CN115060700A - Semiconductor surface enhanced Raman scattering substrate - Google Patents
Semiconductor surface enhanced Raman scattering substrate Download PDFInfo
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- CN115060700A CN115060700A CN202210657279.5A CN202210657279A CN115060700A CN 115060700 A CN115060700 A CN 115060700A CN 202210657279 A CN202210657279 A CN 202210657279A CN 115060700 A CN115060700 A CN 115060700A
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- 239000000758 substrate Substances 0.000 title claims abstract description 61
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 title claims abstract description 42
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- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
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- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
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Abstract
The invention relates to the technical field of spectra, in particular to a semiconductor surface enhanced Raman scattering substrate, which comprises a substrate, a semiconductor layer, a first conductor side wall, a second conductor side wall, a first insulator side wall and a second insulator side wall, wherein the substrate is provided with a first electrode and a second electrode; the semiconductor layer is arranged on the substrate, and the first conductor side wall, the second conductor side wall, the first insulator side wall and the second insulator side wall are arranged on the periphery of the semiconductor layer and enclose a groove. After the semiconductor layer generates heat, a thermophoresis phenomenon is generated in the solution, and the coupling between the noble metal particles and the semiconductor layer is regulated and controlled, so that the surface enhanced Raman scattering factor of the noble metal particle/semiconductor layer composite structure is higher. In the invention, the thermophoresis phenomenon in the solution can be regulated and controlled through the temperature and the appearance of the semiconductor layer and the voltage applied between the side wall of the first conductor and the side wall of the second conductor, the regulation and control means is simple, the regulation and control are convenient, and the method has good application prospect in the field of surface-enhanced Raman scattering application.
Description
Technical Field
The invention relates to the technical field of spectra, in particular to a semiconductor surface enhanced Raman scattering substrate.
Background
Surface enhanced raman scattering has high detection sensitivity, extremely high selectivity, is suitable for nondestructive detection, gives structural information of substances at a molecular level, receives wide attention of researchers, and is applied to a plurality of fields of chemical and biological analysis, electrochemistry, surface science, catalysis, chemical and biological sensing, trace detection and the like.
The traditional surface-enhanced Raman scattering substrate is made of gold, silver, copper and other materials, so that the development of the surface-enhanced Raman scattering technology is limited. Researchers are gradually investigating the surface enhanced raman scattering characteristics of non-metallic materials, particularly metal oxides and semiconductor materials, including nickel oxide, titanium oxide, ferroferric oxide, ferric oxide, zinc oxide, copper oxide, zinc sulfide, copper oxide, aluminum oxide, silver oxide, and the like. Researchers have mainly used metal oxide colloids or metal oxide films to achieve surface-enhanced raman scattering. For example, the raman signal of molecules such as cyanine dye molecules, pyridine, etc. is enhanced using a semiconductor silver oxide colloid, wherein 10 is realized for the cyanine dye molecules 2 Enhancement factors around (Spectrochimica Acta A1997, Vol. 53, p. 1411-. The surface enhanced Raman scattering enhancement factor of the metal oxide is small and is generally less than 10 3 . The semiconductor/noble metal composite substrate overcomes the defects of expensive noble metal, narrow application area, insensitive surface-enhanced Raman scattering signal of a semiconductor material and the like, integrates the advantages of the two materials, and is an important direction for realizing the surface-enhanced Raman scattering with high sensitivity, high biocompatibility and high stability. In the existing semiconductor/noble metal surface enhanced Raman scattering substrate, the gap or coupling between the noble metal and the semiconductor is not easy to regulate and control, so that a higher surface enhanced Raman scattering factor is difficult to obtain.
Disclosure of Invention
In order to solve the above problems, the present invention provides a semiconductor surface enhanced raman scattering substrate, comprising a base, a semiconductor layer, a first conductor sidewall, a second conductor sidewall, a first insulator sidewall, and a second insulator sidewall; the semiconductor layer is arranged on the substrate, the first conductor side wall, the second conductor side wall, the first insulator side wall and the second insulator side wall are arranged on the semiconductor layer in a surrounding mode and form a groove, the first conductor side wall and the second conductor side wall are arranged oppositely, and the first insulator side wall and the second insulator side wall are arranged oppositely. When the device is applied, precious metal particles and a molecular solution to be detected are dropped into the groove, wherein the surfaces of the precious metal particles are modified by a surfactant and are used for linking molecules to be detected; then, an external circuit is connected through the first conductor sidewall and the second conductor sidewall, and a current is formed in the semiconductor layer, and the current causes the semiconductor layer to generate heat, thereby increasing the temperature around the semiconductor layer. The noble metal particles and the molecular solution to be detected generate a thermophoresis phenomenon, and the noble metal particles move towards the semiconductor layer and are gathered on the surface of the semiconductor layer, so that on one hand, the density of the noble metal particles is increased; on the other hand, the distance between the noble metal particles and the semiconductor layer is reduced, and the coupling between the noble metal particles and the semiconductor layer is enhanced. Both of these aspects result in an enhancement of the local electromagnetic field in the vicinity of the noble metal particles and the semiconductor layer, thereby increasing the enhancement factor of surface-enhanced raman scattering.
Further, the substrate is made of an insulating material, such as silicon dioxide, ceramic, or mica, to isolate the surface-enhanced raman scattering substrate of the present invention from the microscope stage.
Furthermore, the sidewall of the first conductor and the sidewall of the second conductor are made of metal, which can be copper, gold, silver, platinum, for connecting with the external circuit.
Further, the material of the first insulator sidewall and the second insulator sidewall is an insulator, the material of the insulator may be the same as the material of the substrate, and the material of the insulator may be silicon dioxide, ceramic, mica, or the like, for electrically isolating the first conductor sidewall and the second conductor sidewall.
Further, the material of the semiconductor layer is a metal oxide.
Further, the metal oxide is zinc oxide, titanium oxide, copper oxide, silver oxide, ferric oxide.
Furthermore, a hole is formed on the semiconductor layer in the groove. Therefore, the noble metal particles are gathered in the holes, the contact area between the noble metal particles and the holes is larger, the coupling effect is stronger, the interaction between incident exciting light and the noble metal particles and between the incident exciting light and the semiconductor layer is enhanced, the local electromagnetic field around the noble metal particles and the semiconductor layer is improved, and the enhancement factor of the surface-enhanced Raman scattering of the molecule to be detected is improved.
Further, the diameter of the holes is larger than 10 nanometers and smaller than 1000 nanometers.
Furthermore, the holes are periodically arranged. The noble metal particles are periodically arranged, the coupling resonance mode is single, and the result is easy to analyze.
Further, the period of the hole arrangement is a square period. Triangular areas can be formed between the square periods and the metal particles, and strong electric fields can be gathered in the areas, so that the local electromagnetic fields around the noble metal particles and the semiconductor layer are improved, and the enhancement factor of the surface enhanced Raman scattering of the molecules to be detected is improved.
The invention has the beneficial effects that: the invention provides a semiconductor surface enhanced Raman scattering substrate, wherein a semiconductor layer generates thermophoresis in a solution after generating heat, and the coupling between noble metal particles and the semiconductor layer is regulated and controlled, so that the surface enhanced Raman scattering enhancement factor of a noble metal particle/semiconductor layer composite structure is higher. In the invention, the thermophoresis phenomenon in the solution can be regulated and controlled through the temperature and the appearance of the semiconductor layer and the voltage applied between the side wall of the first conductor and the side wall of the second conductor, the regulation and control means is simple, the regulation and control are convenient, and the method has good application prospect in the field of surface-enhanced Raman scattering application.
The present invention will be described in further detail below with reference to the accompanying drawings.
Drawings
Fig. 1 is a schematic view of a semiconductor surface enhanced raman scattering substrate.
Fig. 2 is a top view of a semiconductor surface enhanced raman scattering substrate.
Fig. 3 is a schematic view of yet another semiconductor surface enhanced raman scattering substrate.
Fig. 4 is a schematic view of a semiconductor layer.
In the figure: 1. a substrate; 2. a semiconductor layer; 3. a first conductor sidewall; 4. a second conductor sidewall; 5. a first insulator sidewall; 6. a second insulator sidewall; 21. and (4) holes.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application is further described in detail below by referring to the accompanying drawings and examples.
Example 1
The invention provides a semiconductor surface enhanced Raman scattering substrate, which comprises a base 1, a semiconductor layer 2, a first conductor side wall 3, a second conductor side wall 4, a first insulator side wall 5 and a second insulator side wall 6, as shown in figure 1. The semiconductor layer 2 is arranged on the substrate 1, and the first conductor side wall 3, the second conductor side wall 4, the first insulator side wall 5 and the second insulator side wall 6 are arranged on the semiconductor layer 2 at the periphery and enclose a groove. As shown in fig. 2, the first conductor sidewall 3 and the second conductor sidewall 4 are disposed opposite to each other, and the first insulator sidewall 5 and the second insulator sidewall 6 are disposed opposite to each other. The substrate 1 is made of an insulating material, which can be silicon dioxide, ceramic or mica, so as to isolate the surface enhanced Raman scattering substrate and the microscope stage. The thickness of the substrate 1 is greater than 0.2 cm and less than 1 cm. The first conductor sidewall 3 and the second conductor sidewall 4 are made of metal, and the metal can be copper, gold, silver or platinum, and is used for communicating with an external circuit. The thickness of the first conductor sidewall 3 and the second conductor sidewall 4 is greater than 0.01 cm and less than 0.5 cm. The material of the first insulator sidewall 5 and the second insulator sidewall 6 is an insulator, the material of the insulator may be the same as the material of the substrate, and the material of the insulator may be silicon dioxide, ceramic, mica, or the like, for electrically isolating the first conductor sidewall 3 and the second conductor sidewall 4. The first insulator sidewall 5 and the second insulator sidewall 6 have a thickness greater than 0.01 cm and less than 0.5 cm. The material of the semiconductor layer 2 is a metal oxide. The metal oxide is zinc oxide, titanium oxide, copper oxide, silver oxide, ferric oxide. The thickness of the semiconductor layer 2 is greater than 100 nm and less than 2 μm. The substrate 1 is rectangular, and the length of the long side of the rectangle is more than 1 cm and less than 10 cm; the length of the short side of the rectangle is more than 0.5 cm and less than 8 cm. The first conductor sidewall 3 and the second conductor sidewall 4 are rectangular parallelepiped-shaped, and the first conductor sidewall 3 and the second conductor sidewall 4 are along the short side direction of the substrate 1. The first insulator sidewall 5 and the second insulator sidewall 6 are also rectangular parallelepiped-shaped, and the first insulator sidewall 5 and the second insulator sidewall 6 are along the long side direction of the substrate 1. The first conductor sidewall 3 and the second conductor sidewall 4 are equal in height; the first insulator sidewall 5 and the second insulator sidewall 6 are equal in height. The height of the first insulator side wall 5 is smaller than that of the first conductor side wall 3, which is convenient for observation under an objective lens and is also convenient for the first conductor side wall 3 and the second conductor side wall 4 to be connected with an external circuit. In practical application, the first conductor sidewall 3 and the second conductor sidewall 4 may be connected to a dc power supply, or may be connected to an ac power supply; when the first conductor side wall 3 and the second conductor side wall 4 are connected with a direct current power supply, the temperature of the semiconductor layer 2 is regulated and controlled through the voltage of the direct current power supply; when the first conductor sidewall 3 and the second conductor sidewall 4 are connected to an alternating current power source, the temperature of the semiconductor layer 2 is regulated by the voltage and frequency of the alternating current power source.
When in test, the substrate is placed under an objective lens of a micro-Raman spectrum system, laser emitted by a laser irradiates the substrate through the objective lens, molecules on the substrate generate Raman signals, and the Raman signals are collected through the same objective lens and then enter the spectrum system. Specifically, firstly, precious metal particles and a molecule solution to be detected are dropped into the groove, wherein the surfaces of the precious metal particles are modified by a surfactant so as to link the molecules to be detected. The material of the noble metal particles can be gold, silver and platinum, the shape of the noble metal particles can be spherical, ellipsoidal, cubic or other irregular shapes, and the size of the noble metal particles is more than 10 nanometers and less than 100 nanometers. The substrate is then placed on the stage of a micro-raman system and an external circuit is connected through the first conductor sidewall 3 and the second conductor sidewall 4, creating a current in the semiconductor layer 2 which causes the semiconductor layer 2 to generate heat, thereby causing the temperature around the semiconductor layer to increase. The noble metal particles and the molecular solution to be detected generate a thermophoresis phenomenon, and the noble metal particles move towards the semiconductor layer 2 and are gathered on the surface of the semiconductor layer 2, so that on one hand, the density of the noble metal particles is increased; on the other hand, the distance of the noble metal particles from the semiconductor layer 2 is reduced, and the coupling between the noble metal particles and the semiconductor layer 2 is enhanced. Both of these aspects result in an enhancement of the local electromagnetic field in the vicinity of the noble metal particles and the semiconductor layer 2, thereby increasing the enhancement factor of the surface enhanced raman scattering. In the invention, the thermophoresis phenomenon in the solution can be regulated and controlled through the temperature and the appearance of the semiconductor layer 2 and the voltage applied between the first conductor side wall 3 and the second conductor side wall 4, the regulation and control means is simple, the regulation and control are convenient, and the method has good application prospect in the field of surface-enhanced Raman scattering application.
Example 2
On the basis of example 1, the semiconductor layer 2 was prepared by an electron beam evaporation plating method. When the electron beam evaporation coating method is used for preparing the metal oxide, the normal direction of the substrate is not superposed with the connecting line direction of the substrate and the crucible, and the included angle between the normal direction of the substrate and the connecting line direction of the substrate and the crucible is more than 60 degrees. That is, the metal oxide evaporated from the crucible is obliquely deposited on the substrate, and the metal oxide is obliquely grown on the substrate, thereby forming an uneven surface on the surface of the semiconductor layer 2. The noble metal particles can enter the semiconductor layer 2 more deeply, so that the non-flat surface enables the noble metal particles to be in deeper contact with the semiconductor layer 2, the coupling between the noble metal particles and the semiconductor layer 2 is enhanced, the Raman signal of the molecules to be detected is enhanced, and a higher Raman signal enhancement factor is realized. In addition, the semiconductor layer 2 also has more structural singularities, where a strong electric field is formed, enhancing the raman signal of the molecules.
Example 3
On the basis of example 2, the semiconductor layer 2 was prepared by an electron beam evaporation coating method: firstly, the normal direction of a substrate is superposed with the connecting line direction of the substrate and a crucible, namely, metal oxide evaporated from the crucible is vertically deposited on the substrate to form a film; then, the substrate is rotated so that the normal direction of the substrate does not coincide with the direction of the line connecting the substrate and the crucible, and the angle between the normal direction of the substrate and the direction of the line connecting the substrate and the crucible is larger than 60 degrees, so as to deposit metal oxide particles on the metal oxide film. The finally formed semiconductor layer 2 is: the bottom is a thin film and the top is coarse particles. Such a structure is beneficial to enhancing the structural stability of the semiconductor layer 2, so that the semiconductor layer is stably adhered to the substrate 1, and is also beneficial to generating more heat when the first conductor side wall 3 and the second conductor side wall 4 are connected with an external circuit, and generating higher temperature at the metal oxide particles to form a stronger thermophoresis effect, thereby more regulating and controlling the coupling between the noble metal particles and the semiconductor layer 2, and improving the raman signal intensity of the molecules.
Example 4
In example 3, as shown in fig. 3, a hole 21 is formed in the semiconductor layer 2 in the groove formed by the semiconductor layer 2, the first conductor sidewall 3, the second conductor sidewall 4, the first insulator sidewall 5, and the second insulator sidewall 6. The holes 21 are periodically arranged, and the period of the arrangement of the holes 21 can be a square period or a rectangular period. The diameter of the holes 21 is larger than 10 nanometers and smaller than 1000 nanometers.
When the first conductor side wall 3 and the second conductor side wall 4 are connected to an external power source, a current is generated in the semiconductor layer 2, and the current generates heat, resulting in an increase in the temperature around the semiconductor layer 2, particularly, an increase in the temperature inside the semiconductor layer 2. This causes the noble metal particles to gather toward the semiconductor layer 2 and enter the hole 21, and the noble metal particles gather in the hole 21, which not only enhances the coupling between the semiconductor layer 2 and the noble metal particles, but also enhances the coupling between the noble metal particles, that is, the noble metal particles gather in the hole 21, which enhances the interaction between the incident excitation light and the noble metal particles and the semiconductor layer 2, and increases the local electromagnetic field around the noble metal particles and the semiconductor layer 2, thereby increasing the enhancement factor of the raman scattering enhanced by the surface of the molecule to be measured.
During the preparation, the holes 21 may be arranged periodically or non-periodically. The holes 21 may be formed on the surface of the semiconductor layer 2 by ion beam etching.
Example 5
On the basis of embodiment 4, as shown in fig. 3, the hole 21 does not penetrate the semiconductor layer 2. When the first conductor sidewall 3 and the second conductor sidewall 4 are connected to an external power source, a current is generated in the semiconductor layer 2, and when the current generates heat, noble metal particles are gathered into the hole 21 and gathered to the bottom of the hole 21. At the bottom of the hole 21, there is a strong coupling between the semiconductor layer 2 and the noble metal particles. Compared with embodiment 4, in this embodiment, the noble metal particles and the semiconductor layer 2 have stronger coupling, and the raman signal of the molecule can be enhanced more.
The depth of the hole 21 is greater than 200 nm and less than 1 μm, so as to prevent the semiconductor layer 2 itself from generating strong absorption to the molecular raman signal, resulting in less raman signal to be emitted from the sample, and the objective lens only receives weaker raman signal.
Example 6
In example 5, as shown in fig. 4, the hole 21 has a truncated cone shape, the top of the hole 21 is thick, and the bottom of the hole 21 is thin. When the hole 21 structure is prepared by an ion beam etching method, the hole 21 structure can be prepared by a method of inclining the substrate. When the top of the hole 21 is thick and the bottom of the hole 21 is thin, the noble metal particles can enter the hole 21 more easily, aggregation is formed in the hole 21, the inclined side surface of the hole 21 has a larger contact area with the noble metal particles, and coupling between the semiconductor layer 2 and the noble metal particles is enhanced; in addition, when the side surface of the hole 21 is inclined, the hole 21 can collect incident excitation light more, so that the excitation light field in the hole 21 is enhanced, the local electromagnetic field in the hole 21 is enhanced, and finally the raman signal of the molecule is enhanced.
In addition to the hole 21 being a truncated cone, the hole 21 may also be of other shapes. The technical effect of the present embodiment can be achieved as long as the top of the hole 21 is thick and the bottom of the hole 21 is thin.
In summary, the invention applies the semiconductor layer 2, and the first conductor sidewall 3 and the second conductor sidewall 4 at two ends of the semiconductor layer 2 are connected with an external power supply to generate heat, change the temperature of the semiconductor layer 2, and generate a thermophoresis phenomenon in a solution, so that the noble metal particles are gathered near the semiconductor layer 2, the distance between the noble metal particles and the semiconductor layer 2 is reduced, the coupling between the noble metal particles and the semiconductor layer 2 is enhanced, and the raman signal intensity of the molecule is improved. In the invention, the semiconductor layer 2 is not only used for generating heat and generating thermophoresis effect in solution, but also forms strong coupling with the noble metal particles to form a semiconductor layer 2/noble metal particle composite structure, thereby enhancing the local electromagnetic field near the semiconductor layer 2/noble metal particles and improving the Raman signal intensity of molecules. In the invention, the thermophoresis phenomenon in the solution can be regulated and controlled by changing the appearance of the semiconductor layer 2 and applying the power supply voltage, the frequency and the like between the first conductor side wall 3 and the second conductor side wall 4, so that the coupling between the noble metal particles and the semiconductor layer 2 is enhanced, the regulation and control means is simple, the regulation and control are convenient, and the method has a good application prospect in the field of surface-enhanced Raman scattering application. In addition, the regulation and control means or method provided by the invention has good application potential in the spectrum technologies such as infrared absorption, ultraviolet fluorescence and the like.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.
Claims (10)
1. A semiconductor surface enhanced Raman scattering substrate is characterized by comprising a base, a semiconductor layer, a first conductor side wall, a second conductor side wall, a first insulator side wall and a second insulator side wall; the semiconductor layer is arranged on the substrate, the first conductor side wall, the second conductor side wall, the first insulator side wall and the second insulator side wall are arranged on the semiconductor layer, the periphery of the semiconductor layer is surrounded by grooves, the first conductor side wall and the second conductor side wall are arranged oppositely, and the first insulator side wall and the second insulator side wall are arranged oppositely.
2. The semiconductor surface-enhanced raman scattering substrate of claim 1, wherein: the substrate is made of an insulating material.
3. The semiconductor surface-enhanced raman scattering substrate of claim 1, wherein: the material of the first conductor side wall and the second conductor side wall is metal.
4. The semiconductor surface-enhanced raman scattering substrate of claim 1, wherein: the material of the first insulator side wall and the second insulator side wall is an insulator.
5. The semiconductor surface-enhanced raman scattering substrate of claim 1, wherein: the material of the semiconductor layer is metal oxide.
6. The semiconductor surface-enhanced raman scattering substrate according to claim 5, wherein: the metal oxide is zinc oxide, titanium oxide, copper oxide, silver oxide or ferric oxide.
7. The semiconductor surface-enhanced raman scattering substrate according to any one of claims 1 to 6, wherein: in the groove, a hole is formed in the semiconductor layer.
8. The semiconductor surface-enhanced raman scattering substrate according to claim 7, wherein: the diameter of the holes is larger than 10 nanometers and smaller than 1000 nanometers.
9. The semiconductor surface-enhanced raman scattering substrate according to claim 8, wherein: the holes are periodically arranged.
10. The semiconductor surface-enhanced raman scattering substrate according to claim 9, wherein: the arrangement period of the holes is a square period.
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| CN117929353A (en) * | 2024-03-21 | 2024-04-26 | 延安大学 | Semiconductor heterojunction surface enhanced Raman scattering substrate |
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