each other, the metal nanowires 130 can not be controlled, A large amount may be formed on the upper end 120a of the substrate 120. [

When the metal nanowires 130 are formed on the upper end 120a of the micro pillars 120, the metal nanowires 130 are entangled with each other and are formed between the metal nanowires 130 and 130 ' The nano gap 140a is reduced, and a problem that the overall hot spot is reduced occurs.

If the roughness of the surface of the side portions 120b and 120c of the micropillar 120 is 1.5 to 3 times larger than the roughness of the surface of the upper portion 120a of the micropillar 120, There is a problem that the metal nanowire having a sufficient density can not be grown.

An angle between the micropillar 120 and the metal nanowire 130 or the network structure 140 may be in the range of 80 to 100 degrees. The side surface 120b of the micropillar 120 The angle between the micropillar 120 and the metal nanowire 130 or the network structure 140 is 80 to 100 degrees Celsius as the metal nanowires 130 are grown and arranged vertically from the metal nanowires 130, °). If the angle is less than 80 degrees or more than 100 degrees, the metal nanowires 130 are entangled with each other, and the nanogaps 140a formed between the metal nanowires 130 and 130 'are reduced , There is a problem that the overall hot spot decreases.

The metal nanowires 130 may be vertically grown from the side lower end portions 120c and the upper end portions 120b of the micro pillars 120. The average height of the micro pillars 120 may be sufficiently high It is preferable that the metal nanowires 130 are present only in the side upper end portion 120b of the micro pillar 120 in the case of 2.5 to 5 m.

And a network structure 140 formed between the metal nanowires 130 and 130 'grown from different micro pillars 120 and 120', wherein the network structure 140 is formed on side portions of the micro pillars 120 and 120 ' The metal nanowires 130 and 130 'are spaced apart from each other with the nanogap 140a therebetween to form a high-density hot spot. Since the nanogap 140a exhibits a strong SERS signal as the nanogap 140a is smaller, As the nanogap is narrowed, the SERS signal can be maximized.

Conventionally, most of the nanoseconds have a nanogap at a level of several tens of nanometers. However, since nanogaps of less than 1 nm are formed in the present invention, a very excellent SERS signal can be amplified and improved.

Therefore, the three-dimensional complex structure of the above-described structure has a uniform density of the SERS signal as a whole due to the presence of a large number of metal nanowires 130 and a high-density hot spot formed between the metal nanowires 130 You can have sex.

Another aspect of the present invention relates to a method for producing a three-dimensional complex structure including the following steps.

(I) oxygen plasma treatment of the surface of a substrate having micro pillars spaced apart from each other;

(II) contacting the pretreated substrate with a first solution in which a coupling agent is mixed with a solvent;

III) fixing the metal nanoparticles on the surface of the substrate prepared in the step II); And

And (iv) growing a metal nanowire by treating a second solution for growing the metal nanoparticles on a substrate on which the metal nanoparticles are immobilized.

The above-described manufacturing process will be described in more detail below.

First of all, the surface of the substrate on which the micro pillars are spaced apart from each other is subjected to oxygen (O ₂ ) plasma treatment. Through this process, the surface of the substrate where the micro-sized pillars are spaced apart from each other can be hydrophilically modified.

Since the micro-sized pillars are spaced apart from each other according to a known method, those skilled in the art can carry out the present invention without any particular explanation.

However, to describe the above process, the substrate having the micro pillars spaced apart from each other may be formed using a known semiconductor process. In order to form a pattern in which the micro pillars are spaced apart from each other on the substrate, a fine pattern of the micro pillars can be manufactured using a photolithography process.

Preferably, the upper end of the micropillar may have a relatively smoother surface than the side surface of the micropill, to effectively control the locality of the metal nanowire.

Specifically, it is preferable that the surface roughness of the side surface of the micropillar is 1.5 to 3 times larger than that of the upper surface of the micropillar, because if the surface roughness of the side surface of the micropillar is less than or greater than the above range, There may arise a problem in that sufficient density of metal nanowires can not grow on the surface.

If the roughness of the upper surface of the micropillar and the surface of the side surface of the micropillar are similar, the metal nanowires can not be controlled and a large amount of the metal nanowires may be formed on the upper end of the micropillar.

When the metal nanowires are formed at the upper end of the micropillar, the metal nanowires are entangled with each other, and the nanogaps formed between the metal nanowires are reduced, and the overall hot spot is reduced .

The micro-sized column may be made of a silicon material and treated with an oxygen plasma to improve its surface hydrophilicity. The substrate is then treated with a first solution in which 3-amino propyltriethoxysilane (APTES) is mixed with ethanol, So that an APTES monolayer is uniformly formed on the substrate.

The average height and the average diameter of the micro pillars may independently be 1 to 5 占 퐉. If the average height of the micro pillars exceeds 5 占 퐉, A problem that the side lower portion 120c can not sufficiently penetrate may occur.

The micro pillars 120 can be divided into an upper portion 120a of the micro pillars and side portions 120b and 120c of the micro pillars. A detailed description thereof will be given below with reference to FIG. 1, .

The side portions 120b and 120c of the micropillar 120 are referred to as a side upper end portion 120b of the micropillar at a distance of 20 to 70% from the average height of the micropillar 120, Is referred to as a side lower end portion 120c of the micropillar.

If the average height of the micro pillars 120 is 2.5 to 5 占 퐉, the nanogap 140a may be formed only on the side upper end 120b of the micro pillars, The nano gap 140a may be formed over the micro column side upper end portion 120b and the side lower end portion 120c.

The spacing between the micro pillars 120 may be determined according to the length of the metal nanowires 130. The length of the metal nanowires 130 is at least 10 nm and at most 600 nm, The distance between the micro pillars may be 0.1 to 1 占 퐉.

If the length of the metal nanowires 130 is less than 10 nm, the minimum level for achieving the three-dimensional nanogaps can not be achieved. If the length of the metal nanowires grown on the side surfaces of the micropillar is controlled to be less than 10 nm Is difficult. When the length of the metal nanowires 130 is greater than 600 nm, the metal nanowires 120 may not be vertically grown, but may be bent or laid to grow, so that the metal nanowires 130 ') And the network structure.

Preferably, the distance between the micro pillars 120 is 0.1 to 1 占 퐉, because the nanowires 130 and 130 'of the adjacent micro pillars 120 and 120' are spaced apart from each other with the nanogap 140a therebetween In other words, the nanowires 130 and 130 'of the micro pillars 120 and 120' adjacent to each other within a distance between the micro pillars 120 and 120 'overlap with each other to form the network structure 140 The distance between the micro pillars 120 and 120 'may be determined within a range of twice the length of the nanowire 130. [

Next, the first solution mixed with the pretreated substrate and the coupling agent is brought into contact with the metal nanoparticles stabilized by the negatively charged molecules, so that the nanoparticles stabilized easily and fast on the silicon surface will be.

Wherein the negative charge is preferably sodium citrate.

The coupling agent may be at least one aminoalkylsilane selected from the group consisting of 3-aminopropyltriethoxysilane (APTES), 4-aminopropyltrimethoxysilane and 4-aminobutyltrimethoxysilane, Aminopropyltriethoxysilane (APTES). ≪ / RTI >

The solvent may be any one selected from the group consisting of C _{1 -6} alcohols, water, and mixed solvents thereof.

In the first solution, the volume ratio of the coupling agent to the ethanol is preferably 1: 700-1300.

Through the step (II), a coupling agent having a positive charge only on the silicon surface is selectively adsorbed on the surface of the substrate.

Next, III) the metal nanoparticles are fixed on the surface of the substrate manufactured through the step II). Since the surface of the substrate manufactured through step II) is positively charged by the step II), the metal nanoparticles protected with the negatively charged material can be selectively and easily fixed to the silicon surface only selectively on the substrate .

Preferably, in the step (III), the substrate prepared in the step (II) is immersed in the first solution containing the metal nanoparticles as it is, or the first solution containing the metal nanoparticles is allowed to flow, The metal nanoparticles can be fixed on the surface of the substrate. Since the density of the fixed metal nanoparticles can be controlled by changing the immersion time, the substrate prepared through the step (II) 1 < / RTI > solution.

If the immersing time is less than 1 hour, the time required for immersing the substrate prepared in step II) into the first solution containing metal nanoparticles is preferably 1 to 5 hours. If the immersion time is less than 1 hour, The particles can not be fixed and ultimately a high-density hot spot to be obtained can not be obtained. If the time exceeds 5 hours, a large amount of metal nanoparticles are fixed and the growth of metal nanoparticles may be interrupted.

The fixed metal nanoparticles are then used as seeds of metal nanowires.

The metal may be any one selected from the group consisting of gold (Au), platinum (Pt), silver (Ag), copper (Cu), aluminum (Al), and alloys thereof.

In addition, in the step (III), the metal nanoparticles are fixed only to the side surface of the micropillar among the substrates manufactured through the step (II). The micropillar is different in roughness from the upper end to the side surface, Since the upper end of the column has a smoother surface than the surface of the side portion, the growth of the metal nanowires is controlled so that the metal nanoparticles are fixed only to the side portions of the micropillar, thereby forming the structure of the three- .

Finally, the metal nanowires are grown by processing a second solution for growing the metal nanoparticles on a substrate on which the metal nanoparticles are fixed.

Specifically, the metal nanowires may be grown by immersing the substrate on which the nanoparticles are immobilized in a second solution for growing the metal nanoparticles, or by flowing a second solution for growing the metal nanoparticles, IV) A metal nanowire may be grown by immersing a second solution for growing the metal nanoparticles on a substrate on which the metal nanoparticles are immobilized.

Wherein the second solution comprises a ligand, a reducing agent and a metal precursor, wherein the ligand is selected from 4-mercaptobenzoic acid, 4-mercapto- 2-methoxy-benzoic acid, and 3-mercaptopropionic acid.

The reducing agent may be selected from the group consisting of borohydride, hydrazine, citric acid or a salt thereof, and reducing sugar of L-ascorbic acid, an alkali metal or an alkaline earth metal by reducing metal from a metal precursor and growing metal nanowires. , And preferably L-ascorbic acid.

The metal precursor may be at least one selected from the group consisting of AgNO ₃ , AgCl, AgNO ₃ , HAuClO ₄ , HAuCl _{4 ,} H ₂ PtCl ₆ and H ₂ Pt (OH) ₆ .

The three-dimensional composite structure manufactured through the above-described process is characterized in that metal nanowires are grown only on the side surfaces of the micro pillars among various regions in a substrate where micro-sized pillars are spaced apart from each other.

The content of the ligand in the second solution may be 100 to 300 μM. If the content of the ligand is less than 100 μM, the metal nanowire may be in a form other than the metal nanowires grown vertically, Type metal nanostructure may be produced. If the content of the ligand exceeds 300 [mu] M, the density of the metal nanowires may be insufficient, or the metal nanowires may be loosened or bent or may be laid out and grown.

The metal nanoparticles in the step (III) and the metal nanowire in the step (IV) may be the same.

If the immersing time in the second solution is less than 60 minutes, the metal nanowires do not sufficiently grow and the network structure can not be formed. do.

In addition, the distance between the micro pillars may be determined according to the length of the metal nanowire. In consideration of the length of the metal nanowire, the length of the micropillar is at least 10 nm, May be 0.1 to 1 占 퐉.

Preferably, the spacing distance between the micro pillars is 0.1 to 1 占 퐉 because the nanowires of the adjacent micro pillars are spaced apart from each other with the nanogaps interposed therebetween to form a network structure. In other words, The distance between the micro pillars can be determined to be twice the length of the nanowire because the nanowires of the micro pillars adjacent to each other overlap with each other within the separation distance to form a network structure.

To summarize the manufacturing process of the present invention, in order to grow metal nanowires, the ligand is adsorbed on the surface of the exposed metal seed, so that the surface of the seed is covered with the ligand. Thus, since the interface between the metal seed and the substrate is not covered by the ligand, when the substrate to which the seed is fixed is immersed in the growth solution containing the ligand, the reducing agent and the metal precursor, the exposed metal seed surface is covered by the ligand The metal precursor can not be bonded to the metal precursor, and the metal precursor is located only at the interface between the metal seed and the substrate. That is, the metal nanowires can continue to grow perpendicularly to the substrate only at the interface between the SiO ₂ layer and the metal seed.

That is, the concentration of the ligand appears to influence gold nanowire growth.

The above-described manufacturing process is an electron beam lithography. The SERS signal of the three-dimensional composite structure is further strengthened by using a wet chemical process, which is not a meteorological process requiring strict equipment such as sputtering and expensive equipment, while providing a three-dimensional complex structure including a dense hot spot at low cost. .

In addition, since the manufacturing process does not include a lithography process, the manufacturing cost can be reduced, and it is advantageous in that it is effective, convenient, and low in temperature, and can be manufactured in a large area.

Raman scattering is a phenomenon in which the energy (hv) of an incident photon is scattered by energy (hv ') at another frequency while changing the oscillation state of the molecule, and the scattering at this time is inelastic scattering. In other words, Raman scattering can be detected, identified and analyzed by Raman shift, because it exhibits intrinsic photon energy change according to the molecular structure induced by interaction with photons.

Such Raman scattering is inherently weak, requiring long exposure to high power lasers for molecular detection, and one of the techniques used to enhance such Raman signals to obtain high sensitivity detection is Surface Enhanced Raman Scattering or Surface Enhanced Raman Spectroscopy, SERS).

Here, a three-dimensional complex structure having a structure according to the present invention may be included or used as a surface enhanced Raman spectroscopic substrate that can be utilized in various fields such as diagnosis and sensing.

As described above, in the three-dimensional complex structure according to the present invention, the metal nanowires are spaced apart from each other with a nanogap interposed therebetween to form a high-density hot spot, and the nanogap between the metal nanowires is less than several nanometers, The intensity of the SERS signal is significantly higher than that of the metal nano-particle structure deposited on the surface of the liquid nano-particles or the nanoparticles or nanoparticles arranged on the substrate.

In addition, the conventional structure described above has a limitation in increasing the number of nano gaps and reducing the size of nanogaps. However, by providing the three-dimensional complex structure according to the present invention, the surface reinforced Raman A spectroscope plate (SERS substrate) can be provided.

As described above, since the surface enhanced Raman spectroscopy plate has improved SERS characteristics, it can be used as one configuration of an improved performance biosensor capable of detecting a specific substance or an improved microelectrode array.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.

In addition, the experimental results presented below only show representative experimental results of the embodiments and the comparative examples, and the respective effects of various embodiments of the present invention which are not explicitly described below will be specifically described in the corresponding part.

reagent

(3-aminopropyl) triethoxysilane (APTES), 4-mercaptobenzoic acid (MBA), hydrogen tetrachloroaurate (III) III) trihydrate, HAuCl ₄ .3H ₂ O), ascorbic acid (AA) and sodium citrate were purchased from Sigma-Aldrich.

Unless otherwise noted, all samples used reagent grade.

Example  1 to 4. Silicon wafer / gold By nanowire  Dimensional complex structure.

In order to check that the gold nanowire pattern can be controlled according to the ligand, a flat silicon wafer (silicon wafer) without a silicon micro pillar is used as a substrate, and its general process is shown in FIG. 2 below.

One) Spherical  Manufacture of gold seeds.

In making the gold seed, the Frens method, which includes the following steps, is referred to.

Specifically, 100 ml of a 2.5 X 10 ^-4 M HAuCl ₄ solution was heated at 120 ° C in an oil bath and stirred for 30 minutes. 1% sodium citrate solution (5 ml) was added to the solution while maintaining the heating state of the solution, and when the solution color changed to red ruby color after 20 minutes, gold nanoparticles (18 nm , Also referred to as AuNP) was formed, and the reaction was terminated.

2) Gold With nanowires Nanowire  Growth of the bundle.

The following steps are performed to grow Au nanowires on a flat silicon wafer (Si wafer) without silicon micro pillar.

First, i) the substrate is pretreated with oxygen (O ₂ ) plasma for 10 minutes in order to improve the hydrophilicity of the substrate surface.

Ii) The pretreated substrate was immersed in a first solution (30 μl of APTES-solubilized APTES solution in 30 ml of ethanol) for 1 hour, washed with ethanol and baked in an oven at 120 ° C. for 30 minutes to prepare a substrate coated with APTES Respectively.

Iii) Next, the substrate coated with APTES was immersed in a solution containing gold nanoparticles (AuNP; 18 nm) for 2 hours, and then washed with distilled water to prepare a substrate having seeds of gold nanoparticles immobilized thereon.

Iv) The substrate on which the seeds were immobilized was immersed in the final second solution (different concentrations of MBA, HAuCl ₄ (1.7 mM) and L-ascorbic acid (4.1 mM)) for 15 minutes, rinsed with ethanol and air dried .

The concentration of MBA in Example 1 was 1 mM, the concentration of MBA in Example 2 was 500 μM, the concentration of MBA in Example 3 was 200 μM, the concentration of MBA in Example 4 Was 10 [mu] M.

Example  5. Silicon micro pillars / gold By nanowire  Dimensional complex structure.

One) Spherical  Manufacture of gold seeds.

In making the gold seed, the Frens method, which includes the following steps, is referred to.

Specifically, 100 ml of a 2.5 X 10 ^-4 M HAuCl ₄ solution was heated at 120 ° C in an oil bath and stirred for 30 minutes. 5 ml of a 1% sodium citrate solution was added to the solution while maintaining the heating state of the solution, and gold nanoparticles (hereinafter also referred to as AuNPs) were obtained after 20 minutes when the solution color changed to a red ruby color. The reaction was terminated.

2) Preparation of silicon micro pillars.

The silicon wafer was washed with a piranha solution (H ₂ SO ₄ : H ₂ O ₂ = 4: 1) for 90 minutes and a TEOS insulation film of 10 μm was deposited by PECVD on the silicon oxide film.

A photoresist pattern layer (TDMR-AR87) having a concave structure was coated to form a micropillar structure, and a plurality of patterns were formed on the insulating film by a UV photolithography process using the photoresist pattern layer (TDMR-AR87) as an etching master. Specifically, the wafer coated with the photoresist pattern layer was first baked at 88 캜 for 60 seconds, exposed to UV at 400 mJ / min, and then subjected to secondary baking at 88 캜 for 90 seconds. Rinsed again, washed with distilled water, and then subjected to tertiary baking at 110 ° C for 90 seconds.

Then, the silicon oxide film speed of _{3600 Å / ㎝ CH 3 (25} sccm) / CF 4 (5 sccm) / Ar (70 sccm) Etching (ething) using a plasma as an etching gas, and the silicon is SF ₆ / C ₄ F ₈ A silicon micropillar with a finely controlled pattern was fabricated by plasma etching using an etching gas.

The silicon micropillar of Example 5 thus prepared had a diameter of 1 占 퐉, a height of 3 占 퐉 and a separation distance between micropipes of 1 占 퐉.

The diameter, height, and micropillar of the silicon micropillar can be suitably controlled by controlling patterns, etching conditions, and the like formed by the photoresist.

3) Gold With nanowires Nanowire  Growth of the bundle.

The following steps were performed to grow Au nanowires on a silicon pillar-formed array fabricated through step 2).

First, i) the substrate is pretreated with oxygen (O ₂ ) plasma for 10 minutes in order to improve the hydrophilicity of the substrate surface.

Ii) The pretreated substrate was immersed in a first solution (30 μl of APTES solution dissolved in 30 ml of ethanol) for 1 hour, washed with ethanol and baked in an oven at 120 ° C. for 30 minutes to prepare a substrate coated with APTES Respectively.

Iii) Next, the substrate coated with APTES was immersed in a solution containing gold nanoparticles (AuNPs; 18 nm) for 2 hours, and then washed with distilled water to prepare a substrate having seeds of gold nanoparticles immobilized thereon.

Ⅳ) after the seed has a second end solution growing nanowires by immersing for 5 minutes (each of the different concentrations MBA, HAuCl ₄ (1.7 mM) and L- ascorbic acid (4.1 mM)) to a fixed substrate, with ethanol Rinsed and dried in air.

Example  6 to 8. Silicon micro pillars / gold By nanowire  Dimensional complex structure.

The procedure of Example 5 was repeated except that the immersing time in the second solution was changed from 5 minutes to 15 minutes, 30 minutes and 60 minutes in step 3) -iv).

Here, Example 6 was prepared by soaking in a second solution for 15 minutes, Example 7 was prepared by soaking in a second solution for 30 minutes, and Example 8 was prepared by soaking in a second solution for 60 minutes.

Analytical instrument

Field-emission scanning electron microscopy (FE-SEM) was measured using a JEOL instrument (JSM-6700F), where the acceleration voltage was 5 kV.

Raman spectra were obtained using a Renishaw in Via confocal Raman spectrometer with a Reynisk Raman conical system model with an integrated Leica microscope. The integration microscope used a 50 × objective lens (NA = 0.80) with a range of 100-2000 cm ^-1 .

As an excitation source for performing the Raman experiment, 633 nm emission was performed using a HeNe laser (85 μW at the sample surface). Data acquisition time in Raman measurements was approximately 10 seconds.

Experimental Example  One. Ligand  Metal by concentration Nanowire  Shape analysis

In the present invention, it has been found that the growth mode of metal nanowires can be controlled by controlling the concentration of the ligand. In order to verify this, the following experiment was conducted.

In order to observe the influence of the concentration of the ligand in the growth of the gold nanowires from the seed by depositing gold nanoparticles on the substrate and fixing the seeds, gold nanoparticles were deposited on a flat silicon wafer The morphology of growing gold nanowires was observed.

3 is a schematic view showing the structure of the three-dimensional complex structure produced from Examples 1 to 4. FIG.

4 is a SEM photograph of the three-dimensional composite structures manufactured in Examples 1 to 4; Where a is the three-dimensional composite structure prepared in Example 1, b is the three-dimensional composite structure prepared in Example 2, c is the three-dimensional composite structure prepared in Example 3, d is the three- Structure.

FIG. 5 is a SEM image at a low magnification of the three-dimensional composite structure manufactured from Example 1, FIG. 6 is an SEM image at a low magnification of the three-dimensional composite structure prepared from Example 2, FIG. 8 is a SEM image at a low magnification of the three-dimensional composite structure manufactured from Example 4. FIG.

As shown in FIGS. 3 to 8, it was confirmed that the concentration of the ligand plays a very important role in determining the final morphology of the gold nanowire.

Specifically, in the case of Example 3 in which the concentration of MBA was 200 μM, gold nanowires in the form of bundles arranged vertically from pillars applicable to the three-dimensional structure of the present invention were prepared , Gold nanowires aligned in the vertical direction were prepared in the case of Example 2 where the concentration of the MBA was 300 μM or more, and loose gold nanowires having the individual form in the case of Example 1 were produced And MBA less than 100 [mu] M was used, branched nanostructures were prepared.

Although the gold nanowires aligned in the vertical direction in Example 2 are formed, they are formed not individually but finer than the bundle-shaped gold nanowires in Example 3. Therefore, the MBA concentration range (500 [mu] M) When a structure is manufactured, a large amount of hot spots can not be obtained. Therefore, in order to obtain a high-density hot spot, it is most preferable to form a bundle-shaped gold nanowire (Example 3), so that the MBA concentration range can be selected from 100-300 μM.

The reason that various gold structures are formed from loose nanowire form to short spike structure is in the manufacturing process because a gold seed is fixed on the substrate briefly and the exposed surface of the gold seed is coated with a ligand MBA molecules are bound. Here, in the process of growing the gold nanowires from the gold seed, since the surface of the exposed gold seed is covered with the ligand, the approach of the gold precursor is impossible.

Therefore, the gold precursor approaches the interface between the gold seed and the substrate, and gold nanowires can grow perpendicularly from the substrate. As a result, the structure of the short spike is formed as the concentration of the ligand MBA decreases.

In addition, when the MBA concentration is 1 mM at a concentration exceeding 700 [mu] M, the gold seed is almost covered by MBA, which interferes with the approach of the gold precursor for longitudinal growth, so that the limited exposure of the gold nanoparticles There is a problem in that very thin gold nanowires can not be grown from the portion where the gold nanowires are grown and are randomly formed on the substrate in the lying direction (see FIG. 5).

Interestingly, when the concentration of MBA rapidly decreases to half, it is possible to optimize growth of the gold seed in the longitudinal direction as described above, and vertically aligned gold nanowires can be obtained (see FIG. 6).

On the other hand, in the case of the MBA having a MBA concentration of less than 100 μM, a small amount of MBA is added, which interferes with a delicate balance of formation of interactions between MBA molecules, thereby forming a large gold cluster (See FIG. 8).

However, in the case of Example 3 in which the MBA concentration is 100-300 [mu] M, the gold nanowires are grown into bundle-type gold nanowires, and when the gold nanowires are grown at such MBA concentration, a high-density hot spot is formed from the prepared three- .

In the production of the three-dimensional complex structure according to the present invention, the orientation of gold nanowires forming hot spots is very important. Therefore, in order to control the orientation of the gold nanowire, it is required to control the concentration of the ligand within the above range.

In addition, it can be seen that the diameter of the gold nanowires is also dependent on the MBA concentration. The average diameter of the gold nanowires prepared in Example 1 was 6 nm, the average diameter of the gold nanowires prepared in Example 2 was 13 nm, and the average diameter produced in Example 3 was 17 nm. In other words, as the MBA concentration decreases, the average diameter increases.

As described above, since the surface of the gold seed is covered with the ligand, the gold precursor (gold atom) is bonded to the interface between the gold seed and the substrate by blocking the bond with the gold precursor.

On the other hand, when the MBA concentration is decreased, it is considered that not only the vertical growth but also the side surface increase because the bonding with the gold precursor is not limited since the sparse MBA is bonded to the surface of the gold seed.

Experimental Example  2.

In the three-dimensional composite structure according to the present invention, since it is also important to form gold nanowires in order to grow gold nanowires radially from the side of a micropillar, it is very preferable to grow gold nanowires under the conditions in Experimental Example 1. [

In addition, the morphology of the micropillar also affects the formation of gold nanowires.

The silicon micro pillars prepared in the step 2) of Example 5 were manufactured by controlling the diameter, height and interpillar spacing between the micro pillars to 1, 3 and 1 탆, respectively, Is a SEM image (a) taken from above and a SEM image (b) taken from a side direction (60 ° slope) of the silicon micropillar manufactured in the step 2) of Example 5 described above.

As shown in FIG. 9, it can be seen that the top of the silicon micropillar is smoother than the sidewall of the silicon micropillar.

It can be seen that due to the difference in surface state, the gold nanowires do not grow on the upper surface of the silicon micropillar, but the nanowires grow only on the side.

Experimental Example  3.

The effect of nanowire growth time on the density, locality and orientation of the nanowires in the three-dimensional composite structure of the present invention was observed.

The nanowire growth time refers to the time required to immerse the substrate in which the seed layer is formed in the second solution. Therefore, the shape of the three-dimensional composite structure produced by the different method is compared.

FIG. 10 is an image of each of the three-dimensional composite structures manufactured in Examples 5 to 8 taken by SEM. The SEM images (a, b, c, and d) , b ', c', d ').

Specifically, a and a 'are the three-dimensional complex structure prepared in Example 5, b and b' are the three-dimensional complex structure prepared in Example 6, and c and c 'are the three- d and d 'are the three-dimensional complex structures prepared from Example 8.

As shown in FIG. 10, the three-dimensional complex structure produced from Example 5 had a growth time of 5 minutes, and gold nanowires were formed on the upper surface with minimum (see a and a 'in FIG. 10).

On the contrary, in the case of the three-dimensional composite structure prepared in Example 6, the growth time was increased to 15 minutes, and it was confirmed that a long and thick gold nanowire was grown on the side surface of the silicon micropillar and the top surface thereof And b ').

What is interesting here is that the silicon micro pillars are connected to each other by a network structure at a distance of 90 즉. However, this network structure is not formed between diagonally adjacent micro pillars. Since the length of the gold nanowires is 550 nm, when the distance between the micro pillars is at least 1 탆, the gold nanowires are fused to each other through the micro pillars That is, a network structure can be formed. At this time, the angle between the micropillar and the network structure or the gold nanowire is 90 nm (see b and b 'in FIG. 10).

When the nanowire growth time was increased to 30 minutes as in the case of the three-dimensional complex structure prepared in Example 7, the nanowires began to grow radially outward from the side of the micro pillars, , There are regions where the nanowires do not grow, which means that growth of the gold nanowires is incomplete under the growth time conditions (see FIGS. 10C and 10C).

Accordingly, when the growth time of the nanowire is increased to 60 minutes as in the case of the three-dimensional complex structure manufactured in Example 8, it can be confirmed that nanowires are formed at high density without voids on the sides of the silicon micropillar (See d and d 'in FIG. 10).

11 is a SEM image (b) of the three-dimensional composite structure manufactured in Example 8 taken in the lateral direction (60 ° tilt).

As shown in FIG. 11, in the three-dimensional complex structure according to the present invention, gold nanowires are formed on side surfaces of a silicon micropillar, and the gold nanowires have an angle of 90 ° with respect to a silicon micropillar.

In addition, the gold nanowire forms a network with gold nanowires formed on adjacent silicon micro pillars, which forms a hot spot for enhancing the SERS signal due to the network.

Moreover, the silicon micropillar is like a shaft, and the gold nanowire radially grown on the side of the silicon micropillar is like a canopy, and the three-dimensional complex structure according to the present invention composed of the silicon micropillar is entirely made of wire- - It can be seen that it takes the form of a pillar-shaped umbrella.

There are two reasons why it can be formed as an umbrella-like structure. Firstly, the top surface of the silicon surface is smooth and the chemical activity is low to prevent the growth of gold nanowires. Secondly, The gold nanowires can be formed only in the upper region of the side surface of the silicon micropillar, since it is difficult to deposit from the uppermost region to the lower region.

Experimental Example  4.

(SERS) of the three-dimensional complex structure according to the present invention.

In general, sharp metal protrusions and nanogaps have been reported to significantly improve the SERS signal by several orders of magnitude (2-3 orders of magnitude). The area that causes such a dramatic improvement of the SERS signal is called a hotspot. The current simplest way to obtain hot spots through high density assembly of silver nanoparticles or gold nanoparticles on the surface was to create multiple gaps between adjacent nanoparticles.

In recent years, attempts have been made to increase the hot spot density by providing a plurality of functional groups through a single process of depositing nanoparticles having a three-dimensional structure or depositing nanoparticles on silicon nanowires. However, There is a limitation in that it has a significantly lower SERS signal intensity than the present invention.

As a result, the three-dimensional complex structure according to the present invention provides a hot spot having a high-density hierarchical structure due to metal nanowires formed between adjacent micro pillars as well as a three-dimensional structure. This is a new type of SERS hotspot.

Therefore, in order to observe the characteristics of the SERS substrate of the three-dimensional complex structure of the present invention, the following experiment was performed.

12 shows SERS spectra (a, b, c, and d) and SEM images (a ', b', c ', and d) of the three-dimensional complex structure prepared from Comparative Example for R6G, Examples 2, ')to be. Here, a and a 'are for a three-dimensional complex structure prepared from Example 8, b and b' are for a three-dimensional complex structure prepared from Example 3, and c and c ' Structure, and d and d 'are for the comparative example.

Rhodamine 6G (hereinafter also referred to as R6G) was used as a substance to be detected by SERS analysis.

At this time, the comparative example was a silicon micropillar prepared from 2) of Example 5, and the surface of which was not subjected to any treatment was used.

In addition, the size of the three-dimensional complex structure produced from the above Comparative Examples, Examples 2, 3 and Example 8 was unified to 0.5 × 0.5 cm 2.

R6G was first dissolved in ethanol (0.1 mM), and 5 쨉 l of the solution was dropped to the three-dimensional complex structure prepared in the above Comparative Example, Examples 2, 3 and Example 8, respectively, and then measured by the Raman experiment ).

As shown in FIG. 12, the SERS signal intensity was the largest measured in the three-dimensional composite structure of Example 8, which is a significantly improved value as compared with Examples 2 and 3 and Comparative Example. In addition, the detection limit of R6G was confirmed to be 10 μM.

More specifically, in order to compare the detection characteristics, the SERS improvement characteristics are quantified as follows.

Specifically, the averaged enhancement factor (EF) is calculated from the 520 cm ^-1 peak with reference to a signal for R6G from a silicon substrate (bare silicon) that has not been treated.

As a result, the average EF of the three-dimensional composite structure prepared in Example 8 was 8.6 × 10 ⁶ , and the average EF of the three-dimensional composite structure prepared in Example 3 was 1.4 × 10 ⁶ . The average EF of the three-dimensional composite structure was 6.4 × 10 ⁵ .

Taken together, these results indicate that the enhancement of the SERS signal is dependent on the intrinsic structure of the gold nanoparticles (whether in valley form, sharp protrusion form, etc.) and the density of hot spots formed between adjacent gold nanoparticles.

That is, it can be seen that a high-density hot spot formed from the adjacent gold nanowires in the three-dimensional complex structure of the present invention plays an important role in improving the SERS signal. Specifically, the three- Because SERS molecules can be captured more easily than nanowires, SERS is greatly improved.

In all of the above results, the three-dimensional composite structure having the structure according to the present invention has a nanowire structure formed on a new micropillar by growing gold nanowires in a hierarchical and radial manner from a side portion of a micropillar. Such a structure has various advantages as a SERS platform, and when used as a SERS substrate, it is very likely to be applied to an optical imaging field or a sensing field, and is expected to be applied to a solar cell, an electrode array, or a charge storage device.

Claims (24)

Board;
A micro pillars spaced apart from one another on the substrate;
A metal nanowire growing and arranged in a vertical direction from a side portion of the micropillar; And
And a nanogap is formed between the metal nanowires of the micropillar. The method according to claim 1,
Wherein the average height of the micro pillars is 1 to 5 占 퐉. The method according to claim 1,
Wherein the micropillar is divided into a side upper end portion and a side lower end portion of the micropillar based on a point of an average height of 20 to 70%. The method of claim 3,
Wherein the nanogap is formed on a side upper end portion of the micropillar when an average height of the micropillar is 2.5 to 5 占 퐉. The method according to claim 1,
And the distance between the micro pillars is 0.1 to 1 占 퐉. The method according to claim 1,
Wherein the length of the metal nanowire is 10 to 600 nm. The method according to claim 1,
Wherein the upper end of the micropillar is a smoother surface than the side surface of the micropillar. The method according to claim 1,
Wherein an angle between the micropillar and the metal nanowire or the network structure is in a range of 80 to 100 degrees. (I) oxygen plasma treatment of the surface of a substrate having micro pillars spaced apart from each other;
(II) contacting the pretreated substrate with a first solution in which a coupling agent is mixed with a solvent;
III) fixing the metal nanoparticles on the surface of the substrate prepared in the step II); And
And (IV) growing a metal nanowire by treating a second solution for growing the metal nanoparticles on a substrate on which the metal nanoparticles are immobilized. 10. The method of claim 9,
Wherein the average height of the micro pillars is 1 to 5 占 퐉. 10. The method of claim 9,
Wherein the spacing between the micro pillars is 0.1 to 1 占 퐉. 10. The method of claim 9,
Wherein the length of the metal nanowire is 10 to 600 nm. 10. The method of claim 9,
Wherein the upper end of the micropillar is a relatively smooth surface than the side surface of the micropillar. 10. The method of claim 9,
Wherein the coupling agent is at least one aminoalkylsilane selected from the group consisting of 3-aminopropyltriethoxysilane (APTES), 4-aminopropyltrimethoxysilane and 4-aminobutyltrimethoxysilane. A method for producing a three-dimensional complex structure. 10. The method of claim 9,
_Wherein the solvent is any one selected from the group consisting of C _1-6 alcohol, water, and a mixed solvent thereof. 10. The method of claim 9,
Wherein the mixing ratio of the coupling agent to the solvent is 1: 700-1300. 10. The method of claim 9,
Wherein the second solution comprises a ligand, a reducing agent and a metal precursor, and the content of the ligand in the second solution is 100 to 300 μM. 18. The method of claim 17,
The ligand may be 4-mercaptobenzoic acid, 4-mercapto-2-methoxy-benzoic acid and 3-mercaptopropionic acid. And the second layer is formed of at least one selected from the group consisting of silicon nitride, silicon nitride, and silicon nitride. 18. The method of claim 17,
Wherein the reducing agent is at least one selected from the group consisting of borohydride, hydrazine, citric acid or a salt thereof, and reducing sugar of L-ascorbic acid, alkali metal or alkaline earth metal. 18. The method of claim 17,
Wherein the metal precursor is at least one selected from the group consisting of AgNO ₃ , AgCl, AgNO ₃ , HAuClO ₄ , HAuCl _4, H ₂ PtCl ₆ and H ₂ Pt (OH) ₆ . 10. The method of claim 9,
And the immersing time in the second solution of step IV) is performed for 60 to 120 minutes. A surface enhanced Raman spectroscope plate comprising the three-dimensional complex structure of claim 1. A biosensor comprising the surface enhanced Raman spectroscopy plate according to claim 22. 22. A microelectrode array comprising a surface enhanced Raman spectroscopy plate according to claim 22.

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