In-situ electrochemical Z scanning spectrum system

Abstract

The utility model relates to the field of non-linear optics, and particularly provides an in-situ electrochemical Z scanning spectrum system which comprises a laser and a light detector which are arranged at the same height, a focusing lens is arranged between the laser and the light detector, a sample moving mechanism is further arranged between the focusing lens and the light detector, the focusing lens is a plano-convex lens, and the sample moving mechanism is arranged between the plano-convex lens and the light detector. One side of the plane faces the sample moving mechanism, the focus of the focusing lens is located at the light height position corresponding to the length center position of the sample moving mechanism, the power-up mechanism is fixedly arranged on the sample moving mechanism, and a to-be-tested sample is arranged on the side, close to the focusing lens, of the power-up mechanism. According to the power-up mechanism, the nonlinear optical characteristics of the sample are changed by applying voltage, and in-situ detection of the electrically-controlled nonlinear optical response of the material is achieved. The dynamic behavior of the material under the action of an electric field can be researched, important support is provided for developing tunable optical devices such as electro-optical modulators and dynamic optical limiters, and application and development of photoelectric functional materials are promoted.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of nonlinear optics, in particular, to an in-situ electrochemical Z-scan spectroscopy system. BACKGROUND

[0002] Z-scan technique is a technique for studying the third-order nonlinear optical properties of materials by irradiating a sample with laser light and recording the change in transmitted or scattered light intensity with the position of the sample. It can be used to obtain the nonlinear refractive index and nonlinear absorption coefficient of the material. This is crucial for understanding the response of materials under strong light fields and can be used to analyze the optical behavior of samples such as optical limiting performance, self-focusing effect, and multi-photon absorption. This makes the sample have a wide range of applications in optoelectronic devices such as optical limiters, all-optical switches, and optical memories.

[0003] Z-scan testing of samples under electric field regulation can obtain the response of the Z-scan curve of the sample to different intensity electric fields. Studying the electro-optic effect and optical nonlinear properties of the sample under the action of an external electric field can reveal the electrically controlled nonlinear optical response characteristics of the material, including the electro-optic coefficient, the photorefractive effect, and its modulation depth. These characteristics are crucial for the development of tunable optical devices such as electro-optic modulators, electrically controlled all-optical switches, and dynamic optical limiters. Studying the Z-scan of the sample under applied voltage can provide key parameters for designing new functional materials and expanding the application of materials in the fields of optical communication, photonics, laser control, and high-sensitivity optical sensing.

[0004] Existing Z-scan testing systems mainly rely on optical elements and laser technology to measure the nonlinear optical properties of materials by changing the intensity, wavelength, and other parameters of the laser. However, these traditional Z-scan testing systems usually measure under static conditions and cannot achieve in-situ observation of the dynamic response of materials under electrical stimulation. This poses obstacles to understanding the physical mechanisms of materials, developing new functional materials, and optimizing the performance of existing materials. That is, the existing Z-scan system lacks in-situ electrical regulation capability and cannot comprehensively and deeply study the behavior of materials under the coupling of electricity and light, limiting the development of tunable optical devices such as electro-optic modulators and dynamic optical limiters. UTILITY MODEL CONTENT

[0005] The utility model aims at the deficiency in the prior art, provides a kind of in-situ electrochemical Z-scan spectroscopy system, to solve the problem of lack of in-situ electrical regulation capability of Z-scan system in prior art.

[0006] Further, the specific way of power-on is analyzed for the above problem:

[0007] The direct arrangement of the sample on the conductive substrate and the application of voltage to the sample through the conductive substrate are simple in structure and easy to implement, but the uneven distribution of the electric field affects the accurate measurement of the electro-optic effect; the arrangement of the sample on the conductive substrate and in the photoelectrochemical cell has the advantages that the electrolyte can provide a stable ionic environment, the electric field is more uniformly distributed, and the electrochemical state of the sample can be accurately controlled and detected by arranging the reference electrode and the counter electrode; the optical nonlinear characteristics of the sample under different electrochemical conditions can be studied, and the dynamic response behavior of the sample under the electrochemical driving can be revealed, thereby providing more experimental basis for the development of electrochemical optical devices and functional materials.

[0008] The electrolyte in the photoelectrochemical cell can absorb the transmitted light. Since the Z-scan technology analyzes the nonlinear optical response of the sample by recording the change of the transmitted light intensity with the sample position, when the light intensity is large at the focal point, the absorption of the electrolyte will cause part of the light energy to be absorbed by the solution, thereby reducing the light intensity transmitted through the sample and affecting the detection result. This can mask the nonlinear optical characteristics of the sample itself or distort the measurement signal, resulting in errors and inaccurate experimental data. In the electrolyte, photoexcitation processes such as photoelectrochemical reactions or temperature rise of the solution can further change the properties of the electrolyte, causing the refractive index, absorption coefficient, etc. of the electrolyte to change with light, thereby interfering with the Z-scan measurement. The present application reduces the length of the electrolyte solution in the direction of the light path to reduce the absorption of the light signal by the electrolyte solution, and proposes a sandwich type power supply mechanism for use in a Z-scan system. Further, the solid electrolyte layer used in the Z-scan system of the present application avoids the influence of the changes of the refractive index and temperature of the electrolyte on the Z-scan test results.

[0009] To achieve the above object, the technical scheme adopted by the utility model is as follows:

[0010] The present application provides an in-situ electrochemical Z-scan spectral system, which comprises a laser and a light detector arranged at the same height, a focusing lens arranged between the laser and the light detector, a sample moving mechanism arranged between the focusing lens and the light detector, the focusing lens being a plano-convex lens with the plane side facing the sample moving mechanism, the focal point of the focusing lens being at the light height corresponding to the length center position of the sample moving mechanism, a power supply mechanism fixedly arranged on the sample moving mechanism, and a sample to be measured arranged on the side of the power supply mechanism close to the focusing lens.

[0011] Further, the power supply mechanism comprises a first conductive substrate and a second conductive substrate arranged oppositely, the conductive surfaces of the first conductive substrate and the second conductive substrate facing each other, and the sample to be measured being arranged on the conductive surface of the first conductive substrate.

[0012] Further, the solid-state electrolyte layer is arranged between the first conductive substrate and the second conductive substrate, and contacts the conductive surface of the second conductive substrate and the sample to be measured.

[0013] Further, the photoelectrochemical testing structure comprises a third conductive substrate, a sealing ring, and a fourth conductive substrate, the sealing ring is fixedly connected to the conductive surfaces of the third conductive substrate and the fourth conductive substrate, and a closed cavity is formed among the sealing ring, the conductive surface of the third conductive substrate, and the conductive surface of the fourth conductive substrate, the closed cavity is filled with electrolyte, and the sample to be measured is arranged on the conductive surface of the third conductive substrate and contacts the electrolyte.

[0014] Further, the power supply mechanism comprises a transparent electrolytic cell, the fifth conductive substrate is arranged in the middle of the transparent electrolytic cell, the conductive surface of the fifth conductive substrate is provided with the sample to be measured, the light path is perpendicular to the sample to be measured, the fifth conductive substrate is connected to the working electrode and fixed to the cover of the transparent electrolytic cell, the electrolyte in the transparent electrolytic cell is immersed in the sample to be measured, and the counter electrode and the reference electrode are arranged on both sides of the fifth conductive substrate in the electrolyte.

[0015] Further, the focusing lens is provided with a first light barrier on the side close to the laser, and a second light barrier is arranged between the sample moving mechanism and the light detector.

[0016] Further, a chopper is arranged between the laser and the first light barrier, the chopper is connected to the lock-in amplifier, and the lock-in amplifier and the sample moving mechanism are connected to the computer.

[0017] Further, a light parametric amplifier and a first light attenuating sheet are sequentially arranged between the laser and the chopper, and the light parametric amplifier is close to the laser.

[0018] Further, a first total reflection mirror and a second total reflection mirror are arranged between the light parametric amplifier and the first light attenuating sheet, the light output by the light parametric amplifier enters the first total reflection mirror, and the light emitted by the second total reflection mirror is irradiated on the first light attenuating sheet; further, a second light attenuating sheet is arranged between the second light barrier and the light detector.

[0019] Further, a two-dimensional translation stage is arranged between the power supply mechanism and the sample moving mechanism, the two-dimensional translation stage is fixedly arranged on the moving table of the sample moving mechanism, and the power supply mechanism is fixed to the two-dimensional translation stage.

[0020] Compared with the prior art, the photoelectrochemical testing structure has the following beneficial effects:

[0021] (1) The power-on mechanism applies voltage to the Z-scan sample, changing the original nonlinear characteristics of the sample, so that the nonlinear characteristics of the sample under different intensity electric fields can be detected; the electrically controlled nonlinear optical response of the material is studied, which is of great significance to the development of tunable optical devices such as electro-optic modulators and dynamic optical limiters.

[0022] (2) The sample to be tested is arranged on the side of the power-on mechanism close to the focusing lens, and the light beam first irradiates on the sample and then transmits through the electrolyte; the sample first receives high-intensity, undamped laser light field, and if it first passes through the electrolyte, the scattering and thermal lens effect of the electrolyte will change the spatial distribution of the light field, so that the light field interacting with the sample is no longer a Gaussian beam, affecting the generation of nonlinear signals, therefore, the nonlinear optical characteristics of the sample can be more significantly exhibited.

[0023] (3) The system can detect the photoelectric characteristics of the sample while detecting the nonlinear optical characteristics; at the same time, when the sample is far away from the waist of the Gaussian beam, the linear photoelectric characteristics can be measured, and at the focal point, the nonlinear characteristics of the detector can be detected. The system can realize in-situ electric regulation and optical characteristic measurement in the same test environment, and combines electrical and optical technologies, changes the electrical properties of the material through the in-situ electric regulation device, and measures the changes of the nonlinear optical characteristics in real time by using the Z-scan technology, so as to obtain the behavior of the material under the coupling effect of electricity and optics, and provide a new perspective and method for the research and development of materials.

[0024] (4) The solid electrolyte avoids the light absorption and scattering effect of the liquid electrolyte when the light intensity is large at the focal point, which may cause the weakening and distortion of the transmitted light signal, thereby masking the real nonlinear optical characteristics of the sample. Secondly, the solid electrolyte can effectively suppress the photo-thermal effect and photo-chemical reaction, which are common in liquid electrolyte and can cause changes in the optical parameters such as the refractive index and absorption coefficient of the electrolyte, thereby interfering with the Z-scan measurement.

[0025] (5) The application also uses a sealing ring and two conductive substrates to form a sandwich type power-on mechanism, and the length of the electrolyte along the light path direction is the thickness of the sealing ring, which is much smaller than the thickness of the general electrolytic cell. The reduction of the thickness makes the absorption of the electrolyte to the light field smaller, so that the intensity of the Z-scan signal is larger, and the detection result is more accurate.

[0026] In summary, the invention of the in-situ electrochemical Z-scan spectrum system has important significance for promoting the development of the fields of material science and optical engineering. It not only solves the limitations in the prior art, but also provides a powerful tool for the research and development of new materials. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1The utility model provides a kind of in-situ electrochemical Z scanning spectrum system's schematic diagram provided by the utility model;

[0028] Figure 2 The utility model provides a kind of in-situ electrochemical Z scanning spectrum system in the schematic diagram of power supply mechanism provided by embodiment 1;

[0029] Figure 3 The utility model provides a kind of in-situ electrochemical Z scanning spectrum system in the schematic diagram of power supply mechanism and electrochemical workstation three-electrode system connection provided by the utility model;

[0030] Figure 4 The utility model provides a kind of in-situ electrochemical Z scanning spectrum system in the schematic diagram of power supply mechanism provided by embodiment 2;

[0031] Figure 5 The utility model provides a kind of in-situ electrochemical Z scanning spectrum system in the schematic diagram of power supply mechanism and source table formation two-electrode system connection provided by embodiment 2;

[0032] Figure 6 The utility model provides a kind of in-situ electrochemical Z scanning spectrum system in the schematic diagram of power supply mechanism provided by embodiment 3.

[0033] Icon: 1-laser; 2-optical probe; 3-focusing lens; 4-sample moving mechanism; 5-power supply mechanism; 51-solid electrolyte layer; 52-first conductive base; 53-second conductive base; 54-third conductive base; 55-sealing ring; 56-fourth conductive base; 6-first diaphragm; 7-second diaphragm; 8-chopper; 9-lock-in amplifier; 10-computer; 11-optical parametric amplifier; 12-first optical attenuator; 13-first total reflection mirror; 14-second total reflection mirror; 15-second optical attenuator. DETAILED DESCRIPTION

[0034] In order to make the implementation process of the utility model more clear, the following will be combined with the drawing to be explained in detail.

[0035] Embodiment 1:

[0036] The utility model provides a kind of in-situ electrochemical Z scanning spectrum system, such as Figure 1As shown, the system comprises a laser 1 and a light detector 2 arranged at the same height, the height of the laser 1 and the light detector 2 is the optical height of the spectral system, and other optical devices are in the optical path. The laser 1 is an fs pulse laser with a central wavelength of 800 nm, a repetition frequency of 1 kHz, and a pulse width of 150 fs, which provides a light source for the optical path; the light detector 2 is a light power meter, which is used to detect the light intensity projected through the sample, and the moving position of the sample is taken as the horizontal coordinate and the light intensity is taken as the vertical coordinate to form a Z-scan spectrum. The optical elements in the application are fixed and arranged on the optical platform by positioning screws or element racks; further, in order to reduce the influence of dust and airflow in the surrounding environment on the detection process, the system can be placed in a transparent cover or other optical cage cover system. The focusing lens 3 is arranged between the laser 1 and the light detector 2, and the focusing lens 3 is a plano-convex lens, which focuses the light field, and the light field forms a Gaussian beam after passing through the focusing lens 3, and the waist of the beam is the focal point. The plane side of the focusing lens 3 faces the sample moving mechanism 4. The focal point of the focusing lens 3 is located between the focusing lens 3 and the light detector 2.

[0037] The sample moving mechanism 4 is further arranged between the focusing lens 3 and the light detector 2, and the electrifying mechanism 5 is fixedly arranged on the sample moving mechanism 4. The focal point of the focusing lens 3 is located at the optical height corresponding to the length center position of the sample moving mechanism 4, and the sample to be measured is arranged on the electrifying mechanism 5 close to the focusing lens 3. In this way, it can be ensured that the laser beam is not affected by the absorption and scattering of the electrolyte solution before passing through the sample, so as to maintain the high intensity and high quality of the light field; the sample first receives the undamped laser light field, and the generated optical nonlinear response is strong. If the light beam passes through the electrolyte solution first, the electrolyte will cause scattering, absorption and thermal lens effect of the light field, change the spatial distribution of the light beam, especially in the focusing area, the light field will deviate from the Gaussian beam mode, and then affect the interaction between the sample and the light field, reduce the generation of nonlinear effect. Therefore, the sample is arranged on the side close to the focusing lens 3, which avoids the interference of the electrolyte on the light field, can more accurately show the nonlinear optical properties of the sample, and improves the signal-to-noise ratio and measurement accuracy of the Z-scan test.

[0038] The sample moving mechanism 4 comprises a stepping motor track and a moving table fixedly arranged on the free end of the track; further, a two-dimensional translation table is further arranged on the moving table, the two-dimensional translation table can change the position of the object fixed thereon, and a platform and a clamp for fixing the sample or the electrifying mechanism 5 are fixedly arranged above the two-dimensional translation table to prevent the relative movement of the sample or the electrifying mechanism 5 during the movement. That is, the two-dimensional translation table is arranged between the electrifying mechanism 5 and the sample moving mechanism 4, the electrifying mechanism 5 is fixed on the two-dimensional translation table, and the two-dimensional translation table, the clamp and the like are not shown in the figure. The sample moving mechanism 4 can drive the sample in the electrifying mechanism 5 to move back and forth along the optical path near the focal point of the focusing lens 3, and the distance of the back and forth movement is greater than 2 cm. Figure 1 ​

[0039] Further, the focusing lens 3 is provided with a first diaphragm 6 near the side of the laser 1, the aperture size of the first diaphragm 6 is 12 mm, and the range can be adjusted within 1-12 mm, which can be used to adjust the incident beam spot quality; a second diaphragm 7 is arranged between the sample moving mechanism 4 and the light detector 2, which can be used to detect the Z-scan open and closed signals; the first diaphragm 6 and the second diaphragm 7 can also play the role of collimating the light path. When the aperture size of the second diaphragm 7 is small, that is, the aperture size satisfies the following condition: when the sample to be measured is in the linear region away from the focal point, the power received by the light detector 2 when the second diaphragm 7 is adjusted to a certain size is less than 0.4 times the total power received by the light detector 2 when the second diaphragm 7 is fully open, and the obtained Z-scan curve is a closed Z-scan curve, only part of the transmitted light enters the detector, thereby being sensitive to the phase change of the light beam, and the change of the transmitted light intensity is not only affected by the absorption but also affected by the focusing or divergence of the light beam caused by the change of the refractive index. The third-order nonlinear refractive index of the sample can be obtained through the closed Z-scan curve; correspondingly, when the aperture size of the second diaphragm 7 is 12 mm, the aperture size is large, and the blocking effect of the transmitted light is small, the detector 2 can receive all the transmitted light, and the obtained Z-scan curve is an open Z-scan curve, and the third-order nonlinear absorption coefficient of the sample can be obtained through the closed Z-scan curve. A chopper 8 is arranged between the laser 1 and the first diaphragm 6, which is used to modulate and control the light signal, realizes the accurate control of the light and the effective transmission of the information, and is connected with a lock-in amplifier 9, the lock-in amplifier 9, the sample moving mechanism 4 and the light detector 2 are connected with a computer 10. The light detector 2 is connected with the lock-in amplifier 9 to realize the accurate detection and extraction of the weak light signal, the lock-in amplifier 9 transmits the obtained signal to the computer 10, and the Z-scan spectrum is displayed on the computer 10. The chopper 8 and the lock-in amplifier 9 are combined to modulate and control the incident light beam.

[0040] The laser 1 and the chopper 8 are sequentially provided with an optical parametric amplifier 11 and a first light attenuation sheet 12, the optical parametric amplifier 11 is close to the laser 1; the optical parametric amplifier 11 is used for converting the wavelength of the laser output by the laser 1, and can adjust the laser emitted by the laser 1 to any wavelength in the range of 300-2700 nm, so as to facilitate the detection of the Z-scan curve and the photoelectric performance of the sample at different wavelengths; the first light attenuation sheet 12 is used for adjusting the intensity of the transmitted light, so that the intensity of the laser irradiated on the sample changes, so that the nonlinear performance and the photoelectric characteristics of the sample under different light intensities can be detected. The first total reflection mirror 13 and the second total reflection mirror 14 are arranged between the optical parametric amplifier 11 and the first light attenuation sheet 12, and the distance between the second total reflection mirror 14 and the first light diaphragm 6 is 3cm. The first total reflection mirror 13 and the second total reflection mirror 14 are arranged in opposite parallel. The light output by the optical parametric amplifier 11 enters the first total reflection mirror 13, the light field reflected by the first total reflection mirror 13 enters the second total reflection mirror 14, and the light field is totally reflected in the second total reflection mirror 14. The light emitted by the second total reflection mirror 14 irradiates on the first light attenuation sheet 12, and the combination of the first total reflection mirror 13 and the second total reflection mirror 14 is used to change the propagation direction of the optical path, so as to facilitate the detection part to be arranged at the edge part of the optical platform close to the personnel operation. The second light attenuation sheet 15 is arranged between the second light diaphragm 7 and the light detector 2, and the second light attenuation sheet 15 is mainly used for protecting the light detector 2 from the damage of the too large incident light intensity.

[0041] The power-on mechanism 5 includes a first conductive base 52 and a second conductive base 53 arranged opposite to each other, the conductive surfaces of the first conductive base 52 and the second conductive base 53 are opposite to each other, and the sample to be measured is arranged on the conductive surface of the first conductive base 52; by applying a voltage to the first conductive base 52 and the second conductive base 53, a voltage is applied to the sample to be measured.

[0042] Further, as Figure 2As shown, the power-on mechanism 5 includes a solid-state electrolyte layer 51, and a first conductive substrate 52 and a second conductive substrate 53 are respectively arranged on both sides of the solid-state electrolyte layer 51, and the conductive surfaces of the first conductive substrate 52 and the second conductive substrate 53 face the solid-state electrolyte layer 51. The sample to be measured is arranged on the conductive surface of the first conductive substrate 52 and is in contact with the solid-state electrolyte layer 51. The contact area of the sample to be measured and the solid-state electrolyte layer 51 is greater than the spot area incident on the surface of the sample to be measured, so as to ensure that the light beam is irradiated on the sample. The shapes and sizes of the first conductive substrate 52 and the second conductive substrate 53 are completely same, and the oppositely arranged first conductive substrate 52 and second conductive substrate 53 form a symmetrical electrode structure in the solid-state electrolyte layer 51, which helps to reduce the interference caused by the boundary effect or asymmetric electrode. The asymmetric electrode can cause uneven distribution of electric field, especially in the area close to the edge of the electrode, leading to uneven distribution of electric charge, and the difference in charge density seriously affects the electric field strength and charge transport efficiency in the sample, which interferes with the nonlinear dynamics process and photoelectrochemical reaction process of the sample itself, and affects the accuracy of detection. The signal of the sample in the system can be accurately detected, thereby improving the accuracy of Z-scan signal detection. The conductive substrate in the present application can be a rigid conductive substrate or a flexible conductive substrate. Preferably, the conductive substrate in the embodiment is a rigid conductive substrate, which can be indium tin oxide glass (ITO) or fluorine-doped tin oxide glass (FTO), and can better support the sample so that the sample plane is perpendicular to the light beam.

[0043] The liquid electrolyte usually partially absorbs the laser beam, especially when the light intensity is large at the focal point. This absorption effect can weaken the transmitted light signal, leading to a decrease in signal intensity or even distortion, which can mask the true nonlinear optical properties of the sample. The solid-state electrolyte 51 can effectively avoid the light absorption and scattering effect of the liquid electrolyte at the laser focal point caused by high light intensity. The scattering effect in the liquid electrolyte can change the spatial distribution of the light beam, making the light field deviate from the ideal Gaussian distribution mode, thereby affecting the nonlinear interaction of the light field and the sample. The solid-state electrolyte has low light absorption and scattering properties, which can maintain the integrity and Gaussian nature of the light field, providing a more stable and accurate light field environment for Z-scan measurement. The solid-state electrolyte can also effectively suppress the photo-thermal effect and photo-chemical reaction; avoiding local heating of the electrolyte under high light intensity, which can cause dynamic changes in optical parameters such as refractive index and absorption coefficient, thereby interfering with the accurate measurement of the Z-scan signal. Specifically, the electrolyte can be an acidic, neutral or alkaline electrolyte.

[0044] Further, nano-gold particles are arranged in the solid-state electrolyte layer 51 close to the side of the sample to be measured. When the laser is irradiated on the nano-gold particles, local surface plasmon resonance occurs on the surface of the nano-gold particles, which enhances the local electric field, thereby enhancing the interaction between the light field and the sample, increasing the nonlinear signal intensity of the sample, and making it easier to be detected.

[0045] Further, the solid electrolyte layer 51 is designed as a three-layer structure, the middle layer uses a material with high conductivity, such as Li + doped LiPON, to improve ion transmission performance and ensure the formation of a stable and strong electric field distribution during energization. The edge layers on both sides are designed as materials with low light absorption, low scattering and optical transparency, such as PMMA, which not only reduces light field interference, but also ensures that the laser transmission process maintains a high-quality light field. The solid electrolyte layer 51 designed in this way can balance high electric field strength and low light field loss, providing higher signal-to-noise ratio and accuracy for Z-scan measurement.

[0046] The thickness of the above-mentioned solid electrolyte layer 51 is 1-5 mm, and the absorption of the light field is small. Specifically, the smaller the thickness, the less the light absorption, and the greater the intensity of the transmitted light field. The preparation method of the energization mechanism 5 of the present embodiment is as follows:

[0047] S1, prepare an electrolyte sol;

[0048] First, 3 g of polyvinyl alcohol (PVA) is added to 30 ml of deionized water, and a magnetic stirrer is used to stir at 60°C until it is fully dissolved. Then, 10 ml of 0.5 M electrolyte solution is added and stirred for 30 minutes to obtain an electrolyte sol.

[0049] S2, prepare an energization mechanism;

[0050] The sample to be detected is placed on the conductive surface of the first conductive substrate 52, and the prepared electrolyte sol is uniformly spin-coated on the sample to be detected. The second conductive substrate 53 is covered on the electrolyte sol, and the conductive surface is in contact with the electrolyte sol.

[0051] S3, dry.

[0052] The prepared energization mechanism 5 is placed in an oven and dried at 30°C for 12 hours. The electrolyte gel is converted into a solid electrolyte layer 51, and after the end, the energization mechanism 5 of the present embodiment is obtained. When in use, it is placed on the sample moving mechanism 4 and connected to the power supply.

[0053] When in use, the energization mechanism 5 needs to be connected to the power supply; specifically, the energization mechanism 5 can be connected to the source table to form a two-electrode system for energization and photoelectric performance testing. The first conductive substrate 52 and the second conductive substrate 53 are respectively connected to the two electrodes of the source table; the source table is connected to the computer 10, and the software interface matched with the source table on the computer 10 is used to accurately adjust the parameters to control the size of the energization voltage. The energization mechanism 5 can also be connected to an electrochemical workstation to form a three-electrode system, such as Figure 3As shown, specifically, the first conductive substrate 52 serves as the working electrode, and the second conductive substrate 53 is connected to both the counter electrode and the reference electrode. The counter electrode and the reference electrode do not contact each other. For ease of display, the counter electrode and the reference electrode are shown slightly to the side in the figure; in actual use, they are both mounted on the second conductive substrate 53. The power application mechanism 5 is connected to an electrochemical workstation and can be used to probe the photoelectric properties of samples, such as linear voltammetry curves, transient photocurrents, Mott-Schottky curves, etc. This application combines the power application system with a Z-scan system to construct an in-situ electrochemical Z-scan spectroscopy system. When the sample under test moves away from the focal point of the focusing lens 3, linear photoelectric tests such as linear voltammetry curves, transient photocurrent (It curves), Mott-Schottky curves (to determine the semiconductor type and obtain flat band voltage), impedance spectra, and long-cycle tests can be performed based on the power application mechanism 5. When the sample under test moves near the focal point of the focusing lens 3, higher-order nonlinear absorption and refraction measurements can be performed based on the Z-scan system. At the same time, the external electric field provided by the power application mechanism 5 can regulate the band bending degree of the sample under test and the electrolyte or cause changes in the surface structure of the sample under test, achieving in-situ regulation of linear and nonlinear photoelectric properties. This provides an effective means for studying the electrically controlled nonlinear optical response of materials and facilitates the detection of the behavior of samples under electrical and optical coupling.

[0054] Example 2:

[0055] The difference between Embodiment 2 and Embodiment 1 lies in the structure of the power-applying mechanism 5; the other parts are the same as in Embodiment 1. For example... Figure 4 As shown, the power-applying mechanism 5 in this embodiment includes a third conductive base 54, a sealing ring 55, and a fourth conductive base 56. The sealing ring 55 can be a rubber ring, which has good sealing performance; its shape can be circular or elliptical, and with the same perimeter, it has a larger area, thus allowing for the setting of a larger area of ​​the sample to be tested; it is also relatively common and easy to obtain. It can also be any other shape, without specific limitations.

[0056] The sealing ring 55 is fixedly connected to the conductive surfaces of the third conductive substrate 54 and the fourth conductive substrate 56. UV adhesive can be used, and UV light irradiation can be applied to fix the sealing ring 55 and the conductive substrates, achieving both fixation and sealing. A closed chamber is formed between the sealing ring 55, the conductive surface of the third conductive substrate 54, and the conductive surface of the fourth conductive substrate 56. This closed chamber is filled with electrolyte. The sample to be tested is placed on the conductive surface of the third conductive substrate 54, in contact with the electrolyte. When connected to a source meter, the third conductive substrate 54 is connected to the positive electrode of the source meter, and the fourth conductive substrate 56 is connected to the negative electrode of the source meter. Figure 5As shown, for the convenience of the drawing two electrodes are drawn at both ends of the conductive substrate, and in actual use, they are connected with the third conductive substrate 54 and the fourth conductive substrate 56 respectively. They can also be connected with an electrochemical workstation to form a three-electrode system for detecting linear photoelectric characteristics; the third conductive substrate 54 is connected with a working electrode, and the fourth conductive substrate 56 is connected with a counter electrode and a reference electrode, and the counter electrode and the reference electrode are not in contact with each other.

[0057] Embodiment 3:

[0058] The difference between this embodiment and embodiment 1 is that the power-on mechanism 5 of this embodiment is different. The power-on mechanism 5 of this embodiment is a transparent photoelectrochemical cell, as shown in the figure. Figure 6 A fifth conductive substrate is arranged in the transparent electrolytic cell, and the conductive surface of the fifth conductive substrate is provided with a sample to be measured. The light path is perpendicular to the sample to be measured, the fifth conductive substrate is connected with a working electrode and fixed on the cover of the transparent electrolytic cell, the sample to be measured is immersed in the electrolyte in the transparent electrolytic cell, and a counter electrode and a reference electrode are also arranged in the electrolyte. They can be arranged on both sides of the fifth conductive substrate, drawn from the top, or drawn from both sides of the photoelectrochemical cell, and the specific arrangement is not limited. In use, the fifth conductive substrate is a working electrode, the counter electrode is a material with high conductivity and chemical stability, such as platinum or graphite; the reference electrode is a saturated calomel electrode (SCE) and a silver / silver chloride electrode (Ag / AgCl). In a two-electrode system, the positive electrode of the source table is connected with the working electrode, and the negative electrode is connected with the counter electrode.

[0059] The system of the present application can greatly improve the third-order nonlinear optical response of the material, which is conducive to the development and manufacturing of optoelectronic devices. The construction process of the in-situ electrochemical Z-scan spectral system of the present application is as follows:

[0060] First, according to the basic framework of using a small laser to build an experimental optical path: two variable diaphragms are used to collimate the incident laser, a first total reflection mirror 13 and a second total reflection mirror 14 are arranged, the first total reflection mirror 13 is used to adjust the position of the laser, and the second total reflection mirror 14 is used to adjust the position of the laser. Two variable diaphragms are used to collimate them to form parallel light. A femtosecond laser 1 of 800 nm is installed, the wavelength of the incident light is changed through an optical parametric amplifier 11, and the optical power of the incident light beam is adjusted through a first light attenuator 12. Before the experiment starts, the transmittance of the first light attenuator 12 and the second light attenuator 15 is small, and the attenuation degree of the light is large, so as to ensure the safety of the experimenters and the device. Subsequently, the pulse energy is measured by an optical power meter to calculate whether it can be used for experiments. Then, the first total reflection mirror 13 and the second total reflection mirror 14 are arranged to adjust the laser to an appropriate height and incident into the Z-scan system. A first diaphragm 6 and a second diaphragm 7 are installed 3 cm behind the second total reflection mirror 14, a focusing lens 3 is installed behind the first diaphragm 6, and the second diaphragm 7 is collimated about 1 m away from the first diaphragm 6.

[0061] A sample moving mechanism 4 is installed behind the focusing lens 3, and the sample moving mechanism 4 is connected with the computer 10, the translation stage is adjusted to move back and forth along the light path direction, and the collimated light path is behind; an energizing mechanism 5 is fixedly arranged thereon. A second light attenuation piece 15 is installed behind the sample moving mechanism 4, so that the emitted light after attenuation is completely received by the light detector 2, the light detector 2 is perpendicular to the emitted light, and the light detector 2 is connected with the lock-in amplifier 9. After the collimated light path, the second light barrier 7 is removed and fixed between the energizing mechanism 5 and the second light attenuation piece 15. The computer 10 is connected with the lock-in amplifier 9 and the sample moving mechanism 4, the data acquisition program is used to set the start position, the end position, the step length and the like to control the translation speed of the electric translation stage, and the light detector 2 converts the received light signal into an electric signal and inputs into the lock-in amplifier 9. The lock-in amplifier 9 is used to realize accurate detection and extraction of the weak light signal, and the computer is used to present the Z scanning curve of the sample in data access.

[0062] The electrically controlled Z scanning test system provided by the embodiment of the utility model can directly work in an aqueous solution, and does not need complex and expensive packaging processes.

[0063] The above is only the preferred embodiment of the utility model, and is not used for limiting the utility model, and the utility model can have various changes and changes for the person skilled in the art. Any modification, equivalent replacement, improvement and the like within the spirit and principle of the utility model should be included in the protection scope of the utility model.

Claims

1. An in-situ electrochemical Z-scan spectroscopy system, the system comprising a laser and a photodetector arranged at the same height, a focusing lens disposed between the laser and the photodetector, and a sample moving mechanism further disposed between the focusing lens and the photodetector, characterized in that, The focusing lens is a plano-convex lens, with one side of the plane facing the sample moving mechanism. The focal point of the focusing lens is at the light height corresponding to the center position of the length of the sample moving mechanism. The power supply mechanism is fixedly mounted on the sample moving mechanism. The sample to be tested is placed on the side of the power supply mechanism close to the focusing lens. The power supply mechanism is connected to a power source.

2. The in-situ electrochemical Z-scan spectroscopy system according to claim 1, characterized in that, The power-applying mechanism includes a first conductive substrate and a second conductive substrate disposed opposite to each other, with the conductive surfaces of the first conductive substrate and the second conductive substrate facing each other, and the sample to be tested is disposed on the conductive surface of the first conductive substrate.

3. The in-situ electrochemical Z-scan spectroscopy system according to claim 2, characterized in that, A solid electrolyte layer is further disposed between the first conductive substrate and the second conductive substrate. The solid electrolyte layer is disposed between the sample to be tested and the second conductive substrate, and the solid electrolyte layer is in contact with the conductive surfaces of the sample to be tested and the second conductive substrate.

4. The in-situ electrochemical Z-scan spectroscopy system according to claim 1, characterized in that, The power-applying mechanism includes a third conductive substrate, a sealing ring, and a fourth conductive substrate. The sealing ring is fixedly connected to the conductive surfaces of the third and fourth conductive substrates. A closed chamber is formed between the sealing ring, the conductive surfaces of the third and fourth conductive substrates, and the closed chamber is filled with electrolyte. The sample to be tested is placed on the conductive surface of the third conductive substrate and is in contact with the electrolyte.

5. The in-situ electrochemical Z-scan spectroscopy system according to claim 1, characterized in that, The system also includes a transparent electrolytic cell with a fifth conductive substrate disposed in the center. The sample to be tested is disposed on the conductive surface of the fifth conductive substrate. The light path transmits perpendicularly through the sample to be tested. The fifth conductive substrate is connected to the working electrode and fixed on the cover of the transparent electrolytic cell. The sample to be tested is immersed in the electrolyte in the transparent electrolytic cell. A counter electrode and a reference electrode are also disposed in the electrolyte, respectively disposed on both sides of the fifth conductive substrate.

6. The in-situ electrochemical Z-scan spectroscopy system according to any one of claims 1-5, characterized in that, A first aperture is provided on the side of the focusing lens near the laser, and a second aperture is provided between the sample moving mechanism and the photodetector.

7. The in-situ electrochemical Z-scan spectroscopy system according to claim 6, characterized in that, A chopper is provided between the laser and the first aperture. The chopper is connected to a lock-in amplifier. The lock-in amplifier and the sample moving mechanism are both connected to a computer.

8. The in-situ electrochemical Z-scan spectroscopy system according to claim 7, characterized in that, An optical parametric amplifier and a first optical attenuator are sequentially arranged between the laser and the chopper, with the optical parametric amplifier located close to the laser.

9. The in-situ electrochemical Z-scan spectroscopy system according to claim 8, characterized in that, A first total reflection mirror and a second total reflection mirror are disposed between the optical parametric amplifier and the first optical attenuator. The light output from the optical parametric amplifier enters the first total reflection mirror, and the light emitted from the second total reflection mirror illuminates the first optical attenuator. A second optical attenuator is disposed between the second aperture and the photodetector.

10. The in-situ electrochemical Z-scan spectroscopy system according to claim 9, characterized in that, A two-dimensional translation stage is provided between the power-on mechanism and the sample moving mechanism. The two-dimensional translation stage is fixedly mounted on the moving platform of the sample moving mechanism, and the power-on mechanism is fixed on the two-dimensional translation stage.

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