WO2014025032A1 - 表面増強ラマン散乱素子 - Google Patents
表面増強ラマン散乱素子 Download PDFInfo
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- WO2014025032A1 WO2014025032A1 PCT/JP2013/071701 JP2013071701W WO2014025032A1 WO 2014025032 A1 WO2014025032 A1 WO 2014025032A1 JP 2013071701 W JP2013071701 W JP 2013071701W WO 2014025032 A1 WO2014025032 A1 WO 2014025032A1
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- fine structure
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- raman scattering
- enhanced raman
- molding layer
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
- G01N21/658—Raman scattering enhancement Raman, e.g. surface plasmons
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/06—Illumination; Optics
- G01N2201/068—Optics, miscellaneous
Definitions
- One aspect of the present invention relates to a surface-enhanced Raman scattering element.
- a device including a minute metal structure that causes surface enhanced Raman scattering As a conventional surface-enhanced Raman scattering element, a device including a minute metal structure that causes surface enhanced Raman scattering (SERS) is known (see, for example, Patent Document 1 and Non-Patent Document 1).
- SERS surface enhanced Raman scattering
- a sample to be subjected to Raman spectroscopic analysis is brought into contact with a fine metal structure and the sample is irradiated with excitation light in this state, surface-enhanced Raman scattering occurs, For example, Raman scattered light enhanced to about 10 8 times is emitted.
- a fluorine-containing silica glass film and a silica glass film sequentially laminated on a silicon substrate are etched to form a plurality of minute protrusions, and then a metal film is formed by sputtering.
- a film produced by forming a film is known.
- the minute protrusions that are the basis thereof are formed by etching.
- the minute protrusions are formed using a nanoimprint method. Also good.
- the replica mold for nanoimprinting is released from the resin layer for the microprojections, the microprojections that contribute to surface enhanced Raman scattering are damaged, resulting in surface enhancement.
- the Raman scattering characteristics may become unstable.
- One aspect of the present invention has been made in view of such circumstances, and an object thereof is to provide a surface-enhanced Raman scattering element capable of stabilizing the characteristics of surface-enhanced Raman scattering.
- the surface-enhanced Raman scattering element includes a substrate having a main surface, a support portion formed on the main surface so as to extend along the main surface of the substrate, and a fine structure portion formed on the support portion. And a conductive layer that forms an optical function unit that is formed on the microstructure and generates surface-enhanced Raman scattering, and the thickness of the molding layer in the direction intersecting the main surface of the substrate is The outer peripheral portion of the fine structure area is relatively thinner than the central portion of the fine structure area where the fine structure portion of the molding layer is formed.
- the molding layer has a fine structure portion, and a conductor layer is formed on the fine structure portion to constitute an optical function portion that causes surface-enhanced Raman scattering.
- the thickness of the molding layer is relatively thick at the central portion of the fine structure area where the fine structure portion is formed, and relatively thin at the outer edge portion. For this reason, for example, when the mold is released from the molding layer in order to form a molding layer by the nanoimprint method, the microstructure portion easily follows the mold release of the replica mold at the outer edge portion of the microstructure area. The shape of the fine structure portion is easily maintained in the central portion. Therefore, since the occurrence of damage to the fine structure portion is suppressed, the surface enhanced Raman scattering characteristic can be stabilized.
- the fine structure portion includes a plurality of convex portions formed on the support portion, and the formation density of the convex portions is finer than the outer edge portion of the fine structure area. It may be relatively small in the central part of the structure area.
- the molding layer can be formed easily and reliably, for example, by the nanoimprint method so that the thickness thereof is relatively thinner at the outer edge portion than at the central portion of the fine structure area.
- the formation density of a convex part here is prescribed
- the thickness of the molding layer in the direction intersecting the main surface of the substrate is smaller than the central portion of the microstructure area due to the thickness gradient of the support portion.
- the outer edge portion of the structure area may be relatively thin. Also in this case, it is possible to easily and reliably form the molding layer so that the thickness thereof is relatively thinner at the outer edge portion than at the center portion of the fine structure area.
- the fine structure portion may be formed over the entire main surface of the substrate. In this case, it is possible to cause surface enhanced Raman scattering over the entire main surface of the substrate.
- the surface-enhanced Raman scattering element according to one aspect of the present invention can further include a frame portion formed on the main surface of the substrate so as to surround at least the support portion along the main surface of the substrate.
- the fine structure portion can be protected by the frame portion and the reliability can be improved.
- the height of the frame portion from the main surface of the substrate can be lower than the height of the fine structure portion from the main surface of the substrate.
- a relatively thin (low) frame portion can be used as an area for setting a cut line when chipping.
- a surface-enhanced Raman scattering element that can stabilize the characteristics of surface-enhanced Raman scattering.
- FIG. 2 is a cross-sectional view taken along the line II-II in FIG. It is a typical expanded sectional view of the area
- FIG. 1 is a plan view of a surface-enhanced Raman scattering unit according to the present embodiment
- FIG. 2 is a cross-sectional view taken along the line II-II in FIG.
- a SERS unit (surface enhanced Raman scattering unit) 1 according to the present embodiment includes a handling substrate 2 and a SERS element (surface enhanced Raman scattering device) 3 attached on the handling substrate 2.
- the handling substrate 2 is a rectangular plate-shaped slide glass, a resin substrate, a ceramic substrate, or the like.
- the SERS element 3 is arranged on the surface 2 a of the handling substrate 2 in a state of being offset from one end portion in the longitudinal direction of the handling substrate 2.
- the SERS element 3 includes a substrate 4 attached on the handling substrate 2, a molding layer 5 formed on the surface (main surface) 4a of the substrate 4, and a conductor layer 6 formed on the molding layer 5.
- the substrate 4 is formed in a rectangular plate shape with silicon or glass or the like, and has an external shape of about several hundred ⁇ m ⁇ several hundred ⁇ m to several tens of mm ⁇ several tens of mm and a thickness of about 100 ⁇ m to 2 mm. .
- the back surface 4b of the substrate 4 is a surface 2a of the handling substrate 2 by direct bonding, bonding using a metal such as solder, eutectic bonding, fusion bonding by laser light irradiation, anodic bonding, or bonding using a resin. It is fixed to.
- a metal such as solder, eutectic bonding, fusion bonding by laser light irradiation, anodic bonding, or bonding using a resin. It is fixed to.
- FIG. 3 is a schematic enlarged sectional view of the area AR in FIG. In FIG. 3, the conductor layer 6 is omitted.
- the molding layer 5 includes a support portion 7 formed on the surface 4 a of the substrate 4 and a microstructure portion 8 formed on the support portion 7.
- the support portion 7 is formed so as to extend over the entire surface 4 a of the substrate 4.
- the thickness T7 of the support portion 7 has a gradient that gradually decreases from the central portion 7a of the support portion 7 toward the outer edge portion 7b. In other words, the thickness T7 of the support portion 7 is relatively thinner at the outer edge portion 7b than at the central portion 7a.
- the thickness T7 of the support portion 7 is, for example, about 200 nm at the central portion 7a and about 100 nm at the outer edge portion 7b.
- the fine structure portion 8 is formed on the support portion 7 over the entire surface 4 a of the substrate 4.
- the fine structure portion 8 is formed integrally with the support portion 7.
- the molding layer 5 includes a microstructure area A5 in which the microstructure portion 8 is formed.
- the fine structure area A5 is also an area extending over the entire surface 4a of the substrate 4.
- the support portion 7 is also formed over the entire surface 4a of the substrate 4, the central portion 5a and the outer edge portion 5b of the microstructure area A5 coincide with the central portion 7a and the outer edge portion 7b of the support portion 7, respectively. ing.
- the fine structure portion 8 includes a plurality of convex portions 81 formed on the support portion 7.
- the convex portion 81 protrudes from the support portion 7 and is formed integrally with the support portion 7.
- the convex portions 81 are arranged in a two-dimensional array on the support portion 7 (that is, on the surface 4a of the substrate 4).
- the surface 7s of the support part 7 is exposed between the convex parts 81 adjacent to each other.
- the convex portion 81 has a cylindrical shape, for example.
- the arrangement of the convex portions 81 can be a matrix arrangement, a triangular arrangement, a honeycomb arrangement, or the like.
- the shape of the convex portion 81 is not limited to a cylindrical shape, and may be an arbitrary column shape such as an elliptical column shape, a square column shape, or another polygonal column shape, or an arbitrary cone shape.
- the formation density of the convex portions 81 is relatively smaller in the central portion 5a of the fine structure area A5 than in the outer edge portion 5b of the fine structure area A5. That is, the fine structure portion 8 is a region including the central portion 5a of the fine structure area A5, and includes a low density region 8a in which the formation density of the convex portions 81 is relatively small and an outer edge portion 5b of the fine structure area A5. As described above, the low-density region 8a is surrounded by a high-density region 8b in which the formation density of the convex portions 81 is relatively high.
- the formation density of the protrusions 81 is defined by, for example, the total volume of the protrusions 81 formed in the predetermined region R serving as a reference. Therefore, the formation density here increases when the sum of the volumes of the protrusions 81 formed in the predetermined region R is large, and when the sum of the volumes of the protrusions formed in the predetermined region R is small. Becomes smaller.
- the size of the formation density corresponds to the number of the convex portions 81 formed in the predetermined region R.
- the convex portion 81 is formed with a column diameter of about 120 nm, for example.
- the pitch of the convex portions 81 in the low density region 8a is, for example, about 450 nm.
- the pitch of the convex portions 81 in the high density region 8b is narrower than the pitch of the low density region 8a, for example, about 250 nm.
- the height H81 of the convex portion 81 is substantially constant (the shape is uniform) in the low density region 8a and the high density region 8b, for example, about 180 nm. That is, the thickness T8 of the fine structure portion 8 is substantially constant over the entire fine structure area A5.
- the total thickness T5 of the molding layer 5 depends on the thickness T7 of the support portion 7. Has a gradient. More specifically, the thickness T5 of the molding layer 5 is relatively thinner in the outer edge portion 5b of the fine structure area A5 than in the central portion 5a of the fine structure area A5 due to the gradient of the thickness T7 of the support portion 7. ing. In other words, the thickness T5 of the molding layer 5 has a gradient that gradually decreases from the central portion 5a of the microstructure area A5 toward the outer edge portion 5b according to the gradient of the thickness T7 of the support portion 7. is doing.
- the molding layer 5 as described above is, for example, a resin (acrylic, fluorine-based, epoxy-based, silicone-based, urethane-based, PET, polycarbonate, inorganic / organic hybrid material, etc.) disposed on the surface 4a of the substrate 4 or low.
- the melting point glass is integrally formed by molding by a nanoimprint method.
- the conductor layer 6 is formed on the fine structure portion 8. In addition to the surface of the convex portion 81, the conductor layer 6 reaches the surface 7 s of the support portion 7 exposed between the convex portions 81. Therefore, the conductor layer 6 has a fine structure corresponding to the fine structure portion 8 of the molding layer 5.
- the conductor layer 6 has a thickness of about several nm to several ⁇ m, for example.
- Such a conductor layer 6 is formed, for example, by depositing a conductor such as metal (Au, Ag, Al, Cu, Pt, etc.) on the molding layer 5 molded by the nanoimprint method as described above.
- a conductor such as metal (Au, Ag, Al, Cu, Pt, etc.)
- an optical function unit 10 that generates surface-enhanced Raman scattering is configured by the fine structure portion 8 and the conductor layer 6 formed on the surface 7 a of the support portion 7.
- the SERS unit 1 is prepared. Subsequently, using a pipette or the like, a solution sample (or a powder sample dispersed in a solution such as water or ethanol (hereinafter the same)) is dropped, and the sample is placed on the optical function unit 10. The sample is arranged on the conductor layer 6 formed on the surface 7s of the support portion 7 and the surface of the convex portion 81 of the fine structure portion 8. In addition, when dropping the solution sample, a spacer made of silicone or the like may be disposed on the handling substrate 2 in advance to form a sample cell.
- a cover glass is placed on the optical function unit 10 (if a spacer is used, it can be placed on the spacer) Adhere closely.
- the SERS unit 1 is set in the Raman spectroscopic analyzer, and the sample placed on the optical function unit 10 is irradiated with excitation light through the cover glass.
- surface-enhanced Raman scattering occurs at the interface between the optical function unit 10 and the sample, and Raman-scattered light derived from the sample is enhanced to about 10 8 and emitted, for example. Therefore, the Raman spectroscopic analyzer can perform highly sensitive and highly accurate Raman spectroscopic analysis.
- the method for arranging the sample on the optical function unit 10 includes the following method.
- the handling substrate 2 may be grasped, the SERS element 3 may be immersed in a sample that is a solution, pulled up, and blown to dry the sample.
- a small amount of a sample that is a solution may be dropped on the optical function unit 10 and the sample may be naturally dried.
- the powder sample may be dispersed on the optical function unit 10 as it is.
- a mold M is prepared as shown in FIG.
- the mold M has a pattern opposite to that of the fine structure portion 8 of the molding layer 5 described above. More specifically, the mold M has a high density region M8a in the central portion where the convex portion M81 having a relatively large column diameter is formed, and a low density in the outer edge portion where the convex portion M82 having a relatively small column diameter is formed. And a region M8b.
- the concave portion M83 defined by the convex portions M81 and M82 adjacent to each other corresponds to the convex portion 81 in the molding layer 5. Since the column diameter D81 of the convex portion 81 of the molding layer 5 is constant, the width of the concave portion M83 in the mold M is also constant. Therefore, in the high-density region M8a of the mold M in which the relatively large convex portion M81 is formed, the interval between the concave portions M83 is widened, and the total volume of the concave portions M83 is relatively small. On the other hand, in the low density region M8b of the mold M in which the relatively small convex portions M82 are formed, the interval between the concave portions M83 is narrowed, and the total volume of the concave portions M83 is relatively large.
- the mold M may be a master mold for nanoimprinting or a replica mold formed using the master mold.
- the mold M may be a film mold made of, for example, PET, polycarbonate, PMMA, polyimide, silicone, or the like, and is not limited to a film mold, and may be a quartz mold, a nickel mold, a silicon mold, or the like.
- the wafer 40 including the substrate 4 is prepared, and the nanoimprint resin 50 is disposed on the surface 40a.
- the nanoimprint resin 50 for example, a UV curable resin (acrylic, fluorine-based, epoxy-based, silicone-based, urethane-based, PET, polycarbonate, inorganic-organic hybrid material, etc.) or low-melting glass can be used.
- the mold M is pressed against the nanoimprint resin 50 on the wafer 40 to pressurize it.
- the nano-imprint resin 50 is filled in the concave portions M83 of the mold M (there may not be completely filled).
- the total sum of the volumes of the recesses M83 is relatively small, so that the recesses M83 can be filled with a small amount of resin.
- the low density region M8b of the mold M since the total sum of the volumes of the recesses M83 is relatively large, the amount of resin necessary for filling the recesses M83 is relatively large.
- the concave portion M83 of the high density region M8a when the pattern of the mold M is transferred to the nanoimprint resin 50 to form the molding layer 5, when the mold M is pressed against the nanoimprint resin 50 as described above, the concave portion M83 of the high density region M8a.
- a relatively small amount of resin is required for filling, and a relatively large amount of resin is required for filling the recess M83 in the low density region M8b, so that it corresponds to each region M8a, M8b.
- a gradient occurs in the amount of resin used to form the support portion 7, and as a result, the above-described gradient is provided in the thickness of the support portion 7.
- the nanoimprint resin 50 is cured by UV irradiation or the like, and the mold M is released from the molding layer 5 as shown in FIG.
- the amount of resin necessary for forming the convex portion 81 of the high density region 8b (the low density region M8b of the mold M).
- the amount of resin for filling the concave portion M83) is more than the amount of resin necessary for forming the convex portion 81 of the low density region 8a (the amount of resin for filling the concave portion M83 of the high density region M8a of the mold M). Due to the large number, it is possible to easily and reliably form the molding layer 5 (support portion 7) having a gradient in thickness.
- the nanoimprint process shown in FIGS. 4A to 4C may be performed so that a plurality of molding layers 5 are collectively formed at the wafer level by using a wafer size mold M.
- a plurality of molding layers 5 may be formed in sequence by repeatedly using a mold M having a size smaller than that of the wafer (step & repeat).
- a conductor such as metal Au, Ag, Al, Cu, Pt or the like
- a conductor such as metal (Au, Ag, Al, Cu, Pt or the like) is vapor-deposited on the molding layer 5 (fine structure portion 8) to form the conductor layer 6, and the optical function portion 10 is configured.
- the SERS element 3 is configured.
- the wafer 40 is diced for each SERS element 3, and the cut out SERS element 3 is fixed to the handling substrate 2 to obtain the SERS unit 1.
- the molding layer 5 has the fine structure portion 8, the conductor layer 6 is formed on the fine structure portion 8, and the surface enhanced Raman scattering.
- the optical function part 10 which produces is comprised.
- the thickness of the molding layer 5 is relatively thick at the central portion 5a of the fine structure area A5 where the fine structure portion 8 is formed and relatively thin at the outer edge portion 5b. Yes.
- the microstructure portion 8 easily follows the release of the replica mold in the outer edge portion 5b of the microstructure area A5.
- the shape of the fine structure portion 8 is easily maintained in the central portion 5a of the fine structure area A5. Therefore, since damage to the fine structure portion 8 (convex portion 81) is suppressed, the characteristics of surface enhanced Raman scattering can be stabilized.
- the thickness T5 of the molding layer 5 is relatively thin at the outer edge portion 5b of the fine structure area A5 (here, the outer edge portion of the molding layer 5).
- the outer edge portion 5b can be used as an area for setting a cut line for chip formation, and is difficult to peel off during dicing for chip formation.
- the fine structure portion 8 includes a plurality of convex portions 81, and the formation density of the convex portions 81 is relatively higher in the central portion 5a than in the outer edge portion 5b of the fine structure area A5. It is getting smaller.
- a molding layer 5 is easily formed by, for example, the nanoimprint method using the mold M as described above so that the thickness T5 is relatively thinner in the outer edge portion 5b than in the central portion 5a of the microstructure area A5. And it is possible to form reliably. The same applies to the case where the above-described gradient is provided in the thickness T7 of the support portion 7.
- the molding layer 5 has the support portion 7 extending along the surface 4a of the substrate 4, and the fine structure portion 8 (convex portion 81) supports it.
- the unit 7 is configured integrally. For this reason, since the peeling of the fine structure part 8 (falling or dropping of the convex part 81) is suppressed, the reliability is improved.
- the present invention is not limited to the SERS element 3 described above, and the SERS element 3 can be arbitrarily changed without changing the gist of each claim.
- the SERS element 3 can include a molding layer 5A as shown in FIG. 5 instead of the molding layer 5 described above.
- the molding layer 5 ⁇ / b> A the support portion 7 and the fine structure portion 8 are formed in the central portion of the surface 4 a of the substrate 4. Therefore, the fine structure area A5 of the molding layer 5A is not the entire surface 4a of the substrate 4 but only the central portion.
- the total thickness T5 of the molding layer 5A is equal to that of the support portion 7. It has a gradient according to the thickness T7. More specifically, the thickness T5 of the molding layer 5A is relatively thinner in the outer edge portion 5b of the fine structure area A5 than in the central portion 5a of the fine structure area A5 due to the gradient of the thickness T7 of the support portion 7. ing. In other words, the thickness T5 of the molding layer 5A has a gradient that gradually decreases from the central portion 5a of the microstructure area A5 toward the outer edge portion 5b according to the gradient of the thickness T7 of the support portion 7. is doing.
- the molding layer 5A has a frame portion 9 formed on the surface 4a of the substrate 4.
- the frame portion 9 is continuous with the support portion 7 and is formed integrally with the support portion 7.
- the frame portion 9 is disposed on the outer peripheral portion of the surface 4 a of the substrate 4, and is formed in an annular shape so as to surround a portion of the microstructure portion 8 on the support portion 7 side and the support portion 7 along the surface 4 a of the substrate 4.
- the height H9 of the frame portion 9 from the surface 4a of the substrate 4 is equal to the height of the microstructure portion 8 from the surface 4a of the substrate 4 (the thickness T7 of the support portion 7 and the thickness T8 of the microstructure portion 8 are combined). Lower).
- the frame portion 9 is provided on the outer peripheral portion of the substrate 4, the fine structure portion 8 is protected, so that the reliability is improved. Further, the frame portion 9 is used as a space for installing an alignment mark for mounting, used as a space for marking for identifying a chip, and a cut line for setting a chip is set. It can be used as an area. Further, even if chipping occurs in the SERS element 3, the SERS element 3 remains at the frame portion 9, and damage to the effective area including the fine structure portion 8 can be avoided.
- the formation density of the convex portions 81 is constant in the fine structure area A5, but the frame portion 9 can be regarded as a relatively large single convex portion.
- Functions as the high density region 8b that is, the entire fine structure area A5 functions as the low density region 5a).
- a large amount of resin is required to form the frame portion 9. It becomes.
- the support portion 7 can be provided with a gradient.
- the height H9 of the frame portion 9 is set to the height of the fine structure portion 8 (the thickness T7 of the support portion 7 and the thickness T8 of the fine structure portion 8).
- the frame portion 9 may surround the support portion 7 and the fine structure portion 8.
- the recessed part C is formed by the frame part 9 and the support part 7, and the fine structure part 8 will be formed in the bottom face (surface 7s of the support part 7) of the recessed part C. Therefore, the fine structure 8 is reliably protected.
- by setting the frame portion 9 high distortion due to the difference in thermal expansion between the substrate 4 and the molding layer 5 can be relaxed, so that peeling of the molding layer 5 due to a temperature cycle or the like can be prevented.
- the adhesion rate of the sample to the fine structure portion 8 (to the conductor layer 6 on the fine structure portion 8) can be improved.
- the cover glass can be placed on the frame portion 9 and Raman spectroscopic analysis can be performed, it is possible to prevent the solution from volatilizing and to perform the analysis while protecting the fine structure portion 8 (preventing mixing of impurities). it can.
- the distance between the arranged cover glass and the fine structure portion 8 can be kept constant between different elements, and stable measurement can be realized (measurement variation due to distance variation can be suppressed).
- the lens effect of the sample of a solution can be suppressed by arrange
- the SERS element 3 can include a molding layer 5B as shown in FIG.
- the molding layer 5 ⁇ / b> B has a fine structure portion 8 ⁇ / b> B instead of the fine structure portion 8. Since the fine structure 8B is formed over the entire surface 4a of the substrate 4, the fine structure area A5 is also an area extending over the entire surface 4a of the substrate 4.
- the fine structure portion 8 ⁇ / b> B has a plurality of convex portions 81 and 82 protruding from the support portion 7.
- the convex portion 81 has a smaller column diameter than the convex portion 82 and is formed in the central portion 5a of the fine structure area A5.
- the convex part 82 is formed in the outer edge part 5b of the fine structure area A5.
- the space between the convex portions 81 adjacent to each other is larger than the space between the convex portions 82 adjacent to each other. Therefore, the formation density of the protrusions 81 is smaller than the formation density of the protrusions 82.
- the fine structure portion 8B is a region including the central portion 5a of the fine structure area A5, and the low density region 8a in which the formation density of the protrusions 81 is relatively small; It has a high density region 8b that surrounds the low density region 8a so as to include the outer edge portion 5b of the fine structure area A5 and has a relatively high formation density of the protrusions 82.
- the thickness T8 of the fine structure portion 8B is constant and the thickness T7 of the support portion 7 has a gradient, the entire thickness T5 of the molding layer 5B is supported. It has a slope corresponding to the thickness T7 of the portion 7. More specifically, the thickness T5 of the molding layer 5B is relatively thinner in the outer edge portion 5b of the fine structure area A5 than in the central portion 5a of the fine structure area A5 due to the gradient of the thickness T7 of the support portion 7. ing. In other words, the thickness T5 of the molding layer 5A has a gradient that gradually decreases from the central portion 5a of the microstructure area A5 toward the outer edge portion 5b according to the gradient of the thickness T7 of the support portion 7. is doing.
- the shape (column diameter) of the convex portion may be changed between the low density region 8a and the high density region 8b of the fine structure 8B. Also in this case, when the mold M for the molding layer 5B is prepared and pressed against the nanoimprint resin 50 and pressed, the amount of resin necessary to form the convex portion 82 is sufficient to form the convex portion 81. Due to being larger than the resin amount, the support portion 7 can be provided with a gradient.
- the molding layer 5 shall contain the fine structure part 8 which has the low density area
- the thickness T5 (the thickness T7 of the support portion 7) of the molding layer 5 is provided with a gradient due to the formation density of the convex portions 81 (due to the size of the necessary resin).
- the method of providing a gradient in the thickness T5 of the molding layer 5 is not limited to this.
- the molding layer in the SERS element 3 only needs to be relatively thinner in the outer edge portion 5b than in the center portion 5a of the microstructure area A5 where the microstructure portion 8 is formed, and from the center portion 5a to the outer edge portion 5b.
- the thinning may be performed stepwise (for example, two steps or three steps), or may not be formed by the nanoimprint method.
- the formation density of the convex portions 81 in the fine structure portion 8 is set in two levels, high density and low density, but the formation density of the convex portions 81 is higher than that of the outer edge portion 5b of the fine structure area A5. Also, it is sufficient that the central portion 5a is relatively small, and three or more formation density differences may be provided.
- the conductor layer 6 is not limited to what was directly formed on the shaping
- each component of the SERS element 3 described above are not limited to the material and shape described above, and various materials and shapes can be applied.
- the optical functional unit shown in FIG. 10 is electrically connected to a nano-imprinted resin microstructure having a plurality of pillars (diameter 120 nm, height 180 nm) periodically arranged at a predetermined pitch (centerline distance 360 nm).
- a predetermined pitch centerline distance 360 nm.
- a surface-enhanced Raman scattering element that can stabilize the characteristics of surface-enhanced Raman scattering.
- SERS unit surface enhancement Raman scattering unit
- 4 Substrate
- 4a Surface (main surface)
- 5 ... Molding layer 5a ... Center part
- 5b Outer edge part
- 6 ... conductor layer
- 7 ... support part
- 8 fine structure part
- 9 ... frame part
- 10 optical function part
- 81 ... convex part, A5 ... fine structure area.
Abstract
Description
Claims (6)
- 主面を有する基板と、
前記基板の前記主面に沿って延在するように前記主面上に形成された支持部、及び、前記支持部上に形成された微細構造部を有する成形層と、
前記微細構造部上に形成され、表面増強ラマン散乱を生じさせる光学機能部を構成する導電体層と、を備え、
前記基板の前記主面に交差する方向についての前記成形層の厚さは、前記成形層における前記微細構造部が形成された微細構造エリアの中央部分よりも前記微細構造エリアの外縁部分において相対的に薄くなっている、
表面増強ラマン散乱素子。 - 前記微細構造部は、前記支持部上に形成された複数の凸部を含み、
前記凸部の形成密度は、前記微細構造エリアの前記外縁部分よりも前記微細構造エリアの前記中央部分において相対的に小さくなっている請求項1に記載の表面増強ラマン散乱素子。 - 前記基板の前記主面に交差する方向についての前記成形層の厚さは、前記支持部の厚さの勾配によって、前記微細構造エリアの前記中央部分よりも前記微細構造エリアの前記外縁部分において相対的に薄くなっている請求項1又は2に記載の表面増強ラマン散乱素子。
- 前記微細構造部は、前記基板の前記主面の全体にわたって形成されている請求項1~3のいずれか一項に記載の表面増強ラマン散乱素子。
- 前記基板の前記主面に沿って少なくとも前記支持部を囲むように前記基板の前記主面上に形成された枠部をさらに備える請求項1~3のいずれか一項に記載の表面増強ラマン散乱素子。
- 前記基板の前記主面からの前記枠部の高さは、前記基板の主面からの前記微細構造部の高さよりも低い請求項5に記載の表面増強ラマン散乱素子。
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