CN114280028A - Medium-enhanced Raman scattering chip and preparation method and application thereof - Google Patents
Medium-enhanced Raman scattering chip and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a medium-enhanced Raman scattering chip and a preparation method and application thereof, wherein the medium-enhanced Raman scattering chip comprises a substrate and a metal layer which are arranged in a stacked mode; a periodic array of dielectric nanostructures is also arranged between the substrate and the metal layer; the periodic array units of the dielectric nanostructure are independent of each other. The preparation method comprises the following steps: (1) preparing a medium nano structure of a periodic array on the surface of a substrate to obtain an intermediate chip; (2) and (3) depositing a metal layer on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) to obtain the medium enhanced Raman scattering chip. The medium-enhanced Raman scattering chip provided by the invention has the advantages of high sensitivity, high uniformity of detected signals and the like, is easy to realize batch preparation and processing, and has wide application in the detection and monitoring aspects of trace substances in the fields of medicine, environment, food, security and the like.
Description
Technical Field
The invention belongs to the technical field of nano materials, relates to a Raman scattering chip, and particularly relates to a medium enhanced Raman scattering chip and a preparation method and application thereof.
Background
Surface Enhanced Raman Scattering (SERS) is a highly sensitive spectroscopic technique that can be used for substance fingerprint identification, and has wide applications in the fields of biomedicine, environment, food, security, and the like. The SERS chip is generally made of a rough metal, and the principle of the SERS chip is generally considered to be that a substance to be measured and the rough metal, particularly a metal ("hot spot") surface with nanoscale roughness, undergo a plasmon resonance interaction under irradiation of light with a certain wavelength, thereby causing a raman scattering signal of the substance to be measured to be significantly enhanced. The enhancement performance of the chip is mainly determined by the intrinsic electromagnetic field intensity brought by specific micro-nano structures on the surface of the chip and the quantity and distribution of gaps, namely 'hot spots', formed among metal nano particles or among metal/dielectric materials.
The means heretofore employed by those skilled in the art to improve the performance of SERS chips has focused more on the nanoscale gaps formed between the metal and its particles that produce plasmon resonance. On the one hand, however, the gap size cannot be reduced indefinitely due to limitations of the fabrication technology; on the other hand, the reduction of the gap brings great increase of difficulty for the object to be measured to reach the 'hot spot'. Therefore, the metal/dielectric material system has been gaining increasing attention in recent years. The specific three-dimensional structure composed of the metal/medium material can generate Surface Plasmon Polaritons (SPP) on the interface of the specific three-dimensional structure, SPP waves interact with each other and are even coupled with Local Surface Plasmon Resonance (LSPR) waves, and the SERS effect is further enhanced. In addition, LSPR formed by extremely thin layers of media (a few nanometers thick) spaced between the metal nanoparticles and/or the metal film also enhances the SERS effect. However, compared with plasmon metal, the enhancing mechanism and influence rule of the dielectric material and the three-dimensional structure thereof on the SERS effect are rarely studied by technicians, and the SERS chip with the three-dimensional structure of the dielectric material is not reported.
Disclosure of Invention
The invention aims to provide a medium-enhanced Raman scattering chip and a preparation method and application thereof, wherein the medium-enhanced Raman scattering chip has the advantages of high sensitivity, high uniformity of detected signals and the like, is easy to realize batch preparation and processing, and is widely applied to the detection and monitoring of trace substances in the fields of medicines, environments, foods, security and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a dielectric-enhanced raman scattering chip, which includes a substrate and a metal layer stacked together.
And a periodic array of dielectric nanostructures is also arranged between the substrate and the metal layer.
The periodic array units of the dielectric nanostructure are independent of each other.
According to the chip provided by the invention, the three-dimensional structure of the medium material is improved, namely the medium nano structures of the periodic array are arranged between the substrate and the metal layer, and the periodic array units of the medium nano structures are independent from each other, so that the rough metal-air interface SPP effect of the SERS performance, the metal/medium interface SPP effect distributed around the medium and the interference enhancement effect of the two interface SPP effects are enhanced, and the SERS performance and the detection sensitivity of the chip are greatly improved by various enhancement effects brought by the medium nano structures.
Preferably, the substrate is a hard material.
Preferably, the hard material comprises any one or a combination of at least two of glass, quartz, silicon oxide, silicon or doped silicon, typical but non-limiting combinations include combinations of silicon and glass, silicon and quartz, silicon and silicon oxide, silicon and doped silicon, silicon oxide and doped silicon, or silicon, silicon oxide and doped silicon.
Preferably, the metal in the metal layer is a metal material with surface enhanced raman scattering activity.
Preferably, the metallic material comprises any one or a combination of at least two of gold, platinum, palladium, silver or copper, typical but non-limiting combinations include gold and platinum, platinum and palladium, palladium and silver, silver and copper, gold, platinum and palladium, platinum, palladium and silver, or palladium, silver and copper.
Preferably, the metal layer has a thickness of 5 to 500nm, and may be, for example, 5nm, 10nm, 50nm, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the medium in the medium nanostructure is a transparent material.
Preferably, the transparent material comprises any one or a combination of at least two of silicon oxide, silicon nitride, magnesium fluoride, titanium oxide, aluminum oxide, zinc oxide, or photoresist, and typical but non-limiting combinations include a combination of silicon oxide and silicon nitride, a combination of silicon nitride and magnesium fluoride, a combination of magnesium fluoride and titanium oxide, a combination of titanium oxide and aluminum oxide, a combination of aluminum oxide and zinc oxide, or a combination of zinc oxide and photoresist.
Preferably, the array shape of the periodic array unit of the dielectric nanostructure is any one of a line shape, a circle shape, a triangle shape, a quadrangle shape or a hexagon shape.
Preferably, the periodic array of dielectric nanostructures has a height of 50-2000nm, such as 50nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200nm, 1400nm, 1600nm, 1800nm, or 2000nm, but not limited to the values recited, and other values not recited in this range are equally applicable.
Preferably, the dielectric nanostructure has a periodic array of elements with a circle-equivalent diameter of 50-2000nm, such as 50nm, 100nm, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200nm, 1400nm, 1600nm, 1800nm, or 2000nm, but not limited to the values recited, and other values not recited in this range are equally applicable.
In a second aspect, the present invention provides a method for preparing a dielectric-enhanced raman scattering chip as described in the first aspect, the method comprising the following steps:
(1) preparing a medium nano structure of a periodic array on the surface of a substrate to obtain an intermediate chip;
(2) and (3) depositing a metal layer on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) to obtain the medium enhanced Raman scattering chip.
Preferably, the preparation process of the medium nanostructure in the step (1) specifically adopts any one of the following methods:
(A) coating a resist on the surface of the substrate, and sequentially carrying out exposure, development and fixation to obtain a medium nano structure of a periodic array;
(B) growing a medium material on the surface of the substrate, coating a resist, and sequentially carrying out exposure, development, fixation, medium material etching and resist removal to obtain a medium nano structure of a periodic array;
(C) growing a medium material on the surface of the substrate, coating a resist, and sequentially carrying out exposure, development, fixation, mask material deposition, resist removal, medium material etching and mask material removal to obtain a medium nano structure of the periodic array;
(D) and coating a resist on the surface of the substrate, and sequentially carrying out exposure, development, fixation, medium material growth and resist removal to obtain the medium nano structure of the periodic array.
Preferably, the coating of steps (a), (B), (C) and (D) is independently spin coating.
Preferably, the resists of steps (a), (B), (C) and (D) each independently comprise an optical resist or an electron beam resist.
Preferably, the exposure of steps (a), (B), (C) and (D) independently comprises optical exposure or electron beam exposure, respectively.
Preferably, the dielectric material of steps (B), (C) and (D) is grown by chemical vapor deposition or physical vapor deposition.
Preferably, the chemical vapor deposition comprises plasma enhanced chemical vapor deposition.
Preferably, the physical vapour deposition comprises electron beam evaporation coating or magnetron sputtering coating.
In a third aspect, the invention provides a use of the dielectric-enhanced raman scattering chip according to the first aspect in trace substance detection and monitoring.
Compared with the prior art, the invention has the following beneficial effects:
according to the chip provided by the invention, the three-dimensional structure of the medium material is improved, namely the medium nano structures of the periodic array are arranged between the substrate and the metal layer, and the periodic array units of the medium nano structures are independent from each other, so that the rough metal-air interface SPP effect of the SERS performance, the metal/medium interface SPP effect distributed around the medium and the interference enhancement effect of the two interface SPP effects are enhanced, the detection sensitivity of the SERS performance and the chip is greatly improved by various enhancement effects brought by the medium nano structures, the batch preparation and processing are easy to realize, and the chip has wide application in the aspects of trace substance detection and monitoring in the fields of medicine, environment, food, security and the like.
Drawings
FIG. 1 is a schematic structural diagram of a dielectric-enhanced Raman scattering chip provided by the present invention;
FIG. 2 is a scanning electron micrograph of the dielectric enhanced Raman scattering chip provided in example 1;
FIG. 3 is a Raman spectrum of the chip provided in example 1 and comparative example 1 for detecting rhodamine 6G;
FIG. 4 is a Raman spectrum of the chip provided in example 2 and comparative example 2 for detecting 4, 4' -bipyridine;
FIG. 5 is a Raman spectrum of the chip provided in example 3 and comparative example 3 for detecting melamine;
FIG. 6 is a Raman spectrum of 4-mercaptophenylboronic acid detected by the chips provided in example 4 and comparative example 4;
FIG. 7 is a Raman spectrum of the chips provided in example 5 and comparative example 5 for detecting heavy metal mercury ions;
FIG. 8 is the Raman spectrum of the chip provided in example 1 and examples 6-8 for detecting rhodamine 6G.
Wherein: 1-a substrate; 2-a metal layer; 3-dielectric nanostructures.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The invention provides a medium-enhanced Raman scattering chip and a preparation method thereof, and as shown in figure 1, the medium-enhanced Raman scattering chip comprises a substrate 1 and a metal layer 2 which are arranged in a stacking manner, a medium nano structure 3 of a periodic array is also arranged between the substrate 1 and the metal layer 2, and periodic array units of the medium nano structure 3 are independent from each other.
In the invention, the substrate 1 is a hard material, and the hard material comprises any one or a combination of at least two of glass, quartz, silicon oxide, silicon or doped silicon; the metal in the metal layer 2 is a metal material with surface enhanced Raman scattering activity, and the metal material comprises any one or a combination of at least two of gold, platinum, palladium, silver or copper; the medium in the medium nano structure 3 is a transparent material, and the transparent material comprises any one or a combination of at least two of silicon oxide, silicon nitride, magnesium fluoride, titanium oxide, aluminum oxide, zinc oxide or photoresist; the array shape of the periodic array unit of the dielectric nanostructure 3 is any one of a line shape, a circle shape, a triangle shape, a quadrangle shape or a hexagon shape.
In the invention, the thickness of the metal layer 2 is 5-500nm, the height of the periodic array unit of the dielectric nanostructure 3 is 50-2000nm, and the equivalent circle diameter of the periodic array unit is 50-2000 nm.
The preparation method provided by the invention comprises the following steps:
(1) preparing a periodic array of dielectric nanostructures 3 on the surface of a substrate 1 by using an optical resist or an electron beam resist, and specifically adopting any one of the following methods to obtain an intermediate chip;
(A) spin-coating a resist on the surface of the substrate 1, and sequentially carrying out exposure, development and fixation to obtain a medium nano structure 3 of a periodic array;
(B) growing a medium material on the surface of the substrate 1, spin-coating a resist, and sequentially carrying out exposure, development, fixation, medium material etching and resist removal to obtain a medium nano structure 3 of a periodic array;
(C) growing a dielectric material on the surface of a substrate 1, spin-coating a resist, and sequentially carrying out exposure, development, fixation, mask material deposition, resist removal, dielectric material etching and mask material removal to obtain a periodic array of dielectric nanostructures 3;
(D) spin-coating a resist on the surface of the substrate 1, and sequentially carrying out exposure, development, fixation, medium material growth and resist removal to obtain a medium nano structure 3 of a periodic array;
wherein the exposing of steps (A), (B), (C) and (D) independently comprises optical exposure or electron beam exposure, respectively; the growth mode of the dielectric material in the steps (B), (C) and (D) comprises chemical vapor deposition or physical vapor deposition;
(2) and (2) depositing a metal layer 2 on the surface of one side of the medium nano structure 3 of the intermediate chip obtained in the step (1) to obtain the medium enhanced Raman scattering chip.
The following examples are given without specifying the particular techniques or conditions, according to the techniques or conditions described in the literature in the field, or according to the product specifications. The reagents or apparatus used are conventional products commercially available from normal sources, not indicated by the manufacturer.
Example 1
The embodiment provides a medium-enhanced Raman scattering chip and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) spin-coating a negative photoresist with the thickness of 1500nm on the surface of a quartz substrate, and sequentially performing optical exposure, development and fixation to obtain a photoresist medium nanostructure with the equivalent circle diameter of a periodic array unit of 2000nm, the interval of 2000nm and the height of 1500nm, thereby obtaining an intermediate chip;
(2) and (3) depositing a silver metal layer with the thickness of 500nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting a magnetron sputtering coating instrument to obtain the medium-enhanced Raman scattering chip.
Fig. 2 is a scanning electron micrograph of the dielectric-enhanced raman scattering chip obtained in this example.
As can be seen from fig. 2: the periodic array units of the dielectric nano-structure on the surface of the chip obtained by the embodiment are independent from each other.
The dielectric enhanced Raman scattering chip obtained in the embodiment is placed at a concentration of 10-8Taking out M rhodamine 6G molecular water solution after 8h, naturally drying, and testing the obtained chip with a Raman spectrometer, wherein the results are shown in FIG. 3 and FIG. 8。
Example 2
The embodiment provides a medium-enhanced Raman scattering chip and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) growing a silicon oxide film with the thickness of 700nm on the surface of a silicon substrate by using Plasma Enhanced Chemical Vapor Deposition (PECVD), spin-coating a negative electron beam resist on the obtained silicon/silicon oxide substrate, exposing by using electron beam exposure equipment, then developing and fixing in sequence, and drying a sample by using nitrogen; etching silicon oxide by taking the electron beam resist pattern as a mask, removing the resist, and preparing a silicon oxide medium nano structure with the equivalent circle diameter of 650nm, the interval of 500nm and the height of 700nm on a silicon substrate to obtain an intermediate chip;
(2) and (3) depositing a platinum metal layer with the thickness of 160nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting a magnetron sputtering coating instrument to obtain the medium-enhanced Raman scattering chip.
The microstructure of the surface of the dielectric enhanced raman scattering chip obtained in this embodiment is similar to that of embodiment 1, and therefore, the description thereof is omitted.
The dielectric enhanced Raman scattering chip obtained in the embodiment is placed at a concentration of 10-7The chip was obtained by immersing M in an ethanol solution of 4, 4' -Bipyridine (BPY) molecule for 3 hours, drying the solution naturally, and then testing the chip by raman spectroscopy, and the results are shown in fig. 4.
Example 3
The embodiment provides a medium-enhanced Raman scattering chip and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) growing a titanium oxide film with the thickness of 500nm on the surface of a silicon substrate by using Plasma Enhanced Chemical Vapor Deposition (PECVD), spin-coating a positive electron beam resist on the titanium oxide film, exposing by adopting electron beam exposure equipment, then sequentially developing and fixing, and drying a sample by using nitrogen; depositing a metallic aluminum film by adopting an electron beam evaporation coating instrument, and removing the resist by a stripping process to obtain a metallic aluminum film pattern complementary to the exposure pattern; etching titanium oxide by taking the metal aluminum film pattern as a mask, removing metal aluminum, preparing a titanium oxide medium nano structure with the equivalent circle diameter of 600nm, the interval of 700nm and the height of 500nm of the periodic array unit on the silicon substrate, and annealing at 300 ℃ for 1h to obtain an intermediate chip;
(2) and (3) depositing a copper metal layer with the thickness of 260nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting thermal evaporation equipment to obtain the medium-enhanced Raman scattering chip.
The microstructure of the surface of the dielectric enhanced raman scattering chip obtained in this embodiment is similar to that of embodiment 1, and therefore, the description thereof is omitted.
The dielectric enhanced Raman scattering chip obtained in the embodiment is placed at a concentration of 10-8The melamine molecule M was taken out of the ethanol solution for 6 hours, and after drying naturally, the resulting chip was tested by a raman spectrometer, and the results are shown in fig. 5.
Example 4
The embodiment provides a medium-enhanced Raman scattering chip and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) spin-coating a positive electron beam resist on the surface of the sapphire substrate, exposing by adopting an electron beam exposure device, then sequentially developing and fixing, and drying the sample by using nitrogen; evaporating a magnesium fluoride film with the thickness of 55nm by using an electron beam evaporation coating instrument, and removing an etching resist by a stripping process to prepare a magnesium fluoride medium nano structure with the equivalent circle diameter of the periodic array unit of 80nm, the interval of 120nm and the height of 55nm, so as to obtain an intermediate chip;
(2) and (3) depositing a gold film layer with the thickness of 8nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting an electron beam evaporation coating instrument to obtain the medium-enhanced Raman scattering chip.
The microstructure of the surface of the dielectric enhanced raman scattering chip obtained in this embodiment is similar to that of embodiment 1, and therefore, the description thereof is omitted.
The dielectric enhanced Raman scattering chip obtained in the embodiment is placed at a concentration of 10-4Taking out M4-mercaptophenylboronic acid (4-MPBA) molecule in ethanol solution for 0.5h, naturally drying, and performing Raman spectroscopy on the obtained chipThe results of the tests are shown in FIG. 6.
Example 5
The embodiment provides a medium-enhanced Raman scattering chip and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) plating a zinc oxide film with the thickness of 300nm on the surface of the silicon substrate by using a magnetron sputtering coating instrument, spin-coating a negative photoresist, sequentially carrying out optical exposure, development and fixation, and drying a sample by using nitrogen; etching zinc oxide by taking the photoresist pattern as a mask, removing the resist, preparing a zinc oxide medium nano structure with the equivalent circle diameter of 1800nm, the interval of 2000nm and the height of 300nm on a silicon substrate, and annealing at 600 ℃ for 1h to obtain an intermediate chip;
(2) and (3) depositing a palladium-gold alloy layer with the thickness of 75nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting an electron beam evaporation coating instrument to obtain the medium-enhanced Raman scattering chip.
The microstructure of the surface of the dielectric enhanced raman scattering chip obtained in this embodiment is similar to that of embodiment 1, and therefore, the description thereof is omitted.
The dielectric enhanced Raman scattering chip obtained in the embodiment is placed at a concentration of 10-5Taking out M4-mercaptophenylboronic acid (4-MPBA) molecule in ethanol solution for 0.5h, and then placing the M solution in a container of 10-9The obtained chip was tested by raman spectroscopy after 0.5h in M mercury ion aqueous solution, and the results are shown in fig. 7.
Example 6
This embodiment provides a dielectric-enhanced raman scattering chip and a method for manufacturing the same, where the method is the same as that in embodiment 1 except that the equivalent circle diameter of the periodic array unit in step (1) in embodiment 1 is changed to 45nm, and the rest of the steps and conditions are the same as those in embodiment 1, and thus are not described herein again.
Example 7
This embodiment provides a dielectric-enhanced raman scattering chip and a method for manufacturing the same, wherein the method for manufacturing the same is the same as that of embodiment 1 except that the height of the periodic array unit in step (1) of embodiment 1 is changed to 40nm, and thus, the details are not repeated herein.
Example 8
This embodiment provides a dielectric-enhanced raman scattering chip and a method for manufacturing the same, where the method for manufacturing the same is the same as that in embodiment 1 except that the deposition thickness of the silver metal layer in step (2) in embodiment 1 is changed to 3nm, and thus, details are not described herein.
The dielectric-enhanced Raman scattering chips obtained in examples 6 to 8 were each independently placed at a concentration of 10-8And (3) taking out the M rhodamine 6G molecular water solution after 8 hours, naturally drying, and testing the obtained chip by using a Raman spectrometer, wherein the result is shown in figure 8.
As can be seen from fig. 8: when the feature size (equivalent circle diameter or height) of the periodic array unit or the deposition thickness of the metal layer in the chip obtained in examples 6-8 is out of a reasonable range, the raman signal intensity of the chip is reduced and the detection sensitivity is reduced, compared with example 1.
Comparative example 1
The comparative example provides a raman scattering chip and a preparation method thereof, and the preparation method comprises the following steps:
(1) spin-coating a positive photoresist with the thickness of 1500nm on the surface of a quartz substrate, and sequentially carrying out optical exposure, development and fixation to prepare a photoresist medium nanostructure which is connected with each other and has the equivalent circular diameter of a periodic array unit of 2000nm and the height of 1500nm, so as to obtain a complementary array structure intermediate chip with the same size as that of the embodiment 1;
(2) and (3) depositing a silver metal layer with the thickness of 500nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting a magnetron sputtering coating instrument to obtain the Raman scattering chip.
The Raman scattering chip obtained in the comparative example was placed at a concentration of 10-8And (3) taking out the M rhodamine 6G molecular water solution after 8 hours, naturally drying, and testing the obtained chip by using a Raman spectrometer, wherein the result is shown in figure 3.
As can be seen from fig. 3: example 1 testing rhodamine 6G molecule gives Raman spectra with a main characteristic peak of 1360cm-1The intensity was 4 times higher than the characteristic peak intensity of comparative example 1, indicating that the chip obtained in example 1 significantly enhanced the detection sensitivity.
Comparative example 2
The comparative example provides a raman scattering chip and a preparation method thereof, and the preparation method comprises the following steps:
(1) growing a silicon oxide film with the thickness of 700nm on the surface of a silicon substrate by using Plasma Enhanced Chemical Vapor Deposition (PECVD), spin-coating a positive electron beam resist on the obtained silicon/silicon oxide substrate, exposing by using electron beam exposure equipment, then developing and fixing in sequence, and drying a sample by using nitrogen; etching silicon oxide by taking the electron beam resist pattern as a mask, removing the resist, and preparing a silicon oxide medium nano structure which is provided with a periodic array unit equivalent circle with the diameter of 650nm and the height of 700nm and is connected with each other on a silicon substrate to obtain a complementary array structure intermediate chip with the same size as that of the embodiment 2;
(2) and (3) depositing a platinum metal layer with the thickness of 160nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting a magnetron sputtering coating instrument to obtain the Raman scattering chip.
The Raman scattering chip obtained in the comparative example was placed at a concentration of 10-7The chip was obtained by immersing M in an ethanol solution of 4, 4' -Bipyridine (BPY) molecule for 3 hours, drying the solution naturally, and then testing the chip by raman spectroscopy, and the results are shown in fig. 4.
As can be seen from fig. 4: example 2 testing of BPY molecules resulted in a Raman spectrum with a main characteristic peak of 1610cm-1The intensity was 4 times higher than the characteristic peak intensity of comparative example 2, indicating that the chip obtained in example 2 significantly enhanced the detection sensitivity.
Comparative example 3
The comparative example provides a raman scattering chip and a preparation method thereof, and the preparation method comprises the following steps:
(1) growing a titanium oxide film with the thickness of 500nm on the surface of a silicon substrate by using Plasma Enhanced Chemical Vapor Deposition (PECVD), spin-coating a positive electron beam resist on the titanium oxide film, exposing by adopting electron beam exposure equipment, then sequentially developing and fixing, and drying a sample by using nitrogen; etching titanium oxide by taking the resist pattern as a mask, removing the resist, preparing a titanium oxide medium nanostructure which is connected with each other and has the equivalent circle diameter of 600nm and the height of 500nm on a silicon substrate, and annealing at 300 ℃ for 1h to obtain a complementary array structure intermediate chip with the same size as that of the embodiment 3;
(2) and (3) depositing a copper metal layer with the thickness of 260nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting thermal evaporation equipment to obtain the Raman scattering chip.
The Raman scattering chip obtained in the comparative example was placed at a concentration of 10-8The melamine molecule M was taken out of the ethanol solution for 6 hours, and after drying naturally, the resulting chip was tested by a raman spectrometer, and the results are shown in fig. 5.
As can be seen from fig. 5: example 3 testing of melamine molecules gives a Raman spectrum with a main characteristic peak of 702cm-1The intensity is 8 times of the intensity of the characteristic peak of comparative example 3, which shows that the chip obtained in example 3 has significantly enhanced detection sensitivity.
Comparative example 4
The comparative example provides a raman scattering chip and a preparation method thereof, and the preparation method comprises the following steps:
(1) spin-coating a negative electron beam resist on the surface of the sapphire substrate, exposing by adopting an electron beam exposure device, then sequentially developing and fixing, and blow-drying a sample by using nitrogen; evaporating a magnesium fluoride film with the thickness of 55nm by using an electron beam evaporation coating machine, and removing an etching resist by a stripping process to prepare a magnesium fluoride medium nano structure which is connected with each other and has the equivalent circular diameter of a periodic array unit of 80nm and the height of 55nm, so as to obtain a complementary array structure intermediate chip with the same size as that of the embodiment 4;
(2) and (3) depositing a gold film layer with the thickness of 8nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting an electron beam evaporation coating instrument to obtain the Raman scattering chip.
The Raman scattering chip obtained in the comparative example was placed at a concentration of 10-4The chip was obtained by immersing M4-mercaptophenylboronic acid (4-MPBA) molecule in an ethanol solution for 0.5 hour, drying the solution naturally, and then testing the chip by a Raman spectrometer, and the results are shown in FIG. 6.
As can be seen from fig. 6: example 4 testing1080cm of main characteristic peak in Raman spectrogram obtained from 4-MPBA molecule-1The intensity is 5 times of the intensity of the characteristic peak of comparative example 4, which shows that the chip obtained in example 4 has significantly enhanced detection sensitivity.
Comparative example 5
The comparative example provides a raman scattering chip and a preparation method thereof, and the preparation method comprises the following steps:
(1) plating a zinc oxide film with the thickness of 300nm on the surface of the silicon substrate by using a magnetron sputtering coating instrument, then spin-coating a positive photoresist, sequentially carrying out optical exposure, development and fixation, and then drying a sample by using nitrogen; etching zinc oxide by taking the photoresist pattern as a mask, removing the resist, preparing a zinc oxide medium nanostructure which is connected with each other and has the equivalent circle diameter of 1800nm and the height of 300nm on a silicon substrate, and annealing at 600 ℃ for 1h to obtain a complementary array structure intermediate chip with the same size as that of the embodiment 5;
(2) and (3) depositing a palladium-gold alloy layer with the thickness of 75nm on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) by adopting an electron beam evaporation coating instrument to obtain the Raman scattering chip.
The Raman scattering chip obtained in the comparative example was placed at a concentration of 10-5Taking out M4-mercaptophenylboronic acid (4-MPBA) molecule in ethanol solution for 0.5h, and then placing the M solution in a container of 10-9The obtained chip was tested by raman spectroscopy after 0.5h in M mercury ion aqueous solution, and the results are shown in fig. 7.
As can be seen from fig. 7: example 5 testing of Mercury ions yields a Raman spectrum with a dominant peak at 1060cm-1The intensity was 4 times higher than that of the characteristic peak of comparative example 5, indicating that the chip obtained in example 5 significantly enhanced the detection sensitivity.
The Raman spectrometer model used in the above examples 1-8 and comparative examples 1-5 is B & WTEK BWS465(i-Raman Plus), and the test conditions are specifically as follows: the excitation wavelength is 785nm, the power is 10%, the objective lens is 20 times, and the integration time is 10 s.
Therefore, the chip provided by the invention enhances the rough metal-air interface SPP effect of the SERS performance, the metal/medium interface SPP effect distributed around the medium and the interference enhancement effect of the two interface SPP effects by improving the three-dimensional structure of the medium material, namely arranging the medium nano structures of the periodic array between the substrate and the metal layer, wherein the periodic array units of the medium nano structures are independent from each other, and the multiple enhancement effects brought by the medium nano structures greatly improve the SERS performance and the detection sensitivity of the chip, are easy to realize batch preparation and processing, and have wide application in the detection and monitoring aspects of trace substances in the fields of medicine, environment, food, security and the like.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. A dielectric-enhanced Raman scattering chip is characterized by comprising a substrate and a metal layer which are arranged in a stacked mode;
a periodic array of dielectric nanostructures is also arranged between the substrate and the metal layer;
the periodic array units of the dielectric nanostructure are independent of each other.
2. The dielectric-enhanced raman scattering chip according to claim 1, wherein said substrate is a hard material;
preferably, the hard material comprises any one of glass, quartz, silicon oxide, silicon or doped silicon or a combination of at least two thereof.
3. The dielectric-enhanced Raman scattering chip of claim 1 or 2, wherein the metal in the metal layer is a metal material having surface-enhanced Raman scattering activity;
preferably, the metal material comprises any one or a combination of at least two of gold, platinum, palladium, silver or copper.
4. The dielectric-enhanced raman scattering chip according to any one of claims 1 to 3, wherein the thickness of said metal layer is 5 to 500 nm.
5. The dielectric-enhanced Raman scattering chip of any one of claims 1 to 4, wherein the dielectric in the dielectric nanostructure is a transparent material;
preferably, the transparent material comprises any one of silicon oxide, silicon nitride, magnesium fluoride, titanium oxide, aluminum oxide, zinc oxide or photoresist or a combination of at least two of the above.
6. The dielectric-enhanced Raman scattering chip of any one of claims 1 to 5, wherein the array shape of the periodic array unit of the dielectric nanostructure is any one of a line shape, a circle shape, a triangle shape, a quadrangle shape, or a hexagon shape;
preferably, the periodic array unit height of the medium nano structure is 50-2000 nm;
preferably, the equivalent circle diameter of the periodic array unit of the dielectric nanostructure is 50-2000 nm.
7. A method for preparing a dielectric-enhanced Raman scattering chip as recited in any one of claims 1-6, wherein the method comprises the steps of:
(1) preparing a medium nano structure of a periodic array on the surface of a substrate to obtain an intermediate chip;
(2) and (3) depositing a metal layer on the surface of one side of the medium nano structure of the intermediate chip obtained in the step (1) to obtain the medium enhanced Raman scattering chip.
8. The method according to claim 7, wherein the dielectric nanostructure in step (1) is prepared by any one of the following methods:
(A) coating a resist on the surface of the substrate, and sequentially carrying out exposure, development and fixation to obtain a medium nano structure of a periodic array;
(B) growing a medium material on the surface of the substrate, coating a resist, and sequentially carrying out exposure, development, fixation, medium material etching and resist removal to obtain a medium nano structure of a periodic array;
(C) growing a medium material on the surface of the substrate, coating a resist, and sequentially carrying out exposure, development, fixation, mask material deposition, resist removal, medium material etching and mask material removal to obtain a medium nano structure of the periodic array;
(D) and coating a resist on the surface of the substrate, and sequentially carrying out exposure, development, fixation, medium material growth and resist removal to obtain the medium nano structure of the periodic array.
9. The method according to claim 8, wherein the coating of steps (A), (B), (C) and (D) is independently spin coating;
preferably, the resists of steps (a), (B), (C) and (D) each independently comprise an optical resist or an electron beam resist;
preferably, the exposure of steps (a), (B), (C) and (D) independently comprises optical exposure or electron beam exposure, respectively;
preferably, the dielectric material of steps (B), (C) and (D) is grown by chemical vapor deposition or physical vapor deposition;
preferably, the chemical vapor deposition comprises plasma enhanced chemical vapor deposition;
preferably, the physical vapour deposition comprises electron beam evaporation coating or magnetron sputtering coating.
10. Use of a dielectric-enhanced raman scattering chip according to any one of claims 1 to 6 for trace species detection and monitoring.
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