Photoelectric sensor based on flexible transparent conductive glass and method

Abstract

The invention discloses a photoelectric sensor and method based on flexible transparent conductive glass, and the photoelectric sensor comprises a flexible transparent conductive glass substrate, a biological recognition layer, and a hydrophilic packaging layer. The flexible transparent conductive glass substrate comprises a flexible transparent glass supporting substrate, a conductive barrier layer, a metal conductive layer and a photoelectric conversion layer which are sequentially stacked from bottom to top, the biological recognition layer is located on the upper surface of the photoelectric conversion layer, and the hydrophilic packaging layer covers the upper surface of the biological recognition layer; and the conductive barrier layer is connected with a data acquisition and analysis system. The photoelectric sensor is matched with a data acquisition and analysis system, the cortisol molecular level in sweat excreted by human skin can be detected in real time in a non-invasive mode, the detection speed is high, and the detection accuracy is high.

Description

Technical Field

[0001] The present invention belongs to the technical field of biomedical sensors, and in particular relates to a photoelectric sensor and method based on flexible transparent conductive glass. Background Art

[0002] Bioelectronics is an interdisciplinary field that combines biological systems with electronic devices. Its applications are wide-ranging, covering key areas such as healthcare, artificial intelligence, and environmental management. Among the many branches of bioelectronics, biosensor technology is particularly eye-catching, especially those sensors that can accurately capture biological substances and signal molecules, which play a very important role in analyzing biological systems.

[0003] Cortisol is a key stress hormone, and its fluctuations in levels directly reflect the health status and disease progression of the human body, which is especially important for monitoring mental health issues such as depression. Traditional methods for detecting cortisol are limited by the collection of blood or saliva samples, which is not only cumbersome to operate, but also difficult to ensure the immediacy and continuity of detection. Therefore, there is an urgent need to develop new biosensors to achieve real-time and non-invasive monitoring of cortisol.

[0004] Photoelectric sensors stand out in the field of biomedical testing for their excellent sensitivity, fast response speed and non-invasive detection methods. However, in order to meet the direct and efficient detection of specific biomarkers such as cortisol, existing photoelectric sensors still need further breakthroughs in flexibility, transparency and specific recognition capabilities. Summary of the invention

[0005] In view of the above-mentioned defects of the prior art, the present invention provides a photoelectric sensor and method based on flexible transparent conductive glass, which can detect the level of cortisol molecules in the sweat discharged from human skin in real time in a non-invasive manner, and has a fast detection speed and high detection accuracy.

[0006] The technical solution adopted by the present invention to solve its technical problem is:

[0007] A photoelectric sensor based on flexible transparent conductive glass comprises a flexible transparent conductive glass substrate, a biometric recognition layer and a hydrophilic encapsulation layer, wherein the flexible transparent conductive glass substrate comprises a flexible transparent glass supporting substrate, a conductive barrier layer, a metal conductive layer and a photoelectric conversion layer stacked in sequence from bottom to top, wherein the biometric recognition layer is located at the upper surface of the photoelectric conversion layer, and the hydrophilic encapsulation layer covers the upper surface of the biometric recognition layer; the conductive barrier layer is used to connect with a data acquisition and analysis system; the conductive barrier layer is used to block impurity elements in the flexible transparent glass supporting substrate from penetrating into the metal conductive layer and is used for conducting electricity, the hydrophilic encapsulation layer is used to directly contact human skin and collect sweat, the photoelectric conversion layer and the biometric recognition layer are used to cooperate with cortisol molecules in the collected sweat, and the photoelectric conversion layer is used to generate electron-hole pairs under light excitation, the holes in the electron-hole pairs are used to participate in the oxidation reaction of the cortisol molecules, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced, and the photoelectric sensor realizes real-time detection of the level of cortisol molecules in sweat by cooperating with the data acquisition and analysis system.

[0008] Furthermore, the conductive barrier layer is a polycrystalline SnO2 layer, and is deposited on the upper surface of the flexible transparent glass support substrate by thin film deposition technology, and the thickness of the polycrystalline SnO2 layer is controlled between 20-200 nm.

[0009] Furthermore, the metal conductive layer is an Ag metal layer, and is deposited on the upper surface of the conductive barrier layer by a thin film deposition technique, and the thickness of the Ag metal layer is controlled between 5-15 nm.

[0010] Furthermore, the photoelectric conversion layer is an F-doped polycrystalline SnO2 layer, and is deposited on the upper surface of the metal conductive layer by thin film deposition technology; the biorecognition layer is a Cu nanoparticle layer deposited on the upper surface of the F-doped polycrystalline SnO2 layer; the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer are used to form covalent bonds with the hydroxyl groups of the cortisol molecules, and the Cu nanoparticles in the Cu nanoparticle layer are used to bind to the carbonyl groups of the cortisol molecules, and the Cu nanoparticles and the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer together form a dual recognition site for the cortisol molecules.

[0011] Furthermore, the thickness of the F-doped polycrystalline SnO2 layer is controlled between 20-200 nm, the molar ratio of the F element to the Sn element in the F-doped polycrystalline SnO2 layer is greater than 0 and less than or equal to 0.3; the particle size of the Cu nanoparticles in the Cu nanoparticle layer is controlled between 5-20 nm.

[0012] Furthermore, the hydrophilic encapsulation layer is a polyacrylamide hydrogel protective layer, and is formed by photopolymerization of N,N-diethyl-2-acrylamide and N-hydroxyethyl acrylamide in a mass ratio of 1:1, and the thickness of the hydrophilic encapsulation layer is controlled between 100-200 μm.

[0013] Furthermore, the thickness of the flexible transparent glass support substrate is controlled between 30-50 μm.

[0014] A method for preparing a photoelectric sensor based on a flexible transparent conductive glass, which is used to prepare the photoelectric sensor based on the flexible transparent conductive glass described above, comprises the following steps:

[0015] S1, depositing a conductive barrier layer on the upper surface of the flexible transparent glass supporting substrate;

[0016] S2, depositing a metal conductive layer on the upper surface of the conductive barrier layer;

[0017] S3, depositing a photoelectric conversion layer on the upper surface of the metal conductive layer;

[0018] S4, depositing a biorecognition layer on the upper surface of the photoelectric conversion layer to prepare a sensing electrode;

[0019] S5. Covering the upper surface of the biorecognition layer with a hydrophilic encapsulation layer to prepare a photoelectric sensor.

[0020] Furthermore, the following steps are included between step S4 and step S5:

[0021] The sensing electrode prepared in step S4 is subjected to vacuum annealing treatment, wherein the annealing temperature is controlled between 200-700°C.

[0022] A method for detecting the level of cortisol molecules in sweat excreted from human skin is adopted to cooperate with the above-mentioned photoelectric sensor based on flexible transparent conductive glass and a data acquisition and analysis system connected to the photoelectric sensor for detection, specifically: the hydrophilic encapsulation layer in the photoelectric sensor is directly contacted with human skin, and the sweat excreted from human skin is collected through the hydrophilic encapsulation layer, the photoelectric conversion layer and the bio-recognition layer cooperate to combine with the cortisol molecules in the collected sweat, and the external light sequentially passes through the flexible transparent glass support substrate, the conductive barrier layer and the metal conductive layer and irradiates on the photoelectric conversion layer, the photoelectric conversion layer generates electron-hole pairs under light excitation, the holes in the electron-hole pairs participate in the oxidation reaction of the cortisol molecules, the electrons in the electron-hole pairs and the electrons in the oxidation reaction of the cortisol molecules are sequentially transmitted through the photoelectric conversion layer, the metal conductive layer and the conductive barrier layer to the data acquisition and analysis system, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced, and the photoelectric sensor realizes real-time detection of the level of cortisol molecules in sweat by cooperating with the data acquisition and analysis system.

[0023] Compared with the prior art, the beneficial effects of the present invention are:

[0024] The photoelectric sensor based on flexible transparent conductive glass in the present invention comprises a flexible transparent conductive glass substrate, a biometric recognition layer and a hydrophilic encapsulation layer, wherein the flexible transparent conductive glass substrate comprises a flexible transparent glass support substrate, a conductive barrier layer, a metal conductive layer and a photoelectric conversion layer stacked in sequence from bottom to top, the biometric recognition layer is located on the upper surface of the photoelectric conversion layer, the hydrophilic encapsulation layer covers the upper surface of the biometric recognition layer, and the conductive barrier layer is used to connect with a data acquisition and analysis system; when the photoelectric sensor cooperates with the data acquisition and analysis system to detect the level of cortisol molecules in the sweat fluid discharged from the human skin, the hydrophilic encapsulation layer in the photoelectric sensor is directly in contact with the human skin, and the hydrophilic encapsulation layer collects the cortisol molecules in the sweat fluid discharged from the human skin. The sweat discharged from the human skin is collected, and the photoelectric conversion layer and the bio-recognition layer cooperate to combine with the cortisol molecules in the collected sweat. The external light passes through the flexible transparent glass support substrate, the conductive barrier layer and the metal conductive layer in turn and irradiates the photoelectric conversion layer. The photoelectric conversion layer generates electron-hole pairs under light excitation, and the holes in the electron-hole pairs participate in the oxidation reaction of the cortisol molecules. The electrons in the electron-hole pairs and the electrons in the oxidation reaction of the cortisol molecules are transmitted to the data acquisition and analysis system through the photoelectric conversion layer, the metal conductive layer and the conductive barrier layer in turn, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced, thereby realizing real-time detection of the level of cortisol molecules in sweat.In this way, the photoelectric sensor can detect the level of cortisol molecules in the sweat excreted by human skin in real time in a non-invasive manner by cooperating with the data acquisition and analysis system, and realize real-time monitoring of the level of cortisol molecules in the human body. The non-invasive detection can reduce the pain of patients. Specifically, the sweat excreted by human skin is used as the detection sample, which can avoid the pain and discomfort caused by traditional blood collection or saliva detection, and can greatly improve the detection comfort of patients. In addition, the non-invasive detection does not require piercing the skin, which can reduce the chance of bacteria and other pathogens entering the human body, thereby reducing the risk of infection. The photoelectric sensor uses photoelectric sensing technology to specifically identify and convert signals of cortisol molecules in a very short time, and realizes rapid detection by cooperating with the data acquisition and analysis system. In addition, since the photoelectric conversion layer and the bio-recognition layer cooperate with the cortisol molecules in the collected sweat, the photoelectric conversion layer and the bio-recognition layer form a double recognition site for the cortisol molecule, which can improve the accuracy of detection and reduce the possibility of false alarms and missed alarms. In addition, the high sensitivity and rapid response characteristics enable doctors to obtain diagnostic results more quickly, thereby facilitating the preparation of The flexible transparent glass support substrate makes the photoelectric sensor flexible and light-transmissive, and can easily adapt to the needs of various wearable or implantable medical devices, such as smart bracelets, patch sensors, etc., providing possibilities for personalized medical solutions. In addition, the flexible design makes the sensor fit the skin better when worn, reducing the pressure on the user, reducing the user's discomfort, and improving the user's experience. In addition, the transparent design makes the photoelectric sensor more visually concealed, does not affect the user's appearance, and improves the product's acceptability. The photoelectric sensor can continuously record the changes in the level of cortisol molecules in the sweat excreted by the human skin by cooperating with the data acquisition and analysis system, so as to realize the continuous monitoring of the changes in the level of cortisol molecules in the human body, and provide doctors with more comprehensive disease information. In addition, the real-time monitoring function helps doctors to detect and take measures in time before the disease worsens, thereby improving the prevention and treatment of the disease. Based on the real-time monitoring data, doctors can adjust the treatment plan more accurately, realize personalized medicine, and improve the treatment effect and patient satisfaction.

[0025] In summary, this photoelectric sensor can not only fit closely to human skin, and by cooperating with the data acquisition and analysis system, realize real-time non-invasive monitoring of the level of cortisol molecules in the human body, but also reduce the interference of natural light shining on the human body with its high transparency, thereby ensuring the accuracy of detection. In addition, the photoelectric sensor can directly and specifically detect the level of cortisol molecules in the sweat excreted by human skin by cooperating with the data acquisition and analysis system, providing strong technical support for the early diagnosis, treatment monitoring and efficacy evaluation of diseases such as depression. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1This is a schematic diagram of the main structure of the photoelectric sensor based on flexible transparent conductive glass;

[0027] Figure 2 Schematic diagram of the three-dimensional structure of the photoelectric sensor based on flexible transparent conductive glass;

[0028] Explanation of the reference numerals in the figure: 1. flexible transparent glass supporting substrate, 2. polycrystalline SnO2 layer, 3. Ag metal layer, 4. F-doped polycrystalline SnO2 layer, 5. Cu nanoparticle layer, 501. Cu nanoparticles, 6. polyacrylamide hydrogel protective layer, 7. skin, 701. surface of the skin. DETAILED DESCRIPTION

[0029] The specific embodiments of the present invention are further described in detail below in conjunction with the accompanying drawings. These embodiments are only used to illustrate the present invention, but not to limit the present invention.

[0030] In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside" and the like indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore cannot be understood as limiting the present invention. In addition, the terms "first" and "second" are used for descriptive purposes only and cannot be understood as indicating or implying relative importance.

[0031] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be a direct connection, or it can be indirectly connected through an intermediate medium, or it can be the internal communication of two components. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0032] A photoelectric sensor based on flexible transparent conductive glass comprises a flexible transparent conductive glass substrate, a biometric identification layer and a hydrophilic packaging layer. The flexible transparent conductive glass substrate comprises a flexible transparent glass supporting substrate 1, a conductive barrier layer, a metal conductive layer and a photoelectric conversion layer stacked in sequence from bottom to top. The biometric identification layer is located at the upper surface of the photoelectric conversion layer, and the hydrophilic packaging layer covers the upper surface of the biometric identification layer. The conductive barrier layer is used to connect with a data acquisition and analysis system. The conductive barrier layer is used to block impurity elements in the flexible transparent glass supporting substrate 1 from penetrating into the metal conductive layer and is used for conducting electricity. The hydrophilic packaging layer is used to directly contact human skin 7 and collect sweat. The photoelectric conversion layer and the biometric identification layer cooperate to combine with cortisol molecules in the collected sweat. The photoelectric conversion layer is used to generate electron-hole pairs under light excitation. The holes in the electron-hole pairs are used to participate in the oxidation reaction of the cortisol molecules, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced. The photoelectric sensor cooperates with the data acquisition and analysis system to achieve real-time detection of the level of cortisol molecules in sweat.

[0033] When the photoelectric sensor cooperates with the data acquisition and analysis system to detect the level of cortisol molecules in the sweat discharged from the human skin 7, the hydrophilic packaging layer in the photoelectric sensor is directly contacted with the human skin 7, and the sweat discharged from the human skin 7 is collected through the hydrophilic packaging layer. The photoelectric conversion layer and the bio-recognition layer cooperate to combine with the cortisol molecules in the collected sweat, and the external light passes through the flexible transparent glass support substrate 1, the conductive barrier layer and the metal conductive layer in sequence and irradiates the photoelectric conversion layer. The photoelectric conversion layer generates electron-hole pairs under light excitation, and the holes in the electron-hole pairs participate in the oxidation reaction of the cortisol molecules. The electrons in the electron-hole pairs and the electrons in the oxidation reaction of the cortisol molecules are transmitted to the data acquisition and analysis system through the photoelectric conversion layer, the metal conductive layer and the conductive barrier layer in sequence, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced, thereby realizing real-time detection of the level of cortisol molecules in sweat.

[0034] In this way, the photoelectric sensor can detect the level of cortisol molecules in the sweat of human skin 7 in real time in a non-invasive manner by cooperating with the data acquisition and analysis system, and realize real-time monitoring of the level of cortisol molecules in the human body. The non-invasive detection can reduce the pain of patients. Specifically, the sweat of human skin 7 is used as the detection sample, which can avoid the pain and discomfort caused by traditional blood collection or saliva detection, and can greatly improve the detection comfort of patients. In addition, the non-invasive detection does not require piercing the skin 7, which can reduce the chance of bacteria and other pathogens entering the human body, thereby reducing the risk of infection. The photoelectric sensor uses photoelectric sensing technology to specifically identify and convert signals of cortisol molecules in a very short time, and realizes rapid detection by cooperating with the data acquisition and analysis system. In addition, since the photoelectric conversion layer and the bio-recognition layer cooperate with the cortisol molecules in the collected sweat, the photoelectric conversion layer and the bio-recognition layer form a double recognition site for the cortisol molecule, which can improve the accuracy of detection and reduce the possibility of false alarms and missed alarms. In addition, the high sensitivity and rapid response characteristics enable doctors to obtain diagnostic results more quickly, thereby facilitating the preparation of A more timely treatment plan can be determined; the flexible transparent glass supporting substrate 1 makes the photoelectric sensor flexible and light-transmissive, and can easily adapt to the needs of various wearable or implantable medical devices, such as smart bracelets, patch sensors, etc., providing possibilities for personalized medical solutions. In addition, the flexible design makes the sensor fit the skin 7 more closely when worn, reducing the sense of oppression on the user, reducing the user's discomfort, and improving the user's experience. In addition, the transparent design makes the photoelectric sensor more visually concealed, does not affect the user's appearance, and improves the product's acceptability; the photoelectric sensor can continuously record the changes in the level of cortisol molecules in the sweat fluid of the human skin 7 by cooperating with the data acquisition and analysis system, so as to realize continuous monitoring of the changes in the level of cortisol molecules in the human body, and provide doctors with more comprehensive disease information. In addition, the real-time monitoring function helps doctors to detect and take measures in time before the disease worsens, thereby improving the prevention and treatment effects of the disease, and according to the real-time monitoring data, doctors can adjust the treatment plan more accurately, realize personalized medicine, and improve the treatment effect and patient satisfaction.

[0035] Among them Figure 1 and Figure 2As shown, the conductive barrier layer is a polycrystalline SnO2 layer 2, and is deposited on the upper surface of the flexible transparent glass support substrate 1 by thin film deposition technology; the metal conductive layer is an Ag metal layer 3, and is deposited on the upper surface of the conductive barrier layer by thin film deposition technology; the photoelectric conversion layer is an F-doped polycrystalline SnO2 layer 4, and is deposited on the upper surface of the metal conductive layer by thin film deposition technology, and the F element in the F-doped polycrystalline SnO2 layer 4 can enhance the photoelectric activity and stability of SnO2; the biorecognition layer is a Cu nanoparticle layer 5 deposited on the upper surface of the F-doped polycrystalline SnO2 layer 4; the hydrophilic encapsulation layer is a polyacrylamide hydrogel protective layer 6, and is formed by photopolymerization of N,N-diethyl-2-acrylamide and N-hydroxyethyl acrylamide, and has high transparency. Among them Figure 1 and Figure 2 The thickness of each film layer in this photoelectric sensor does not represent the actual thickness of each diaphragm. Figure 1 and Figure 2 Reference numeral 701 indicates the surface of the skin.

[0036] The SnO2 in the polycrystalline SnO2 layer 2 has high density and stability. Compared with amorphous SnO2, it can more effectively prevent impurity elements such as sodium and potassium in the flexible transparent glass supporting substrate 1 from penetrating into the Ag metal layer 3, thereby ensuring the purity of the Ag metal layer 3 and improving the overall conductive performance of the flexible transparent conductive glass substrate.

[0037] The hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer 4 are used to form a covalent bond with the hydroxyl groups of the cortisol molecule, and the Cu nanoparticles 501 in the Cu nanoparticle layer 5 are used to form a covalent bond with the carbonyl groups of the cortisol molecule, so that the sensing electrode has a highly selective capture capability of the cortisol molecules in the sweat, and the Cu nanoparticles 501 and the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer 4 jointly form a dual recognition site for the cortisol molecule. As a key element for biorecognition and signal amplification, the Cu nanoparticles 501 can significantly improve the sensitivity and response speed of the photoelectric sensor.

[0038] The hydrophilic encapsulation layer serves as the outer protection of the sensing electrode, which not only promotes the penetration of sweat into the surface of the sensing electrode and improves the contact efficiency between the sensing electrode and the cortisol molecules, but also the pore size of the hydrophilic encapsulation layer is relatively small, which can effectively block protein fragments on the surface of the skin 7 from entering the pores and contaminating the surface of the sensing electrode. Therefore, the hydrophilic encapsulation layer can provide an additional protective barrier for the sensing electrode, significantly enhancing the long-term stability and reliability of the photoelectric sensor. In addition, the selection of the hydrophilic encapsulation layer material also takes into account the safety and comfort of the photoelectric sensor when in contact with human skin 7, ensuring that the photoelectric sensor will not cause discomfort or damage to the user during long-term wearing and use.

[0039] The thickness of the polycrystalline SnO2 layer 2 is controlled between 20-200 nm. This can optimize the conductivity and barrier effect of the polycrystalline SnO2 layer 2 and ensure light transmittance. If the thickness of the polycrystalline SnO2 layer 2 is less than 20 nm, the barrier effect is weak. If the thickness of the polycrystalline SnO2 layer 2 is greater than 200 nm, the electron transmission capacity is weak and affects light transmittance.

[0040] The thickness of the Ag metal layer 3 is controlled to be between 5-15 nm, which can fully ensure the conductivity and avoid adverse effects on light transmittance.

[0041] Among them, the thickness of the F-doped polycrystalline SnO2 layer 4 is controlled between 20-200nm, which can optimize the photoelectric activity of the F-doped polycrystalline SnO2 layer 4 and ensure the light transmittance. If the thickness of the F-doped polycrystalline SnO2 layer 4 is less than 20nm, the photoelectric activity is low. If the thickness of the F-doped polycrystalline SnO2 layer 4 is higher than 200nm, the light transmittance is affected. The molar ratio of the F element to the Sn element in the F-doped polycrystalline SnO2 layer 4 is greater than 0 and less than or equal to 0.3.

[0042] The particle size of the Cu nanoparticles 501 in the Cu nanoparticle layer 5 is controlled between 5 and 20 nm. This can enhance the selective recognition of the carbonyl group in the cortisol molecule and ensure that the photoelectric activity of the F-doped polycrystalline SnO2 layer 4 is not interfered with, further improving the detection accuracy and sensitivity of the photoelectric sensor.

[0043] Among them, the mass ratio of N,N-diethyl-2-acrylamide to N-hydroxyethylacrylamide is 1:1; the thickness of the hydrophilic encapsulation layer is controlled between 100-200 μm. This thickness design can not only ensure that sweat can penetrate into the surface of the sensing electrode smoothly, promote the effective capture of cortisol molecules in sweat, but also ensure that the photoelectric sensor can maintain stable performance when bent or deformed, thereby enhancing the durability and reliability of the photoelectric sensor in practical applications.

[0044] The thickness of the flexible transparent glass support substrate 1 is controlled between 30-50 μm.

[0045] A method for preparing a photoelectric sensor based on a flexible transparent conductive glass, which is used to prepare the above-mentioned photoelectric sensor based on a flexible transparent conductive glass, comprises the following steps:

[0046] S1, selecting a flexible transparent glass support substrate 1 with a thickness controlled between 30-50 μm, and uniformly depositing a layer of polycrystalline SnO2 layer 2 on the upper surface of the flexible transparent glass support substrate 1 by thin film deposition technology, and by accurately controlling the deposition time, the thickness of the polycrystalline SnO2 layer 2 is controlled between 20-200 nm;

[0047] S2, uniformly depositing a layer of Ag metal layer 3 on the upper surface of the polycrystalline SnO2 layer 2 by thin film deposition technology, and controlling the thickness of the Ag metal layer 3 to be between 5-15 nm by precisely controlling the deposition time;

[0048] S3, uniformly depositing a layer of F-doped polycrystalline SnO2 layer 4 on the upper surface of the Ag metal layer 3 by thin film deposition technology, and controlling the thickness of the F-doped polycrystalline SnO2 layer 4 to be between 20-200 nm by precisely controlling the deposition time;

[0049] S4, depositing a Cu nanoparticle layer 5 on the upper surface of the F-doped polycrystalline SnO2 layer 4 to prepare a sensing electrode, wherein the particle size of the Cu nanoparticles 501 in the Cu nanoparticle layer 5 is controlled to be between 5-20 nm;

[0050] S5, performing vacuum annealing treatment on the prepared sensing electrode at a temperature of 200-700° C.;

[0051] S6. Cover the upper surface of the Cu nanoparticle layer 5 with a polyacrylamide hydrogel protective layer 6 with a thickness controlled between 100-200 μm to prepare a photoelectric sensor.

[0052] Among them, in step S1, the thin film deposition technology is magnetron sputtering deposition technology or chemical vapor deposition technology; if the online chemical vapor deposition technology is used, the coating process of the polycrystalline SnO2 layer 2 can be closely combined with the forming process of the flexible transparent glass support substrate 1. Specifically, in the annealing furnace, as the flexible transparent glass support substrate 1 is gradually formed, the SnO2 coating process is carried out at the same time. The coating temperature of this technology is relatively high, usually set between 500-800°C, which is conducive to the full crystallization of SnO2 and the formation of a dense layer; if the offline chemical vapor deposition technology is used, the operation mode is more flexible, and the flexible After the transparent glass support substrate 1 has been formed and preliminarily processed, an independent coating process is performed, wherein the coating temperature can be set between 400-650°C to ensure the quality of the polycrystalline SnO2 layer 2 while reducing the potential thermal stress on the flexible transparent glass support substrate 1; if magnetron sputtering deposition technology is used, the coating temperature is set between 200-650°C, and a uniform and dense SnO2 thin film can be deposited on the upper surface of the flexible transparent glass support substrate 1. This technology is not only suitable for large-scale production, but also can ensure good bonding between the polycrystalline SnO2 layer 2 and the flexible transparent glass support substrate 1.

[0053] Among them, in step S2, the thin film deposition technology is magnetron sputtering deposition technology, and the Ag metal layer 3 is deposited at room temperature. This technology ensures the uniformity and high purity of the Ag metal layer 3, and can provide a high-quality conductive substrate for the subsequent multi-layer structure construction.

[0054] Among them, in step S3, the thin film deposition technology is a magnetron sputtering deposition technology. Specifically, the F element is pre-doped into the SnO2 target to make a F-doped SnO2 target, wherein the molar ratio of the F element to the Sn element is controlled to be greater than 0 and less than or equal to 0.3 to optimize the doping effect, and the coating process is carried out in a relatively low temperature range, i.e., between 23°C and 200°C. This temperature setting not only protects the substrate from high temperature, but also effectively prevents the Ag metal layer 3 from being oxidized during the preparation process.

[0055] Wherein, in step S4, a Cu nanoparticle layer 5 is deposited on the upper surface of the F-doped polycrystalline SnO2 layer 4 by using magnetron sputtering deposition technology.

[0056] Among them, in step S5, the crystallinity of each film layer in the sensing electrode can be improved by vacuum annealing treatment. Specifically, during the annealing process, heat can promote the rearrangement and bonding of atoms inside the film layer, reduce defects and stress, thereby improving the crystallization quality of the polycrystalline SnO2 layer 2, the Ag metal layer 3 and the F-doped polycrystalline SnO2 layer 4. In addition, annealing also helps the Cu nanoparticles 501 to be more evenly and stably distributed on the upper surface of the F-doped polycrystalline SnO2 layer 4, thereby enhancing the interaction ability between the Cu nanoparticles 501 and the cortisol molecules. The sensing electrode after annealing treatment is significantly improved in terms of crystallinity, stability, conductivity, photoelectric activity and biometric sensitivity, thereby enhancing the comprehensive performance of the photoelectric sensor and laying a solid foundation for its wide application in the fields of biosensing, medical diagnosis, health monitoring, etc.

[0057] In step S6, the polyacrylamide hydrogel protective layer 6 is formed by photopolymerization of N,N-diethyl-2-acrylamide and N-hydroxyethylacrylamide in a mass ratio of 1:1.

[0058] The preparation method of the photoelectric sensor based on flexible transparent conductive glass in the present invention has the advantages of low process difficulty, environmental friendliness, and easy large-scale production. The prepared photoelectric sensor based on flexible transparent conductive glass maintains high transparency and flexibility while showing excellent stability and sensitivity, opening up new possibilities for applications in the field of biosensing. Specific embodiment 1

[0060] A method for preparing a photoelectric sensor based on flexible transparent conductive glass comprises the following steps:

[0061] S1. A piece of 30 μm thick ultra-thin flexible glass is selected as the flexible transparent glass support substrate 1. The flexible transparent glass support substrate 1 is first placed in acetone, anhydrous ethanol and deionized water in turn, and ultrasonically cleaned for 10 minutes respectively to ensure that the surface is clean and free of impurities. The cleaned flexible transparent glass support substrate 1 is then dried. After drying, a 50 nm thick SnO2 film is deposited on the upper surface of the flexible transparent glass support substrate 1 by radio frequency magnetron sputtering deposition technology to form a polycrystalline SnO2 layer 2. In this process, the target material used is SnO2 material, and the sputtering gas is argon to ensure the stability of the coating process and the coating quality. At the same time, the coating temperature is controlled at 400°C to optimize the crystallization quality and performance of the SnO2 film.

[0062] S2. Take out the sample processed in step S1, and deposit a 10 nm thick Ag metal film on the upper surface of the polycrystalline SnO2 layer 2 by direct current magnetron sputtering deposition technology at room temperature to form an Ag metal layer 3. In this process, a high-purity Ag target material is selected as the sputtering source, and argon is used as the sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only simplify the process flow, but also effectively avoid the risk of substrate deformation or material performance changes caused by high temperature, thereby ensuring high-quality deposition of the Ag metal layer 3.

[0063] S3, taking out the sample processed in step S2, and depositing a 50nm thick F-doped SnO2 film on the upper surface of the Ag metal layer 3 by direct current magnetron sputtering deposition technology at room temperature to form a F-doped polycrystalline SnO2 layer 4. In this process, a F-doped SnO2 target is selected as a sputtering source to ensure the uniform distribution of the doping elements and the specific properties of the film. At the same time, argon is used as a sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only simplify the process flow, but also avoid the adverse effects of high temperature on the underlying structure, and ensure the high-quality deposition of the F-doped polycrystalline SnO2 layer 4.

[0064] S4, taking out the sample processed in step S3, and using radio frequency magnetron sputtering deposition technology on the upper surface of the F-doped polycrystalline SnO2 layer 4, the sputtering time is precisely controlled to be 1 min at room temperature to deposit a layer of uniformly distributed Cu nanoparticles 501, and form a Cu nanoparticle layer 5. In this process, the sputtering parameters are precisely controlled to ensure that the particle size of the Cu nanoparticles 501 is 10 nm, and argon is used as the sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only avoid the adverse effects of high temperature on the underlying structure, but also ensure the high-quality deposition of the Cu nanoparticle layer 5;

[0065] S5, taking out the sample processed in step S4 and placing it in a muffle furnace, then vacuumizing the muffle furnace to remove oxygen and other impurity gases in the furnace that may affect the annealing effect. After ensuring that the furnace environment meets the requirements, the temperature is set to 500° C. and the sample is annealed for 30 minutes. During the annealing process, the high temperature environment helps to optimize the distribution and crystallization state of the Cu nanoparticles 501 on the upper surface of the F-doped polycrystalline SnO2 layer 4, further improving the sensing efficiency. After the annealing is completed, the sample is naturally cooled to room temperature to obtain a sensing electrode containing Cu nanoparticles 501;

[0066] S6. Take out the sample processed in step S5, and prepare a uniform polyacrylamide hydrogel precursor solution, then evenly drop the polyacrylamide hydrogel precursor solution on the upper surface of the Cu nanoparticle layer 5 of the sample until a coating with a thickness of 100 μm is formed, and then place the sample under a UV curing device, and use 365 nm wavelength light for photopolymerization reaction, and continue for 5 minutes. During this process, the ultraviolet light can effectively induce the polymerization of monomers in the precursor to form a flexible and transparent polyacrylamide hydrogel protective layer 6. The protective layer not only has excellent biocompatibility and moisture retention ability, but also can effectively protect the underlying Cu nanoparticle layer 5 and F-doped polycrystalline SnO2 layer 4, thereby extending the service life of the entire sensing electrode. Specific embodiment 2

[0068] A method for preparing a photoelectric sensor based on flexible transparent conductive glass comprises the following steps:

[0069] S1. A piece of 30 μm thick ultra-thin flexible glass is selected as a flexible transparent glass support substrate 1. The flexible transparent glass support substrate 1 is first placed in acetone, anhydrous ethanol and deionized water in turn, and ultrasonically cleaned for 10 minutes respectively to ensure that the surface is clean and free of impurities. The cleaned flexible transparent glass support substrate 1 is then dried. After drying, a 70 nm thick SnO2 thin film is deposited on the upper surface of the flexible transparent glass support substrate 1 by chemical vapor deposition technology to form a polycrystalline SnO2 layer 2. During this process, the gas introduced is a mixed gas of butyltin trichloride, fluoroacetic acid and nitrogen, and the coating temperature is controlled at 550°C.

[0070] S2. Take out the sample processed in step S1, and deposit a 10 nm thick Ag metal film on the upper surface of the polycrystalline SnO2 layer 2 by direct current magnetron sputtering deposition technology at room temperature to form an Ag metal layer 3. In this process, a high-purity Ag target material is selected as the sputtering source, and argon is used as the sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only simplify the process flow, but also effectively avoid the risk of substrate deformation or material performance changes caused by high temperature, thereby ensuring high-quality deposition of the Ag metal layer 3.

[0071] S3, taking out the sample processed in step S2, and depositing a 50nm thick F-doped SnO2 film on the upper surface of the Ag metal layer 3 by direct current magnetron sputtering deposition technology at room temperature to form a F-doped polycrystalline SnO2 layer 4. In this process, a F-doped SnO2 target is selected as a sputtering source to ensure the uniform distribution of the doping elements and the specific properties of the film. At the same time, argon is used as a sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only simplify the process flow, but also avoid the adverse effects of high temperature on the underlying structure, and ensure the high-quality deposition of the F-doped polycrystalline SnO2 layer 4.

[0072] S4, taking out the sample processed in step S3, and depositing a layer of uniformly distributed Cu nanoparticles 501 on the upper surface of the F-doped polycrystalline SnO2 layer 4 by direct current magnetron sputtering deposition technology, and precisely controlling the sputtering time to be 90s at room temperature, to form a Cu nanoparticle layer 5. In this process, the target material is a Cu target material, and the particle size of the Cu nanoparticles 501 is ensured to be 15nm by precisely controlling the sputtering parameters. At the same time, argon is used as the sputtering gas to ensure the purity and stability of the coating process. The coating operation at room temperature can not only avoid the adverse effects of high temperature on the underlying structure, but also ensure the high-quality deposition of the Cu nanoparticle layer 5.

[0073] S5, taking out the sample processed in step S4 and placing it in a muffle furnace, then vacuumizing the muffle furnace to remove oxygen and other impurity gases in the furnace that may affect the annealing effect. After ensuring that the furnace environment meets the requirements, the temperature is set to 500° C. and the sample is annealed for 30 minutes. During the annealing process, the high temperature environment helps to optimize the distribution and crystallization state of the Cu nanoparticles 501 on the upper surface of the F-doped polycrystalline SnO2 layer 4, further improving the sensing efficiency. After the annealing is completed, the sample is naturally cooled to room temperature to obtain a sensing electrode containing Cu nanoparticles 501;

[0074] S6. Take out the sample processed in step S5, and prepare a uniform polyacrylamide hydrogel precursor solution, then evenly drop the polyacrylamide hydrogel precursor solution on the upper surface of the Cu nanoparticle layer 5 of the sample until a coating with a thickness of 100 μm is formed, and then place the sample under a UV curing device, and use 365 nm wavelength light for photopolymerization reaction, and continue for 5 minutes. During this process, the ultraviolet light can effectively induce the polymerization of monomers in the precursor to form a flexible and transparent polyacrylamide hydrogel protective layer 6. The protective layer not only has excellent biocompatibility and moisture retention ability, but also can effectively protect the underlying Cu nanoparticle layer 5 and F-doped polycrystalline SnO2 layer 4, thereby extending the service life of the entire sensing electrode.

[0075] A method for detecting the level of cortisol molecules in the sweat excreted from human skin 7 is used to detect the above-mentioned photoelectric sensor based on flexible transparent conductive glass and the data acquisition and analysis system connected to the photoelectric sensor. Specifically, the polyacrylamide hydrogel protective layer 6 in the photoelectric sensor is directly contacted with the human skin 7, and the sweat excreted from the human skin 7 is collected through the polyacrylamide hydrogel protective layer 6, the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer 4 are covalently bonded with the hydroxyl groups of the cortisol molecules in the sweat, and the Cu nanoparticles 501 in the Cu nanoparticle layer 5 are covalently bonded with the carbonyl groups of the cortisol molecules in the sweat, so as to capture the cortisol molecules in the sweat to the surface of the sensing electrode, and the external light is sequentially The light is irradiated onto the F-doped polycrystalline SnO2 layer 4 through the flexible transparent glass supporting substrate 1, the polycrystalline SnO2 layer 2 and the Ag metal layer 3. The F-doped polycrystalline SnO2 layer 4 generates electron-hole pairs under light excitation. The holes in the electron-hole pairs participate in the oxidation reaction of the cortisol molecules. The electrons in the electron-hole pairs and the electrons in the oxidation reaction of the cortisol molecules are successively transmitted to the external data acquisition and analysis system through the F-doped polycrystalline SnO2 layer 4, the Ag metal layer 3 and the polycrystalline SnO2 layer 2, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced. The photoelectric sensor cooperates with the data acquisition and analysis system to realize real-time, accurate and selective detection of the cortisol molecular level in sweat.

[0076] Traditional biosensors rely on DNA materials as recognition elements to capture and analyze specific target molecules in DNA materials. However, the stability shortcomings of DNA materials in practical applications will limit their long-term effectiveness and wide applicability. In order to solve this problem, the present invention designs the structure of the sensing electrode by utilizing the unique interaction mechanism between transition metals and specific functional groups, so that the sensing electrode can be accurately matched and reversely customized to the chemical structure of the target molecule, thereby significantly enhancing the stability and reliability of the photoelectric sensor and opening up broader prospects for practical applications.

[0077] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and substitutions can be made without departing from the technical principles of the present invention. These improvements and substitutions should also be regarded as the scope of protection of the present invention.

Claims

1. A photoelectric sensor based on flexible transparent conductive glass, characterized in that: The invention comprises a flexible transparent conductive glass substrate, a biometric identification layer and a hydrophilic packaging layer. The flexible transparent conductive glass substrate comprises a flexible transparent glass support substrate (1), a conductive barrier layer, a metal conductive layer and a photoelectric conversion layer which are sequentially stacked from bottom to top. The biometric identification layer is located on the upper surface of the photoelectric conversion layer, and the hydrophilic packaging layer covers the upper surface of the biometric identification layer. The conductive barrier layer is used to connect with a data acquisition and analysis system. The conductive barrier layer is used to block impurity elements in the flexible transparent glass support substrate (1) from penetrating into the metal conductive layer and is used for conducting electricity. The hydrophilic packaging layer is used to directly contact human skin (7) and collect sweat. The photoelectric conversion layer and the biometric identification layer are used to combine with cortisol molecules in the collected sweat. The photoelectric conversion layer is used to generate electron-hole pairs under light excitation. The holes in the electron-hole pairs are used to participate in the oxidation reaction of the cortisol molecules, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced. The photoelectric sensor realizes real-time detection of the level of cortisol molecules in sweat by cooperating with the data acquisition and analysis system.

2. The photoelectric sensor based on flexible transparent conductive glass according to claim 1, characterized in that: The conductive barrier layer is a polycrystalline SnO2 layer (2) and is deposited on the upper surface of the flexible transparent glass support substrate (1) by thin film deposition technology, and the thickness of the polycrystalline SnO2 layer (2) is controlled between 20-200 nm.

3. The photoelectric sensor based on flexible transparent conductive glass according to claim 1, characterized in that: The metal conductive layer is an Ag metal layer (3) and is deposited on the upper surface of the conductive barrier layer by means of a thin film deposition technique, and the thickness of the Ag metal layer (3) is controlled to be between 5 and 15 nm.

4. The photoelectric sensor based on flexible transparent conductive glass according to claim 1, characterized in that: The photoelectric conversion layer is an F-doped polycrystalline SnO2 layer (4) and is deposited on the upper surface of the metal conductive layer by a thin film deposition technique; the biorecognition layer is a Cu nanoparticle layer (5) deposited on the upper surface of the F-doped polycrystalline SnO2 layer (4); the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer (4) are used to form a covalent bond with the hydroxyl groups of the cortisol molecules, the Cu nanoparticles (501) in the Cu nanoparticle layer (5) are used to bind to the carbonyl groups of the cortisol molecules, and the Cu nanoparticles (501) and the hydroxyl groups on the upper surface of the F-doped polycrystalline SnO2 layer (4) together form a dual recognition site for the cortisol molecules.

5. The photoelectric sensor based on flexible transparent conductive glass according to claim 4, characterized in that: The thickness of the F-doped polycrystalline SnO2 layer (4) is controlled to be between 20-200 nm, and the molar ratio of the F element to the Sn element in the F-doped polycrystalline SnO2 layer (4) is greater than 0 and less than or equal to 0.3; the particle size of the Cu nanoparticles (501) in the Cu nanoparticle layer (5) is controlled to be between 5-20 nm.

6. The photoelectric sensor based on flexible transparent conductive glass according to claim 1, characterized in that: The hydrophilic encapsulation layer is a polyacrylamide hydrogel protective layer (6), and is formed by photopolymerization of N,N-diethyl-2-acrylamide and N-hydroxyethyl acrylamide in a mass ratio of 1:1, and the thickness of the hydrophilic encapsulation layer is controlled between 100-200 μm.

7. The photoelectric sensor based on flexible transparent conductive glass according to claim 1, characterized in that: The thickness of the flexible transparent glass support substrate (1) is controlled between 30-50 μm.

8. A method for preparing a photoelectric sensor based on a flexible transparent conductive glass, for preparing a photoelectric sensor based on a flexible transparent conductive glass as claimed in any one of claims 1 to 7, characterized in that: The following steps are involved: S1, depositing a conductive barrier layer on the upper surface of the flexible transparent glass supporting substrate (1); S2, depositing a metal conductive layer on the upper surface of the conductive barrier layer; S3, depositing a photoelectric conversion layer on the upper surface of the metal conductive layer; S4, depositing a biorecognition layer on the upper surface of the photoelectric conversion layer to prepare a sensing electrode; S5. Covering the upper surface of the biorecognition layer with a hydrophilic encapsulation layer to prepare a photoelectric sensor.

9. The method for preparing a photoelectric sensor based on flexible transparent conductive glass according to claim 8, characterized in that: The following steps are also included between steps S4 and S5: The sensing electrode prepared in step S4 is subjected to vacuum annealing treatment, wherein the annealing temperature is controlled between 200-700°C.

10. A method for detecting the level of cortisol molecules in human sweat, using a photoelectric sensor based on flexible transparent conductive glass as described in any one of claims 1 to 7 and a data acquisition and analysis system connected to the photoelectric sensor for detection, characterized in that: Specifically, the hydrophilic encapsulation layer in the photoelectric sensor is directly contacted with human skin (7), and sweat discharged from the human skin (7) is collected through the hydrophilic encapsulation layer. The photoelectric conversion layer and the bio-recognition layer cooperate to bind to the cortisol molecules in the collected sweat, and external light sequentially passes through the flexible transparent glass support substrate (1), the conductive barrier layer and the metal conductive layer and irradiates the photoelectric conversion layer. The photoelectric conversion layer generates electron-hole pairs under light excitation, and the holes in the electron-hole pairs participate in the oxidation reaction of the cortisol molecules. The electrons in the electron-hole pairs and the electrons in the oxidation reaction of the cortisol molecules are sequentially transmitted through the photoelectric conversion layer, the metal conductive layer and the conductive barrier layer to the data acquisition and analysis system, so that the photocurrent signal transmitted to the data acquisition and analysis system is significantly enhanced. The photoelectric sensor cooperates with the data acquisition and analysis system to achieve real-time detection of the level of cortisol molecules in sweat.

Images