TW201326024A - Micro/nano metallic structure of molecular detector and method for manufacturing the same - Google Patents

Abstract

A micro/nano metallic structure of a molecular detector and method for manufacturing the structure are provided. The method includes steps of: providing a substrate, forming an organic material layer on the substrate, forming a resist material layer on the organic material layer, patterning the resist material layer to form a micro/nano patterned resist layer, etching the organic material layer to form a micro/nano patterned organic layer and expose a portion of the surface of the substrate by using the micro/nano patterned resist layer as a mask, depositing a metal layer on the micro/nano patterned resist layer, the micro/nano patterned organic layer, and the exposed portion of the surface of the substrate, and removing the micro/nano patterned resist layer, the micro/nano patterned organic layer to form the micro/nano metallic structure.

Description

Micronano metal structure of molecular detection sensor and manufacturing method thereof

The invention relates to a molecular detection sensor and a manufacturing method thereof, and in particular to a micro-nano metal structure of a molecular detection sensor and a manufacturing method thereof.

At present, the widely used biochips are fluorescent biochips and enzyme-colored bio-chips. However, the process of combining the fluorescing cursor with the multiplex antibody antigen not only increases the detection complexity, but also greatly increases the detection cost. In view of this, many non-fluorescent detection technologies have been researched and developed, including the detection of color changes when metal nanoparticles are concentrated or dispersed, and the excitation source causes surface plasmon resonance (SPR) of the metal film. A method for detecting a change in a resonance angle or a reflected light intensity due to biomolecular deposition, a Rayleigh Scattering detection method of a metal nanoparticle, an excitation light source to generate a metal micronanoparticle or a metal micronite structure Localized surface plasmon resonance (LSPR) is used to detect the change of resonance frequency caused by trace biomolecule deposition, and the excitation source causes local electromagnetic field surface enhancement of metal micro-nanoparticles or metal micro-nanostructures. Surface enhanced raman scattering (SERS) for detecting the Raman Shift of trace biomolecules and using nano-junctions or nanowires ) Isoelectric detection method. Although these methods can achieve the goal of label free (Label Free) and low concentration detection, most of them involve nano-chemical processes, such as micro-nano metal particle fabrication or micro-nano structure fabrication, resulting in cost increase and mass production. Poor question. The excitation light source makes the surface film plasma resonance detection method of the metal film, although it does not involve the nanocrystallization process, but the requirements for detecting the light source, the mechanism precision and the temperature stability are also extremely high.

The localized surface plasma resonance sensing wafer inspection method is a detection technology developed by the international advanced research laboratory in the past ten years. Its working principle is to use the full-band light source to stimulate the localization of micro-nano metal particles or metal micro-nanostructures. The surface plasma resonates to produce a localized electric field on the metal particles or structure. Different from the surface plasma resonance of general metal film, the effective range of localized electric field can be less than tens of nanometers, and the effective range of surface evanescent wave generated by surface plasma resonance is about 200 nm. In general, a surface-plasma resonance wafer is detected by using an extremely precise angle to scan a reflectance change or to fix a multi-wavelength or multi-point reflection intensity detection at a specific angle for detecting light source, mechanism accuracy, and temperature stability. The requirements are extremely high. In contrast, a localized electric field can sense small refractive index changes caused by very small amounts of molecules.

The localized surface plasma resonance sensing wafer detection method can be divided into two methods: penetration spectrum detection and reflection spectrum detection. The excitation light source is a full-wavelength light source with a vertical incidence, and the detection end is a high-resolution one wavelength. A spectrometer, when a trace molecule is combined with a functionalized biochip, detects the extinction spectrum shift of the characteristic spectrum. Due to the high sensitivity and easy detection method of this type of sensing wafer, it is widely studied and applied to various biomolecule detections, such as biomarker amyloid-derived soluble coordination for detecting Alzheimer's disease. Biomarker amyloid-derived diffusible ligands (ADDLs), and biomarker prostate-specific antigen (PSA) for detecting prostate cancer.

Although the localized surface plasma resonance sensing wafer has the advantages of high sensitivity and simple detection method, there are high technical thresholds in wafer fabrication and mass production. The localized surface plasma resonance sensing wafer types can be classified into three types: nano-particle dispersions, surface-immobilized nanoparticles, and nanostructure arrays. Although the first two methods can achieve high-sensitivity detection, the preparation of nano metal particles and the process of fixing them on the surface of the substrate are not easy to mass-produce. The third method can use nanosphere lithography (NSL), block copolymer lithography, colloidal lithography, metal thin film evaporation, And localized surface plasma resonance wafers are fabricated by techniques such as e-beam lithography. Although these methods can successfully produce ordered or disordered micro-nanostructured wafers and are applied to localized surface plasma resonance detection, they still have problems such as overly complex processes, large-area fabrication, and poor re-production. To be overcome, it is not currently mass-produced.

In view of the above problems, the present invention provides a micro-nano metal structure of a molecular detection sensor and a manufacturing method thereof, which can improve the stability and uniformity of large-area manufacturing, control the shape and periodicity of the structure, and at the same time simplify the process.

According to an aspect of the present invention, a method for fabricating a micro-nano metal structure of a molecular detection sensor includes: providing a substrate; forming an organic material layer on the substrate; forming a photoresist material layer on the organic material On the layer; patterning the photoresist layer to form a micro-nano-patterned photoresist layer; masking the organic material layer with a micro-nano-patterned photoresist layer to form a micro-nano-patterned organic layer a layer and exposing a portion of the surface of the substrate; depositing a metal layer on the micro-nano patterned photoresist layer, on the micro-nano-patterned organic layer, and on a portion of the exposed surface of the substrate; and removing the micro-nene The rice-scale patterned photoresist layer and the micro-nano-patterned organic layer form a micro-nano metal structure.

According to another aspect of the present invention, a method for fabricating a micro-nano metal structure of a molecular detection sensor includes: forming a substrate; depositing a metal layer on the substrate; forming an organic material layer on the metal layer Forming a photoresist layer on the organic material layer; patterning the photoresist layer to form a micro-nano-patterned photoresist layer, and exposing a portion of the surface of the organic material layer; patterning the light at a micron-level The resist layer is a mask etched organic material layer to form a micro-nano-patterned organic layer, and exposes a part of the surface of the metal layer; depositing a mask material layer on the micro-nano-patterned photoresist layer, micro On the nano-patterned organic layer and on the metal layer; removing the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer to form a micro-nano-patterned mask layer on the metal layer; And etching the metal layer according to the micro-nano patterned mask layer to form a micro-nano metal structure.

According to still another aspect of the present invention, a micro-nano metal structure for a molecular detection sensor is provided, comprising at least a substrate and a metal nano-pillar array formed on the substrate, the metal nano-pillar array comprising a plurality of metals Nano cylinder.

In order to provide a better understanding of the above and other aspects of the present invention, the following detailed description of the embodiments and the accompanying drawings

The following is a micro-nano metal structure of a molecular detection sensor and a manufacturing method thereof, by depositing a metal layer on a micro-nano-patterned photoresist layer, a micro-nano-patterned organic layer, and a substrate exposed On a portion of the surface, the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer are subsequently removed to form a micro-nano metal structure. This method can improve the stability and uniformity of large-area manufacturing, control the shape and periodicity of the structure, and at the same time simplify the process. However, the detailed structure and process steps set forth in the examples are for illustrative purposes only and are not intended to limit the scope of the invention. These steps are for illustrative purposes only and are not intended to limit the invention. Those having ordinary knowledge may modify or change the steps as needed according to the actual implementation.

First embodiment

Please refer to Figures 1A to 1E. FIG. 1A is a schematic view showing a substrate, an organic material layer and a photoresist layer according to a first embodiment of the present invention. FIG. 1B is a schematic view showing the formation of a micro-nano-patterned photoresist layer after patterning the photoresist layer of FIG. 1A. FIG. 1C is a schematic view showing the micro-nano-patterned organic layer formed by etching the organic material layer with the micro-nano-patterned photoresist layer of FIG. 1B as a mask. FIG. 1D is a schematic view showing a deposited metal layer on the micro-nano-patterned photoresist layer, the micro-nano-patterned organic layer, and the substrate of FIG. 1C. FIG. 1E is a schematic view showing the formation of a micro-nano metal structure after removing the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer of FIG. 1D.

First, as shown in Fig. 1A, a substrate 101 is provided. The substrate 101 is, for example, a polycarbonate (PC) substrate having a thickness of about 0.6 millimeters (mm). The substrate 101 of the embodiment is, for example, a transparent substrate. Next, an organic material layer 102 is formed on the substrate 101. The organic material layer 102 has good adhesion to the substrate 101, such as an organic dye layer or a polymer layer, but is not limited thereto. The organic material layer 102 includes, for example, a bis-styryl compound represented by the chemical formula I:

Among them, Y is one selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom containing a substituent (CR ⁵ ), and a nitrogen atom (NR ⁶ ) having a substituent.

R ¹ is selected from the group consisting of an alkyl group _{having a} carbon number of 1 to 18 ("C _1-18 "), a phenyl group, an alkyl group containing a halogen atom, and an alkoxyl group substitute. a C _1-18 alkyl group, a ketone group (Cetone) C _1-18 alkyl group, a C _1-18 ether group, and a p-alkyl benzyl group. one.

R ² , R ³ , R ⁵ , R ⁶ , and R ⁷ may be the same or different groups selected from a hydrogen atom, a nitrogen atom, a sulfur atom, a halogen atom, and a carbon number of 1 to 8 ("C _1-8" ") alkyl, C _1-8 alkoxyl group, C _1-8 alkylate group, carboxyl group, C _1-8 alkoxycarbonyl group , alkyl _1-6 alkylalkylene alkylene carboxy group, adamantyl group, amide group, amino group (NR ₂ ), oxygen containing amino group Group, NR ₂ ), sulfo group, sulfonyl group, boronic acid, nitro group (NO ₂ ), trifluoromethyl group, fluorinated sulfonic acid group (sulfonic acid fluoride group), sulfonic acid group, hydroxyl group, ferrocenyl group, cyano group (CN), heterocyclic group, and nitrogen One of the nitrogen containing heterocyclic groups.

R ⁴ is selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, an acid group, a sulfonic acid group, a substituent-containing or a benzene ring having no substituent. One.

X is selected from the group consisting of a halogen atom, perchlorate (ClO ₄ ^- ), tetrafluoroborate (BF ₄ ^- ), tetraphenyl boron (BPh ₄ ^- ), and hexafluorophoshpate (hexfluorophoshpate, PF ₆ ^- ), hexfluoroantimonate (SbF ₆ ^- ), tetracyanoquinonedimethane (TCNQ ^- ), tetracyanoethylene ion (tetracyanoethylene ion) , TCNE ^- ), naphthalenesulfonic acid, benzenesulfonates, and organometallic complex.

In an embodiment, the organic material layer 102 comprises the compound I-1, represented by the chemical formula I-1:

Next, a photoresist material layer 103 is formed on the organic material layer 102. The photoresist layer 103 is, for example, a thermally sensitive photoresist layer or an inorganic photoresist layer, for example, a Ge-Sb-Sn-O _x layer.

Then, as shown in FIG. 1B, the photoresist layer 103 is patterned to form a micro-nano patterned photoresist layer 104. The method of patterning the photoresist layer 103 may include irradiating the photoresist layer 103 with a focused laser to form an exposed region, and removing the exposed region to form the micro-nano patterned photoresist layer 104. The focused laser may be a focused laser spot constructed on an R-Θ mobile platform or an XY stage, the wavelength of which is, for example, 405 nm (nm), and the numerical aperture (NA) is, for example, 0.65, but not limited thereto. The wavelength range of the focused laser used in the application may be substantially the wavelength of ultraviolet light, visible light to near infrared light, as long as the micro-nano-patterned photoresist layer 104 of the embodiment can be formed. The photoresist material layer 103 is heated and exposed by focusing the laser spot, and a part of the photoresist material layer 103 is exposed by laser power and pulse adjustment, and developed by using a developing solution (for example, a diluted KOH solution), which can effectively break through At the optical diffraction limit, a micro-nano-scale structure is formed on the photoresist layer 103 to form a micro-nano-patterned photoresist layer 104. The micro-nano structure of the micro-nano patterned photoresist layer 104 of the embodiment may be a micro-nano-scale hole periodically or non-periodically arranged, and the half-height of the hole may be controlled to be less than 200 nm, for example 150 nm. When the micro-nano structure is periodically arranged, it may be a periodic concentric circle arrangement or a spiral arrangement of micro-nano holes.

By controlling the position of the laser pulse focusing and the time of staying, the heat accumulation of the laser focused on different positions on the photoresist layer 103 can be adjusted, and the cross-sectional shape of the formed micro-nano hole can be controlled, for example, a circle Shape, ellipse, drop shape or rod. When the focused laser is a focused laser spot constructed on the R-Θ mobile platform, a periodic concentric circle of micro-nano holes can be formed. By arranging the first period P1 in the circumferential direction and the second period P2 in the radial direction, the arrangement positions of the micro-nano holes and the relative arrangement between them can be adjusted.

Next, as shown in FIG. 1C, the organic material layer 102 is etched by using the micro-nano-patterned photoresist layer 104 as a mask to form a micro/nano patterned organic layer 105, and A portion of the surface 101a of the substrate 101 is exposed. The organic material layer 102 can be etched to the surface 101a of the substrate 101 by a dry etching method, for example, by an oxygen plasma etching method, but is not limited thereto.

Next, as shown in FIG. 1D, the deposited metal layer 106 is deposited on the micro-nano-patterned photoresist layer 104, the micro-nano-patterned organic layer 105, and a portion of the surface 101a exposed by the substrate 101. The material of the metal layer 106 is, for example, gold (Au), silver (Ag), aluminum (Al) or platinum (Pt), but is not limited thereto. As long as the chemical stability is good, it does not react with the detection molecule, and it can be combined with the spectral characteristics such as the resonance wavelength and the coupling efficiency of the localized surface plasma resonance. The metal layer 106 may also be a composite metal layer, for example, including a gold layer and a titanium (Ti) layer, first depositing a titanium layer on the micro-nano-patterned photoresist layer 104, the micro-nano-patterned organic layer 105, and the substrate. On the exposed portion of the surface 101a, a gold layer is deposited on the titanium layer. The thickness of the gold layer is, for example, about 40 nm, and the thickness of the titanium layer is, for example, 3 nm. In another embodiment, the composite metal layer may include a gold layer and a chromium (Cr) layer, and the chromium layer is first deposited on the micro-nano-patterned photoresist layer 104, the micro-nano-patterned organic layer 105, and the substrate 101. On the exposed portion of the surface 101a, a gold layer is then deposited on the chromium layer. When the metal layer 106 is a composite metal layer, for example, a titanium layer or a chromium layer can increase the adhesion between the gold layer and the substrate.

Then, as shown in FIG. 1E, the micro-nano-patterned photoresist layer 104 and the micro-nano-patterned organic layer 105 are removed to form the micro-nano metal structure 10. The micro-nano-patterned photoresist layer 104 and the micro-nano-patterned organic layer 105 may be removed by a wet etching method or a lift-off process, for example, by dissolving micro-nano patterning in an organic solvent. The organic layer 105 and the micro-nano patterned photoresist layer 104 and the partial metal layer 106 on the micro-nano patterned organic layer 105 are simultaneously removed. The organic solvent may be an alcohol, but is not limited thereto. The micro-nano metal structure 10 can include a periodic or non-periodically arranged array of metal nanopillars 107. For example, as shown in FIG. 1, a top view of a metal nanocolumn of a micronano metal structure of a molecular detection sensor in accordance with an embodiment of the present invention is shown. In an embodiment, the metal nano-pillar has a full width at half maximum of about 150 nanometers. When the metal nano-pillar array 107 is periodically arranged, it may be a periodic concentric circular array or spiral array of metal nano-pillar arrays. The shape, size and arrangement of the metal nano-pillar array 107 correspond to the shape, size and arrangement of the micro-nano holes of the micro-nano patterned photoresist layer 104. In an embodiment, removing the micro-nano-patterned organic layer 105 by wet etching or a lift-off process can improve the stability and uniformity of the large-area fabrication of the metal nano-pillar array 107, and control the micro-nano metal structure 10 Shape and periodicity. Moreover, dissolving the micro-nano-patterned organic layer 105 in an organic solvent has a simple process.

By fabricating the micro-nano metal structure 10 of the molecular detection sensor in the above manner, the shape and arrangement of the metal nano-column array 107 can be easily changed. When the detection source of the appropriate frequency and incident angle illuminates the micro-nano metal structure 10, a localized electromagnetic field is generated on the metal nano-column array 107, which can be applied to the localized surface plasma detecting wafer or surface-enhanced Raman scattering. The wafer is detected. For example, as shown in FIG. 5, a localized surface plasma resonance absorption spectrum measured by a molecular detection sensor according to an embodiment of the present invention is irradiated with a normal incident light source. For example, when the focused laser is a focused laser spot constructed on the R-Θ mobile platform, the micro-nano metal structure 10 formed in the embodiment may have a periodic concentric arrangement of metal nano-pillar arrays 107. Adjusting the size and arrangement period of the metal nano-pillar array 107 by controlling the first period P1 in the circumferential direction and the second period P2 in the radial direction, the wavelength and efficiency of the excitation source coupling to the localized surface plasma mode can be adjusted. Further, the detection characteristics such as the sensing mode and sensitivity of the micro-nano metal structure 10 of the adjustment molecular detection sensor are changed.

Second embodiment

Please refer to the 2A to 2G drawings. 2A is a schematic view showing a substrate and a metal layer in accordance with a second embodiment of the present invention. FIG. 2B is a schematic view showing that the organic material layer and the photoresist layer are formed on the metal layer of FIG. 2A. FIG. 2C is a schematic view showing the formation of a micro-nano-patterned photoresist layer after patterning the photoresist layer of FIG. 2B. FIG. 2D is a schematic view showing the micro-nano-patterned organic layer formed by etching the organic material layer with the micro-nano-patterned photoresist layer of FIG. 2C as a mask. FIG. 2E is a schematic view showing the deposition of the mask material layer on the micro-nano-patterned photoresist layer, the micro-nano-patterned organic layer and the metal layer of FIG. 2D. FIG. 2F is a schematic view showing the formation of a micro-nano-patterned mask layer after removing the micro-nano-patterned photoresist layer of FIG. 2E and the micro-nano-patterned organic layer. FIG. 2G is a schematic view showing the formation of a micro-nano metal structure after etching the metal layer according to the micro-nano patterning mask layer of FIG. 2F.

First, as shown in FIG. 2A, a substrate 201 is provided, and then a metal layer 208 is deposited on the substrate 201. Next, as shown in FIG. 2B, an organic material layer 202 is formed on the substrate 201, and a photoresist material layer 203 is formed on the organic material layer 202. The substrate, the organic material layer, the photoresist material, and the metal layer are as described in the foregoing first embodiment, and are not described herein again.

Then, as shown in FIG. 2C, the photoresist layer 203 is patterned to form the micro-nano patterned photoresist layer 204, and a portion of the surface 202a of the organic material layer 202 is exposed. Next, as shown in FIG. 2D, the organic material layer 202 is etched by the micro-nano patterned photoresist layer 204 to form the micro-nano-patterned organic layer 205, and a part of the surface of the metal layer 208 is exposed. 208a. The micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer and the formation manner thereof are as described in the foregoing first embodiment, and are not described herein again.

Next, as shown in FIG. 2E, a masking material layer 209 is deposited on the micro-nano-patterned photoresist layer 204, the micro-nano-patterned organic layer 205, and a portion of the surface 208a of the metal layer 208. The material of the mask material layer 209 is, for example, tantalum nitride (SiN), but is not limited thereto. Next, as shown in FIG. 2F, the micro-nano-patterned photoresist layer 204 and the micro-nano-patterned organic layer 205 are removed to form a micro-nano-patterned mask layer 210 on the metal layer 208. The micro-nano-patterned photoresist layer 204 and the micro-nano-patterned organic layer 205 may be removed by a wet etching method or a lift-off process, for example, the micro-nano-patterned organic layer 205 is dissolved in an organic solvent, and At the same time, the micro-nano-patterned photoresist layer 204 and the partial mask material layer 209 on the micro-nano-patterned organic layer 205 are removed. The organic solvent may be an alcohol, but is not limited thereto. The micro-nano-patterned mask layer 210 may be a periodic or non-periodically arranged array of mask pillars, the shape, size and arrangement of which correspond to the micro-nano scale of the micro-nano-patterned photoresist layer 204. The shape, size and arrangement of the holes. The embodiment removes the micro-nano-patterned organic layer 205 by wet etching or a lift-off process, which can improve the stability and uniformity of the large-area fabrication of the micro-nano patterned mask layer 210 and the subsequent micro-nano metal structure. Sex, as well as control structure shape and periodicity. Moreover, dissolving the micro-nano-patterned organic layer 205 in an organic solvent has a simple process.

Then, as shown in FIG. 2G, the metal layer 208 is etched according to the micro-nano patterning mask layer 210 to form the micro-nano metal structure 20. The metal layer 208 can be etched to a portion of the surface 201a of the substrate 201 by a dry etching method, such as a reactive ion etching (RIE) method, but is not limited thereto. After the metal layer 208 is etched, the structure of the micronano-patterned mask layer 210 is transferred to the metal layer 208 to form the metal nano-pillar array 207 of the embodiment.

In the above embodiment, after the micro-nano-patterned organic layer 205 is removed by a wet etching method or a lift-off process, a large-area micro-nano-patterned mask layer 210 is formed, and then the micro-nano patterning mask layer 210 is formed by dry etching. The structure of the nano-patterned mask layer 210 is transferred to the metal layer 208 to form a metal nano-pillar array 207. Since the material of the micro-nano-patterned mask layer 210 is strong and the edges are flat, the metal nano-pillar array 207 of the micro-nano metal structure 20 of the embodiment also has the advantages of a neat boundary and a neat shape.

Micro-nano metal structure of molecular detection sensor

As shown in FIG. 1E, the micro-nano metal structure 10 for a molecular detection sensor of the embodiment includes a substrate 101 and a metal nano-pillar array 107 formed on the substrate 101, and the metal nano-column array 107 includes a plurality of metals. Nano cylinder. The metal nano-pillar array 107 may be periodically or non-periodically arranged on the substrate 101, and the half-height of the metal nano-pillar may be less than 200 nanometers, for example, 150 nanometers. The cross section of the metal nano cylinder may be circular, elliptical, drop-shaped or rod-shaped. When the cross-sectional shape of the metal nano-cylinder is elliptical, drop-shaped or rod-shaped, the wavelength and efficiency of the excitation source coupled to the localized surface plasma mode are also rounded when the cross section of the metal nano-cylinder is circular. The resulting wavelength differs from the efficiency. Therefore, the user can select the micro-nano metal structure 10 of the molecular detection sensor whose cross-sectional shape of the metal nano-cylinder is elliptical, drop-shaped or rod-shaped for a specific molecule to be tested.

3 is a top view of a micro-nano metal structure of a molecular detection sensor in accordance with an embodiment of the present invention. When the metal nano-pillar array 307 is periodically arranged on the substrate 301, it may be a periodic spiral array of metal nano-pillars, or as shown in FIG. 3, may also be a periodic concentrically arranged metal. Nano column array 307. In the embodiment, the first period P1 of the metal nano-pillar array 307 in the circumferential direction and the second period P2 in the radial direction are not constant, and the first period P1 and the second period P2 may be adjusted as needed to adjust the metal nano-column. The arrangement period of the array 307 further adjusts the wavelength and efficiency of the excitation source coupling to the localized surface plasma mode, and can change the sensing characteristics and sensitivity of the micro-nano metal structure 30 of the modified molecular detection sensor. .

4 is a schematic view showing a micro-nano metal structure of a molecular detection sensor according to another embodiment of the present invention. The micro-nano metal structure 40 for the molecular detection sensor of the embodiment includes a substrate 401 and a metal nano-pillar array 407 formed on the substrate 401. The substrate 401 further includes a substrate 4011 and a dielectric layer 4012 formed on the substrate 401. On the substrate 4011. When the substrate 401 is, for example, a polycarbonate substrate, the dielectric layer 4012 can prevent damage of the substrate 4011 by an excitation light source (for example, a laser beam), and can also provide appropriate interface conditions for the molecular detection sensor, for example, according to different The need for a molecular detection sensor adjusts the refractive index of the dielectric layer 4012 and the like.

Accordingly, the micro-nano metal structure of the molecular detection sensor of the embodiment and the manufacturing method thereof are performed by depositing a metal layer on the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer, and then removing The micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer form a micro-nano metal structure, which not only improves the stability and uniformity of large-area manufacturing, but also controls the shape and periodicity of the structure, and at the same time simplifies the process. . Moreover, by adjusting the size and arrangement period of the metal nano-column array of the micro-nano metal structure, the sensing characteristics such as the sensing mode and sensitivity of the micro-nano metal structure of the molecular detection sensor can be changed.

In conclusion, the present invention has been disclosed in the above embodiments, but it is not intended to limit the present invention. A person skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

10, 20, 30, 40. . . Micro-nano metal structure of molecular detection sensor

101, 201, 301, 401. . . Substrate

101a, 201a, 208a. . . Partial surface

102, 202. . . Organic material layer

103, 203. . . Photoresist material layer

104, 204. . . Micro-nano patterned photoresist layer

105, 205. . . Micro-nano patterned organic layer

106, 208. . . Metal layer

107, 207, 307, 407. . . Metal nanocolumn array

209. . . Mask material layer

210. . . Micro-nano patterned mask layer

4011. . . Substrate

4012. . . Dielectric layer

FIG. 1A is a schematic view showing a substrate, an organic material layer and a photoresist layer according to a first embodiment of the present invention.

FIG. 1B is a schematic view showing the formation of a micro-nano-patterned photoresist layer after patterning the photoresist layer of FIG. 1A.

FIG. 1C is a schematic view showing the micro-nano-patterned organic layer formed by etching the organic material layer with the micro-nano-patterned photoresist layer of FIG. 1B as a mask.

FIG. 1D is a schematic view showing a deposited metal layer on the micro-nano-patterned photoresist layer, the micro-nano-patterned organic layer, and the substrate of FIG. 1C.

FIG. 1E is a schematic view showing the formation of a micro-nano metal structure after removing the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer of FIG. 1D.

2A is a schematic view showing a substrate and a metal layer in accordance with a second embodiment of the present invention.

FIG. 2B is a schematic view showing that the organic material layer and the photoresist layer are formed on the metal layer of FIG. 2A.

FIG. 2C is a schematic view showing the formation of a micro-nano-patterned photoresist layer after patterning the photoresist layer of FIG. 2B.

FIG. 2D is a schematic view showing the micro-nano-patterned organic layer formed by etching the organic material layer with the micro-nano-patterned photoresist layer of FIG. 2C as a mask.

FIG. 2E is a schematic view showing the deposition of the mask material layer on the micro-nano-patterned photoresist layer, the micro-nano-patterned organic layer and the metal layer of FIG. 2D.

FIG. 2F is a schematic view showing the formation of a micro-nano-patterned mask layer after removing the micro-nano-patterned photoresist layer of FIG. 2E and the micro-nano-patterned organic layer.

FIG. 2G is a schematic view showing the formation of a micro-nano metal structure after etching the metal layer according to the micro-nano patterning mask layer of FIG. 2F.

3 is a top view of a micro-nano metal structure of a molecular detection sensor in accordance with an embodiment of the present invention.

4 is a schematic view showing a micro-nano metal structure of a molecular detection sensor according to another embodiment of the present invention.

Figure 5 is a diagram showing the localized surface plasma resonance absorption spectrum measured by a molecular detection sensor according to an embodiment of the present invention by irradiating a vertical incident light source.

1 is a top view of a metal nanocolumn of a micronano metal structure of a molecular detection sensor in accordance with an embodiment of the present invention.

10. . . Micro-nano metal structure of molecular detection sensor

101. . . Substrate

107. . . Metal nanocolumn array

Claims (21)

A method for fabricating a micro-nano metal structure of a molecular detection sensor, comprising: providing a substrate; forming an organic material layer on the substrate; forming a photoresist layer on the organic material layer; patterning the photoresist The material layer is formed to form a micro-nano-patterned photoresist layer; the organic material layer is etched by masking the micro-nano-patterned photoresist layer to form a micro-nano-patterned organic layer (micro/nano) a patterned organic layer) and exposing a portion of the surface of the substrate; depositing a metal layer on the micro-nano patterned photoresist layer, the micro-nano patterned organic layer, and the portion exposed by the substrate And removing the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer to form the micro-nano metal structure. The manufacturing method according to claim 1, wherein the organic material layer is an organic dye layer or a polymer layer. The production method according to claim 2, wherein the organic dye layer comprises a bis-styryl compound represented by the chemical formula I: Wherein Y is selected from the group consisting of an oxygen atom, a sulfur atom, a carbon atom containing a substituent (CR ⁵ ), and a nitrogen atom (NR ⁶ ) having a substituent; and R ¹ is selected from a carbon number of 1 to 18 (" C _1-18 ") of the alkyl (alkyl group), a phenyl group, an alkyl group containing a halogen atom (halogen atom), the substituent containing an alkoxy group (alkoxyl group substitute) of the C _1-18 alkyl group containing a keto group (Ketone) a C _1-18 alkyl group, a C _1-18 ether group, and one of a p-alkyl benzyl group; R ² , R ³ , R ⁵ , R ⁶ and R ⁷ may be the same or different groups selected from the group consisting of a hydrogen atom, a nitrogen atom, a sulfur atom, a halogen atom, an alkyl group having a carbon number of 1 to 8 ("C _1-8 "), and C _{1- 8} alkoxyl group, C _1-8 alkylate group, carboxyl group, C _1-8 alkoxycarbonyl group, C _1-6 alkyl ammonium An alkylaminoalkylenecarboxy group, an adamantyl group, an amide group, an amino group (NR ₂ ), an oxygen containing amino group (NR ₂ ), a sulfur group ( Sulfo group, sulfonyl group ), boonic acid, nitro group (NO ₂ ), trifluoromethyl group, sulfonic acid fluoride group, sulfonic acid group, hydroxyl group a hydroxyl group), a ferrocenyl group, a cyano group (CN), a heterocyclic group, and a nitrogen containing heterocyclic group; the R ⁴ system is selected from the group consisting of hydrogen One of an atom, an alkyl group, an alkoxy group, a halogen atom, a nitro group, a sulfonic acid group, an acid group, a sulfonic acid group, a substituent-containing or a substituent-free benzene ring; Halogen atom, perchlorate (ClO ₄ ^- ), fluoroborate (BF ₄ ^- ), tetraphenyl boron (BPh ₄ ^- ), hexfluorophoshpate (PF ₆ ^- ) , hexfluoroantimonate (SbF ₆ ^- ), tetracyanoquinonedimethane (TCNQ ^- ), tetracyanoethylene (TCNE ^- ) , naphthalenesulfonic acid, benzenesulfonates and organometallics Material (organometallic complex) one. The manufacturing method of claim 1, wherein the photoresist layer is a thermal photoresist layer or an inorganic photoresist layer. The manufacturing method of claim 4, wherein the step of patterning the photoresist layer further comprises: irradiating the photoresist layer with a focused laser to form an exposed region; and removing the exposed region to The micronano-patterned photoresist layer is formed. The manufacturing method of claim 1, wherein the organic material layer is etched by a dry etching method. The manufacturing method of claim 1, wherein the micro-nano-patterned photoresist layer and the micro-nano patterning are removed by a wet etching method or a lift-off process. Organic layer. The manufacturing method of claim 1, wherein the micro-nano metal structure comprises one of a series of metal nano-columns arranged periodically or non-periodically. The manufacturing method of claim 1, wherein the micro-nano metal structure comprises a periodic array of metal nano-columns arranged in a concentric arrangement or a spiral arrangement. The manufacturing method of claim 1, wherein the substrate further comprises a substrate and a dielectric layer formed on the substrate. A method for fabricating a micro-nano metal structure of a molecular detection sensor, comprising: forming a substrate; depositing a metal layer on the substrate; forming an organic material layer on the metal layer; forming a photoresist material layer thereon Coating the photoresist layer to form a micro-nano-patterned photoresist layer and exposing a portion of the surface of the organic material layer; masking the photoresist layer with the micro-nano pattern Etching the organic material layer to form a micro-nano-patterned organic layer and exposing a portion of the surface of the metal layer; depositing a mask material layer on the micro-nano patterned photoresist layer, the micro-nano And patterning the organic layer on the metal layer; removing the micro-nano-patterned photoresist layer and the micro-nano-patterned organic layer to form a micro-nano-patterned mask layer on the metal layer And etching the metal layer according to the micro-nano patterned mask layer to form the micro-nano metal structure. The manufacturing method of claim 11, wherein the photoresist layer is a thermal photoresist layer or an inorganic photoresist layer, and the step of patterning the photoresist layer further comprises: focusing on Laser exposing the layer of photoresist material to form an exposed region; and removing the exposed region to form the micronano-patterned photoresist layer. The manufacturing method according to claim 11, wherein the organic material layer is etched by a dry etching method. The manufacturing method of claim 11, wherein the micro-nano-patterned photoresist layer and the micro-nano patterning are removed by a wet etching method or a lift-off process. Organic layer. The manufacturing method of claim 11, wherein the metal layer is etched by a dry etching to form the micro-nano metal structure. A micro-nano metal structure for a molecular detection sensor, comprising: a substrate; and a metal nano-pillar array formed on the substrate, the metal nano-pillar array comprising a plurality of metal nano-pillars. The micro-nano metal structure of claim 16, wherein the metal nano-pillar array is periodically or non-periodically arranged on the substrate. The micro-nano metal structure according to claim 16, wherein the metal nano-column array is arranged on the substrate in a periodic concentric or spiral shape. The micro-nano metal structure according to claim 16, wherein the material of the metal nano-cylinder is selected from the group consisting of gold (Au) and silver (Ag), aluminum (Al), and platinum (Pt). At least one of the groups. The micro-nano metal structure according to claim 16, wherein the metal nano-pillars have a circular, elliptical, tear-shaped or rod-shaped cross section. The micro-nano metal structure according to claim 16, wherein the substrate further comprises a substrate and a dielectric layer is formed on the substrate.