WO2023087332A1 - Bismuth oxide p-n type transition potential-based photoelectrochemical flexible wearable sweat ph sensor - Google Patents

Bismuth oxide p-n type transition potential-based photoelectrochemical flexible wearable sweat ph sensor Download PDF

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WO2023087332A1
WO2023087332A1 PCT/CN2021/132235 CN2021132235W WO2023087332A1 WO 2023087332 A1 WO2023087332 A1 WO 2023087332A1 CN 2021132235 W CN2021132235 W CN 2021132235W WO 2023087332 A1 WO2023087332 A1 WO 2023087332A1
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bismuth oxide
flexible
sweat
substrate
photoelectrochemical
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PCT/CN2021/132235
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French (fr)
Chinese (zh)
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汪福宪
董博恒
卫莉玲
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广东省科学院测试分析研究所(中国广州分析测试中心)
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Priority to DE112021003193.7T priority Critical patent/DE112021003193T5/en
Publication of WO2023087332A1 publication Critical patent/WO2023087332A1/en

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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416Systems
    • G01N27/4166Systems measuring a particular property of an electrolyte
    • G01N27/4167Systems measuring a particular property of an electrolyte pH
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/327Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements

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  • the invention relates to the technical field of photoelectrochemical sensing, in particular to a photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential.
  • the pH value of human sweat can provide a lot of important information about health status.
  • Various skin diseases such as dermatitis, acne and fungal infection, etc.
  • Provide important reference [Balaji A N, Yuan C, et al.pH Watch-Leveraging pulse oximeters in existing wearables for reusable, real-time monitoring of pH in sweat[C].The 17th Annual International Conference.2019:262-274 .].
  • flexible wearable sensors to monitor sweat pH is an effective method. Compared with traditional sensors, flexible wearable sensors are not only lighter, more beautiful, and more comfortable, but also can achieve continuous monitoring [Yu Mengke, Zhang Guojun. Flexible and wearable sensors] A review of the application of wearable sensors in sweat monitoring [J]. Medical and Health Equipment, 2020, 41(12): 90-96.].
  • the vibration caused by human body movement and power consumption may cause the light intensity of the photoelectrochemical sensor to fluctuate; when the human body sweats low, the sweat may not completely cover the sensing electrodes. In these cases, traditional sensing signal mechanisms can generate large measurement errors.
  • the purpose of the present invention is to provide a photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential .
  • the transition potential can adapt to the complex wearing environment, and can well resist the interference of changes in light intensity and changes in the area of the sweat-covered sensing electrode, and realize accurate and continuous monitoring of the pH value of sweat, which solves the problem of inaccurate measurement in the prior art question.
  • a photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential characterized in that it includes a bismuth oxide (Bi 2 O 3 ) working electrode, a reference electrode, a counter electrode, a transparent flexible Substrate and light source, the preparation of bismuth oxide (Bi 2 O 3 ) working electrode comprises the following steps:
  • ITO film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide (ITO) target with a purity of 99.99%, and the sputtering power is 50 -150W, substrate temperature is room temperature -350°C, argon flow rate is 10-50sccm, sputtering pressure is 0.5-3pa, deposition time is 300-3600s, substrate rotation speed is 10-30r/min;
  • step (2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 20-60W, and the substrate temperature is room temperature-350°C.
  • the argon flow rate is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-600s, and the substrate rotation speed is 10-30r/min;
  • step (3) Heating the bismuth oxide (Bi 2 O 3 ) film obtained in step (2) for 30-120 min at a heating temperature of 250-350° C., and the heating tool is one of a heating table, an oven, and a tube furnace to obtain bismuth oxide (Bi 2 O 3 ) working electrode.
  • the preparation of the bismuth oxide (Bi 2 O 3 ) working electrode includes the following steps:
  • ITO film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide (ITO) target with a purity of 99.99%, and the sputtering power is 100 -150W, substrate temperature is 200-350°C, argon gas flow is 10-50sccm, sputtering pressure is 1.5-2pa, deposition time is 1200-2400s, substrate rotation speed is 20-30r/min;
  • step (2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 40-60W, and the substrate temperature is 100-350°C.
  • the argon flow rate is 30-50sccm, the sputtering pressure is 1-2pa, the deposition time is 100-240s, and the substrate rotation speed is 20-30r/min;
  • step (3) Heating the bismuth oxide (Bi 2 O 3 ) film obtained in step (2) for 30-60 min at a heating temperature of 270-350° C., and the heating tool is one of a heating table, an oven, and a tube furnace to obtain bismuth oxide (Bi 2 O 3 ) working electrode.
  • the preparation of reference electrode comprises the following steps:
  • Agar is added in the mixed solution of saturated KCl, the content of agar is 1wt% ⁇ 5wt%, and mixed solution is heated to boiling to make agar dissolve completely;
  • step (1) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, and the mixed solution obtained in step (1) is drip-coated on the surface of the flexible Ag/AgCl film, and the coating amount is 10-50 ⁇ L/cm 2 , cooled to Obtain an agar gel film comprising KCl after room temperature;
  • step (3) On the surface of the agar gel film obtained in step (2), drop-coat Nafion solution with a content of 5 wt % in a coating amount of 5-30 ⁇ L/cm 2 , and dry at room temperature to form a film to obtain a reference electrode.
  • Counter electrode preparation includes the following steps:
  • Thin films are deposited on transparent and flexible substrates by DC magnetron sputtering, using targets with a purity of 99.99%, sputtering power at 10-100W, substrate temperature at room temperature -350°C, argon gas flow at 10-50sccm, and sputtering pressure 0.5-3pa, the deposition time is 60-3600s, and the substrate rotation speed is 10-30r/min.
  • the substrate is one of flexible polyester (PET), mica, and polyimide (PI).
  • the target material is one of graphite and Pt.
  • the width of the working electrode, the reference electrode and the counter electrode is 0.5-5mm, and the distance between the electrodes is 0.5-2mm.
  • the light source is 0.1-1W, and the wavelength is 400-500nm.
  • the packaging of the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential includes the following steps:
  • step 2) Encapsulate the film obtained in step 2) with PDMS glue, exposing the detection end and the wire connection end;
  • step (3) Curing the film obtained in step (3) at 95-105° C. for 50-70 minutes to obtain the finished product.
  • the present invention also protects the application of the above-mentioned photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential for detecting sweat pH, comprising the following steps:
  • the amphoteric bismuth oxide (Bi 2 O 3 ) semiconductor is used as the photoelectrode for the first time, and its unique pn-type transition potential is used as the sensing signal to prepare a photoelectrochemical flexible wearable sweat pH sensor.
  • the sensor can adapt to the complex wearing environment, and can well resist the interference of changes in light intensity and changes in the area of the sensing electrode covered by sweat.
  • the magnetron sputtering coating method is easy to achieve low-cost mass production of bismuth oxide (Bi 2 O 3 ) working electrodes.
  • the senor of the present invention has low preparation cost, is simple and portable, easy to use, has strong anti-interference ability, realizes accurate and continuous monitoring of sweat pH value, has high application value, and solves the problem of inaccurate measurement in the prior art.
  • Figure 1 is a schematic top view of the structure of the present invention.
  • Fig. 2 is a schematic side view of the structures of the reference electrode and the working electrode of the present invention.
  • Example 3 is an X-ray diffraction pattern (XRD) of the working electrode prepared in Example 1.
  • Fig. 4 shows the cyclic voltammetry scanning results of the flexible wearable sweat pH sensor under different pH values of sweat.
  • Figure 5 is the standard curve of the wearable sweat pH sensor.
  • Figure 6 shows the cyclic voltammetry scanning results of the wearable sweat pH sensor under different light intensities.
  • Figure 7 shows the cyclic voltammetry scanning results of the wearable sweat pH sensor at different sweat coverage rates.
  • a photoelectrochemical flexible wearable sweat pH sensor based on Bi 2 O 3 pn transition potential including Bi 2 O 3 working electrode, reference electrode, counter electrode, transparent flexible substrate and light source.
  • the width of the working electrode, the reference electrode and the counter electrode is 5mm, the distance between the electrodes is 1.5mm (as shown in Figure 1), the light source is 0.2W, and the wavelength is 440nm.
  • ITO indium-doped tin oxide
  • ITO indium-doped tin oxide
  • the substrate temperature is 200° C.
  • the argon flow rate is 30 sccm
  • the sputtering pressure is 1.5 pa
  • the deposition time is 2400 s
  • the substrate rotation speed is 20 r/min.
  • step (2) Deposit Bi metal on the ITO thin film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, sputtering power of 40W, substrate temperature of 100°C, and argon flow of 30sccm, the sputtering pressure is 1.0pa, the deposition time is 240s, and the substrate rotation speed is 20r/min.
  • step (3) The Bi 2 O 3 thin film obtained in step (2) was calcined on a heating platform for 60 min at a calcining temperature of 270° C. to obtain a Bi 2 O 3 working electrode (as shown in FIG. 2 ).
  • the resulting Bi 2 O 3 working electrode was analyzed by X-ray diffractometer (XRD) (as shown in Figure 3), and the working electrode film was made of ⁇ -Bi 2 O 3 (PDF#76-1730) and ⁇ -Bi2O3 (PDF# 78-1793) composition.
  • XRD X-ray diffractometer
  • Agar is added in the mixed solution of saturated KCl (the content of agar is 1%), and the mixed solution is heated to boiling to completely dissolve the agar.
  • step (1) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film.
  • the mixed solution obtained in step (1) is drop-coated on the surface of the flexible Ag/AgCl film with a coating amount of 10 ⁇ L/cm 2 , and cooled to room temperature An agar gel film containing KCl was obtained.
  • Pt metal was deposited on flexible polyester (PET) by DC magnetron sputtering, using a Pt metal target with a purity of 99.99%, the sputtering power was 50W, the substrate temperature was room temperature, the argon flow rate was 30sccm, and the sputtering pressure was 1.0pa, the deposition time is 600s, and the substrate rotation speed is 20r/min to obtain the counter electrode.
  • the packaging steps of the sensor are as follows:
  • a flexible polyester (PET) film with a thickness of 50 mm was selected as the transparent flexible substrate.
  • step (3) Encapsulating the thin film obtained in step (2) with PDMS glue, exposing the detection end and the wire connection end.
  • step (3) Curing the film obtained in step (3) at 100°C for 60 minutes to obtain the finished product.
  • Example 1 the difference lies in the preparation of Bi 2 O 3 working electrode, reference electrode and counter electrode.
  • ITO indium-doped tin oxide
  • ITO indium-doped tin oxide
  • the substrate temperature is 350° C.
  • the argon flow rate is 30 sccm
  • the sputtering pressure is 2 pa
  • the deposition time is 1200 s
  • the substrate rotation speed is 30 r/min.
  • step (2) Deposit Bi metal on the ITO thin film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, sputtering power of 60W, substrate temperature of 350°C, and argon flow of 50sccm, the sputtering pressure is 2pa, the deposition time is 100s, and the substrate rotation speed is 30r/min.
  • step (3) Calcining the Bi 2 O 3 film obtained in step (2) for 30 min on a heating platform at a temperature of 350° C. to obtain a Bi 2 O 3 working electrode.
  • Agar is added in the mixed solution of saturated KCl (the content of agar is 5%), and the mixed solution is heated to boiling to completely dissolve the agar.
  • step (1) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film.
  • the mixed solution obtained in step (1) is drop-coated on the surface of the flexible Ag/AgCl film with a coating amount of 50 ⁇ L/cm 2 , and cooled to room temperature An agar gel film containing KCl was obtained.
  • step (3) Drop-coat 5% Nafion solution on the surface of the agar gel film obtained in step (2), the coating amount is 30 ⁇ L/cm 2 , and dry at room temperature to form a film to obtain a reference electrode.
  • Pt metal was deposited on flexible polyester (PET) by DC magnetron sputtering, using a Pt metal target with a purity of 99.99%, the sputtering power was 70W, the substrate temperature was 150°C, the argon gas flow rate was 50sccm, and the sputtering pressure was is 2.0pa, the deposition time is 100s, and the substrate rotation speed is 30r/min to obtain the counter electrode.
  • the difference lies in the preparation of the counter electrode.
  • Graphite was deposited on flexible polyester (PET) by DC magnetron sputtering, using a graphite target with a purity of 99.99%, the sputtering power was 100W, the substrate temperature was 200°C, the argon flow rate was 30sccm, and the sputtering pressure was 1.0 pa, the deposition time is 60 min, and the substrate rotation speed is 30 r/min to obtain the counter electrode.
  • PET flexible polyester

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Abstract

A bismuth oxide p-n type transition potential-based photoelectrochemical flexible wearable sweat pH sensor, comprising a bismuth oxide working electrode, a reference electrode, a counter electrode, a transparent flexible substrate, and a light source. An amphoteric bismuth oxide semiconductor is used for the first time as a photoelectrode, and a specific p-n type transition potential thereof is used as a sensing signal, thus preparing a photoelectrochemical flexible wearable sweat pH sensor. The sensor may adapt to complex wearing environments, and may very well resist interference from changes in light intensity and the area of the sensing electrode covered by sweat covered; in addition, the sensor has low preparation costs, is simple and portable, easy to use, achieves the accurate and continuous monitoring of sweat pH value, and has high use value, thus solving the problem in the existing technology of inaccurate measurement.

Description

一种基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器A photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n transition potential 技术领域:Technical field:

本发明涉及光电化学传感技术领域,具体涉及一种基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器。The invention relates to the technical field of photoelectrochemical sensing, in particular to a photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential.

背景技术:Background technique:

人体汗液的pH值能够提供很多关于健康状况的重要信息,各类皮肤疾病(例如皮炎、痤疮和真菌感染等)会导致汗液的pH值发生变化,因此监测汗液的pH值可以为评估个人健康状况提供重要的参考[Balaji A N,Yuan C,et al.pH Watch-Leveraging pulse oximeters in existing wearables for reusable,real-time monitoring of pH in sweat[C].The 17th Annual International Conference.2019:262-274.]。The pH value of human sweat can provide a lot of important information about health status. Various skin diseases (such as dermatitis, acne and fungal infection, etc.) will cause changes in the pH value of sweat. Provide important reference [Balaji A N, Yuan C, et al.pH Watch-Leveraging pulse oximeters in existing wearables for reusable, real-time monitoring of pH in sweat[C].The 17th Annual International Conference.2019:262-274 .].

利用柔性可穿戴传感器对汗液pH进行监测是一种行之有效的方法,相比于传统的传感器,柔性可穿戴传感器不仅更加轻便、美观、舒适,而且能够实现连续监测[余梦珂,张国军.柔性可穿戴传感器在汗液监测中的应用综述[J].医疗卫生装备,2020,41(12):90-96.]。Using flexible wearable sensors to monitor sweat pH is an effective method. Compared with traditional sensors, flexible wearable sensors are not only lighter, more beautiful, and more comfortable, but also can achieve continuous monitoring [Yu Mengke, Zhang Guojun. Flexible and wearable sensors] A review of the application of wearable sensors in sweat monitoring [J]. Medical and Health Equipment, 2020, 41(12): 90-96.].

基于电化学和光电化学原理的柔性可穿戴传感器因其高精确度、高灵敏度、快速响应受到了广泛的关注。目前市场上已经出现许多基于电化学和光电化学的柔性可穿戴pH传感器[Shi X M,Mei L P,et al.A polymer dots-based photoelectrochemical pH sensor:simplicity,high sensitivity,and broad-range pH measurement[J].Analytical chemistry,2018,90(14):8300-8303.],但是它们均是基于恒电流(或恒电位)下的电压(或电流)信号来判断pH值,这种信号机制在对复杂多变的穿戴环境的适应能力较差。在真实的使用场景下,人体运动带来的振动、电量的消耗可能会导致光电化学传感器的光强发生波动;在人体排汗量低时,可能导致汗液 无法完全覆盖传感电极。在这些情况下,传统的传感信号机制会产生巨大的测量误差。Flexible wearable sensors based on electrochemical and photoelectrochemical principles have attracted extensive attention due to their high accuracy, high sensitivity, and fast response. At present, many flexible and wearable pH sensors based on electrochemical and photoelectrochemical methods have appeared on the market [Shi X M, Mei L P, et al. A polymer dots-based photoelectrochemical pH sensor:simplicity, high sensitivity, and broad-range pH measurement [J].Analytical chemistry,2018,90(14):8300-8303.], but they are all based on the voltage (or current) signal under constant current (or constant potential) to judge the pH value, this signal mechanism is in Poor adaptability to complex and changeable wearing environments. In real usage scenarios, the vibration caused by human body movement and power consumption may cause the light intensity of the photoelectrochemical sensor to fluctuate; when the human body sweats low, the sweat may not completely cover the sensing electrodes. In these cases, traditional sensing signal mechanisms can generate large measurement errors.

发明内容:Invention content:

本发明的目的是提供一种基于氧化铋(Bi 2O 3)p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,首次采用双性Bi 2O 3半导体作为光电极,利用其特有的p-n型转变电位作为传感信号,能够适应复杂穿戴环境,可很好的抵抗光强变化以及汗液覆盖传感电极面积变化的干扰,实现汗液pH值的准确连续监测,解决了现有技术测量不准确的问题。 The purpose of the present invention is to provide a photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential . As the sensing signal, the transition potential can adapt to the complex wearing environment, and can well resist the interference of changes in light intensity and changes in the area of the sweat-covered sensing electrode, and realize accurate and continuous monitoring of the pH value of sweat, which solves the problem of inaccurate measurement in the prior art question.

本发明是通过以下技术方案予以实现的:The present invention is achieved through the following technical solutions:

一种基于氧化铋(Bi 2O 3)p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,包括氧化铋(Bi 2O 3)工作电极、参比电极、对电极、透明柔性基底和光源,氧化铋(Bi 2O 3)工作电极的制备包括以下步骤: A photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential, characterized in that it includes a bismuth oxide (Bi 2 O 3 ) working electrode, a reference electrode, a counter electrode, a transparent flexible Substrate and light source, the preparation of bismuth oxide (Bi 2 O 3 ) working electrode comprises the following steps:

(1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡(ITO)薄膜:用纯度为99.99%的铟掺杂氧化锡(ITO)靶材,溅射功率为50-150W,基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为300-3600s,基底旋转速度为10-30r/min;(1) Deposit indium-doped tin oxide (ITO) film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide (ITO) target with a purity of 99.99%, and the sputtering power is 50 -150W, substrate temperature is room temperature -350°C, argon flow rate is 10-50sccm, sputtering pressure is 0.5-3pa, deposition time is 300-3600s, substrate rotation speed is 10-30r/min;

(2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为20-60W,基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为60-600s,基底旋转速度为10-30r/min;(2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 20-60W, and the substrate temperature is room temperature-350°C. The argon flow rate is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-600s, and the substrate rotation speed is 10-30r/min;

(3)将步骤(2)所得氧化铋(Bi 2O 3)薄膜加热30-120min,加热温度为250-350℃,加热工具为加热台、烘箱、管式炉中的一种,得到氧化铋(Bi 2O 3)工作电极。 (3) Heating the bismuth oxide (Bi 2 O 3 ) film obtained in step (2) for 30-120 min at a heating temperature of 250-350° C., and the heating tool is one of a heating table, an oven, and a tube furnace to obtain bismuth oxide (Bi 2 O 3 ) working electrode.

优选地,氧化铋(Bi 2O 3)工作电极的制备包括以下步骤: Preferably, the preparation of the bismuth oxide (Bi 2 O 3 ) working electrode includes the following steps:

(1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡(ITO)薄膜:用纯度为99.99%的铟掺杂氧化锡(ITO)靶材,溅射功率为100-150W,基底温度为200-350℃,氩气流量为10-50sccm,溅射压力为1.5-2pa,沉积时间为1200-2400s,基底旋转速度为20-30r/min;(1) Deposit indium-doped tin oxide (ITO) film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide (ITO) target with a purity of 99.99%, and the sputtering power is 100 -150W, substrate temperature is 200-350℃, argon gas flow is 10-50sccm, sputtering pressure is 1.5-2pa, deposition time is 1200-2400s, substrate rotation speed is 20-30r/min;

(2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为40-60W,基底温度为100-350℃,氩气流量为30-50sccm,溅射压力为1-2pa,沉积时间为100-240s,基底旋转速度为20-30r/min;(2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 40-60W, and the substrate temperature is 100-350°C. The argon flow rate is 30-50sccm, the sputtering pressure is 1-2pa, the deposition time is 100-240s, and the substrate rotation speed is 20-30r/min;

(3)将步骤(2)所得氧化铋(Bi 2O 3)薄膜加热30-60min,加热温度为270-350℃,加热工具为加热台、烘箱、管式炉中的一种,得到氧化铋(Bi 2O 3)工作电极。 (3) Heating the bismuth oxide (Bi 2 O 3 ) film obtained in step (2) for 30-60 min at a heating temperature of 270-350° C., and the heating tool is one of a heating table, an oven, and a tube furnace to obtain bismuth oxide (Bi 2 O 3 ) working electrode.

参比电极的制备包括如下步骤:The preparation of reference electrode comprises the following steps:

(1)琼脂加入饱和KCl的混合溶液中,琼脂的含量为1wt%~5wt%,将混合溶液加热至沸腾使琼脂完全溶解;(1) Agar is added in the mixed solution of saturated KCl, the content of agar is 1wt%~5wt%, and mixed solution is heated to boiling to make agar dissolve completely;

(2)将Ag/AgCl固定在透明柔性基底上得到柔性Ag/AgCl薄膜,步骤(1)所得混合溶液滴涂在柔性Ag/AgCl薄膜表面,涂覆量为10-50μL/cm 2,冷却到室温后得到包含KCl的琼脂凝胶膜; (2) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, and the mixed solution obtained in step (1) is drip-coated on the surface of the flexible Ag/AgCl film, and the coating amount is 10-50 μ L/cm 2 , cooled to Obtain an agar gel film comprising KCl after room temperature;

(3)在步骤(2)所得琼脂凝胶膜表面滴涂含量为5wt%的Nafion溶液,涂覆量为5-30μL/cm 2,并在室温下干燥成膜,得到参比电极。 (3) On the surface of the agar gel film obtained in step (2), drop-coat Nafion solution with a content of 5 wt % in a coating amount of 5-30 μL/cm 2 , and dry at room temperature to form a film to obtain a reference electrode.

对电极制备包括如下步骤:Counter electrode preparation includes the following steps:

采用直流磁控溅射法在透明柔性基底上沉积薄膜,使用纯度99.99%的靶材,溅射功率为10-100W、基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为 60-3600s,基底旋转速度为10-30r/min。Thin films are deposited on transparent and flexible substrates by DC magnetron sputtering, using targets with a purity of 99.99%, sputtering power at 10-100W, substrate temperature at room temperature -350°C, argon gas flow at 10-50sccm, and sputtering pressure 0.5-3pa, the deposition time is 60-3600s, and the substrate rotation speed is 10-30r/min.

对电极制备中,所述基底为柔性聚酯(PET)、云母、聚酰亚胺(PI)中的一种。所述靶材为石墨、Pt中的一种。In the preparation of the counter electrode, the substrate is one of flexible polyester (PET), mica, and polyimide (PI). The target material is one of graphite and Pt.

优选地,所述工作电极、参比电极和对电极的宽度为0.5-5mm,电极间距为0.5-2mm。Preferably, the width of the working electrode, the reference electrode and the counter electrode is 0.5-5mm, and the distance between the electrodes is 0.5-2mm.

优选地,所述光源为0.1-1W,波长为400-500nm。Preferably, the light source is 0.1-1W, and the wavelength is 400-500nm.

基于氧化铋(Bi 2O 3)p-n型转变电位的光电化学柔性可穿戴汗液pH传感器的封装包括如下步骤: The packaging of the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential includes the following steps:

1)选取厚度为45-55mm的柔性聚酯(PET)薄膜作为透明柔性基底;1) Select a flexible polyester (PET) film with a thickness of 45-55mm as the transparent flexible substrate;

2)用聚二甲基硅氧烷(PDMS)胶将所述工作电极、参比电极和对电极贴在透明柔性聚酯(PET)薄膜上;2) Paste the working electrode, reference electrode and counter electrode on the transparent flexible polyester (PET) film with polydimethylsiloxane (PDMS) glue;

3)将步骤2)所得薄膜用PDMS胶封装,露出检测端和导线连接端;3) Encapsulate the film obtained in step 2) with PDMS glue, exposing the detection end and the wire connection end;

4)将步骤(3)所得薄膜在95-105℃下固化50-70min,即得成品。4) Curing the film obtained in step (3) at 95-105° C. for 50-70 minutes to obtain the finished product.

本发明还保护上述基于氧化铋(Bi 2O 3)p-n型转变电位的光电化学柔性可穿戴汗液pH传感器的应用,用于检测汗液pH,包括以下步骤: The present invention also protects the application of the above-mentioned photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide (Bi 2 O 3 ) pn-type transition potential for detecting sweat pH, comprising the following steps:

(1)采用三电极体系,在柔性可穿戴pH传感器的测试区域滴加1-7μL/mm 2人工汗液,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流; (1) Using a three-electrode system, add 1-7μL/mm 2 artificial sweat to the test area of the flexible wearable pH sensor, scan the dark current by cyclic voltammetry under no light conditions, and use cyclic voltammetry to obtain dark current under light conditions. An method to scan to get photocurrent;

(2)依次测试不同pH的人工汗液,获得不同pH下的p-n型转变电位(光电流和暗电流交点处的电位),然后对数据进行拟合并获得标准曲线;(2) Test the artificial sweat with different pH in sequence to obtain the p-n transition potential (potential at the intersection of photocurrent and dark current) at different pH, and then fit the data and obtain a standard curve;

3)将柔性可穿戴pH传感器贴合在皮肤上,待汗液浸润测试区域后,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流,获得此时的p-n 型转变电位,对照标准曲线得到此时汗液的pH值。3) Attach the flexible wearable pH sensor to the skin. After the sweat infiltrates the test area, the dark current is scanned by cyclic voltammetry under no light conditions, and the photocurrent is obtained by cyclic voltammetry scanning under light conditions. The p-n transition potential at this time is obtained, and the pH value of the sweat at this time is obtained by comparing with the standard curve.

本发明的有益效果为:The beneficial effects of the present invention are:

1)本发明首次采用双性氧化铋(Bi 2O 3)半导体作为光电极,利用其特有的p-n型转变电位作为传感信号,制备了光电化学柔性可穿戴汗液pH传感器。该传感器能够适应复杂穿戴环境,可很好的抵抗光强变化以及汗液覆盖传感电极面积变化的干扰。 1) In the present invention, the amphoteric bismuth oxide (Bi 2 O 3 ) semiconductor is used as the photoelectrode for the first time, and its unique pn-type transition potential is used as the sensing signal to prepare a photoelectrochemical flexible wearable sweat pH sensor. The sensor can adapt to the complex wearing environment, and can well resist the interference of changes in light intensity and changes in the area of the sensing electrode covered by sweat.

2)磁控溅射镀膜法易于实现氧化铋(Bi 2O 3)工作电极的低成本大规模生产。 2) The magnetron sputtering coating method is easy to achieve low-cost mass production of bismuth oxide (Bi 2 O 3 ) working electrodes.

总之,本发明传感器制备成本低廉、简单便携、使用简易,抗干扰能力强,实现汗液pH值的准确连续监测,具有较高的应用价值,解决了现有技术测量不准确的问题。In a word, the sensor of the present invention has low preparation cost, is simple and portable, easy to use, has strong anti-interference ability, realizes accurate and continuous monitoring of sweat pH value, has high application value, and solves the problem of inaccurate measurement in the prior art.

附图说明:Description of drawings:

图1为本发明结构俯视示意图。Figure 1 is a schematic top view of the structure of the present invention.

图2为本发明参比电极和工作电极的结构侧视示意图。Fig. 2 is a schematic side view of the structures of the reference electrode and the working electrode of the present invention.

图3为实施例1制备得到的工作电极的X射线衍射图(XRD)。3 is an X-ray diffraction pattern (XRD) of the working electrode prepared in Example 1.

图4为不同pH值汗液下柔性可穿戴汗液pH传感器的循环伏安法扫描结果。Fig. 4 shows the cyclic voltammetry scanning results of the flexible wearable sweat pH sensor under different pH values of sweat.

图5为可穿戴汗液pH传感器的标准曲线。Figure 5 is the standard curve of the wearable sweat pH sensor.

图6为可穿戴汗液pH传感器在不同光强下的循环伏安法扫描结果。Figure 6 shows the cyclic voltammetry scanning results of the wearable sweat pH sensor under different light intensities.

图7为可穿戴汗液pH传感器在汗液覆盖率不同时的循环伏安法扫描结果。Figure 7 shows the cyclic voltammetry scanning results of the wearable sweat pH sensor at different sweat coverage rates.

具体实施方式:Detailed ways:

以下是对本发明的进一步说明,而不是对本发明的限制。The following is a further description of the present invention, rather than a limitation of the present invention.

实施例1:Example 1:

一种基于Bi 2O 3p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,包括Bi 2O 3工作 电极、参比电极、对电极、透明柔性基底和光源。工作电极、参比电极和对电极的宽度为5mm,电极间距为1.5mm(如图1所示),光源为0.2W,波长为440nm。 A photoelectrochemical flexible wearable sweat pH sensor based on Bi 2 O 3 pn transition potential, including Bi 2 O 3 working electrode, reference electrode, counter electrode, transparent flexible substrate and light source. The width of the working electrode, the reference electrode and the counter electrode is 5mm, the distance between the electrodes is 1.5mm (as shown in Figure 1), the light source is 0.2W, and the wavelength is 440nm.

Bi 2O 3工作电极的制备步骤: Preparation steps of Bi2O3 working electrode:

(1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡(ITO)薄膜,使用纯度为99.99%的铟掺杂氧化锡(ITO)靶材,溅射功率为100W,基底温度为200℃,氩气流量为30sccm,溅射压力为1.5pa,沉积时间为2400s,基底旋转速度20r/min。(1) Deposit an indium-doped tin oxide (ITO) film on a transparent and flexible mica substrate by radio frequency magnetron sputtering, using an indium-doped tin oxide (ITO) target with a purity of 99.99%, and a sputtering power of 100W , the substrate temperature is 200° C., the argon flow rate is 30 sccm, the sputtering pressure is 1.5 pa, the deposition time is 2400 s, and the substrate rotation speed is 20 r/min.

(2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为40W,基底温度为100℃,氩气流量为30sccm,溅射压力为1.0pa沉积时间为240s,基底旋转速度为20r/min。(2) Deposit Bi metal on the ITO thin film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, sputtering power of 40W, substrate temperature of 100°C, and argon flow of 30sccm, the sputtering pressure is 1.0pa, the deposition time is 240s, and the substrate rotation speed is 20r/min.

(3)将步骤(2)所得Bi 2O 3薄膜在加热台上锻烧60min,锻烧温度为270℃,得到Bi 2O 3工作电极(如图2所示)。 (3) The Bi 2 O 3 thin film obtained in step (2) was calcined on a heating platform for 60 min at a calcining temperature of 270° C. to obtain a Bi 2 O 3 working electrode (as shown in FIG. 2 ).

将所得Bi 2O 3工作电极采用X射线衍射仪(XRD)分析(如图3所示),工作电极薄膜是由α-Bi 2O 3(PDF#76-1730)和β-Bi2O3(PDF#78-1793)组成。 The resulting Bi 2 O 3 working electrode was analyzed by X-ray diffractometer (XRD) (as shown in Figure 3), and the working electrode film was made of α-Bi 2 O 3 (PDF#76-1730) and β-Bi2O3 (PDF# 78-1793) composition.

参比电极的制备步骤:Preparation steps of the reference electrode:

(1)琼脂加入饱和KCl的混合溶液中(琼脂的含量为1%),将混合溶液加热至沸腾使琼脂完全溶解。(1) Agar is added in the mixed solution of saturated KCl (the content of agar is 1%), and the mixed solution is heated to boiling to completely dissolve the agar.

(2)将Ag/AgCl固定在透明柔性基底上得到柔性Ag/AgCl薄膜,步骤(1)所得混合溶液滴涂在柔性Ag/AgCl薄膜表面,涂覆量为10μL/cm 2,冷却到室温后得到包含KCl的琼脂凝胶膜。 (2) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film. The mixed solution obtained in step (1) is drop-coated on the surface of the flexible Ag/AgCl film with a coating amount of 10 μL/cm 2 , and cooled to room temperature An agar gel film containing KCl was obtained.

(3)在步骤(2)所得琼脂凝胶膜表面滴涂含量为5%的Nafion溶液,涂覆量为5μL/cm 2, 并在室温下干燥成膜,得到参比电极(如图2所示)。 (3) The Nafion solution with a content of 5% was drip-coated on the surface of the agar gel film obtained in step (2), and the coating amount was 5 μL/cm 2 , and dried at room temperature to form a film to obtain a reference electrode (as shown in Figure 2 Show).

对电极的的制备步骤:The preparation steps of the counter electrode:

采用直流磁控溅射法在柔性聚酯(PET)上沉积Pt金属,使用纯度99.99%的Pt金属靶材,溅射功率为50W,基底温度为室温,氩气流量为30sccm,溅射压力为1.0pa,沉积时间为600s,基底旋转速度为20r/min,得到对电极。Pt metal was deposited on flexible polyester (PET) by DC magnetron sputtering, using a Pt metal target with a purity of 99.99%, the sputtering power was 50W, the substrate temperature was room temperature, the argon flow rate was 30sccm, and the sputtering pressure was 1.0pa, the deposition time is 600s, and the substrate rotation speed is 20r/min to obtain the counter electrode.

传感器的封装步骤如下:The packaging steps of the sensor are as follows:

(1)选取厚度为50mm的柔性聚酯(PET)薄膜作为透明柔性基底。(1) A flexible polyester (PET) film with a thickness of 50 mm was selected as the transparent flexible substrate.

(2)使用聚二甲基硅氧烷(PDMS)胶将工作电极、参比电极和对电极贴在透明柔性聚酯(PET)薄膜上。(2) Using polydimethylsiloxane (PDMS) glue to stick the working electrode, reference electrode and counter electrode on the transparent flexible polyester (PET) film.

(3)将步骤(2)所得薄膜用PDMS胶封装,露出检测端和导线连接端。(3) Encapsulating the thin film obtained in step (2) with PDMS glue, exposing the detection end and the wire connection end.

(4)将步骤(3)所得薄膜在100℃下固化60min,即得成品。(4) Curing the film obtained in step (3) at 100°C for 60 minutes to obtain the finished product.

实施例2Example 2

参考实施例1,不同之处在于Bi 2O 3工作电极、参比电极和对电极的制备。 Referring to Example 1, the difference lies in the preparation of Bi 2 O 3 working electrode, reference electrode and counter electrode.

Bi 2O 3工作电极的制备步骤: Preparation steps of Bi2O3 working electrode:

(1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡(ITO)薄膜,使用纯度为99.99%的铟掺杂氧化锡(ITO)靶材,溅射功率为150W,基底温度为350℃,氩气流量为30sccm,溅射压力为2pa,沉积时间为1200s,基底旋转速度30r/min。(1) Deposit an indium-doped tin oxide (ITO) film on a transparent and flexible mica substrate by radio frequency magnetron sputtering, using an indium-doped tin oxide (ITO) target with a purity of 99.99%, and a sputtering power of 150W , the substrate temperature is 350° C., the argon flow rate is 30 sccm, the sputtering pressure is 2 pa, the deposition time is 1200 s, and the substrate rotation speed is 30 r/min.

(2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为60W,基底温度为350℃,氩气流量为50sccm,溅射压力为2pa沉积时间为100s,基底旋转速度为30r/min。(2) Deposit Bi metal on the ITO thin film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, sputtering power of 60W, substrate temperature of 350°C, and argon flow of 50sccm, the sputtering pressure is 2pa, the deposition time is 100s, and the substrate rotation speed is 30r/min.

(3)将步骤(2)所得Bi 2O 3薄膜在加热台上锻烧30min,锻烧温度为350℃,得到Bi 2O 3工作电极。 (3) Calcining the Bi 2 O 3 film obtained in step (2) for 30 min on a heating platform at a temperature of 350° C. to obtain a Bi 2 O 3 working electrode.

参比电极的制备步骤:Preparation steps of the reference electrode:

(1)琼脂加入饱和KCl的混合溶液中(琼脂的含量为5%),将混合溶液加热至沸腾使琼脂完全溶解。(1) Agar is added in the mixed solution of saturated KCl (the content of agar is 5%), and the mixed solution is heated to boiling to completely dissolve the agar.

(2)将Ag/AgCl固定在透明柔性基底上得到柔性Ag/AgCl薄膜,步骤(1)所得混合溶液滴涂在柔性Ag/AgCl薄膜表面,涂覆量为50μL/cm 2,冷却到室温后得到包含KCl的琼脂凝胶膜。 (2) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film. The mixed solution obtained in step (1) is drop-coated on the surface of the flexible Ag/AgCl film with a coating amount of 50 μL/cm 2 , and cooled to room temperature An agar gel film containing KCl was obtained.

(3)在步骤(2)所得琼脂凝胶膜表面滴涂含量为5%的Nafion溶液,涂覆量为30μL/cm 2,并在室温下干燥成膜,得到参比电极。 (3) Drop-coat 5% Nafion solution on the surface of the agar gel film obtained in step (2), the coating amount is 30 μL/cm 2 , and dry at room temperature to form a film to obtain a reference electrode.

对电极的的制备步骤:The preparation steps of the counter electrode:

采用直流磁控溅射法在柔性聚酯(PET)上沉积Pt金属,使用纯度99.99%的Pt金属靶材,溅射功率为70W、基底温度为150℃,氩气流量为50sccm,溅射压力为2.0pa,沉积时间为100s,基底旋转速度为30r/min,得到对电极。Pt metal was deposited on flexible polyester (PET) by DC magnetron sputtering, using a Pt metal target with a purity of 99.99%, the sputtering power was 70W, the substrate temperature was 150°C, the argon gas flow rate was 50sccm, and the sputtering pressure was is 2.0pa, the deposition time is 100s, and the substrate rotation speed is 30r/min to obtain the counter electrode.

实施例3Example 3

参考实施例1,不同之处在于对电极的制备。Referring to Example 1, the difference lies in the preparation of the counter electrode.

对电极的的制备步骤:The preparation steps of the counter electrode:

采用直流磁控溅射法在柔性聚酯(PET)上沉积石墨,使用纯度99.99%的石墨靶材,溅射功率为100W、基底温度为200℃,氩气流量为30sccm,溅射压力为1.0pa,沉积时间为60min,基底旋转速度为30r/min,得到对电极。Graphite was deposited on flexible polyester (PET) by DC magnetron sputtering, using a graphite target with a purity of 99.99%, the sputtering power was 100W, the substrate temperature was 200°C, the argon flow rate was 30sccm, and the sputtering pressure was 1.0 pa, the deposition time is 60 min, and the substrate rotation speed is 30 r/min to obtain the counter electrode.

实验例1Experimental example 1

1、获得标准曲线1. Obtain the standard curve

采用三电极体系,在上述实施例1得到的柔性可穿戴pH传感器的测试区域滴加3μL/mm 2人工汗液,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流。依次测试不同pH的人工汗液,得到如图4所示结果。获得不同pH下的p-n型转变电位(光电流和暗电流交点处的电位),拟合得到如图5所示的标准曲线,拟合度良好。 Using a three-electrode system, add 3 μL/mm 2 of artificial sweat to the test area of the flexible wearable pH sensor obtained in Example 1 above, scan the dark current by cyclic voltammetry under no light conditions, and use cyclic voltammetry under light conditions to obtain the dark current. Photocurrent was obtained by voltammetry scan. The artificial sweat with different pH was tested sequentially, and the results shown in Figure 4 were obtained. The pn-type transition potentials (potentials at the intersection of photocurrent and dark current) at different pHs were obtained, and a standard curve as shown in Figure 5 was obtained by fitting, and the fitting degree was good.

将柔性可穿戴pH传感器贴合在皮肤上,待汗液浸润测试区域后,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流,获得此时的p-n型转变电位,对照标准曲线得到此时汗液的pH值。Attach the flexible wearable pH sensor to the skin. After the sweat infiltrates the test area, the dark current is scanned by cyclic voltammetry under no light conditions, and the photocurrent is obtained by cyclic voltammetry scanning under light conditions. When the p-n type transition potential is compared with the standard curve, the pH value of the sweat at this time is obtained.

实验例2Experimental example 2

1、抗光强干扰测试1. Anti-light interference test

在上述实施例1制备得到的柔性可穿戴pH传感器测试区域滴加3μL/mm 2pH为5的人工汗液,在15mW/cm 2-35mW/cm 2的光强下分别测试,在光强发生变化时,p-n型转变电位基本上没有发生变化,而电流却发生了巨大的变化,如图6所示。由此可见,在光强发生变化的情况下,以p-n型转变电位为信号获得的pH检测结果准确度将远高于以电流为信号获得的pH检测结果。 Add 3 μL/mm 2 of artificial sweat with a pH of 5 to the test area of the flexible wearable pH sensor prepared in the above-mentioned Example 1, and test under the light intensity of 15mW/cm 2 -35mW/cm 2 respectively, when the light intensity changes , the pn-type transition potential basically does not change, but the current has a huge change, as shown in Figure 6. It can be seen that when the light intensity changes, the accuracy of the pH detection result obtained by using the pn-type transition potential as a signal will be much higher than the pH detection result obtained by using the current as a signal.

2、汗液部分覆盖干扰测试2. Partial coverage of sweat interferes with the test

在上述实施例1制备得到的柔性可穿戴pH传感器测试区域滴加3μL/mm 2pH为5的人工汗液,控制人工汗液覆盖工作电极的面积,在不同的覆盖度下分别测试,同样发现,在汗液对电极部分覆盖时,p-n型转变电位基本上没有发生变化,而电流却发生了巨大的变化,如图 7所示。由此可见,在汗液对电极部分覆盖时,以p-n型转变电位为信号获得的pH检测结果准确度将远高于以电流为信号获得的pH检测结果。 Add 3 μL/mm 2 of artificial sweat with a pH of 5 to the test area of the flexible wearable pH sensor prepared in the above-mentioned Example 1, control the area of the working electrode covered by the artificial sweat, and test separately under different coverage degrees. It is also found that in When sweat partially covers the electrode, the pn-type transition potential basically does not change, but the current changes greatly, as shown in Figure 7. It can be seen that when sweat partially covers the electrode, the accuracy of the pH detection result obtained by using the pn-type transition potential as a signal will be much higher than that obtained by using the current as a signal.

以上实施例的说明只是用于帮助理解本发明的技术方案及其核心思想,应当指出,对于The description of the above embodiments is only used to help understand the technical scheme of the present invention and its core idea, it should be pointed out that for

本技术领域的技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求的保护范围内。For those skilled in the art, without departing from the principles of the present invention, some improvements and modifications can be made to the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (10)

一种基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,包括氧化铋工作电极、参比电极、对电极、透明柔性基底和光源,氧化铋工作电极的制备包括以下步骤:A photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential is characterized in that it includes a bismuth oxide working electrode, a reference electrode, a counter electrode, a transparent flexible substrate and a light source, and the preparation of the bismuth oxide working electrode includes the following step: (1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡薄膜:用纯度为99.99%的铟掺杂氧化锡靶材,溅射功率为50-150W,基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为300-3600s,基底旋转速度为10-30r/min;(1) Deposit indium-doped tin oxide film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide target with a purity of 99.99%, sputtering power is 50-150W, and the substrate temperature is Room temperature -350°C, argon gas flow rate of 10-50sccm, sputtering pressure of 0.5-3pa, deposition time of 300-3600s, substrate rotation speed of 10-30r/min; (2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为20-60W,基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为60-600s,基底旋转速度为10-30r/min;(2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 20-60W, and the substrate temperature is room temperature-350°C. The argon flow rate is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-600s, and the substrate rotation speed is 10-30r/min; (3)将步骤(2)所得氧化铋薄膜加热30-120min,加热温度为250-350℃,加热工具为加热台、烘箱、管式炉中的一种,得到氧化铋工作电极。(3) Heating the bismuth oxide thin film obtained in step (2) for 30-120 min at a heating temperature of 250-350° C., and the heating tool is one of a heating table, an oven, and a tube furnace to obtain a bismuth oxide working electrode. 根据权利要求1所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,氧化铋工作电极的制备包括以下步骤:The photoelectrochemical flexible wearable sweat pH sensor based on the bismuth oxide p-n type transition potential according to claim 1, wherein the preparation of the bismuth oxide working electrode comprises the following steps: (1)采用射频磁控溅射法在透明柔性的云母基底上沉积铟掺杂氧化锡薄膜:用纯度为99.99%的铟掺杂氧化锡靶材,溅射功率为100-150W,基底温度为200-350℃,氩气流量为10-50sccm,溅射压力为1.5-2pa,沉积时间为1200-2400s,基底旋转速度为20-30r/min;(1) Deposit indium-doped tin oxide film on a transparent and flexible mica substrate by radio frequency magnetron sputtering: use an indium-doped tin oxide target material with a purity of 99.99%, the sputtering power is 100-150W, and the substrate temperature is 200-350°C, argon gas flow rate of 10-50sccm, sputtering pressure of 1.5-2pa, deposition time of 1200-2400s, substrate rotation speed of 20-30r/min; (2)采用直流磁控溅射法在步骤(1)所得ITO薄膜上沉积Bi金属,使用纯度为99.99%的Bi金属靶材,溅射功率为40-60W,基底温度为100-350℃,氩气流量为30-50sccm,溅射压力为1-2pa,沉积时间为100-240s,基底旋转速度为20-30r/min;(2) Depositing Bi metal on the ITO film obtained in step (1) by DC magnetron sputtering, using a Bi metal target with a purity of 99.99%, the sputtering power is 40-60W, and the substrate temperature is 100-350°C. The argon flow rate is 30-50sccm, the sputtering pressure is 1-2pa, the deposition time is 100-240s, and the substrate rotation speed is 20-30r/min; (3)将步骤(2)所得氧化铋薄膜加热30-60min,加热温度为270-350℃,加热工具为加热 台、烘箱、管式炉中的一种,得到氧化铋工作电极。(3) Heating the bismuth oxide thin film obtained in step (2) for 30-60min, the heating temperature is 270-350°C, and the heating tool is one of a heating table, an oven, and a tube furnace to obtain a bismuth oxide working electrode. 根据权利要求1所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,参比电极的制备包括如下步骤:The photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 1, wherein the preparation of the reference electrode comprises the following steps: (1)琼脂加入饱和KCl的混合溶液中,琼脂的含量为1wt%~5wt%,将混合溶液加热至沸腾使琼脂完全溶解;(1) Agar is added in the mixed solution of saturated KCl, the content of agar is 1wt%~5wt%, and mixed solution is heated to boiling to make agar dissolve completely; (2)将Ag/AgCl固定在透明柔性基底上得到柔性Ag/AgCl薄膜,步骤(1)所得混合溶液滴涂在柔性Ag/AgCl薄膜表面,涂覆量为10-50μL/cm 2,冷却到室温后得到包含KCl的琼脂凝胶膜; (2) Fix Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, and the mixed solution obtained in step (1) is drip-coated on the surface of the flexible Ag/AgCl film, and the coating amount is 10-50 μ L/cm 2 , cooled to Obtain an agar gel film comprising KCl after room temperature; (3)在步骤(2)所得琼脂凝胶膜表面滴涂含量为5wt%的Nafion溶液,涂覆量为5-30μL/cm 2,并在室温下干燥成膜,得到参比电极。 (3) On the surface of the agar gel film obtained in step (2), drop-coat Nafion solution with a content of 5 wt % in a coating amount of 5-30 μL/cm 2 , and dry at room temperature to form a film to obtain a reference electrode. 根据权利要求1所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,对电极制备包括如下步骤:采用直流磁控溅射法在透明柔性基底上沉积薄膜,使用纯度99.99%的靶材,溅射功率为10-100W、基底温度为室温-350℃,氩气流量为10-50sccm,溅射压力为0.5-3pa,沉积时间为60-3600s,基底旋转速度为10-30r/min。According to the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 1, it is characterized in that the preparation of the counter electrode comprises the following steps: depositing a thin film on a transparent flexible substrate by DC magnetron sputtering, using For a target with a purity of 99.99%, the sputtering power is 10-100W, the substrate temperature is room temperature-350°C, the argon flow rate is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-3600s, and the substrate rotation speed is 10-30r/min. 根据权利要求4所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,所述基底为柔性聚酯、云母、聚酰亚胺中的一种。The photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 4, wherein the substrate is one of flexible polyester, mica, and polyimide. 根据权利要求4所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,所述靶材为石墨、Pt中的一种。The photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 4, wherein the target material is one of graphite and Pt. 根据权利要求1或2所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,工作电极、参比电极和对电极的宽度为0.5-5mm,电极间距为0.5-2mm。According to the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 1 or 2, it is characterized in that the width of the working electrode, reference electrode and counter electrode is 0.5-5mm, and the electrode spacing is 0.5-5mm. 2mm. 根据权利要求1或2所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器,其特征在于,光源为0.1-1W,波长为400-500nm。According to claim 1 or 2, the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential is characterized in that the light source is 0.1-1W and the wavelength is 400-500nm. 基于权利要求1所述氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器的封装方法,其特征在于,包括如下步骤:The encapsulation method of the photoelectrochemical flexible wearable sweat pH sensor based on the p-n type transition potential of bismuth oxide described in claim 1, is characterized in that, comprises the steps: 1)选取厚度为45-55mm的柔性聚酯薄膜作为透明柔性基底;1) Select a flexible polyester film with a thickness of 45-55mm as the transparent flexible substrate; 2)用聚二甲基硅氧烷胶将所述工作电极、参比电极和对电极贴在透明柔性聚酯薄膜上;2) Paste the working electrode, reference electrode and counter electrode on the transparent flexible polyester film with polydimethylsiloxane glue; 3)将步骤2)所得薄膜用PDMS胶封装,露出检测端和导线连接端;3) Encapsulate the film obtained in step 2) with PDMS glue, exposing the detection end and the wire connection end; 4)将步骤(3)所得薄膜在95-105℃下固化50-70min,即得成品。4) Curing the film obtained in step (3) at 95-105° C. for 50-70 minutes to obtain the finished product. 权利要求1所述基于氧化铋p-n型转变电位的光电化学柔性可穿戴汗液pH传感器的应用,其特征在于,用于检测汗液pH,包括以下步骤:The application of the photoelectrochemical flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential according to claim 1 is characterized in that, for detecting sweat pH, comprising the following steps: 1)采用三电极体系,在柔性可穿戴pH传感器的测试区域滴加1-7μL/mm 2人工汗液,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流; 1) Using a three-electrode system, add 1-7μL/mm 2 artificial sweat to the test area of the flexible wearable pH sensor, scan the dark current by cyclic voltammetry under no light conditions, and use cyclic voltammetry under light conditions to obtain the dark current. Scanning method to obtain photocurrent; 2)依次测试不同pH的人工汗液,获得不同pH下的光电流和暗电流交点处的电位,然后对数据进行拟合并获得标准曲线;2) Test the artificial sweat with different pH in turn, obtain the potential at the intersection of photocurrent and dark current at different pH, then fit the data and obtain a standard curve; 3)将柔性可穿戴pH传感器贴合在皮肤上,待汗液浸润测试区域后,在无光照条件下用循环伏安法扫描得到暗电流,在光照条件下用循环伏安法扫描得到光电流,获得此时的p-n型转变电位,对照标准曲线得到此时汗液的pH值。3) Attach the flexible wearable pH sensor to the skin. After the sweat infiltrates the test area, the dark current is scanned by cyclic voltammetry under no light conditions, and the photocurrent is obtained by cyclic voltammetry scanning under light conditions. The p-n transition potential at this time is obtained, and the pH value of the sweat at this time is obtained by comparing with the standard curve.
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