Multifunctional electrochemical gas sensor
By designing multiple independent U-shaped working electrodes and a branched reference electrode in the gas sensor, combined with the mesh heating layer, the selectivity and detection accuracy of the sensor are improved, and the problem of insufficient selectivity and sensitivity of solid-state electrolyte sensors is solved.
Patent Information
- Application Number
- CN202420809053.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-18
- Publication Date
- 2025-06-17
- Estimated Expiration
- 2034-04-18
AI Technical Summary
The selectivity and sensitivity of solid electrolyte gas sensors need to be improved.
A multifunctional electrochemical gas sensor was designed, including four independent working electrodes and a reference electrode. The working electrode adopts a U-shaped structure, the reference electrode is branched, and the heating layer is mesh structure.
Through the design of multiple independent working electrodes and reference electrodes, the detection function and selectivity of the sensor are improved, signal processing is simplified, detection accuracy is improved, and working power consumption is reduced.
Smart Images
Figure CN222994384U_ABST
Abstract
Description
Technical Field
[0001] The utility model relates to the technical field of gas sensors, in particular to a multifunctional electrochemical gas sensor. Background Art
[0002] There are various types of electrochemical gas sensors. Among them, potential sensors are widely used in the field of gas detection due to their advantages of simple structure, stable signal, and low cost. In potential sensors, solid electrolyte sensors have greatly improved the safety of sensor use and expanded the application scenarios by replacing liquid electrolytes with solid electrolytes. However, the selectivity and sensitivity of solid electrolyte gas sensors need to be further improved. Summary of the Utility Model
[0003] Aiming at the problems existing in the prior art, the utility model provides a multifunctional electrochemical gas sensor, which specifically includes the following:
[0004] A multifunctional electrochemical gas sensor includes a heating layer, a base layer, and an electrode layer. The base layer includes a substrate layer and an electrolyte layer, and the electrolyte layer is disposed above the substrate layer; the electrode layer is disposed above the electrolyte layer, and the electrode layer includes a first working electrode, a second working electrode, a third working electrode, a fourth working electrode, and a reference electrode. The first working electrode, the second working electrode, the third working electrode, and the fourth working electrode all include a U-shaped structure region; the reference electrode includes a main body and four branches disposed on the main body, and the four branches of the reference electrode are respectively disposed in the U-shaped structure regions of the first working electrode, the second working electrode, the third working electrode, and the fourth working electrode.
[0005] Preferably, the first working electrode, the second working electrode, the third working electrode, and the fourth working electrodes are porous structure electrodes.
[0006] Preferably, the heating layer is disposed below the substrate layer, and the heating layer is a heating electrode with a mesh structure.
[0007] Preferably, the substrate layer is made of silicon or alumina, and / or the electrolyte layer is a yttrium-doped zirconia film layer; and / or, the working electrode material is Pt, Ag, WO3, SnO2, Co3O4, ZnO, TiO2, and / or their composites; and / or, the reference electrode material is Ag or Pt; and / or, the heating electrode material is Pt, W, or Ag.
[0008] Advantages of the Utility Model
[0009] (1) The multi-functional electrochemical gas sensor disclosed by the present utility model has four independent working electrodes, namely the first working electrode, the second working electrode, the third working electrode, and the fourth working electrode. By loading different electrode sensitive materials on the four working electrodes, four relatively independent sensing units can be obtained, which are used to detect different gases and their concentrations in a complex environment, and can improve the detection function and selectivity of the sensor.
[0010] (2) The multi-functional electrochemical gas sensor disclosed by the present utility model is provided with the same reference electrode. By grounding the reference electrode and other methods, the signal processing of the array-type sensor can be greatly simplified, and the measurement accuracy of the detection data can be improved.
[0011] (3) All four working electrodes of the multi-functional electrochemical gas sensor disclosed by the present utility model include a U-shaped structure area; the reference electrode is in a branch shape, and the four branches of the reference electrode are respectively arranged in the U-shaped structure areas of the four working electrodes (the reference electrode is nested in the four working electrodes). This structure can, on the one hand, increase the effective working area of the electrode, and on the other hand, shorten the charge transfer distance between the electrodes and enhance the detection accuracy.
[0012] (4) The heating layer of the multi-functional electrochemical gas sensor disclosed by the present utility model is a heating electrode with a mesh structure. This electrode can make the heating temperature zone more uniform. At the same time, the heating electrode corresponds to the structure of the working electrode and the reference electrode, which can further reduce the working power consumption of the sensor.
[0013] (5) The multi-functional electrochemical gas sensor of the present utility model has a planar structure, which simplifies the manufacturing process, greatly reduces the volume size, is easy to mass-produce, and is conducive to the further integration and use of the sensor. Brief Description of the Drawings
[0014] Figure 1 is a side view of the multi-functional electrochemical gas sensor disclosed by the present utility model;
[0015] Figure 2 is a schematic diagram of the electrode layer of the multi-functional electrochemical gas sensor disclosed by the present utility model;
[0016] Figure 3 is a schematic diagram of the heating layer of the multi-functional electrochemical gas sensor disclosed by the present utility model;
[0017] In the figure, 11 - substrate layer, 12 - electrolyte layer, 21 - first working electrode, 22 - second working electrode, 23 - third working electrode, 24 - fourth working electrode, 25 - reference electrode, 31 - heating electrode. Detailed Description of the Preferred Embodiment
[0018] The following combines the attached Figures 1-3The present utility model will be described in detail with reference to the specific embodiments. The embodiments shown below do not limit the content of the utility model described in the claims in any way. In addition, all the contents of the configurations shown in the following embodiments are not limited to those necessary for the solution of the utility model described in the claims.
[0019] Refer to the attached Figures 1-3 , a multifunctional electrochemical gas sensor, comprising a heating layer, a base layer, and an electrode layer. The base layer includes a substrate layer 11 and an electrolyte layer 12, and the electrolyte layer 12 is disposed above the substrate layer 11; the electrode layer is disposed above the electrolyte layer 12. The electrode layer includes a first working electrode 21, a second working electrode 22, a third working electrode 23, a fourth working electrode 24, and a reference electrode 25. The first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24 all include a U-shaped structure region; the reference electrode 25 includes a main body and four branches disposed on the main body, and the four branches of the reference electrode 25 are respectively disposed in the U-shaped structure regions of the first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24.
[0020] In an embodiment of the present utility model, the first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24 are porous structure electrodes.
[0021] In an embodiment of the present utility model, the heating layer is disposed below the substrate layer 11, and the heating layer is a heating electrode 31 with a mesh structure.
[0022] In an embodiment of the present utility model, the substrate layer 11 is made of silicon or alumina, and the electrolyte layer 12 is a yttrium-doped zirconia film layer; the working electrode material is Pt, Ag, WO3, SnO2, Co3O4, ZnO, TiO2 or a composite thereof; the reference electrode 25 material is Ag or Pt; the heating electrode 31 material is Pt, W or Ag.
[0023] Refer to the attached Figure 2, in an embodiment of the present utility model, the first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24 each include a straight section and a U-shaped section. The straight sections of the first working electrode 21 and the second working electrode 22 are arranged on the same straight line, and the straight sections of the third working electrode 23 and the fourth working electrode 24 are arranged on the same straight line. The U-shaped sections of the first working electrode 21 and the fourth working electrode 24 are oppositely arranged, and the U-shaped sections of the second working electrode 22 and the third working electrode 23 are oppositely arranged. The main part of the reference electrode 25 is arranged between the first working electrode 21, the second working electrode 22 and the third working electrode 23, the fourth working electrode 24, and the four branches of the reference electrode 25 respectively extend into the U-shaped sections of the first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24 (without directly contacting the first working electrode 21, the second working electrode 22, the third working electrode 23, and the fourth working electrode 24).
[0024] The preparation method of the multifunctional electrochemical gas sensor disclosed in the present invention includes the following steps:
[0025] (1) Pretreatment of the substrate layer 11: Treat the substrate layer 11 with a sulfuric acid solution, and then wash and dry it to obtain the treated substrate layer 11. When the substrate layer 11 is a silicon wafer, the pretreatment method is: Stew the silicon wafer with concentrated sulfuric acid at a high temperature for 20 - 60 min (such as 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, etc.), then ultrasonically clean the silicon wafer with deionized water and ethanol in sequence, and then dry it at 80 - 110 °C (such as 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, etc.) to obtain the treated substrate layer 11. When the substrate layer 11 is an alumina sheet, the pretreatment method is: Immerse the alumina sheet in dilute sulfuric acid for 60 - 120 min (such as 70 min, 80 min, 90 min, 100 min, 110 min, etc.), then ultrasonically clean the alumina sheet with ethanol, and then dry it to obtain the treated substrate layer 11.
[0026] (2) Preparation of the electrolyte layer 12: Use the screen printing method to print a yttrium-doped zirconia film layer with a thickness of 10 - 50 μm (such as 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm) on the upper surface of the treated substrate layer 11, dry it and sinter it at 1000 - 1500 °C (1000 °C, 1100 °C, 1200 °C, 1300 °C, 1400 °C, 1500 °C, etc.) to form the electrolyte layer 12.
[0027] (3) Preparation of the electrode layer: Using photolithography, define the patterns of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25 on the upper surface of the electrolyte layer 12, and use magnetron sputtering, or electrochemical deposition, or screen printing to prepare an electrode material with a thickness of 0.3 - 5 μm (such as 0.5 μm, 1 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm) at the corresponding positions, finally forming the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25; when using magnetron sputtering, first sputter a layer of the corresponding electrode material with a thickness of 0.3 - 0.8 μm (such as 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, 0.6 μm, 0.7 μm, etc.) at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then soak in acetone for 30 - 60 min (such as 35 min, 40 min, 45 min, 50 min, 55 min, etc.), then wash with ultrapure water, and finally dry at 80 - 110 °C (such as 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, etc.) for 10 - 30 min (such as 12 min, 15 min, 20 min, 25 min, 28 min, etc.); when using electrochemical deposition, first deposit a layer of the corresponding electrode material with a thickness of 0.5 - 3 μm (such as 0.8 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, etc.) at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then wash with ultrapure water and ethanol, and finally dry at 80 - 110 °C (such as 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, etc.) for 10 - 30 min (such as 12 min, 15 min, 20 min, 25 min, 28 min, etc.); when using screen printing, first design the electrode stencil pattern, and print a layer of the corresponding electrode material with a thickness of 2 - 5 μm (such as 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, etc.) at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then dry at 60 - 130 °C (such as 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, etc.) for 10 - 30 min (such as 12 min, 15 min, 20 min, 25 min, 28 min, etc.), and finally calcine at 600 - 1000 °C (such as 650 °C, 700 °C, 750 °C, 800 °C, 900 °C, etc.) for 1 - 3 h (such as 1.2 h, 1.5 h, 1.8 h, 2 h, 2.5 h, 2.8 h, etc.).
[0028] (4) Preparation of the heating layer: The heating electrode 31 is prepared on the lower surface of the substrate layer 11 by screen printing or photolithography to form the heating layer. When using screen printing, first print the corresponding material with the pattern of the heating electrode 31 on the lower surface of the substrate layer 11, and then dry it in an oven at 60 - 130 °C (such as 70 °C, 80 °C, 90 °C, 100 °C, 120 °C, etc.) for 10 - 30 min (such as 12 min, 15 min, 20 min, 25 min, 28 min, etc.), and finally calcine it at 600 - 1000 °C (such as 650 °C, 700 °C, 750 °C, 800 °C, 900 °C, etc.) for 1 - 3 h (such as 1.2 h, 1.5 h, 1.8 h, 2 h, 2.5 h, 2.8 h, etc.) to form the heating electrode 31; when using photolithography, first define the pattern of the heating electrode 31 on the lower surface of the substrate layer 11, and deposit a layer of heating electrode 31 material with a thickness of 0.3 - 5 μm (such as 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, etc.) at the corresponding position by magnetron sputtering or electrochemical deposition, then soak it in acetone for 30 - 60 min (such as 35 min, 40 min, 45 min, 50 min, 55 min, etc.), and finally clean it with ultrapure water and dry it at 80 - 110 °C (such as 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, etc.) for 10 - 30 min (such as 12 min, 15 min, 20 min, 25 min, 28 min, etc.) to form the heating electrode 31.
[0029] The following will describe the present utility model in detail with specific embodiments.
[0030] Embodiment 1
[0031] A multifunctional electrochemical gas sensor and its preparation method include the following steps:
[0032] Step 1: Preparation of the base layer
[0033] The N-type (100) double-polished silicon wafer is cooked in concentrated sulfuric acid at high temperature for 30 min, and then ultrasonically cleaned with deionized water and ethanol in sequence, and dried at 80 °C to form the substrate layer 11;
[0034] Step 2: Preparation of the electrolyte layer
[0035] Using the screen printing method, a 15-μm yttrium-doped zirconia film layer is printed on the surface of the substrate layer 11. After drying at 70 °C for 15 min, it is sintered at 1000 °C for 1.5 h to form the electrolyte layer 12;
[0036] Step 3: Preparation of the electrode layer
[0037] Using photolithography, define the shapes of the working electrode 21 and the reference electrode 25 on the surface of the electrolyte layer 12. Then, use magnetron sputtering to deposit a 300-nm Pt film layer at the surface electrode. Next, soak it in acetone for 30 min, wash it with ultrapure water, and dry it in an oven at 110 °C for 20 min to form the working electrode 21;
[0038] Using photolithography, define the shape of the working electrode 22 on the surface of the electrolyte layer 12. Then, use electrochemical deposition to deposit a 0.5-μm WO3 film layer at the surface electrode. Next, wash it with ultrapure water and ethanol, and dry it in an oven at 80 °C for 10 min to form the working electrode 22;
[0039] Using photolithography, define the shape of the working electrode 23 on the surface of the electrolyte layer 12. Then, use electrochemical deposition to deposit a 2-μm SnO2 film layer at the surface electrode. Next, wash it with ultrapure water and ethanol, and dry it in an oven at 80 °C for 10 min to form the working electrode 23;
[0040] Using photolithography, define the shape of the working electrode 24 on the surface of the electrolyte layer 12. Then, use screen printing to print a 5-μm ZnO film layer at the surface electrode. Next, dry it in an oven at 60 °C for 10 min and sinter it at 850 °C for 1.5 h to form the working electrode 24;
[0041] Step 4: Prepare the heating layer
[0042] Using photolithography, define the pattern of the heating electrode on the lower surface of the substrate layer 11. Then, use magnetron sputtering to deposit a 500-nm Pt film layer electrode material at the electrode position. After soaking it in acetone for 45 min, wash it with ultrapure water and dry it in an oven at 110 °C for 30 min to form the heating electrode.
[0043] Example 2
[0044] In this example, the structure of the multifunctional electrochemical gas sensor and the materials of each electrode are the same as those in Example 1.
[0045] The preparation method of the multifunctional electrochemical gas sensor described in this example includes the following steps:
[0046] Step 1: Prepare the substrate layer
[0047] Cook the P-type (100) double-polished silicon wafer in concentrated sulfuric acid at high temperature for 60 min, and then ultrasonically clean it with deionized water and ethanol in sequence, and dry it at 80 °C to form the substrate layer 11;
[0048] Step 2: Prepare the electrolyte layer
[0049] Using the screen printing method, a yttrium-doped zirconia film layer with a thickness of 15 μm is printed on the surface of the substrate layer 11. After drying at 70 °C for 15 min, it is sintered at 1400 °C for 1.5 h to form the electrolyte layer 12;
[0050] Step 3: Prepare the electrode layer
[0051] Using the photolithography method, the shapes of the working electrode 21 and the reference electrode 25 are defined on the surface of the electrolyte layer 12. A 500-nm Pt film layer is deposited on the surface electrode by magnetron sputtering. Then, it is soaked in acetone for 60 min, washed with ultrapure water, and dried in an oven at 105 °C for 20 min to form the working electrode 21;
[0052] Using the photolithography method, the shape of the working electrode 22 is defined on the surface of the electrolyte layer 12. A 500-nm WO3 film layer is deposited on the surface electrode by magnetron sputtering. Then, it is washed with ultrapure water and ethanol, and dried in an oven at 80 °C for 10 min to form the working electrode 22;
[0053] Using the photolithography method, the shape of the working electrode 23 is defined on the surface of the electrolyte layer 12. A 500-nm SnO2 film layer is deposited on the surface electrode by magnetron sputtering. Then, it is washed with ultrapure water and ethanol, and dried in an oven at 80 °C for 10 min to form the working electrode 23;
[0054] Using the photolithography method, the shape of the working electrode 24 is defined on the surface of the electrolyte layer 12. A 500-nm ZnO film layer is deposited on the surface electrode by magnetron sputtering. Then, it is washed with ultrapure water and ethanol, and dried in an oven at 90 °C for 10 min to form the working electrode 24;
[0055] Step 4: Prepare the heating layer
[0056] Using the photolithography method, the pattern of the heating electrode is defined on the lower surface of the substrate layer 11. A 500-nm Pt film layer electrode material is deposited at the electrode position by magnetron sputtering. After soaking in acetone for 45 min, it is washed with ultrapure water and dried in an oven at 100 °C for 30 min to form the heating electrode.
[0057] Example 3
[0058] In this example, the structure of the multifunctional electrochemical gas sensor is the same as that in Example 1, except that: the material of the substrate layer 11 is alumina, the material of the working electrode 11 is Pt / WO3, the material of the working electrode 22 is Co3O4, the material of the working electrode 23 is ZnO / SnO2, the material of the working electrode 24 is TiO2, the material of the reference electrode is Ag, and the material of the heating electrode is W.
[0059] In this example, the preparation method of the multifunctional electrochemical gas sensor includes the following steps:
[0060] Step 1: Prepare the base layer
[0061] Soak the alumina sheet in dilute sulfuric acid for 90 min, then ultrasonically clean it with ethanol, and dry it at 80 °C for 30 min to form the substrate layer 11.
[0062] Step 2: Prepare the electrolyte layer
[0063] Using the screen printing method, print a 20-μm yttrium-doped zirconia film layer on the surface of the substrate layer 11. After drying at 70 °C for 15 min, sinter it at 1300 °C for 1.5 h to form the electrolyte layer 12;
[0064] Step 3: Prepare the electrode layer
[0065] Using the photolithography method, define the shape of the working electrode 21 on the surface of the electrolyte layer 12, and sequentially deposit a 500-nm W film and a 300-nm Pt film on the surface electrode by magnetron sputtering. Then soak it in acetone for 30 min, wash it with ultrapure water, and dry it in an oven at 110 °C for 20 min to form the working electrode 21;
[0066] Using the photolithography method, define the shape of the working electrode 22 on the surface of the electrolyte layer 12, and deposit a 1-μm Co3O4 film layer on the surface electrode by electrochemical deposition. Sequentially wash it with ultrapure water and ethanol, and dry it in an oven at 90 °C for 20 min to form the working electrode 22;
[0067] Using the photolithography method, define the shape of the working electrode 23 on the surface of the electrolyte layer 12, and sequentially deposit a 500-nm SnO2 film and a 500-nm ZnO film layer on the surface electrode by magnetron sputtering. Then soak it in acetone for 30 min, wash it with ultrapure water, and dry it in an oven at 105 °C for 20 min to form the working electrode 23;
[0068] Using the photolithography method, define the shape of the working electrode 24 on the surface of the electrolyte layer 12, and deposit a 600-nm TiO2 film layer on the surface electrode by magnetron sputtering. Then soak it in acetone for 30 min, wash it with ultrapure water, and dry it in an oven at 110 °C for 20 min to form the working electrode 24;
[0069] Using the photolithography method, define the shape of the reference electrode 25 on the surface of the electrolyte layer 12, and deposit a 600-nm Ag film layer on the surface electrode by magnetron sputtering. Then soak it in acetone for 20 min, wash it with ultrapure water, and dry it in an oven at 110 °C for 20 min to form the reference electrode 25;
[0070] Step 4: Prepare the heating layer
[0071] Using the screen printing method, a stencil with the shape of a heating electrode was designed and prepared, and a 5-μm W film was printed at the position of the lower electrode of the substrate layer 11, and then dried in an oven at 125 °C for 30 min to form the heating electrode 31.
[0072] Example 4
[0073] In this example, the structure and the materials of each electrode of the multifunctional electrochemical gas sensor are the same as those in Example 3.
[0074] In this example, the preparation method of the structure of the multifunctional electrochemical gas sensor includes the following steps:
[0075] Step 1: Prepare the base layer
[0076] The alumina sheet was soaked in dilute sulfuric acid for 120 min, then ultrasonically cleaned with ethanol, and dried at 80 °C for 30 min to form the substrate layer 11.
[0077] Step 2: Prepare the electrolyte layer
[0078] Using the screen printing method, a 20-μm yttrium-doped zirconia film layer was printed on the surface of the substrate layer 11. After drying at 70 °C for 15 min, it was sintered at 1100 °C for 2.5 h to form the electrolyte layer 12;
[0079] Step 3: Prepare the electrode layer
[0080] The electrode stencil pattern was designed, the shape of the working electrode 21 was defined on the surface of the electrolyte layer 12, and a 3-μm Pt film layer was printed at the surface electrode using the screen printing method. After drying at 70 °C for 15 min, it was sintered at 800 °C for 0.5 h; then a 500-nm WO3 film layer was deposited on the electrode surface by magnetron sputtering to form the working electrode 21;
[0081] The electrode stencil pattern was designed, the shape of the working electrode 22 was defined on the surface of the electrolyte layer 12, and a 4-μm Co3O4 film layer was printed at the surface electrode using the screen printing method. After drying at 110 °C for 15 min, the working electrode 22 was formed;
[0082] The electrode stencil pattern was designed, the shape of the working electrode 23 was defined on the surface of the electrolyte layer 12, and a 2-μm SnO2 film layer was printed at the surface electrode using the screen printing method. After drying at 120 °C for 15 min, a 2-μm ZnO film layer was printed at the surface electrode again using the screen printing method. After drying at 120 °C for 15 min, the working electrode 23 was formed;
[0083] Design the electrode grid pattern, define the shape of the working electrode 24 on the surface of the electrolyte layer 12, and use the screen printing method to print a 4-μm TiO₂ film layer at the surface electrode, and then dry it in an oven at 130 °C for 20 min to form the working electrode 24;
[0084] Design the electrode grid pattern, define the shape of the reference electrode 25 on the surface of the electrolyte layer 12, and use the screen printing method to print a 4-μm Ag film layer at the surface electrode, and then dry it in an oven at 125 °C for 30 min to form the working electrode 25;
[0085] Step 4: Prepare the heating layer
[0086] Adopt the screen printing method, design and prepare a screen for the shape of the heating electrode, and print a 5-μm W film at the lower electrode position of the substrate layer 11, and then dry it in an oven at 130 °C for 20 min to form the heating electrode 31.
[0087] Example 5
[0088] A preparation method of the multifunctional electrochemical gas sensor as described above, comprising the following steps:
[0089] (1) Pretreatment of the substrate layer 11: Cook the silicon wafer with concentrated sulfuric acid at high temperature for 20 - 30 min, then ultrasonically clean the silicon wafer with deionized water and ethanol in sequence, and then dry it at 80 - 90 °C to obtain the treated substrate layer 11.
[0090] (2) Prepare the electrolyte layer 12: Use the screen printing method to print a 10-μm thick yttrium-doped zirconia film layer on the upper surface of the treated substrate layer 11, dry it and sinter it at 1500 °C to form the electrolyte layer 12.
[0091] (3) Prepare the electrode layer: Use photolithography to define the patterns of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25 on the upper surface of the electrolyte layer 12, and use magnetron sputtering to prepare an electrode material with a thickness of 0.3 μm at the corresponding positions, and finally form the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25; The specific method of magnetron sputtering is: First, sputter a layer of corresponding electrode material with a thickness of 0.3 μm at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then soak it in acetone for 30 min, clean it with ultrapure water, and finally dry it at 80 °C for 10 min.
[0092] (4) Preparation of the heating layer: The heating electrode 31 is prepared on the lower surface of the substrate layer 11 by screen printing to form the heating layer. The specific method is as follows: First, print the corresponding material with the pattern of the heating electrode 31 on the lower surface of the substrate layer 11, then dry it at 60 °C for 10 min, and finally calcine it at 600 °C for 1 h to form the heating electrode 31.
[0093] Example 6
[0094] A preparation method of the multifunctional electrochemical gas sensor described above, comprising the following steps:
[0095] (1) Pretreatment of the substrate layer 11: The silicon wafer is cooked with concentrated sulfuric acid at high temperature for 40 - 60 min, then the silicon wafer is ultrasonically cleaned with deionized water and ethanol in sequence, and then dried at 100 - 110 °C to obtain the treated substrate layer 11.
[0096] (2) Preparation of the electrolyte layer 12: A yttrium-doped zirconia film layer with a thickness of 50 μm is printed on the upper surface of the treated substrate layer 11 by screen printing, dried and sintered at 1350 °C for 2 h to form the electrolyte layer 12.
[0097] (3) Preparation of the electrode layer: The patterns of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25 are defined on the upper surface of the electrolyte layer 12 by photolithography, and an electrode material with a thickness of 5 μm is prepared at the corresponding positions by electrochemical deposition. Finally, the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25 are formed; The specific method of the electrochemical deposition method is as follows: First, deposit a layer of the corresponding electrode material with a thickness of 3 μm at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then clean it with ultrapure water and ethanol, and finally dry it at 110 °C for 30 min.
[0098] (4) Preparation of the heating layer: The heating electrode 31 is prepared on the lower surface of the substrate layer 11 by photolithography to form the heating layer. The specific method is as follows: First, define the pattern of the heating electrode 31 on the lower surface of the substrate layer 11, and deposit a layer of the heating electrode 31 material with a thickness of 5 μm at the corresponding position by magnetron sputtering or electrochemical deposition. Then soak it in acetone for 60 min, and finally clean it with ultrapure water and dry it at 110 °C for 30 min to form the heating electrode 31.
[0099] Example 7
[0100] A preparation method of the multifunctional electrochemical gas sensor described above, comprising the following steps:
[0101] (1) Pretreatment of the substrate layer 11: Soak the alumina sheet in dilute sulfuric acid for 60 - 80 min, then ultrasonically clean the alumina sheet with ethanol, and then dry it to obtain the treated substrate layer 11.
[0102] (2) Preparation of the electrolyte layer 12: Use screen printing to print a 25 - μm - thick yttrium - doped zirconia film layer on the upper surface of the treated substrate layer 11, dry it and sinter it at 1350 - 1380 °C to form the electrolyte layer 12.
[0103] (3) Preparation of the electrode layer: Use photolithography to define the patterns of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25 on the upper surface of the electrolyte layer 12, and use screen printing to prepare an electrode material with a thickness of 1 - 2 μm at the corresponding positions, finally forming the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25; The specific operation of screen printing is: First, design the electrode stencil pattern, and print a layer of corresponding electrode material with a thickness of 3 - 4 μm at the corresponding positions of the first working electrode 21, the second working electrode 22, the third working electrode 23, the fourth working electrode 24, and the reference electrode 25, then dry it at 70 - 125 °C for 15 - 25 min, and finally calcine it at 600 - 1000 °C for 2 - 2.5 h.
[0104] (4) Preparation of the heating layer: Use photolithography to prepare the heating electrode 31 on the lower surface of the substrate layer 11 to form the heating layer. The specific operation of photolithography is: First, define the pattern of the heating electrode 31 on the lower surface of the substrate layer 11, and use magnetron sputtering or electrochemical deposition to deposit a layer of heating electrode 31 material with a thickness of 1 - 3 μm at the corresponding positions, then soak it in acetone for 40 - 50 min, and finally clean it with ultrapure water and dry it at 90 - 100 °C for 15 - 25 min to form the heating electrode 31.
[0105] In the description of the present application, it should be noted that the orientation or positional relationship indicated by terms such as "upper" and "lower" is based on the orientation or positional relationship shown in the drawings, and is only for the convenience of describing the present application 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, so it cannot be understood as a limitation to the present application. In addition, terms such as "first", "second", and "third" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance.
[0106] Unless otherwise clearly defined and limited, the terms "arranged" and "connected" shall 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 directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two components. For those of ordinary skill in the art, the specific meanings of the above terms in this application can be understood according to specific circumstances.
[0107] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present utility model. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present utility model. Therefore, the present utility model will not be limited to the embodiments shown herein, but rather to the broadest scope consistent with the principles and novel features disclosed herein.
Claims
1. A multifunctional electrochemical gas sensor, characterized in that: It includes a heating layer, a base layer, and an electrode layer, wherein the base layer includes a substrate layer and an electrolyte layer, and the electrolyte layer is arranged above the substrate layer; the electrode layer is arranged above the electrolyte layer, and the electrode layer includes a first working electrode, a second working electrode, a third working electrode, a fourth working electrode, and a reference electrode, and the first working electrode, the second working electrode, the third working electrode, and the fourth working electrode all include a U-shaped structure area; the reference electrode includes a trunk and four branches arranged on the trunk, and the four branches of the reference electrode are respectively arranged in the U-shaped structure areas of the first working electrode, the second working electrode, the third working electrode, and the fourth working electrode.
2. A multifunctional electrochemical gas sensor according to claim 1, characterized in that: The first working electrode, the second working electrode, the third working electrode and the fourth working electrode are porous structure electrodes.
3. A multifunctional electrochemical gas sensor according to claim 1, characterized in that: The heating layer is arranged below the substrate layer, and the heating layer is a heating electrode with a mesh structure.