Nanoshell in-situ processing and micro-area photoelectric detection method on photovoltaic device

Abstract

The invention relates to an in-situ processing and micro-area photoelectric detection method for a nano shell on a photovoltaic device. The in-situ processing and micro-area photoelectric detection method specifically comprises the following steps: 1, mounting a positioning micro beaker on the photovoltaic device; 2, realizing in-situ assembly of the silver-silicon dioxide core-shell structure by adopting a self-assembly method; 3, finding the nanostructure to be detected under an optical microscope, recording the relative coordinates of the nanostructure to be detected and the microbeaker by means of focused laser, and carrying out photoelectric detection; 4, carrying out in-situ etching on the silver core, finding an original to-be-detected nano structure under a microscope, and carrying out photoelectric detection, wherein the step can be repeated for many times; and 5, testing geometric parameters of the nano shell structure by using an electron microscope, and establishing a relation between the geometric parameters and the previous test results. The method aims at a nano core-shell structure, and solves the problem of accurately finding the same nano structure for in-situ processing and in-situ photoelectric detection.

Description

Technical Field

[0001] The present invention belongs to the field of micro-area optoelectronic measurement, and particularly relates to a method for in-situ processing of nanoshells on a photovoltaic device and micro-area optoelectronic detection. Background Art

[0002] With the development of science and technology, the research on photovoltaic devices has also entered the micron and nanometer scales. Research on devices at the microscale has shown that performance such as the open-circuit voltage generated by photocurrent is closely related to the microstructure. It has become a trend to study photovoltaic devices from the micro-nano scale and then improve their optoelectronic performance.

[0003] Among many nanostructures, metal nanoparticles have become a focus. Metal nanoparticles on the surface of a solar cell interact with incident light, and their surface electrons vibrate and form a local electromagnetic field on the metal surface, enhancing the propagation and absorption of light waves. This is the surface plasmon effect of metal nanoparticles. The local surface plasmon resonance of silver and gold in noble metals is in the ultraviolet to near-infrared band, and such properties have made the research on the plasmon effect of gold and silver highly favored. Although the plasmon effect of metal nanoparticles can improve the performance of solar cells, the metal nanoparticles located on the device surface in contact with air are easily oxidized and deformed, making the enhancement effect on the performance of photovoltaic devices worse. Therefore, some people have tried to use dielectric nanoparticles to replace metal nanoparticles. However, the improvement of the performance of solar cells by single-component nanoparticles is also limited. In order to protect metal nanoparticles and also to maximize their gain effect on photovoltaic devices, researchers have begun to try to coat the metal nanoparticles with a shell. These shells include materials such as metal oxides, noble metals, and electrolytes.

[0004] The development of new nanomaterial devices also requires the development of matching characterization techniques. Due to the fluctuations in the performance of individual photovoltaic devices, in order to prove the performance improvement of photovoltaic devices in previous macroscopic-scale experiments, a large number of devices often needed to be used for statistics. At the micro-nano scale, macroscopic tests are difficult to accurately evaluate the impact of micro-nano structures on device performance, and macroscopic test methods and standards are no longer applicable. Therefore, how to accurately and intuitively measure the impact of nanostructures on the performance of photovoltaic devices has become an urgent problem to be solved.

[0005] The development of micro-area optoelectronic characterization techniques has provided an effective solution for studying the properties of optoelectronic devices at the micron or even nanoscale. However, such techniques often can only detect the influence of nanostructures with specific structural parameters on the performance of optoelectronic devices. When it is desired to study the influence of changes in the geometric parameters of nanostructures on the device, it is often necessary to fabricate structures with different parameters and conduct a large amount of optoelectronic detection and statistical work, because there are often certain errors in the fabrication of nanostructures. To solve this problem, new and more efficient detection schemes need to be proposed, such as combining in-situ fabrication with in-situ detection. However, photovoltaic devices are usually on the centimeter scale, and the number of nanostructures on their surface can reach more than one million. How to accurately find the same nanostructure for in-situ fabrication and in-situ detection has not been reported before. Summary of the Invention

[0006] Technical Problem: The object of the present invention is to provide a method for in-situ fabrication of nanoshells and micro-area optoelectronic detection on a photovoltaic device, aiming at the nanocore-shell structure, to solve the problem of how to accurately find the same nanostructure for in-situ fabrication and in-situ optoelectronic detection.

[0007] Technical Solution: A method for in-situ fabrication of nanoshells and micro-area optoelectronic detection on a photovoltaic device according to the present invention specifically includes the following steps:

[0008] First step: Installation of the positioning of the microbeaker: Array microbeakers (1) with an inner diameter of 100 to 500 microns on the surface of the photovoltaic device.

[0009] Second step: In-situ assembly of the silver-silica core-shell structure: Assemble the dispersed or densely arranged silver-silica core-shell structure in the microbeaker by self-assembly.

[0010] Third step: Positioning and optoelectronic detection of the nanostructure: Under an optical microscope, use a low-power objective lens so that the empty area in the entire microbeaker can be observed in the field of view; switch to a high-power objective lens, find the position of a certain nanostructure to be measured in the microbeaker and irradiate the position with a focused laser; then switch back to the low-power objective lens, take the lowest point of the empty area in the microbeaker as the origin, record the relative coordinates of the laser spot and the origin, and conduct in-situ optoelectronic detection and optical detection.

[0011] Fourth step: In-situ etching of the silver core and optoelectronic detection: Drop a mixture of dilute hydrochloric acid and hydrogen peroxide inside the microbeaker. After etching, the size of the silver core is reduced. According to the relative coordinates of the spot and the origin recorded in the third step, use a focused laser to determine the position of the nanostructure to be measured under the low-power objective lens, switch to the high-power objective lens to find the nanostructure to be measured for optoelectronic detection and optical detection.

[0012] Step 5: Optical microscope - electron microscope correlation test: Under the electron microscope, use the relative coordinates of the laser spot and the origin under the optical microscope to find the position of the nanostructure to be measured, test the size, material, and morphology of the nanoshell structure, and establish the relationship between the geometric parameters of the nanostructure and its impact on the optoelectronic performance of the photovoltaic device.

[0013] Repeat the fourth step multiple times to observe the evolution of the optoelectronic performance of the microregion under different etching degrees; when the microregion detection results are consistent for 2 to 3 times, it is considered that the silver core has been completely etched, and only the silica nanoshell structure remains. The measured optoelectronic performance is the impact of the nanoshell structure on the performance of the photovoltaic device.

[0014] The scale of the microbeaker array is M×N, where 1≤M, N≤10; the microbeaker is annular; its material is copper, gold, polypropylene, quartz, or stainless steel.

[0015] The assembly method of the silver - silica core - shell structure is as follows:

[0016] Method 1: First, disperse the silver - silica core - shell structure in an alcohol solvent to obtain a silver - silica core - shell structure solution; use the oxygen plasma treatment method to perform surface treatment on the photovoltaic device to change its surface from hydrophobic to hydrophilic; place the treated photovoltaic device on a base and put it into a clean container, add an appropriate amount of ultrapure water to submerge the photovoltaic device, and add a small amount of n - hexane. Slowly drip the silver - silica core - shell structure solution until the silver - silica core - shell structure is uniformly and densely arranged on the n - hexane / water interface; slowly evaporate the n - hexane to enable the self - assembly of the silver - silica core - shell structure; when the evaporation of n - hexane is complete, a self - assembled monolayer film of the silver - silica core - shell structure is formed on the n - hexane / water surface; suck out the water under the self - assembled monolayer film to make the self - assembled monolayer film of the silver - silica core - shell structure cover the surface of the photovoltaic device; let it stand or heat it at a low temperature below 45 °C to completely evaporate the moisture on the surface of the photovoltaic device, and complete the assembly of the densely arranged silver - silica core - shell structure.

[0017] The assembly method of the silver - silica core - shell structure is as follows:

[0018] Method 2: First, disperse the silver - silica core - shell structure in an alcohol solvent to obtain a silver - silica core - shell structure solution and dilute it; suck a small amount of the diluted silver - silica core - shell structure solution and drip it into the microbeaker; evaporate the remaining solvent to complete the assembly of the dispersed silver - silica core - shell structure.

[0019] The magnification of the low - power objective lens is 5 times, 10 times, 20 times, or 40 times.

[0020] The magnification of the high - power objective lens is 50 times or 100 times.

[0021] The focused laser is a laser with a visible light wavelength.

[0022] In-situ photoelectric detection includes: volt-ampere characteristics under illumination, quantum efficiency, photocurrent imaging, and photovoltage imaging; optical detection includes: reflection spectroscopy, Raman spectroscopy, fluorescence spectroscopy, fluorescence lifetime detection, scattering spectroscopy, reflection optical imaging, scattering optical imaging, fluorescence imaging, and fluorescence lifetime imaging.

[0023] The mixture of dilute hydrochloric acid and hydrogen peroxide, wherein the concentration of dilute hydrochloric acid is 1 mol / L to 4 mol / L, and hydrogen peroxide is 30% concentrated hydrogen peroxide; the ratio of dilute hydrochloric acid to hydrogen peroxide is 1:1 to 4:1; the volume of the dropped mixture is 1 μL to 2 μL.

[0024] Beneficial effects: Compared with the existing technology, the present invention has the following advantages:

[0025] 1. The method for in-situ processing of nano-shells on a photovoltaic device and micro-area photoelectric detection proposed by the present invention realizes the in-situ positioning, in-situ etching, and photoelectric characterization during the etching evolution process of a single silver-silica core-shell nanostructure by introducing a micro beaker into the micro-area photoelectric detection system.

[0026] 2. Compared with the traditional nano-structure enhanced photovoltaic device detection technology, the present invention proposes a method for in-situ processing of nano-shells on a photovoltaic device and micro-area photoelectric detection. This method does not require processing a large number of photovoltaic devices and conducting macroscopic performance statistics, and can realize mechanism research and structure optimization on the same battery, greatly improving device utilization rate and shortening the research cycle.

[0027] 3. In the same photovoltaic device, multiple micro beakers are constructed. Each micro beaker serves as both a positioning means for the micro-area optical microscopy system and the electron microscope, and a container for self-assembly and etching reactions, which can greatly reduce the concentration of the etching agent, thereby facilitating the control of the reaction rate and reducing by-products. Description of the Drawings

[0028] Figure 1 It is a schematic diagram of a photovoltaic device equipped with 2×2 micro beakers and the in-situ assembly-in-situ etching process.

[0029] Figure 2 It is a schematic diagram of in-situ positioning-in-situ photoelectric detection through a microscopic device.

[0030] Figure 3 It is a schematic diagram of the assembly method process of the silver-silica core-shell structure described in Method 1.

[0031] In the figure: there are micro beakers 1, photovoltaic devices 2, silver-silica core-shell structures 3, low-magnification objective lenses 4, high-magnification objective lenses 5, nanostructures to be measured 6, focused lasers 7, silver-silica core-shell structure solutions 8, and mixtures of dilute hydrochloric acid and hydrogen peroxide 9. Detailed implementation manners

[0032] A method for in-situ processing of nano-shells on a photovoltaic device and micro-region optoelectronic detection according to the present invention specifically includes the following steps:

[0033] First step: Installation of the micro beaker positioning: On the photovoltaic device, an array of rings with an inner diameter of 100 to 500 microns (hereinafter referred to as micro beakers) is installed on the surface of the photovoltaic device using tape, ensuring that the "micro beakers" are stable on the photovoltaic device and will not easily fall off.

[0034] Second step: In-situ assembly of the silver-silica core-shell structure: Dispersed or densely arranged silver-silica core-shell structures are assembled in the "micro beakers" by self-assembly.

[0035] Third step: Positioning and optoelectronic detection of the nanostructure: Under an optical microscope, using a low-magnification objective lens, ensure that the empty area of the complete "micro beaker" can be observed in the field of view. Switch to a high-magnification objective lens, find the position of a certain nanostructure to be measured in the micro beaker, and irradiate the focused laser at this position. Then switch back to the low-magnification objective lens, taking the lowest point of the empty area of the "micro beaker" as the origin, record the relative coordinates of the laser spot and the origin, and perform in-situ optoelectronic detection.

[0036] Fourth step: In-situ etching of the silver core and optoelectronic detection: Drop the mixture of dilute hydrochloric acid and hydrogen peroxide inside the "micro beaker", etch for 30 seconds to 2 minutes to reduce the size of the silver core. Use methods such as rinsing with ultrapure water to wash away the etchant and other impurities, and end the etching reaction. According to the relative coordinates of the spot and the origin recorded in the third step, use the focused laser to determine the position of the nanostructure to be measured under the low-magnification objective lens. Switch to the high-magnification objective lens to find the nanostructure to be measured and perform optoelectronic detection. The above process can be repeated multiple times to observe the evolution of the micro-region optoelectronic properties under different etching degrees. When the micro-region detection results are consistent 2 to 3 times, it can be considered that the silver core has been completely etched, leaving only the silica nano-shell structure, and the measured optoelectronic properties are the influence of the nano-shell structure on the performance of the photovoltaic device.

[0037] Fifth step: Correlation test of the optical microscope - electron microscope: Under the electron microscope, use the relative coordinates of the laser spot and the origin under the optical microscope to find the position of the nanostructure to be measured, test the size, material, morphology, etc. of the nano-shell structure, and establish the relationship between the geometric parameters of the nanostructure and its influence on the optoelectronic properties of the photovoltaic device.

[0038] The materials of the "micro beaker" include: copper, gold, polypropylene, quartz, and stainless steel.

[0039] The scale of the "micro beaker" array is M×N, where 1≤M, N≤10.

[0040] The assembly method of the silver-silica core-shell structure is as follows:

[0041] Method 1: First, disperse the silver-silica core-shell structure in an alcohol solvent to obtain a silver-silica core-shell structure solution; use an oxygen plasma treatment method to perform surface treatment on the photovoltaic device to change its surface from hydrophobic to hydrophilic; place the treated photovoltaic device on a base and put it into a clean container, add an appropriate amount of ultrapure water to submerge the photovoltaic device, and add a small amount of n-hexane, and slowly drop the silver-silica core-shell structure solution until the silver-silica core-shell structure is uniformly and densely arranged on the n-hexane / water interface; slowly evaporate the n-hexane to enable the self-assembly of the silver-silica core-shell structure; when the evaporation of n-hexane is completed, a self-assembled monolayer film of the silver-silica core-shell structure is formed on the n-hexane / water surface; suck out the water under the self-assembled monolayer film to make the self-assembled monolayer film of the silver-silica core-shell structure cover the surface of the photovoltaic device; let it stand or heat it at a low temperature below 45 °C to completely evaporate the water on the surface of the photovoltaic device, and complete the assembly of the densely arranged silver-silica core-shell structure.

[0042] Method 2: First, disperse the silver-silica core-shell structure in an alcohol solvent to obtain a silver-silica core-shell structure solution and dilute it; suck a small amount of the diluted silver-silica core-shell structure solution and drop it into the "micro beaker"; evaporate the remaining solvent to complete the assembly of the dispersed silver-silica core-shell structure.

[0043] The magnification of the low-power objective lens is 5 times, 10 times, 20 times, and 40 times.

[0044] The magnification of the high-power objective lens is 50 times and 100 times.

[0045] The focused laser is a laser with a visible light wavelength.

[0046] The in-situ photoelectric detection includes: volt-ampere characteristics, quantum efficiency, photocurrent imaging, and photovoltage imaging under illumination; the optical detection includes: reflection spectrum, Raman spectrum, fluorescence spectrum, fluorescence lifetime detection, scattering spectrum, reflection optical imaging, scattering optical imaging, fluorescence imaging, and fluorescence lifetime imaging.

[0047] The mixed solution of dilute hydrochloric acid and hydrogen peroxide, where the concentration of dilute hydrochloric acid is 1 mole per liter to 4 moles per liter, and the hydrogen peroxide is 30% concentrated hydrogen peroxide; the ratio of dilute hydrochloric acid to hydrogen peroxide is 1:1 to 4:1; the volume of the dropped mixed solution is 1 microliter to 2 microliters.

[0048] The technical solution of the present invention will be further described below in conjunction with the accompanying drawings.

[0049] A method for in-situ processing of nanoshells and micro-area optoelectronic detection on a photovoltaic device proposed by the present invention, the technical principle of specifically realizing in-situ processing of nanoshells and micro-area optoelectronic detection on a photovoltaic device is as follows:

[0050] After introducing a microbeaker on the photovoltaic device, the microbeaker serves both as a positioning means for the micro-area optical microscopy system and the electron microscope. Under objective lenses with different magnifications, the relative position between the laser beam and the nanostructure to be measured can be located and accurately measured. It can also serve as a container for self-assembly and silver core etching reaction. The mixed solution of dilute hydrochloric acid and concentrated hydrogen peroxide is used as the etchant after being optimized. The chemical reaction equation is: 2Ag + 2HCl + H 2 O 2 = 2AgCl + 2H 2 O. In this reaction, there are the following advantages:

[0051] 1. Selective etching: Etching metal structures has no impact on the battery surface

[0052] 2. No other by-products: After etching, the products do not affect the device performance

[0053] 3. Safety: The reaction can be carried out in the air, without toxic and harmful gases, and the concentration of hydrochloric acid in the reactants is relatively low, with high safety.

[0054] 4. Etching rate control: It can not only achieve etching but also form a structural gradient to realize in-situ detection

[0055] Since the microbeaker has the function of aggregating the mixed solution, and the silver-silica core-shell structure in the microbeaker is monolayer, high-efficiency etching can be achieved when the concentrations of hydrochloric acid and hydrogen peroxide in the etchant mixed solution are relatively low. In contrast, in the macroscopic silver-silica core-shell structure solution, the number of silver-silica core-shell structures is often large, and the concentration of hydrochloric acid in the etchant mixed solution needs to be increased by about one time. Therefore, the microbeaker can also greatly reduce the concentration of the etchant, which is beneficial to controlling the reaction rate, reducing by-products, and increasing safety.

[0056] Example 1:

[0057] Self-assembly of silver-silica core-shell structure is carried out on the photovoltaic device, and the method for in-situ processing of nanoshells and micro-area optoelectronic detection on the photovoltaic device proposed by the present invention is applied. The specific operation steps are as Figure 1 、 Figure 2 and Figure 3 shown:

[0058] Step 1: Installation of the positioning of the micro beaker 1: On the photovoltaic device, a copper ring with an inner diameter of 300 microns is installed on the surface of the photovoltaic device 2 using tape, ensuring that the micro beaker 1 remains stable on the photovoltaic device and does not fall off easily.

[0059] Step 2: In-situ assembly of the silver-silica core-shell structure: Densely arranged silver-silica core-shell structures 3 are assembled in the micro beaker 1 by self-assembly.

[0060] Step 3: Positioning of the nanostructure and optoelectronic detection: Under an optical microscope, using a 10x objective lens 4, the entire empty area in the micro beaker 1 can be observed in the field of view. Switch to a 50x objective lens 5 to find the position of a certain nanostructure 6 to be measured in the micro beaker, and irradiate this position with a focused laser 7 of 532 nm. Then switch back to the 10x objective lens 4. Taking the lowest point of the empty area in the "micro beaker" as the origin, record the relative coordinates of the laser spot and the origin, and perform in-situ quantum efficiency detection.

[0061] Step 4: In-situ etching of the silver core and optoelectronic detection: A 1 μL mixture of dilute hydrochloric acid (1 mol / L) and concentrated hydrogen peroxide prepared in a ratio of 1:1 is dropped into the interior of the "micro beaker" 1 and etched for 30 seconds to reduce the size of the silver core. Wash with ultrapure water to rinse off the etchant and other impurities, ending the etching reaction. According to the relative coordinates of the laser spot and the origin recorded in Step 3, use the focused laser 7 to determine the position of the nanostructure to be measured under the 10x objective lens 4. Switch to the 50x objective lens 5 to find the nanostructure 6 to be measured and perform quantum efficiency detection. Repeat the above process 5 times to observe the evolution of the micro-region quantum efficiency performance under different etching degrees. When the micro-region detection results of the fourth and fifth times are consistent, it can be considered that the silver core has been completely etched, leaving only the silica nanoshell structure, and the measured quantum efficiency is the influence of the nanoshell structure on the quantum efficiency of the photovoltaic device.

[0062] Step 5: Correlation test of optical microscope - electron microscope: Under the electron microscope, use the relative coordinates of the laser spot and the origin under the optical microscope to find the position of the nanostructure 6 to be measured, and test the size, material, morphology, etc. of the nanoshell structure to establish the relationship between the geometric parameters of the nanostructure and its influence on the optoelectronic performance of the photovoltaic device.

[0063] The assembly method of the silver-silica core-shell structure is as follows:

[0064] First, disperse the silver-silica core-shell structure in an alcohol solvent to obtain a silver-silica core-shell structure solution 8; use an oxygen plasma treatment method to perform surface treatment on the photovoltaic device 2 to change its surface from hydrophobic to hydrophilic; place the treated photovoltaic device on a base and put it into a clean container together, add an appropriate amount of ultrapure water to submerge the photovoltaic device, and add a small amount of n-hexane. Slowly drop the silver-silica core-shell structure solution 8 until the silver-silica core-shell structure 3 is uniformly and densely arranged on the n-hexane / water interface; slowly evaporate the n-hexane to self-assemble the silver-silica core-shell structure 3; when the evaporation of the n-hexane is completed, a self-assembled monolayer film of the silver-silica core-shell structure 3 is formed on the n-hexane / water surface; suck out the water under the self-assembled monolayer film so that the self-assembled monolayer film of the silver-silica core-shell structure 3 covers the surface of the photovoltaic device 2; let it stand or heat it at a low temperature below 45 °C to completely evaporate the water on the surface of the photovoltaic device 2, and complete the assembly of the densely arranged silver-silica core-shell structure.

Claims

1. A method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection, characterized in that The specific steps include: Step 1: Installation of positioning micro-beakers (1): An array of micro-beakers (1) with an inner diameter of 100 to 500 micrometers is installed on the surface of the photovoltaic device (2); Step 2: In-situ assembly of the silver-silicon dioxide core-shell structure (3): assembling dispersed or densely arranged silver-silicon dioxide core-shell structures (3) in the micro-beaker (1) by self-assembly; Step 3: Positioning and photoelectric detection of nanostructures: Under an optical microscope, a low-power objective lens (4) is used to observe the complete hollow area of ​​the microbeaker (1) in the field of view; the high-power objective lens (5) is switched to find the position of a nanostructure (6) to be measured in the microbeaker and irradiate the position with a focused laser (7); then the low-power objective lens (4) is switched back to take the lowest point of the hollow area of ​​the microbeaker (1) as the origin, the relative coordinates of the laser spot and the origin are recorded, and in-situ photoelectric detection and optical detection are performed; Step 4: In-situ etching and photoelectric detection of the silver core: a mixture of dilute hydrochloric acid and hydrogen peroxide (9) is dripped into the micro-beaker (1), and the size of the silver core is reduced after etching. According to the relative coordinates of the light spot and the origin recorded in the third step, the position of the nanostructure to be measured (6) is determined under the low-power objective lens (4) with the help of a focused laser (7), and the nanostructure to be measured (6) is found by switching to a high-power objective lens (5) for photoelectric detection and optical detection; Step 5: Optical microscope-electron microscope correlation test: Under an electron microscope, the relative coordinates of the laser spot and the origin under the optical microscope are used to find the position of the nanostructure to be tested (6), and the size, material and morphology of the nanoshell structure are tested to establish the relationship between the geometric parameters of the nanostructure and its effect on the photoelectric performance of the photovoltaic device (2).

2. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The fourth step is repeated multiple times to observe the evolution of the photoelectric performance of the micro-area under different etching degrees; when the micro-area detection results are consistent for 2 to 3 times, it is considered that the silver core has been completely etched and only the silicon dioxide nanoshell structure remains. The measured photoelectric performance is the influence of the nanoshell structure on the performance of the photovoltaic device (2).

3. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The scale of the micro-beaker (1) array is M×N, wherein 1≤M, N≤10; the micro-beaker (1) is in the shape of a ring; and its material is copper, gold, polypropylene, quartz or stainless steel.

4. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The assembly method of the silver-silicon dioxide core-shell structure (3) is: Method 1: First, the silver-silicon dioxide core-shell structure (3) is dispersed in an alcohol solvent to obtain a silver-silicon dioxide core-shell structure solution (8); the photovoltaic device (2) is surface treated by an oxygen plasma treatment method to change its surface from hydrophobic to hydrophilic; the treated photovoltaic device (2) is placed on a base and placed in a clean container, an appropriate amount of ultrapure water is added to cover the photovoltaic device (2), and a small amount of n-hexane is added, and the silver-silicon dioxide core-shell structure solution (8) is slowly added dropwise until the silver-silicon dioxide core-shell structure (3) is evenly and densely arranged on the positive The invention relates to a method for preparing a photovoltaic device (2) comprising: placing the photovoltaic device (2) on a hexane / water interface; slowly evaporating the n-hexane to allow the silver-silicon dioxide core-shell structure (3) to self-assemble; after the n-hexane is evaporated, a self-assembled monolayer film of the silver-silicon dioxide core-shell structure (3) is formed on the n-hexane / water surface; sucking out the water in the lower layer of the self-assembled monolayer film to allow the self-assembled monolayer film of the silver-silicon dioxide core-shell structure (3) to cover the surface of the photovoltaic device (2); allowing the water on the surface of the photovoltaic device (2) to completely evaporate by standing or heating at a temperature below 45 degrees Celsius, thereby completing the assembly of the densely arranged silver-silicon dioxide core-shell structure (3).

5. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The assembly method of the silver-silicon dioxide core-shell structure (3) is: Method 2: First, the silver-silicon dioxide core-shell structure (3) is dispersed in an alcohol solvent to obtain a silver-silicon dioxide core-shell structure solution (8) and then diluted; a small amount of the diluted silver-silicon dioxide core-shell structure solution (8) is taken and dripped into a micro-beaker (1); the residual solvent is evaporated to complete the assembly of the dispersed silver-silicon dioxide core-shell structure (3).

6. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The magnification of the low-power objective lens (4) is 5 times, 10 times, 20 times, and 40 times.

7. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The magnification of the high-power objective lens (5) is 50 times or 100 times.

8. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The focused laser (7) is a laser with a visible light wavelength.

9. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that In-situ photoelectric detection includes: volt-ampere characteristics under illumination, quantum efficiency, photocurrent imaging, and photovoltage imaging; optical detection includes: reflection spectroscopy, Raman spectroscopy, fluorescence spectroscopy, fluorescence lifetime detection, scattering spectroscopy, reflection optical imaging, scattering optical imaging, fluorescence imaging, and fluorescence lifetime imaging.

10. The method for in-situ processing of nanoshells on photovoltaic devices and micro-area photoelectric detection according to claim 1, characterized in that The mixed solution (9) of dilute hydrochloric acid and hydrogen peroxide, wherein the concentration of the dilute hydrochloric acid is 1 mol / L to 4 mol / L, the hydrogen peroxide is 30% concentrated hydrogen peroxide; the ratio of the dilute hydrochloric acid to the hydrogen peroxide is 1:1 to 4:1; and the volume of the mixed solution added dropwise is 1 μL to 2 μL.

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