CN114280125B - Photoelectrochemistry flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential - Google Patents
Photoelectrochemistry flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential Download PDFInfo
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- 210000004243 sweat Anatomy 0.000 title claims abstract description 60
- 229910000416 bismuth oxide Inorganic materials 0.000 title claims abstract description 28
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000007704 transition Effects 0.000 title claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000004544 sputter deposition Methods 0.000 claims description 32
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000000151 deposition Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 229920001817 Agar Polymers 0.000 claims description 20
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 18
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- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000013077 target material Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 238000002484 cyclic voltammetry Methods 0.000 claims description 15
- 230000008021 deposition Effects 0.000 claims description 15
- 238000012360 testing method Methods 0.000 claims description 13
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 12
- 239000008272 agar Substances 0.000 claims description 12
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- 239000011259 mixed solution Substances 0.000 claims description 12
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 12
- 229910001887 tin oxide Inorganic materials 0.000 claims description 12
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
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- 239000010439 graphite Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 8
- 238000012544 monitoring process Methods 0.000 abstract description 8
- 238000005259 measurement Methods 0.000 abstract description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
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- 238000001139 pH measurement Methods 0.000 description 3
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- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
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- 208000017520 skin disease Diseases 0.000 description 1
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Abstract
The invention discloses a photoelectrochemistry flexible wearable sweat pH sensor based on a bismuth oxide p-n type transition potential, which comprises a bismuth oxide working electrode, a reference electrode, a counter electrode, a transparent flexible substrate and a light source. The sensor can adapt to a complex wearing environment, can well resist the interference of light intensity change and sweat covering sensing electrode area change, is low in preparation cost, simple and portable, is easy to use, realizes accurate and continuous monitoring of the pH value of the sweat, has high application value, and solves the problem of inaccurate measurement in the prior art.
Description
The technical field is as follows:
the invention relates to the technical field of photoelectrochemical sensing, in particular to a photoelectrochemical flexible wearable sweat pH sensor based on a bismuth oxide p-n type transition potential.
Background art:
the pH of human sweat provides a lot of important information about health, and various skin diseases (e.g., dermatitis, acne, fungal infections, etc.) cause changes in The pH of sweat, so monitoring The pH of sweat can provide important references for assessing The health of an individual [ Balaji A N, Yuan C, et al, pH Watch-influencing pulses in existing utilities for reusable, real-time monitoring of pH in sweat [ C ]. The 17th national conference.2019: 262-.
The method for monitoring the sweat pH value by utilizing the flexible wearable sensor is an effective method, compared with the traditional sensor, the flexible wearable sensor is lighter, more attractive and more comfortable, and can realize continuous monitoring [ Simmonke, Zhangjun ] application of the flexible wearable sensor in sweat monitoring for medical and health equipment [ J ], 2020,41(12) and 90-96 ].
Flexible wearable sensors based on electrochemical and photoelectrochemical principles have received much attention due to their high accuracy, high sensitivity, and fast response. A plurality of flexible wearable pH sensors based on electrochemistry and photoelectrochemistry (Shi X M, Mei L P, et al A polymer dots-based electrochemical pH sensors: silicon, high sensitivity, and anode-range pH measurement [ J ]. Analytical chemistry,2018,90(14):8300-8303 ]) are appeared on the market at present, but the signals are based on voltage (or current) signals under constant current (or constant potential) to judge the pH value, and the signal mechanism has poor adaptability to complex and varied wearing environments. In a real use scene, the light intensity of the photoelectrochemical sensor may fluctuate due to vibration caused by human motion and consumption of electric quantity; when the sweat amount of the human body is low, the sweat may not completely cover the sensing electrode. In these cases, the conventional sense signal mechanism can generate huge measurement errors.
The invention content is as follows:
the invention aims to provide a bismuth (Bi) -based oxide 2 O 3 ) The photoelectrochemistry flexible wearable sweat pH sensor with p-n type transition potential adopts Bi for the first time 2 O 3 The semiconductor is used as a photoelectrode, a special p-n type conversion potential of the semiconductor is used as a sensing signal, the semiconductor can adapt to a complex wearing environment, the interference of light intensity change and sweat covering sensing electrode area change can be well resisted, the accurate and continuous monitoring of the sweat pH value is realized, and the problem of inaccurate measurement in the prior art is solved.
The invention is realized by the following technical scheme:
bismuth (Bi) oxide-based material 2 O 3 ) A p-n type potential-converted photoelectrochemical flexible wearable sweat pH sensor, comprising bismuth oxide (Bi) 2 O 3 ) Working electrode, reference electrode, counter electrode, transparent flexible substrate and light source, bismuth oxide (Bi) 2 O 3 ) The preparation of the working electrode comprises the following steps:
(1) depositing an indium-doped tin oxide (ITO) film on a transparent flexible mica substrate by adopting a radio frequency magnetron sputtering method: indium with the purity of 99.99 percent is doped with tin oxide (ITO) target materials, the sputtering power is 50-150W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 300-3600s, and the substrate rotation speed is 10-30 r/min;
(2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct current magnetron sputtering method, using a Bi metal target material with the purity of 99.99%, wherein the sputtering power is 20-60W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-600s, and the substrate rotation speed is 10-30 r/min;
(3) bismuth oxide (Bi) obtained in the step (2) 2 O 3 ) Heating the film for 30-120min at 250-350 deg.C, and heating in one of heating table, oven and tubular furnace to obtain bismuth oxide (Bi) 2 O 3 ) A working electrode.
Preferably, bismuth oxide (Bi) 2 O 3 ) The preparation of the working electrode comprises the following steps:
(1) depositing an indium-doped tin oxide (ITO) film on a transparent flexible mica substrate by adopting a radio frequency magnetron sputtering method: indium with the purity of 99.99 percent is used for doping tin oxide (ITO) target materials, the sputtering power is 150W, the substrate temperature is 200-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 1.5-2pa, the deposition time is 1200-2400s, and the substrate rotation speed is 20-30 r/min;
(2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct current magnetron sputtering method, using a Bi metal target with the purity of 99.99%, wherein the sputtering power is 40-60W, the substrate temperature is 100-;
(3) bismuth oxide (Bi) obtained in the step (2) 2 O 3 ) Heating the film for 30-60min at 270-350 deg.C, and heating in one of heating table, oven and tubular furnace to obtain bismuth oxide (Bi) 2 O 3 ) A working electrode.
The preparation of the reference electrode comprises the following steps:
(1) adding agar into a mixed solution of saturated KCl, wherein the content of the agar is 1-5 wt%, and heating the mixed solution to boiling to completely dissolve the agar;
(2) fixing Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, dripping the mixed solution obtained in the step (1) on the surface of the flexible Ag/AgCl film, wherein the coating amount is 10-50 mu L/cm 2 Cooling to room temperature to obtain an agar gel film containing KCl;
(3) dripping 5wt% Nafion solution on the surface of the agar gel membrane obtained in the step (2), wherein the coating amount is 5-30 mu L/cm 2 And drying the membrane at room temperature to obtain the reference electrode.
The preparation of the counter electrode comprises the following steps:
depositing a film on a transparent flexible substrate by adopting a direct current magnetron sputtering method, using a target material with the purity of 99.99 percent, wherein the sputtering power is 10-100W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-3600s, and the substrate rotating speed is 10-30 r/min.
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.
Preferably, the width of the working electrode, the reference electrode and the counter electrode is 0.5-5mm, and the electrode spacing is 0.5-2 mm.
Preferably, the light source is 0.1-1W, and the wavelength is 400-500 nm.
Based on bismuth oxide (Bi) 2 O 3 ) The packaging of the p-n type potential-converted photoelectrochemical flexible wearable sweat pH sensor comprises the following steps:
1) selecting a flexible Polyester (PET) film with the thickness of 45-55mm as a transparent flexible substrate;
2) attaching the working electrode, the reference electrode and the counter electrode to a transparent flexible Polyester (PET) film by Polydimethylsiloxane (PDMS) glue;
3) packaging the film obtained in the step 2) by PDMS glue, and exposing the detection end and the wire connecting end;
4) and (4) curing the film obtained in the step (3) at the temperature of 95-105 ℃ for 50-70min to obtain a finished product.
The invention also protects the bismuth (Bi) oxide base 2 O 3 ) Use of a p-n type potential-switched photoelectrochemical flexible wearable sweat pH sensor for detecting sweat pH comprising the steps of:
(1) dropping 1-7 mu L/mm in the testing area of the flexible wearable pH sensor by adopting a three-electrode system 2 Artificial sweat, scanning by cyclic voltammetry under the condition of no illumination to obtain dark current, and scanning by cyclic voltammetry under the condition of illumination to obtain photocurrent;
(2) sequentially testing artificial sweat with different pH values to obtain p-n type conversion potentials (potentials at the intersection points of photocurrent and dark current) under different pH values, and then fitting data to obtain a standard curve;
(3) attaching the flexible wearable pH sensor to the skin, after the sweat infiltrates the test area, scanning by using a cyclic voltammetry method under the condition of no illumination to obtain dark current, scanning by using the cyclic voltammetry method under the condition of illumination to obtain photocurrent, obtaining a p-n type conversion potential at the moment, and obtaining the pH value of the sweat at the moment by contrasting a standard curve.
The invention has the beneficial effects that:
1) the invention adopts the bisexual bismuth oxide (Bi) for the first time 2 O 3 ) The semiconductor is used as a photoelectrode, and a specific p-n type transition potential of the semiconductor is used as a sensing signal to prepare the photoelectrochemical flexible wearable sweat pH sensor. The sensor can adapt to a complex wearing environment, and can well resist the interference of light intensity change and sweat covering area change of the sensing electrode.
2) The magnetron sputtering coating method is easy to realize bismuth (Bi) oxide 2 O 3 ) Low cost mass production of working electrodes.
In a word, the sensor disclosed by the invention is low in preparation cost, simple and portable, easy to use, strong in anti-interference capability, capable of realizing accurate and continuous monitoring of the pH value of sweat, high in application value and capable of solving the problem of inaccurate measurement in the prior art.
Description of the drawings:
FIG. 1 is a schematic top view of the structure of the present invention.
FIG. 2 is a schematic side view of the structure of a reference electrode and a working electrode of the present invention.
Fig. 3 is an X-ray diffraction pattern (XRD) of the working electrode prepared in example 1.
Fig. 4 is the cyclic voltammetry scan results of a flexible wearable sweat pH sensor under different pH sweat.
Fig. 5 is a standard curve for a wearable sweat pH sensor.
Fig. 6 is the result of cyclic voltammetry scans of a wearable sweat pH sensor at different light intensities.
Fig. 7 is a result of cyclic voltammetry scans of a wearable sweat pH sensor at different sweat coverage rates.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1:
based on Bi 2 O 3 A p-n type potential-switched photoelectrochemical flexible wearable sweat pH sensor comprising Bi 2 O 3 The device comprises a working electrode, a reference electrode, a counter electrode, a transparent flexible substrate and a light source. The width of the working electrode, the reference electrode and the counter electrode was 5mm, the electrode spacing was 1.5mm (as shown in FIG. 1), the light source was 0.2W, and the wavelength was 440 nm.
Bi 2 O 3 The preparation steps of the working electrode are as follows:
(1) an indium-doped tin oxide (ITO) film is deposited on a transparent flexible mica substrate by adopting a radio frequency magnetron sputtering method, an indium-doped tin oxide (ITO) target material with the purity of 99.99 percent is used, the sputtering power is 100W, the substrate temperature is 200 ℃, the argon flow is 30sccm, the sputtering pressure is 1.5pa, the deposition time is 2400s, and the substrate rotation speed is 20 r/min.
(2) And (2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct-current magnetron sputtering method, using a Bi metal target material with the purity of 99.99%, wherein the sputtering power is 40W, the substrate temperature is 100 ℃, the argon flow is 30sccm, the sputtering pressure is 1.0pa, the deposition time is 240s, and the substrate rotation speed is 20 r/min.
(3) Bi obtained in the step (2) 2 O 3 Calcining the film on a heating table for 60min at the calcining temperature of 270 ℃ to obtain Bi 2 O 3 The working electrode (as shown in figure 2).
The obtained Bi 2 O 3 The working electrode was analyzed by X-ray diffractometer (XRD) (as shown in FIG. 3), and the working electrode film was made of α -Bi 2 O 3 (PDF #76-1730) and β -Bi2O3(PDF # 78-1793).
The preparation steps of the reference electrode are as follows:
(1) agar was added to a mixed solution of saturated KCl (agar content: 1%), and the mixed solution was heated to boiling to completely dissolve the agar.
(2) Fixing Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, and dropwise coating the mixed solution obtained in the step (1) on the surface of the flexible Ag/AgCl film, wherein the coating amount is 10 mu L/cm 2 After cooling to room temperature, agar gel films containing KCl were obtained.
(3) Dripping 5 percent Nafion solution on the surface of the agar gel membrane obtained in the step (2), wherein the coating amount is 5 mu L/cm 2 And dried at room temperature to form a membrane, resulting in a reference electrode (shown in FIG. 2).
The preparation steps of the counter electrode are as follows:
depositing Pt metal on flexible Polyester (PET) by a direct-current magnetron sputtering method, using a Pt metal target material with the purity of 99.99%, wherein the sputtering power is 50W, the substrate temperature is room temperature, the argon flow is 30sccm, the sputtering pressure is 1.0pa, the deposition time is 600s, and the substrate rotation speed is 20r/min, so as to obtain the counter electrode.
The packaging steps of the sensor are as follows:
(1) a flexible Polyester (PET) film with a thickness of 50mm was selected as the transparent flexible substrate.
(2) The working electrode, the reference electrode and the counter electrode were attached to a transparent flexible Polyester (PET) film using Polydimethylsiloxane (PDMS) paste.
(3) And (3) packaging the film obtained in the step (2) by PDMS glue, and exposing the detection end and the wire connecting end.
(4) And (4) curing the film obtained in the step (3) at 100 ℃ for 60min to obtain a finished product.
Example 2
Reference example 1, except that Bi 2 O 3 And preparing a working electrode, a reference electrode and a counter electrode.
Bi 2 O 3 The preparation steps of the working electrode are as follows:
(1) an indium-doped tin oxide (ITO) film is deposited on a transparent flexible mica substrate by adopting a radio frequency magnetron sputtering method, an indium-doped tin oxide (ITO) target material with the purity of 99.99 percent is used, the sputtering power is 150W, the substrate temperature is 350 ℃, the argon flow is 30sccm, the sputtering pressure is 2pa, the deposition time is 1200s, and the substrate rotation speed is 30 r/min.
(2) And (2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct-current magnetron sputtering method, using a Bi metal target material with the purity of 99.99%, wherein the sputtering power is 60W, the substrate temperature is 350 ℃, the argon flow is 50sccm, the sputtering pressure is 2pa, the deposition time is 100s, and the substrate rotation speed is 30 r/min.
(3) Bi obtained in the step (2) 2 O 3 Calcining the film on a heating table for 30min at the temperature of 350 ℃ to obtain Bi 2 O 3 A working electrode.
The preparation steps of the reference electrode are as follows:
(1) agar was added to a mixed solution of saturated KCl (agar content: 5%), and the mixed solution was heated to boiling to completely dissolve the agar.
(2) Fixing Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, and dropwise coating the mixed solution obtained in the step (1) on the surface of the flexible Ag/AgCl film, wherein the coating amount is 50 mu L/cm 2 After cooling to room temperature, agar gel films containing KCl were obtained.
(3) In the step of(2) Dripping 5% Nafion solution on the surface of the obtained agar gel film, wherein the coating amount is 30 mu L/cm 2 And drying at room temperature to form a film, thus obtaining the reference electrode.
The preparation steps of the counter electrode are as follows:
depositing Pt metal on flexible Polyester (PET) by adopting a direct-current magnetron sputtering method, using a Pt metal target material with the purity of 99.99%, wherein the sputtering power is 70W, the substrate temperature is 150 ℃, the argon flow is 50sccm, the sputtering pressure is 2.0pa, the deposition time is 100s, and the substrate rotation speed is 30r/min, so as to obtain the counter electrode.
Example 3
Reference example 1 was made, except for the preparation of the counter electrode.
The preparation steps of the counter electrode are as follows:
depositing graphite on flexible Polyester (PET) by a direct current magnetron sputtering method, using a graphite target material with the purity of 99.99 percent, sputtering power of 100W, substrate temperature of 200 ℃, argon flow of 30sccm, sputtering pressure of 1.0pa, deposition time of 60min and substrate rotation speed of 30r/min to obtain the counter electrode.
Experimental example 1
1. Obtaining a standard curve
Using a three-electrode system, 3. mu.L/mm was added dropwise to the test area of the flexible wearable pH sensor obtained in example 1 above 2 And (3) artificial sweat, scanning by cyclic voltammetry under the condition of no illumination to obtain dark current, and scanning by cyclic voltammetry under the condition of illumination to obtain photocurrent. Artificial sweat at different pH was tested sequentially and the results shown in figure 4 were obtained. The p-n type transition potentials (potentials at the intersection points of the photocurrent and dark current) at different pH values were obtained, and a standard curve as shown in FIG. 5 was obtained by fitting, with good fitting degree.
Attaching the flexible wearable pH sensor to the skin, after the sweat infiltrates the test area, scanning by cyclic voltammetry under the condition of no illumination to obtain dark current, scanning by cyclic voltammetry under the condition of illumination to obtain photocurrent, obtaining the p-n type conversion potential at the moment, and obtaining the pH value of the sweat at the moment by contrasting with a standard curve.
Experimental example 2
1. Anti-light interference test
3 mu L/mm of flexible wearable pH sensor test area prepared in the above example 1 is dripped into 2 Artificial sweat with pH of 5 at 15mW/cm 2 When tested at a light intensity of-35 mW/cm2, the p-n type transition potential was substantially unchanged and the current was greatly changed as shown in FIG. 6. It can be seen that the accuracy of the pH detection result obtained by using the p-n type transition potential as a signal is much higher than that obtained by using the current as a signal under the condition of the change of the light intensity.
2. Sweat partial coverage interference test
3 mu L/mm of flexible wearable pH sensor test area prepared in the above example 1 is dripped into 2 Artificial sweat with pH 5, controlling the area of the working electrode covered by artificial sweat, and testing separately at different coverage, also found that when sweat covered the electrode portion, there was essentially no change in the p-n type transition potential, but the current changed dramatically, as shown in fig. 7. It follows that the accuracy of the pH measurements obtained with the p-n type transition potential as a signal will be much higher than the pH measurements obtained with the current as a signal when sweat partially covers the electrode.
The above description of the embodiments is only for helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that,
it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit of the invention, and these modifications and variations also fall within the scope of the claims of the present invention.
Claims (10)
1. The photoelectrochemistry flexible wearable sweat pH sensor based on the bismuth oxide p-n type transition potential is characterized by comprising a bismuth oxide working electrode, a reference electrode, a counter electrode, a transparent flexible substrate and a light source, wherein the preparation of the bismuth oxide working electrode comprises the following steps:
(1) depositing an indium-doped tin oxide film on a transparent and flexible mica substrate by adopting a radio frequency magnetron sputtering method: doping tin oxide target material with indium with the purity of 99.99%, wherein the sputtering power is 50-150W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 300-3600s, and the substrate rotation speed is 10-30 r/min;
(2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct current magnetron sputtering method, using a Bi metal target material with the purity of 99.99%, wherein the sputtering power is 20-60W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-600s, and the substrate rotation speed is 10-30 r/min;
(3) and (3) heating the product obtained in the step (2) for 30-120min at the heating temperature of 250-350 ℃, wherein the heating tool is one of a heating table, an oven and a tubular furnace, and thus the bismuth oxide working electrode is obtained.
2. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 1, wherein the preparation of bismuth oxide working electrode comprises the following steps:
(1) depositing an indium-doped tin oxide film on a transparent flexible mica substrate by adopting a radio frequency magnetron sputtering method: doping a tin oxide target material with indium with the purity of 99.99 percent, wherein the sputtering power is 150W, the substrate temperature is 200-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 1.5-2Pa, the deposition time is 1200-2400s, and the substrate rotation speed is 20-30 r/min;
(2) depositing Bi metal on the ITO film obtained in the step (1) by adopting a direct current magnetron sputtering method, using a Bi metal target with the purity of 99.99%, wherein the sputtering power is 40-60W, the substrate temperature is 100-;
(3) and (3) heating the product obtained in the step (2) for 30-60min at the heating temperature of 270-.
3. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 1, wherein the preparation of the reference electrode comprises the following steps:
(1) adding agar into a mixed solution of saturated KCl, wherein the content of the agar is 1-5 wt%, and heating the mixed solution to boiling to completely dissolve the agar;
(2) fixing Ag/AgCl on a transparent flexible substrate to obtain a flexible Ag/AgCl film, dripping the mixed solution obtained in the step (1) on the surface of the flexible Ag/AgCl film, wherein the coating amount is 10-50 mu L/cm 2 Cooling to room temperature to obtain an agar gel film containing KCl;
(3) dripping 5wt% Nafion solution on the surface of the agar gel membrane obtained in the step (2), wherein the coating amount is 5-30 mu L/cm 2 And drying the membrane at room temperature to obtain the reference electrode.
4. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 1, wherein counter electrode preparation comprises the following steps: depositing a film on a transparent flexible substrate by adopting a direct current magnetron sputtering method, using a target material with the purity of 99.99 percent, wherein the sputtering power is 10-100W, the substrate temperature is room temperature-350 ℃, the argon flow is 10-50sccm, the sputtering pressure is 0.5-3pa, the deposition time is 60-3600s, and the substrate rotating speed is 10-30 r/min.
5. The flexible photoelectric and flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 4, wherein the substrate is one of flexible polyester, mica, polyimide.
6. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 4, wherein the target is one of graphite, Pt.
7. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential of claim 1 or 2, wherein the width of the working, reference and counter electrodes is 0.5-5mm and the electrode spacing is 0.5-2 mm.
8. The flexible photoelectric chemical wearable sweat pH sensor based on bismuth oxide p-n type transition potential as claimed in claim 1 or 2, wherein the light source is 0.1-1W, and the wavelength is 400-500 nm.
9. The packaging method of the photoelectrochemical flexible wearable sweat pH sensor based on the bismuth oxide p-n type transition potential of claim 1, comprising the steps of:
1) selecting a flexible polyester film with the thickness of 45-55mm as a transparent flexible substrate;
2) attaching the working electrode, the reference electrode and the counter electrode to a transparent flexible polyester film by using polydimethylsiloxane adhesive;
3) packaging the film obtained in the step 2) by PDMS glue, and exposing the detection end and the wire connecting end;
4) and (4) curing the film obtained in the step (3) at the temperature of 95-105 ℃ for 50-70min to obtain a finished product.
10. The use of a bismuth oxide p-n type transition potential based photoelectrochemical flexible wearable sweat pH sensor according to claim 1 to detect sweat pH comprising the steps of:
1) dropping 1-7 mu L/mm in the testing area of the flexible wearable pH sensor by adopting a three-electrode system 2 Artificial sweat, scanning by cyclic voltammetry under the condition of no illumination to obtain dark current, and scanning by cyclic voltammetry under the condition of illumination to obtain photocurrent;
2) sequentially testing artificial sweat with different pH values to obtain the potentials at the intersection points of the photocurrent and the dark current under different pH values, and then fitting the data to obtain a standard curve;
3) attaching the flexible wearable pH sensor to the skin, after the sweat infiltrates the test area, scanning by cyclic voltammetry under the condition of no illumination to obtain dark current, scanning by cyclic voltammetry under the condition of illumination to obtain photocurrent, obtaining the p-n type conversion potential at the moment, and obtaining the pH value of the sweat at the moment by contrasting with a standard curve.
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| CN202111363406.2A CN114280125B (en) | 2021-11-17 | 2021-11-17 | Photoelectrochemistry flexible wearable sweat pH sensor based on bismuth oxide p-n type transition potential |
| PCT/CN2021/132235 WO2023087332A1 (en) | 2021-11-17 | 2021-11-23 | Bismuth oxide p-n type transition potential-based photoelectrochemical flexible wearable sweat ph sensor |
| DE112021003193.7T DE112021003193T5 (en) | 2021-11-17 | 2021-11-23 | PHOTOELECTROCHEMICAL FLEXIBLE PORTABLE PH SENSOR FOR SWEAT BASED ON A PN CONVERSION POTENTIAL OF BISMUTH OXIDE |
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