Silver-modified copper oxide compound eye array SERS (Surface Enhanced Raman Scattering) substrate with self-cleaning function
By modifying the copper oxide compound eye array SERS substrate with silver, the problems of high preparation cost, low sensitivity and signal inhomogeneity in the existing technology are solved, and the self-cleaning function and recyclability are achieved, which improves the efficiency and signal stability of SERS detection.
Patent Information
- Application Number
- CN202520709212.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-15
- Publication Date
- 2026-01-27
- Estimated Expiration
- 2035-04-15
AI Technical Summary
Existing SERS substrates are costly to prepare, have low detection sensitivity, uneven signal spatial distribution, and are difficult to clean, which affects detection efficiency and signal stability.
A silver-modified copper oxide compound eye array SERS substrate, comprising a supporting substrate, a PS microsphere array, a copper oxide compound eye array, and silver nanoparticles, is prepared by vapor deposition to form a large-area ordered structure. The self-cleaning function is achieved by photocatalytic degradation of adsorbed molecules.
It achieves low cost, high sensitivity, uniform signal distribution, and recyclability, reducing detection costs and improving detection efficiency and signal stability.
Smart Images
Figure CN223841782U_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of nanomaterials and surface-enhanced Raman scattering technology, and relates to a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function. Background Technology
[0002] Surface-enhanced Raman scattering (SERS) is a spectroscopic detection technique with single-molecule recognition capabilities, widely used in medical diagnostics, chemical engineering, life sciences, and environmental protection. Constructing inexpensive, high-performance SERS substrates is of significant application value. The detection sensitivity, spatial distribution uniformity, and substrate recyclability of the Raman signal are important indicators for evaluating SERS substrate performance. Currently, SERS substrates composed of noble metal nanoparticle aggregates with high-density electromagnetic "hot spots" can be prepared using chemical methods, but the spatial distribution uniformity of the SERS signal is poor. Highly ordered noble metal micro / nano array structures can be constructed using physical precision fabrication methods, achieving high-sensitivity and spatially uniform SERS signal detection, but the preparation process is cumbersome and costly. Furthermore, the noble metal micro / nano structures prepared by these methods are difficult to remove after adsorbing probe molecules, requiring a new SERS substrate for each detection, increasing the time and cost of SERS detection, affecting the stability of the SERS signal, and limiting their application in SERS detection. Therefore, there is an urgent need to develop a SERS substrate with low preparation cost, high detection sensitivity, uniform signal spatial distribution, and self-cleaning function to reduce the cost of SERS detection and improve detection efficiency. Summary of the Invention
[0003] The purpose of this invention is to provide a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function, which improves the sensitivity and signal spatial distribution uniformity of SERS detection, enables the SERS substrate to be recycled, and reduces the cost of SERS detection.
[0004] To achieve the above objectives, the technical solution adopted by this utility model is as follows:
[0005] A silver-modified copper oxide compound eye array SERS substrate with self-cleaning function includes: a support substrate; a polystyrene (PS) microsphere array disposed on the upper surface of the support substrate; a copper oxide compound eye array disposed on the upper surface of the PS microsphere array; and silver nanoparticles disposed on the upper surface of the copper oxide compound eye array structure.
[0006] Furthermore, the supporting substrate material is a silicon-based material, including monocrystalline silicon, polycrystalline silicon, or silicon dioxide.
[0007] Furthermore, the diameter of the PS microspheres is 1~20 μm, the cavity structure diameter of the copper oxide compound eye array is 150~600 nm, and the ratio of the diameter of the PS microspheres to the cavity structure diameter of the copper oxide compound eye array is greater than 5.
[0008] Furthermore, the silver nanoparticles are prepared by vapor deposition, with a vapor deposition thickness of 10~30 nm.
[0009] The principle of this invention lies in the following: When light is incident on a silver-modified copper oxide compound eye array SERS substrate, the cavity array structure efficiently confines the light field from free space within the cavity and interacts with the silver nanoparticles on the cavity surface, forming a strong local electric field. This strong local electric field efficiently excites the Raman spectra of probe molecules adsorbed on the substrate surface, improving the SERS detection sensitivity. Under white light irradiation, the silver-modified copper oxide compound eye array SERS substrate can catalytically degrade molecules adsorbed on the substrate, exhibiting excellent self-cleaning ability and enabling the recycling of the SERS substrate.
[0010] Beneficial effects of this invention: This invention provides a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function, which has the following advantages:
[0011] (1) The preparation process is simple, easy to operate, and low in cost;
[0012] (2) It has a large-area and highly ordered double-period structure, and has excellent spatial distribution uniformity of SERS signals;
[0013] (3) It has excellent SERS signal detection sensitivity;
[0014] (4) It has excellent recycling capabilities. Attached Figure Description
[0015] Figure 1 This is a schematic diagram of a silver-modified copper oxide compound eye array (SERS) substrate with self-cleaning function according to this utility model.
[0016] Figure 2 This is a flowchart illustrating the fabrication process of a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function, as provided in Embodiment 1 of this utility model.
[0017] Figure 3 This is a scanning electron microscope image of the copper oxide compound eye array structure prepared in Embodiment 1 of this utility model.
[0018] Figure 4 This is a scanning electron microscope image of the silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 of this utility model.
[0019] Figure 5This is an XRD pattern of the copper oxide compound eye array structure prepared in Example 1 of this utility model.
[0020] Figure 6 This is the Raman spectrum of the silver-modified copper oxide compound eye array SERS substrate prepared according to this invention against R6G solutions of different concentrations.
[0021] Figure 7 (a) is the SERS spectrum of the silver-modified copper oxide compound eye array SERS substrate prepared according to this invention at 30 random positions; (b) is the Raman characteristic peak at 612 cm⁻¹. -1 Intensity distribution histogram at the location.
[0022] Figure 8 (a) shows the SERS substrate of the silver-modified copper oxide compound eye array prepared according to this invention, with an adsorption concentration of 10. -8 The R6G molecule of M was subjected to SERS spectroscopy three times. (b) shows the Raman characteristic peak at 612 cm⁻¹. -1 The relationship between intensity and number of cycles.
[0023] In the figure: 1. Supporting substrate; 2. Polystyrene (PS) microsphere array; 3. Copper oxide compound eye array; 4. Silver nanoparticles; 5. Copper film; 6. Second PS microsphere array. Detailed Implementation
[0024] The technical solution of this utility model will now be described in detail with reference to the accompanying drawings and specific embodiments. In the drawings, the same reference numerals always indicate the same parts.
[0025] like Figure 1 As shown, a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function is disclosed. The substrate includes: a support substrate 1; a PS microsphere array 2 disposed on the upper surface of the support substrate 1; a copper oxide compound eye array 3 disposed on the upper surface of the PS microsphere array 2; and silver nanoparticles 4 disposed on the upper surface of the copper oxide compound eye array structure 3.
[0026] The supporting substrate material 1 is a silicon-based material, including monocrystalline silicon, polycrystalline silicon, or silicon dioxide.
[0027] The PS microspheres 2 have a diameter of 1~20 μm, the cavity structure diameter of the copper oxide compound eye array 3 has a diameter of 150~600 nm, and the ratio of the diameter of the PS microspheres 2 to the cavity structure diameter of the copper oxide compound eye array 3 is greater than 5.
[0028] The silver nanoparticles 4 are prepared by vapor deposition, with a vapor deposition thickness of 10~30 nm.
[0029] Example 1
[0030] like Figure 2 The diagram shown is a flowchart of the preparation process and a schematic diagram of each step in Embodiment 1 of this utility model. Embodiment 1 of this utility model describes a method for preparing a silver-modified copper oxide compound eye array SERS substrate with self-cleaning function, comprising the following steps:
[0031] S1: As Figure 2 As shown in -A, a single layer of closely packed PS microsphere array 2 is self-assembled on the surface of a cleaned support substrate 1. The diameter of the PS microsphere array 2 is 1~20 μm, preferably 2 μm.
[0032] S2: As Figure 2 As shown in -B, the substrate obtained in step S1 is placed in a plasma cleaner and etched at low speed for 3 to 10 minutes to reduce the diameter of the PS microsphere array 2, preferably 6 minutes.
[0033] S3: As Figure 2 As shown in -C, a copper film 5 with a thickness of 100~300 nm, preferably 200 nm, is deposited on the upper surface of the substrate PS microsphere array 2 obtained in step S2 using vacuum thermal evaporation technology.
[0034] S4: As Figure 2 As shown in -D, a single-layer densely packed PS microsphere array 6 is self-assembled on the upper surface of the substrate obtained in step S3. The diameter of the PS microsphere array 6 is 150~600 nm, preferably 350 nm.
[0035] S5: As Figure 2 As shown in -E, an appropriate amount of sodium hypochlorite solution with a concentration of 10% is dropped onto the substrate obtained in step S4. After natural drying, it is rinsed with chloroform solution to remove the PS microsphere array 6 and obtain the copper oxide compound eye array structure 3.
[0036] S6: As Figure 2 As shown in -F, silver particles 4 are modified on the surface of copper oxide compound eye array structure 3 using vacuum thermal evaporation technology to obtain silver-modified copper oxide compound eye array SERS substrate. The thickness of the silver evaporation is 10~30 nm, preferably 18 nm.
[0037] Figure 3 and Figure 4 The images shown are SEM images of a copper oxide compound eye array structure and a silver-modified copper oxide compound eye array SERS substrate, respectively, exhibiting a large-area and highly ordered dual-period structure. Figure 5 The image shows the XRD pattern of the copper oxide compound eye array structure. The peaks at 32.49° and 61.53° correspond to the (-110) and (-113) crystal planes of CuO, respectively.
[0038] Example 2
[0039] The SERS detection sensitivity and signal spatial distribution uniformity of the silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 were evaluated.
[0040] The silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 was placed in a solution with a concentration of 10... -7 ~10 -10 After soaking in a Rhodamine 6G (R6G) ethanol solution for 60 minutes and drying with nitrogen, the silver-modified copper oxide compound eye array SERS substrate was irradiated with a 50 μW laser at a wavelength of 532 nm. The SERS spectrum was measured as follows: Figure 6 As shown. The substrate exhibits high SERS detection sensitivity at an R6G concentration of 10. -10 Even at M, the Raman peak signal of the R6G molecule can still be detected.
[0041] The two silver-modified copper oxide compound eye arrays prepared in Example 1 were adsorbed onto SERS substrates with a concentration of 10. -7 The R6G molecule of M was randomly selected at 15 different locations on each substrate, and its Raman spectrum was measured. Figure 7 As shown, the 30 Raman spectra are basically consistent. The calculated Raman peak intensity is at 612 cm⁻¹. -1 The relative standard deviation at 6.4% indicates that the SERS substrate prepared in Example 1 has good spatial distribution uniformity of SERS signals.
[0042] Example 3
[0043] The photocatalytic degradation and recycling capacity of the silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 were tested.
[0044] The silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 was placed in a solution with a concentration of 10... -8 After soaking in the R6G solution of M for 60 minutes, the substrate was dried with nitrogen and subjected to Raman spectroscopy. The SERS substrate was then placed in deionized water and photocatalytically degraded under a xenon lamp for 60 minutes. The substrate was then removed, dried with nitrogen, and the corresponding Raman spectrum was measured again. The characteristic peak of the R6G molecule disappeared, indicating that the probe molecules adsorbed on the substrate had been catalytically degraded. After three consecutive cycles, the SERS substrate maintained good enhancement and degradation capabilities, such as... Figure 8 As shown, the silver-modified copper oxide compound eye array SERS substrate prepared in Example 1 of this invention has good photocatalytic degradation and recycling capabilities.
[0045] The above embodiments provide a detailed description of a silver-modified copper oxide compound eye array SERS substrate. This description is illustrative rather than limiting. Many equivalent substitutions and improvements can be made without departing from the principle of this utility model, and these should also be considered within the scope of protection of this utility model.
Claims
1. A silver-modified copper oxide compound eye array SERS substrate with self-cleaning function, characterized in that, The SERS substrate includes: a supporting substrate; a polystyrene (PS) microsphere array disposed on the upper surface of the supporting substrate; a copper oxide compound eye array disposed on the upper surface of the PS microsphere array; and silver nanoparticles disposed on the upper surface of the copper oxide compound eye array structure.
2. The silver-modified copper oxide compound eye array SERS substrate with self-cleaning function according to claim 1, characterized in that, The supporting substrate material is a silicon-based material, including monocrystalline silicon, polycrystalline silicon, or silicon dioxide.
3. The silver-modified copper oxide compound eye array SERS substrate with self-cleaning function according to claim 1, characterized in that, The diameter of the PS microspheres is 1~20 μm, the cavity structure diameter of the copper oxide compound eye array is 150~600 nm, and the ratio of the diameter of the PS microspheres to the cavity structure diameter of the copper oxide compound eye array is greater than 5.
4. The silver-modified copper oxide compound eye array SERS substrate with self-cleaning function according to claim 1, characterized in that, The silver nanoparticles are prepared by vapor deposition, with a vapor deposition thickness of 10~30 nm.