A two-dimensional-three-dimensional composite electrode, a preparation method, a 2.5D small chip packaging method and application

CN118032889BActive Publication Date: 2026-09-15ANHUI UNIV
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Patent Information

Application Number
CN202410045240.7
Authority / Receiving Office
CN · China
Patent Type
Patents(China)
Current Assignee / Owner
Filing Date
2024-01-11
Publication Date
2026-09-15
Estimated Expiration
2044-01-11

AI Technical Summary

Technical Problem

这种传感器采用滴铸金属有机框架的方法制成,相比于原位生长金属有机框架,其稳定性较差

Benefits of technology

[0050] 1) Compared to the ion sensor combining a conductive metal-organic framework and an ion-selective membrane described in the paper "Conductive Metal–Organic Frameworks as Ion-to-Electron Transducers in Potentiometric Sensors" (ACS Applied Materials & Interfaces 2018, 10, 19248-19257), the in-situ growth method of the metal-organic framework used in this invention produces electrodes with a lower detection limit than the droplet method. The detection limit of the electrode in the paper is 10. –7 M, the detection limit of the electrode in this invention is 2.0 × 10⁻⁶. -9 M.

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Abstract

This invention provides a two-dimensional-three-dimensional composite electrode for detecting ammonium ions, its preparation method, encapsulation method, and applications. The composite electrode forms a Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene structure. The preparation method of the composite electrode includes: preparing a Si / Ag structure; preparing a Si / Ag / Zn structure; preparing Cu3(HHTP)2; preparing MXene; and preparing the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode. When detecting ammonium ions based on this composite electrode, ZIF-8 and Cu3(HHTP)2 in the electrode, as porous materials with a large specific surface area, greatly enhance the efficiency of ion enrichment; MXene has excellent conductivity, accelerating electron transport; the linear range for ammonium ion concentration detection is 10 nM to 100 μM, and the detection limit is 2.0 × 10⁻⁶. ‑9 M, sensitivity is 2.416×10 ‑4 mA·μM ‑6 The sweat monitoring chip of the two-dimensional-three-dimensional composite electrode of the present invention can be integrated into smart wearable devices, thereby being applied to artificial intelligence technology equipment to realize real-time monitoring of data related to the human ecosystem, especially ammonium ions in sweat.
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Description

Technical Field

[0001] This invention belongs to the field of integrated circuit detection technology, specifically relating to a two-dimensional-three-dimensional composite electrode for detecting ammonium ions, its preparation method, 2.5D chip packaging and application. Background Technology

[0002] The level of cations in human blood can reflect an individual's metabolic state, dietary status, and liver health. During exercise, the concentration of ammonium ions in the blood changes from an aerobic to an anaerobic state. Furthermore, since the liver converts ammonia into urea before excretion, ammonium ions can be used as a biomarker for liver diseases such as hepatitis or cirrhosis. However, detecting ammonium ions in the blood requires collecting blood samples, which is cumbersome and time-consuming. Therefore, developing a high-precision method for real-time detection of ammonium ion levels is essential.

[0003] Studies have shown that ammonium ions can be diffused from blood plasma into sweat, and the level of ammonium ions in sweat is directly related to their concentration in the blood. Czarnowski et al. investigated the relationship between blood ammonium ion concentration and urea levels and the concentration of ammonium ions in sweat. Their research indicated that ammonia in blood plasma is the main source of ammonium ions in sweat. Furthermore, during short-term exercise, ammonium ions are primarily secreted through sweat. Long-term studies on athletes have shown a significant increase in blood ammonium ion concentration before and after exercise, with blood ammonium ion concentration during exercise almost three times the normal level. In addition, prolonged low-carbohydrate diets also affect the concentration of ammonium ions in sweat. In conclusion, the concentration of ammonium ions in sweat can be used as an indicator of protein metabolism and breakdown, providing physiological information about the human body under many different conditions, such as changes from aerobic to anaerobic exercise, and information about individual dietary status.

[0004] Currently, conventional ion detection and research typically rely on fixed biological research instruments such as high-performance liquid chromatography (HPLC) and mass spectrometry (MS), which are not conducive to real-time monitoring of ion concentrations. Furthermore, existing miniature portable sensors have limitations in detection limits and sensitivity. Therefore, the development of sweat monitoring chips with high sensitivity, wide detection range, and ease of operation holds great promise.

[0005] Chinese patent CN115856035A, entitled "An Ammonium Ion Sensor and Its Preparation Method," discloses an ammonium ion sensor and its preparation method. The ammonium ion sensor includes a substrate, a reference electrode spaced apart on the substrate, and a working electrode. The working electrode comprises a metal electrode layer, a dendritic gold nanomaterial layer, a conductive polymer layer, and an ammonium ion selective membrane sequentially stacked. The metal electrode layer is attached to one side of the dendritic gold nanomaterial layer, wrapping around the dendritic gold surface according to its shape. This sensor uses an ammonium ion selective membrane. Generally, the materials constituting the ion selective membrane are expensive, resulting in a higher cost compared to electrodes without a membrane.

[0006] The paper "Conductive Metal–Organic Frameworks as Ion-to-Electron Transducers in Potentiometric Sensors" (ACS Applied Materials & Interfaces 2018, 10, 19248-19257) introduces an ion sensor combining a conductive metal-organic framework and an ion-selective membrane. Several conductive three-dimensional metal-organic frameworks were drop-cast onto a glassy carbon electrode and then covered with an ion-selective membrane to form the ion sensor. Results show that the device exhibits a wide dynamic range (1 mM–2 mM) and a low detection limit (10⁻⁶ mM). –7 This sensor is fabricated using a drop-cast metal-organic framework method, which results in poorer stability compared to in-situ grown metal-organic frameworks. Summary of the Invention

[0007] To address the problems existing in the prior art, this invention provides a two-dimensional-three-dimensional composite electrode and its preparation method, a 2.5D small chip packaging method and its application, which solves the difficulties in the detection and signal transmission of ammonium ions, and enables the use of an ammonium ion sensing chip with ammonium ion detection and signal transmission functions for sweat monitoring.

[0008] To achieve the above objectives, this invention employs a two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 /

[0009] Cu3(HHTP)2-MXene; ZIF-8 is a 2-methylimidazolium zinc MOF.

[0010] Preferably, the substrate of the two-dimensional-three-dimensional composite electrode is a smooth and flat Si / Ag, with a thin Zn layer on top, a three-dimensional ZIF-8 layer with a nano-dodecahedral structure on top, and a composite layer consisting of a three-dimensional Cu3(HHTP)2 layer with a nano-needle structure and a two-dimensional MXene layer on top of the ZIF-8 layer.

[0011] The Ag layer has a thickness of (30-80) nm; the thin Zn layer has a thickness of (30-60) nm and is located above the Ag layer; the ZIF-8 layer has a thickness of (200-400) nm, is internally connected by NC bonds, and is connected to the Zn layer by Zn-N bonds; the Cu3(HHTP)2-MXene composite layer has a thickness of (240-390) nm, with Cu3(HHTP)2 vertically and intersectingly attached to the surface of ZIF-8, and the hydrogen atoms of Cu3(HHTP)2 and ZIF-8 forming hydrogen bonds, which connect to form a porous structure; MXene is embedded in the porous structure formed by ZIF-8 and Cu3(HHTP)2 through Ti-C bonds.

[0012] The electrode contains the elements C, N, O, Zn, Cu, and Ti, with the following mass percentages: Ti = (0.1–0.5)%, Cu = (0.5–1)%, Zn = (0.5–1.5)%, N = (10–20)%, O = (25–35)%, and the remainder being C.

[0013] In addition, the present invention also provides a method for preparing a composite electrode, comprising the following steps:

[0014] 1) Preparation of Si / Ag structure: Clean Si wafers are cut into (1-2) cm × (1-2) cm electrodes, washed in an ultrasonic cleaner with deionized water, acetone and ethanol for (10-20) minutes, dried with nitrogen, and then treated with ultraviolet ozone for (10-20) minutes; an Ag layer is deposited on the Si wafer by thermal evaporation technology.

[0015] 2) Preparation of Si / Ag / Zn structure: A Zn layer is deposited on the surface of the Ag layer using magnetron sputtering technology;

[0016] 3) Preparation of Cu3(HHTP)2: Copper acetate and hydrated terphenyl powder were dissolved in N,N-dimethylformamide aqueous solution, reacted, centrifuged and dried to obtain Cu3(HHTP)2 powder; the hydrated terphenyl was 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP).

[0017] 4) Preparation of MXene: Dissolve 1–2 g of lithium fluoride in 15–25 mL of 5–10 M hydrochloric acid solution. Heat in a water bath at 30–50 °C with continuous stirring. Add 1–2 g of aluminum titanium carbide powder every 2–4 minutes. After adding the powder 5–10 times, centrifuge at 3000–5000 rpm. Collect the precipitate and wash it several times with deionized water to obtain a concentration of 0.1–0.3 g / mL.-1 MXene solution;

[0018] 5) Preparation of Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode: Dissolve (8-9) g of 2-methylimidazole and (10-11) g of triethylamine in (90-110) mL of deionized water; then, take (2-4) mL of the above mixed solution and mix it with (5-8) mL of deionized water and (0.2-0.6) mL of 20-40% hydrogen peroxide to prepare a reaction solution; then, add (30-60) mg of Cu3(HHTP)2 powder and (3-6) mL of [unspecified chemical] from step 3). The MXene solution was reacted in a water bath at (60-70)℃ for (0.5-1) hours with magnetic stirring. Finally, the prepared Si / Ag / Zn substrate was added, and the reaction was continued for (0.5-1) hours. After the reaction was completed, the electrode was washed and dried at (40-80)℃ to obtain the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode.

[0019] As a preferred embodiment, a three-electrode electrochemical detection electrode system is constructed, consisting of a Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode, a reference electrode, a counter electrode, and PBS (phosphate buffer solution), for monitoring ammonium ions and sweat. When detecting ammonium ions using this composite electrode, the ZIF-8 and Cu3(HHTP)2 components, as porous materials with a large specific surface area, significantly enhance the efficiency of ion enrichment; MXene exhibits excellent conductivity, accelerating electron transport; the linear range for ammonium ion concentration detection is 10 nM to 100 μM, with a detection limit of 2.0 × 10⁻⁶. -9 M, sensitivity is 2.416×10 - 4 mA·μM -1 .

[0020] In addition, the present invention also provides an ammonium ion monitoring chip with a two-dimensional-three-dimensional composite electrode, including an ammonium ion detection module, a filtering module, an analog-to-digital conversion module, a storage module, a wireless transceiver module, a microprocessor module and a power management module. The ammonium ion detection module includes an ammonium ion detection electrode system and a temperature sensor.

[0021] The ammonium ion detection module is responsible for receiving the electrical signal collected by the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode of the ammonium ion detection electrode and the temperature signal collected by the temperature sensor, and applying a bias voltage to the ammonium ion detection electrode.

[0022] The filtering module is responsible for filtering the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode signal collected by the ammonium ion detection module. The input signal is filtered by the second-order Butterworth low-pass filter built into the filtering module and then output. Its function is to remove high-frequency noise and interference from the signal and retain the low-frequency components in the signal, so as to achieve a clear and accurate signal.

[0023] The analog-to-digital conversion module is responsible for converting the analog signal after filtering by the filtering module into a digital signal; the input analog signal is converted into a discrete digital signal after sampling, quantization and encoding.

[0024] The storage module is responsible for storing the digital signal after analog-to-digital conversion.

[0025] The wireless transceiver module is responsible for sending data results to external terminal devices or receiving control signals from external terminal devices; the input signal undergoes encoding and modulation, power amplification and filtering, generates a radio frequency (RF) signal, and amplifies and filters the RF signal. Finally, the amplified RF signal is transmitted through a wireless antenna.

[0026] The microprocessor module is responsible for issuing instructions to the ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, and power management module, and controlling the operation of each module.

[0027] The power management module is used to supply power to the ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, and microprocessor module.

[0028] Furthermore, this invention provides a 2.5D chiplet packaging method that allows chip dies with similar port characteristics to be directly integrated into a "3D stacked structure" in the vertical direction. This "3D stacked structure" is then horizontally connected to other chip dies with different port characteristics, reducing the length of inter-chip interconnects and minimizing the overall chip size. This results in a high-density chip packaging structure. In the 2.5D packaged IC, the logic chip and other stacked memory components are arranged side-by-side on the Si interposer layer.

[0029] Specifically, in the ammonium ion monitoring chip structure of the two-dimensional-three-dimensional composite electrode, the ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, microprocessor module, and power management module are all located on PI (polyimide) adhesive, which is located on a silicon interposer layer; the ammonium ion detection module, storage module, and wireless transceiver module are stacked together, with the ammonium ion detection module at the bottom, the wireless transceiver module at the top, and the storage module sandwiched in between; the filtering module and the analog-to-digital conversion module are stacked together, with the filtering module located below the analog-to-digital conversion module; the microprocessor module and the power management module exist as separate modules.

[0030] More specifically, the ammonium ion detection module includes ten pins: power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, working electrode 1, counter electrode 1, reference electrode 1, and temperature 1, as well as ammonium ion detection electrode 1 and temperature sensor 1; the filtering module includes eight pins: power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, data input 1, and data output 1; the analog-to-digital conversion module includes eight pins: power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, data input 1, and data output 1; the storage module includes power supply 1... The wireless transceiver module has eight pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output, as well as a transmitting antenna. The microprocessor module has eight pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output, as well as a transmitting antenna. The power management module has eight pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output.

[0031] Between the ammonium ion detection module and the filter module: One pin of the working electrode for ammonium ions is connected to one pin of the data input of the filter module via a copper wire printed on PI adhesive.

[0032] Between the filtering module and the analog-to-digital converter module: The data input pin of the analog-to-digital converter module passes through the filtering module via a through-silicon via (TSV) and is connected to the solder ball of the data output pin of the filtering module via a copper wire printed on the PI adhesive.

[0033] Between the analog-to-digital converter (ADC) module and the storage module: One pin of the ADC module's data output passes through a through-silicon via (TSV) through the filter module and connects to the solder ball below. One pin of the storage module's data input passes through a TSV through the ammonium ion detection module and connects to the solder ball below. The two solder balls are connected by copper wires printed on PI adhesive.

[0034] Between the storage module and the wireless transceiver module: One pin of the storage module's data output passes through a through-silicon via (TSV) through the ammonium ion detection module and connects to the solder ball below. One pin of the wireless transceiver module's data input passes through both the storage module and the ammonium ion detection module and connects to the solder ball below. The two solder balls are connected by copper wires printed on PI adhesive.

[0035] Between the ammonium ion detection module and the substrate base: the power supply, grounding, debugging, debugging, reset, clock, working electrode, counter electrode, reference electrode, and temperature pin of the ammonium ion detection module pass through the PI adhesive and silicon interlayer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interlayer through metallic copper.

[0036] Between the filter module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1 and clock 1 pins of the filter module pass through the PI glue and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through metal copper.

[0037] Between the analog-to-digital converter module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1 and clock 1 pins of the analog-to-digital converter module pass through the filter module, PI glue and silicon interposer below through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through copper.

[0038] Between the storage module and the substrate base: The power supply, ground, debugging, reset, and clock pins of the storage module pass through the ammonium ion detection module, PI adhesive, and silicon interposer below via through-silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer via metallic copper.

[0039] Between the wireless transceiver module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, and data output 1 pins of the wireless transceiver module pass through the storage module, ammonium ion detection module, PI adhesive, and silicon interposer below via silicon vias, and are connected to the corresponding solder balls at the bottom of the silicon interposer via metallic copper.

[0040] Between the microprocessor module and the substrate base: the power supply 1, ground 1, reset 1, clock 1, debug 1, debug 2, data input 1 and data output 1 pins of the microprocessor module pass through the PI adhesive and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through metallic copper.

[0041] Between the power management module and the substrate base: the power management module's power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, data input 1 and data output 1 pins pass through PI adhesive and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through copper.

[0042] In addition, this invention also provides a method for operating the ammonium ion monitoring chip. First, the chip performs a self-test upon power-on. The microprocessor module reads the unloaded readings of the ammonium ion detection electrode and temperature sensor of the ammonium ion detection module and determines whether the readings are normal. If the readings are abnormal, a warning signal is issued; if they are normal, the chip enters normal operating mode. The ammonium ion detection module applies a bias voltage to the external electrochemical electrode and receives the ammonium ion concentration electrical signal and the temperature electrical signal, converting them into electrical signals and transmitting them to the filtering module. The filtering module performs low-pass filtering on the input signal and sends the data to the analog-to-digital conversion module. The analog-to-digital conversion module performs analog-to-digital conversion on the input signal and sends the data to the microprocessor module. When the temperature is between -30 and 5°C or between 25 and 150°C, the microprocessor module performs temperature compensation on the ammonium ion concentration electrical signal in conjunction with the temperature signal; otherwise, the data is directly sent to the storage module. Subsequently, the storage module stores the corrected data. Finally, the wireless transmission module transmits the signal to the receiving terminal via a wireless transmitting antenna.

[0043] Preferably, the effective range of temperature compensation is (-30~5)℃ and (25~150)℃. When the ammonium ion detection module detects a temperature of (-30~5)℃ or (25~150)℃, the microprocessor module performs error compensation on the data according to the temperature compensation formula. The temperature compensation formula for the temperature of (-30~5)℃ is I=I0*[1+a*(5-t)], and the temperature compensation formula for the temperature of (25~150)℃ is I=I0*[1+a*(t-25)], where I is the temperature compensation result, I0 is the actual value of the current, a is the temperature compensation coefficient, and t is the current temperature.

[0044] The working principle of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode of this invention is as follows:

[0045] As shown in Figure 1(a), without applying an external bias voltage, the anion (SO4) 2- (marked as dotted pattern spheres) and cations (NH4) + (The spheres, marked as having a mesh pattern, are randomly distributed in the electrolyte solution.)

[0046] As shown in Figure 1(b), the bias voltage applied by the differential pulse voltammetry method is a combination of a stepped potential and a pulse with a fixed amplitude (as shown in Figure 2(a)). After the bias voltage is applied, the working electrode generates a charging current, which is caused by the electrode itself. On the other hand, the pulse voltage causes an electrode reaction between the working electrode and ammonium ions, generating a Faraday current, which is generated by substances in the solution. The current i is obtained by sampling the current twice, at time t1 before the pulse and at time t2 after the pulse, and subtracting the samples. n =i t2 -it1 As the voltage changes, a series of currents i1, i2...i will be obtained. n Plotting voltage on the x-axis and current i on the y-axis n The current peak curve is shown in Figure 2(b) with the vertical axis as the ordinate. The peak values ​​differ at different concentrations and are directly proportional to the concentration, thus it can be used to detect ammonium ions at different concentrations.

[0047] Under the applied bias voltage, an electric field exists between the working electrode and the counter electrode, with the direction from the counter electrode to the working electrode. Therefore, ammonium ions of the cation are enriched on the surface of the working electrode. Cu3(HHTP)2 and ZIF-8, as porous materials with a large specific surface area, greatly enhance the efficiency of ion enrichment. Sulfate ions of the anion are enriched on the surface of the counter electrode, the platinum electrode. Since ZIF-8 is a sensitive material for ammonium ions, ammonium ions undergo selective reduction on the surface of the working electrode, losing electrons and being reduced to NH3. MXene, as an excellent conductive material, allows the electrons lost by ammonium ions to be transported through the MXene layer, Cu3(HHTP)2 layer, and ZIF-8 layer to the Ag layer and external circuitry.

[0048] As shown in Figure 1(c), with the external bias voltage off, the NH4 near the electrode... + and SO4 2- Ions migrate to regions of lower concentration until an equilibrium is reached.

[0049] Compared with the prior art, the beneficial effects of the present invention are:

[0050] 1) Compared to the ion sensor combining a conductive metal-organic framework and an ion-selective membrane described in the paper "Conductive Metal–Organic Frameworks as Ion-to-Electron Transducers in Potentiometric Sensors" (ACS Applied Materials & Interfaces 2018, 10, 19248-19257), the in-situ growth method of the metal-organic framework used in this invention produces electrodes with a lower detection limit than the droplet method. The detection limit of the electrode in the paper is 10. –7 M, the detection limit of the electrode in this invention is 2.0 × 10⁻⁶. -9 M.

[0051] 2) The ammonium ion detection electrode based on the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode exhibits a linear range of 10 nM to 100 μM for ammonium ion concentration detection, with a detection limit of 2.0 × 10⁻⁶. -9M, sensitivity is 2.416×10 -4 mA·μM -6 Compared to the electrodes in the aforementioned paper (which have a linear range of 1mM–2nM), this has a wider linear range.

[0052] 3) The sweat monitoring chip with a two-dimensional-three-dimensional composite electrode proposed in this invention adopts a 2.5D small chip packaging method, which greatly reduces the size of the chip and reduces the power consumption of the chip.

[0053] 4) The sweat monitoring chip of the two-dimensional-three-dimensional composite electrode of the present invention has a temperature compensation function, which minimizes the influence of temperature on the detection results.

[0054] 5) The sweat monitoring chip of the two-dimensional-three-dimensional composite electrode of the present invention can be integrated into smart wearable devices, thereby being applied to artificial intelligence technology equipment to realize real-time monitoring of data related to the human ecosystem, especially ammonium ions in sweat. Attached Figure Description

[0055] Figures 1(a)(b)(c) are schematic diagrams illustrating the principle of ammonium ion detection implemented by the sensing module of the present invention; Figure 1(a) is a schematic diagram of the working electrode of the present invention in the state without applied bias voltage, where 101 is the counter electrode (Pt electrode), 102 is the working electrode (Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene), and 103 is SO4. 2- The label 104 is NH4. + Figure 1(b) is a schematic diagram of the working electrode under bias voltage applied according to the present invention. Identifier 105 is the counter electrode (Pt electrode), Identifier 106 is the working electrode (Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene), and Identifier 107 is SO4. 2- The label 108 is NH4. + Figure 1(c) is a schematic diagram of the working electrode of the present invention in the off bias state. Identifier 109 is the counter electrode (Pt electrode), Identifier 110 is the working electrode (Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene), and Identifier 111 is SO4. 2- Identifier 112 is NH4 +Figure 1(d) is a schematic diagram of the two-dimensional-three-dimensional composite electrode structure of the present invention. Identifier 113 is a schematic diagram of the connection between Cu3(HHTP)2 and ZIF-8, which are connected by hydrogen bonds. Identifier 114 is a schematic diagram of the connection between MXene and Cu3(HHTP)2, which are connected by Ti-C bonds. Identifier 115 is a schematic diagram of the MXene structure. Identifier 116 is a schematic diagram of the Cu3(HHTP)2 structure. Identifier 117 is a schematic diagram of the ZIF-8 structure.

[0056] Figure 2(a) is a schematic diagram of the bias voltage applied by the differential pulse voltammetry method; Figure 2(b) is a schematic diagram of the test results of the differential pulse voltammetry method.

[0057] Figure 3 This is a schematic diagram of the two-dimensional-three-dimensional composite electrode sweat monitoring chip structure of the present invention. In the diagram, 301 represents the analog-to-digital conversion module; 302 represents the filtering module; 303 represents the microprocessor module; 304 represents the power management module; 305 represents the PI (polyimide) adhesive; 306 represents the wireless transceiver module; 307 represents the storage module; 308 represents the ammonium ion detection module; and 309 represents the silicon interposer. The ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, microprocessor module, and power management module are all located on the PI (polyimide) adhesive, which is located on the silicon interposer. The ammonium ion detection module, storage module, and wireless transceiver module are stacked together, with the ammonium ion detection module at the bottom, the wireless transceiver module at the top, and the storage module sandwiched in between. The filtering module and the analog-to-digital conversion module are stacked together, with the filtering module located below the analog-to-digital conversion module. The microprocessor module and power management module exist as separate modules.

[0058] Figure 4 This is a top view schematic diagram of the 3D packaging structure of the two-dimensional-three-dimensional composite electrode sweat detection chip of the present invention.

[0059] Figure 5 for Figure 4 Enlarged view of part A.

[0060] Figure 6 for Figure 4 Enlarged view of section B.

[0061] Figure 7 This is a bottom view schematic diagram of the 3D packaging structure of the two-dimensional-three-dimensional composite electrode sweat detection chip of the present invention.

[0062] Figure 8 for Figure 7 Enlarged view of section C.

[0063] Figure 9 for Figure 7Enlarged view of a portion of D.

[0064] Figure 10 This is a schematic diagram of the two-dimensional-three-dimensional composite electrode sweat monitoring chip of the present invention being worn.

[0065] Figure 11 This is a schematic diagram illustrating the preparation method of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode in this invention.

[0066] Figure 12 This is a flowchart illustrating the workflow of the two-dimensional-three-dimensional composite electrode sweat monitoring chip of the present invention.

[0067] Figure 13 (a) TEM (transmission electron microscopy) image of MXene nanosheets. Figure 13 b、 Figure 13 c shows the SEM (scanning electron microscope) images of Cu3(HHTP)2 and ZIF-8, respectively. Figure 13 (d) SEM image of Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene Figure 13 (e) Figure 13 (f) Figure 13 (g) Figure 13 (h) Figure 13 (i) Figure 13 (k) is the energy-dispersive X-ray spectrum of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode, where, Figure 13 (e) represents C elements. Figure 13 (f) represents N elements, Figure 13 (g) represents element O. Figure 13 (h) represents the Zn element. Figure 13 (i) represents Cu element, Figure 13 (k) represents the Ti element.

[0068] SEM image of Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene

[0069] Figure 14(a) shows the XPS (X-ray photoelectron spectroscopy) spectrum of N1s, indicating the presence of N-Zn bonds; Figure 14(b) shows the XPS spectrum of Ti2p, indicating the presence of Ti-C bonds.

[0070] Figure 15 shows the repeatability experiment of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode (a). The relative standard deviation calculated from 20 consecutive tests was 1.6%, proving that the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode has good repeatability. Figure 15(b) shows the anti-interference experiment. By adding NaCl, NaHCO3, K2CO3, Ca(NO3)2 and Mg(NO3)2, many interfering cations and anions in water, such as Na+, were measured. + K + Ca 2+ Mg 2+ Cl - HCO3 - and CO3 2- These ions showed slight interference, indicating that the Cu3(HHTP)2-MXene / ZIF-8 electrode has good selectivity; Figure 15(c) shows the stability test results. The relative standard deviation calculated from the test results over 10 consecutive days was 4.7%, proving that the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode has good stability. Detailed Implementation

[0071] The following embodiments are further illustrations of the present invention to illustrate its technical content. However, the essence of the present invention is not limited to the embodiments described below. Those skilled in the art can and should know that any simple changes or substitutions based on the spirit of the present invention should fall within the scope of protection claimed by the present invention.

[0072] Example 1. A method for preparing a two-dimensional-three-dimensional composite electrode, comprising the following steps:

[0073] 1) Preparation of Si / Ag structure: Clean n-Si wafers were cut into 1cm×1cm electrodes, washed with deionized water, acetone and ethanol in an ultrasonic cleaner for 10 minutes, dried with nitrogen, and then treated with ultraviolet ozone for 10 minutes; Ag layer was deposited on the n-Si wafer by thermal evaporation technology.

[0074] 2) Preparation of Si / Ag / Zn structure: A Zn layer is deposited on the surface of the Ag layer using magnetron sputtering technology;

[0075] 3) Preparation of Cu3(HHTP)2: 15g of copper acetate and 15g of hydrated terphenyl powder were dissolved in 3mL of N,N-dimethylformamide aqueous solution. After reaction, centrifugation and drying, Cu3(HHTP)2 powder was obtained.

[0076] 4) Preparation of MXene: Dissolve 1g of lithium fluoride in 15mL of 5M hydrochloric acid solution, heat in a 30℃ water bath with continuous stirring, add 1g of titanium aluminum carbide powder every 2 minutes, and repeat 5 times. After centrifugation at 3000 rpm, collect the precipitate and wash it several times with deionized water to obtain a concentration of 0.1g / mL. -1 MXene solution;

[0077] 5) Preparation of Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode: Dissolve 8g of 2-methylimidazole and 10g of triethylamine in 90mL of deionized water; then, take 2mL of the above mixed solution and mix it with 5mL of deionized water and 0.2mL of 30% hydrogen peroxide to prepare a reaction solution; next, add 30mg of Cu3(HHTP)2 powder and 3mL of MXene solution from step 3), and react fully in a water bath at 60℃ for 0.5 hours with magnetic stirring; finally, add the prepared Si / Ag / Zn substrate, continue the reaction for 0.5 hours, and after the reaction is completed, wash and dry at 40℃ to obtain the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode.

[0078] Preparation process such as Figure 11 As shown, the prepared Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode contains the elements C, N, O, Zn, Cu, and Ti, with the following mass percentages: Ti = 0.1%, Cu = 0.5%, Zn = 0.5%, N = 10%, O = 25%, and the remainder being C. Figure 13 (e) Figure 13 (f) Figure 13 (g) Figure 13 (h) Figure 13 (i) Figure 13 As shown in (k).

[0079] As shown in Figure 1(d), the structure of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode is as follows: a 30nm thick Ag layer on the n-Si sheet; a 30nm thick Zn layer located above the Ag layer; and a 200nm thick ZIF-8 layer. Figure 13 As shown in (c), a single ZIF-8 crystal exhibits a regular dodecahedral structure; the thickness of the Cu3(HHTP)2-MXene composite layer is 240 nm, and Cu3(HHTP)2 is vertically and intersectingly attached to the surface of ZIF-8, as shown in (c). Figure 13 As shown in (b), a single Cu3(HHTP)2 cell exhibits a needle-like shape, such as Figure 13 As shown in (a), MXene exhibits a membrane morphology and has strong extensibility.

[0080] Example 2. A method for preparing a two-dimensional-three-dimensional composite electrode, comprising the following steps:

[0081] 1) Preparation of Si / Ag structure: Clean n-Si wafers were cut into 2cm×2cm electrodes, washed in an ultrasonic cleaner with deionized water, acetone and ethanol for 20 minutes, dried with nitrogen, and then treated with ultraviolet ozone for 20 minutes; Ag layer was deposited on the n-Si wafer by thermal evaporation technology.

[0082] 2) Preparation of Si / Ag / Zn structure: A Zn layer is deposited on the surface of the Ag layer using magnetron sputtering technology;

[0083] 3) Preparation of Cu3(HHTP)2: 12g of copper acetate and 12g of hydrated terphenyl powder were dissolved in 3mL of N,N-dimethylformamide aqueous solution. After reaction, centrifugation and drying, Cu3(HHTP)2 powder was obtained.

[0084] 4) Preparation of MXene: Dissolve 2g of lithium fluoride in 25mL of 10M hydrochloric acid solution, heat in a 50℃ water bath with continuous stirring, add 2g of aluminum titanium carbide powder every 4 minutes, repeat 10 times, centrifuge at 5000 rpm, collect the precipitate and wash it several times with deionized water to obtain a concentration of 0.3g / mL. -1 MXene solution;

[0085] 5) Preparation of Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode: 9g of 2-methylimidazole and 11g of triethylamine were dissolved in 110mL of deionized water; then, 4mL of the above mixed solution was mixed with 8mL of deionized water and 0.6mL of 30% hydrogen peroxide to prepare a reaction solution; next, 60mg of Cu3(HHTP)2 powder and 6mL of MXene solution from step 3) were added to it, and the mixture was fully reacted in a water bath at 70℃ for 1 hour with magnetic stirring; finally, the prepared Si / Ag / Zn substrate was added, and the reaction was continued for 1 hour. After the reaction was completed, the mixture was washed and dried at 80℃ to obtain the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode.

[0086] Preparation process such as Figure 11 As shown, the prepared Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode contains the elements C, N, O, Zn, Cu, and Ti. The mass percentages of each element are Ti = 0.5%, Cu = 1%, Zn = 1.5%, N = 10%, O = 25%, and the rest is C.

[0087] As shown in Figure 1(d), the structure of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene composite electrode is as follows: an Ag layer with a thickness of 70 nm on the n-Si sheet; a thin Zn layer with a thickness of 50 nm located above the Ag layer; a ZIF-8 layer with a thickness of 400 nm, as shown in Figure 14(a), which is internally connected by NC bonds and connected to the Zn layer by Zn-N bonds; a Cu3(HHTP)2-MXene composite layer with a thickness of 390 nm, where Cu3(HHTP)2 is vertically and intersectingly attached to the surface of ZIF-8, and hydrogen atoms of Cu3(HHTP)2 and ZIF-8 form hydrogen bonds, which connect to form a porous structure; as shown in Figure 14(b), MXene is embedded in the porous structure formed by ZIF-8 and Cu3(HHTP)2 through Ti-C bonds.

[0088] Combining Examples 1 and 2, based on the repeatability experiment (Figure 15(a), anti-interference experiment (Figure 15(b), and stability test results) and the stability test results (Figure 15(c), the relative standard deviation of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode, calculated from 20 consecutive tests, is 1.6%, indicating good repeatability. By adding NaCl, NaHCO3, K2CO3, Ca(NO3)2, and Mg(NO3)2, many interfering cations and anions in water, such as Na+, were determined. + K + Ca 2+ Mg 2+ Cl - HCO3 - and CO3 2- These ions showed slight interference, indicating good selectivity; the relative standard deviation calculated from the test results over 10 consecutive days was 4.7%, indicating good stability.

[0089] Example 3. A 2.5D packaging method for a sweat monitoring chip.

[0090] A 2.5D chiplet packaging method for reducing the length of inter-chip interconnects, such as... Figure 3As shown, the overall chip size is reduced. Identifier 301 is the analog-to-digital converter module; Identifier 302 is the filter module; Identifier 303 is the microprocessor module; Identifier 304 is the power management module; Identifier 305 is the PI adhesive; Identifier 306 is the wireless transceiver module; Identifier 307 is the storage module; Identifier 308 is the ammonium ion detection module; and Identifier 309 is the silicon interposer. The ammonium ion detection module, filter module, analog-to-digital converter module, storage module, wireless transceiver module, microprocessor module, and power management module are all located on the PI adhesive, which is placed on the silicon interposer. The ammonium ion detection module, storage module, and wireless transceiver module are stacked together, with the ammonium ion detection module at the bottom, the wireless transceiver module at the top, and the storage module sandwiched in between. The filter module and analog-to-digital converter module are stacked together, with the filter module located below the analog-to-digital converter module. The microprocessor module and power management module exist as separate modules.

[0091] like Figure 4 , 5 Figure 6 shows a top view of the discrete structure of the 3D package of the two-dimensional-three-dimensional composite electrode sweat detection chip, as shown in Figure 6. Figure 7 , 8 Figure 9 shows a bottom view of the discrete structure of the 3D package of the two-dimensional-three-dimensional composite electrode sweat detection chip. The ammonium ion detection module has ten pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Working Electrode 1, Counter Electrode 1, Reference Electrode 1, and Temperature 1, as well as Ammonium Ion Detection Electrode 1 and Temperature Sensor 1. The filtering module has eight pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1. The analog-to-digital conversion module has four pins: Power Supply 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1. Output 1 has eight pins; the storage module has eight pins: Power 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1; the wireless transceiver module has eight pins: Power 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1, as well as a transmitting antenna; the microprocessor module has eight pins: Power 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1; the power management module has eight pins: Power 1, Ground 1, Debug 1, Debug 2, Reset 1, Clock 1, Data Input 1, and Data Output 1.

[0092] Between the ammonium ion detection module and the filter module: One pin of the working electrode for ammonium ions is connected to one pin of the data input of the filter module via a copper wire printed on PI adhesive.

[0093] Between the filtering module and the analog-to-digital converter module: The data input pin of the analog-to-digital converter module passes through the filtering module via a through-silicon via (TSV) and is connected to the solder ball of the data output pin of the filtering module via a copper wire printed on the PI adhesive.

[0094] Between the analog-to-digital converter (ADC) module and the storage module: One pin of the ADC module's data output passes through a through-silicon via (TSV) through the filter module and connects to the solder ball below. One pin of the storage module's data input passes through a TSV through the ammonium ion detection module and connects to the solder ball below. The two solder balls are connected by copper wires printed on PI adhesive.

[0095] Between the storage module and the wireless transceiver module: One pin of the storage module's data output passes through a through-silicon via (TSV) through the ammonium ion detection module and connects to the solder ball below. One pin of the wireless transceiver module's data input passes through both the storage module and the ammonium ion detection module and connects to the solder ball below. The two solder balls are connected by copper wires printed on PI adhesive.

[0096] Between the ammonium ion detection module and the substrate base: the power supply, grounding, debugging, debugging, reset, clock, working electrode, counter electrode, reference electrode, and temperature pin of the ammonium ion detection module pass through the PI adhesive and silicon interlayer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interlayer through metallic copper.

[0097] Between the filter module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1 and clock 1 pins of the filter module pass through the PI glue and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through metal copper.

[0098] Between the analog-to-digital converter module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1 and clock 1 pins of the analog-to-digital converter module pass through the filter module, PI glue and silicon interposer below through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through copper.

[0099] Between the storage module and the substrate base: The power supply, ground, debugging, reset, and clock pins of the storage module pass through the ammonium ion detection module, PI adhesive, and silicon interposer below via through-silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer via metallic copper.

[0100] Between the wireless transceiver module and the substrate base: the power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, and data output 1 pins of the wireless transceiver module pass through the storage module, ammonium ion detection module, PI adhesive, and silicon interposer below via silicon vias, and are connected to the corresponding solder balls at the bottom of the silicon interposer via metallic copper.

[0101] Between the microprocessor module and the substrate base: the power supply 1, ground 1, reset 1, clock 1, debug 1, debug 2, data input 1 and data output 1 pins of the microprocessor module pass through the PI adhesive and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through metallic copper.

[0102] Between the power management module and the substrate base: the power management module's power supply 1, ground 1, debugging 1, debugging 2, reset 1, clock 1, data input 1 and data output 1 pins pass through PI adhesive and silicon interposer through silicon vias and are connected to the corresponding solder balls at the bottom of the silicon interposer through copper.

[0103] Identifier 401 indicates that the wireless transceiver module has a through-hole on the storage module after the power supply is connected to the storage module. Identifier 402 indicates that the wireless transceiver module has a through-hole on the storage module after the clock is connected to ...

[0104] Identifier 414 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after power supply is applied. Identifier 415 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after grounding is applied. Identifier 417 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after reset is applied. Identifier 418 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after debugging is applied. Identifier 420 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after debugging is applied. Identifier 421 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after data output is applied. Identifier 424 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after data input is applied. Identifier 426 indicates that the wireless transceiver module has a through-hole on the ammonium ion detection module after clock is applied. Identifier 412 indicates that the storage module has a through-hole on the ammonium ion detection module after power supply is applied.

[0105] Identifier 413 indicates that the storage module has a through-hole for grounding on the ammonium ion detection module; Identifier 416 indicates that the storage module has a through-hole for resetting on the ammonium ion detection module; Identifier 419 indicates that the storage module has a through-hole for debugging on the ammonium ion detection module; Identifier 422 indicates that the storage module has a through-hole for data output on the ammonium ion detection module; Identifier 423 indicates that the storage module has a through-hole for debugging on the ammonium ion detection module; Identifier 425 indicates that the storage module has a through-hole for data input on the ammonium ion detection module; Identifier 427 indicates that the storage module has a through-hole for clocking on the ammonium ion detection module.

[0106] Identifier 409 indicates that the analog-to-digital converter (ADC) module has a through-hole on the filter module after being reset. Identifier 410 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 411 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 428 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 429 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 430 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 431 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 432 indicates that the ADC module has a through-hole on the filter module after being reset. Identifier 432 indicates that the ADC module has a through-hole on the filter module after being reset.

[0107] Marker 557 indicates the clock position on the PI adhesive after the filter module has a through hole made downwards; Marker 558 indicates the reset position on the PI adhesive after the filter module has a through hole made downwards; Marker 501 indicates the data input position on the PI adhesive after the filter module has a through hole made downwards; Marker 544 indicates the data output position on the PI adhesive after the filter module has a through hole made downwards; Marker 553 indicates the power supply position on the PI adhesive after the filter module has a through hole made downwards; Marker 551 indicates the grounding position on the PI adhesive after the filter module has a through hole made downwards; Marker 550 indicates the debugging position on the PI adhesive after the filter module has a through hole made downwards; Marker 547 indicates the debugging position on the PI adhesive after the filter module has a through hole made downwards.

[0108] Marker 555 indicates the clock position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 556 indicates the reset position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 548 indicates the data input position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 545 indicates the data output position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 554 indicates the power supply position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 552 indicates the ground position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 548 indicates the debugging position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards; Marker 546 indicates the debugging position on the PI glue after the analog-to-digital converter module has a through hole drilled downwards.

[0109] Marker 541 indicates a clock signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 539 indicates a reset signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 537 indicates a data input signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 532 indicates a data output signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 543 indicates a power supply signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 542 indicates a ground signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 540 indicates a debugging signal on the PI adhesive after a through-hole is made downwards from the microprocessor module; Marker 538 indicates a debugging signal on the PI adhesive after a through-hole is made downwards from the microprocessor module.

[0110] Marker 531 indicates the clock position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 530 indicates the reset position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 528 indicates the data input position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 529 indicates the data output position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 536 indicates the power supply position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 535 indicates the ground position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 534 indicates the debugging position on the PI adhesive after the power management module has a through hole drilled downwards; Marker 533 indicates the debugging position on the PI adhesive after the power management module has a through hole drilled downwards.

[0111] Mark 506 indicates the ammonium ion detection module has a through-hole drilled downwards and is grounded on the PI adhesive. Mark 510 indicates the ammonium ion detection module has a through-hole drilled downwards and is reset on the PI adhesive. Mark 515 indicates the ammonium ion detection module has a through-hole drilled downwards and is adjusted on the PI adhesive. Mark 520 indicates the ammonium ion detection module has a through-hole drilled downwards and is adjusted on the PI adhesive. Mark 524 indicates the ammonium ion detection module has a through-hole drilled downwards and is reference electrode on the PI adhesive. Mark 502 indicates the ammonium ion detection module has a through-hole drilled downwards and is power supply on the PI adhesive. Mark 505 indicates the ammonium ion detection module has a through-hole drilled downwards and is clock on the PI adhesive. Mark 514 indicates the ammonium ion detection module has a through-hole drilled downwards and is working electrode on the PI adhesive. Mark 521 indicates the ammonium ion detection module has a through-hole drilled downwards and is temperature on the PI adhesive. Mark 527 indicates the ammonium ion detection module has a through-hole drilled downwards and is counter electrode on the PI adhesive.

[0112] Marker 507 indicates grounding on the PI adhesive after the storage module has a through hole drilled downwards; Marker 512 indicates reset on the PI adhesive after the storage module has a through hole drilled downwards; Marker 518 indicates debugging on the PI adhesive after the storage module has a through hole drilled downwards; Marker 522 indicates debugging on the PI adhesive after the storage module has a through hole drilled downwards; Marker 503 indicates power supply on the PI adhesive after the storage module has a through hole drilled downwards; Marker 509 indicates clock on the PI adhesive after the storage module has a through hole drilled downwards; Marker 516 indicates input on the PI adhesive after the storage module has a through hole drilled downwards; Marker 522 indicates output on the PI adhesive after the storage module has a through hole drilled downwards.

[0113] Mark 508 indicates that the wireless transceiver module has a through hole at the bottom and is grounded on the PI glue. Mark 513 indicates that the wireless transceiver module has a through hole at the bottom and is reset on the PI glue. Mark 519 indicates that the wireless transceiver module has a through hole at the bottom and is adjusted on the PI glue. Mark 523 indicates that the wireless transceiver module has a through hole at the bottom and is adjusted on the PI glue. Mark 504 indicates that the wireless transceiver module has a through hole at the bottom and is powered on the PI glue. Mark 511 indicates that the wireless transceiver module has a through hole at the bottom and is clocked on the PI glue. Mark 518 indicates that the wireless transceiver module has a through hole at the bottom and is inputted on the PI glue. Mark 526 indicates that the wireless transceiver module has a through hole at the bottom and is outputted on the PI glue.

[0114] Marker 604 indicates the clock position on the substrate after the analog-to-digital converter module has a through-hole facing downwards; Marker 605 indicates the reset position on the substrate after the analog-to-digital converter module has a through-hole facing downwards; Marker 690 indicates the power supply position on the substrate after the analog-to-digital converter module has a through-hole facing downwards; Marker 688 indicates the ground position on the substrate after the analog-to-digital converter module has a through-hole facing downwards; Marker 683 indicates the debugging position on the substrate after the analog-to-digital converter module has a through-hole facing downwards; Marker 680 indicates the debugging position on the substrate after the analog-to-digital converter module has a through-hole facing downwards.

[0115] Marker 601 indicates that the filter module has a through-hole on the substrate after clock signal 1 is made downwards; Marker 602 indicates that the filter module has a through-hole on the substrate after reset signal 1 is made downwards; Marker 693 indicates that the filter module has a through-hole on the substrate after power supply signal 1 is made downwards; Marker 689 indicates that the filter module has a through-hole on the substrate after grounding signal 1 is made downwards; Marker 684 indicates that the filter module has a through-hole on the substrate after debugging signal 1 is made downwards; Marker 680 indicates that the filter module has a through-hole on the substrate after debugging signal 2 is made downwards.

[0116] Identifier 677 indicates a clock signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 672 indicates a reset signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 666 indicates a data output signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 676 indicates a power supply signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 674 indicates a ground signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 671 indicates a debugging signal on the substrate after the microprocessor module has a through-hole drilled downwards; Identifier 670 indicates a debugging signal on the substrate after the microprocessor module has a through-hole drilled downwards.

[0117] Identifier 657 indicates the power management module has a through-hole on the substrate with a clock signal. Identifier 656 indicates the power management module has a through-hole on the substrate with a reset signal. Identifier 655 indicates the power management module has a through-hole on the substrate with a data input signal. Identifier 664 indicates the power management module has a through-hole on the substrate with a power supply signal. Identifier 663 indicates the power management module has a through-hole on the substrate with a ground signal. Identifier 660 indicates the power management module has a through-hole on the substrate with a debugging signal. Identifier 659 indicates the power management module has a through-hole on the substrate with a debugging signal.

[0118] Marker 617 indicates the ammonium ion detection module has a through-hole on the substrate after being grounded; Marker 625 indicates the ammonium ion detection module has a through-hole on the substrate after being reset; Marker 633 indicates the ammonium ion detection module has a through-hole on the substrate after being adjusted; Marker 638 indicates the ammonium ion detection module has a through-hole on the substrate after being adjusted; Marker 644 indicates the ammonium ion detection module has a through-hole on the substrate after being referenced; Marker 611 indicates the ammonium ion detection module has a through-hole on the substrate after being powered; Marker 623 indicates the ammonium ion detection module has a through-hole on the substrate after being clocked; Marker 651 indicates the ammonium ion detection module has a through-hole on the substrate after being powered; Marker 648 indicates the ammonium ion detection module has a through-hole on the substrate after being temperature-controlled; Marker 647 indicates the ammonium ion detection module has a through-hole on the substrate after being counter-electrode.

[0119] Identifier 620 indicates that the storage module has a through-hole on the substrate after grounding; Identifier 628 indicates that the storage module has a through-hole on the substrate after resetting; Identifier 635 indicates that the storage module has a through-hole on the substrate after debugging; Identifier 643 indicates that the storage module has a through-hole on the substrate after debugging; Identifier 615 indicates that the storage module has a through-hole on the substrate after power supply; Identifier 623 indicates that the storage module has a through-hole on the substrate after clock; Identifier 648 indicates that the storage module has a through-hole on the substrate after input.

[0120] Identifier 622 indicates that the wireless transceiver module has a through-hole on the substrate after being grounded. Identifier 619 indicates that the wireless transceiver module has a through-hole on the substrate after being reset. Identifier 638 indicates that the wireless transceiver module has a through-hole on the substrate after being debugged. Identifier 645 indicates that the wireless transceiver module has a through-hole on the substrate after being debugged. Identifier 619 indicates that the wireless transceiver module has a through-hole on the substrate after being powered. Identifier 632 indicates that the wireless transceiver module has a through-hole on the substrate after being clocked. Identifier 649 indicates that the wireless transceiver module has a through-hole on the substrate after being output.

[0121] Identifier 694 indicates a via on the ADC module clock (on the substrate) with solder balls facing upwards; Identifier 695 indicates a via on the ADC module reset (on the substrate) with solder balls facing upwards; Identifier 687 indicates a via on the ADC module power supply (on the substrate) with solder balls facing upwards; Identifier 684 indicates a via on the ADC module grounding (on the substrate) with solder balls facing upwards; Identifier 682 indicates a via on the ADC module debugging (on the substrate) with solder balls facing upwards; Identifier 679 indicates a via on the ADC module debugging (on the substrate) with solder balls facing upwards.

[0122] Marker 688 indicates a via on the substrate with solder balls facing upwards, placed on the clock position of the filter module on the substrate; Marker 689 indicates a via on the substrate with solder balls facing upwards, placed on the reset position of the filter module on the substrate; Marker 687 indicates a via on the substrate with solder balls facing upwards, placed on the power supply position of the filter module on the substrate; Marker 683 indicates a via on the substrate with solder balls facing upwards, placed on the ground position of the filter module on the substrate; Marker 685 indicates a via on the substrate with solder balls facing upwards, placed on the debugging position of the filter module on the substrate; Marker 678 indicates a via on the substrate with solder balls facing upwards, placed on the debugging position of the filter module on the substrate.

[0123] Marker 602 indicates a via on the microprocessor module clock 1 after the solder balls on the substrate are made upwards; Marker 668 indicates a via on the microprocessor module reset 1 after the solder balls on the substrate are made upwards; Marker 653 indicates a via on the microprocessor module data output 1 after the solder balls on the substrate are made upwards; Marker 675 indicates a via on the microprocessor module power supply 1 after the solder balls on the substrate are made upwards; Marker 673 indicates a via on the microprocessor module grounding 1 after the solder balls on the substrate are made upwards; Marker 670 indicates a via on the microprocessor module debugging 1 after the solder balls on the substrate are made upwards; Marker 667 indicates a via on the microprocessor module debugging 2 after the solder balls on the substrate are made upwards.

[0124] Identifier 652 indicates a through-hole on the power management module clock 1 after the solder balls on the substrate are made upwards; Identifier 650 indicates a through-hole on the power management module reset 1 after the solder balls on the substrate are made upwards; Identifier 654 indicates a through-hole on the power management module data input 1 after the solder balls on the substrate are made upwards; Identifier 665 indicates a through-hole on the power management module power 1 after the solder balls on the substrate are made upwards; Identifier 662 indicates a through-hole on the power management module ground 1 after the solder balls on the substrate are made upwards; Identifier 661 indicates a through-hole on the power management module debugging 1 after the solder balls on the substrate are made upwards; Identifier 658 indicates a through-hole on the power management module debugging 2 after the solder balls on the substrate are made upwards.

[0125] Label 610 indicates the ammonium ion detection module grounding point 1 on the substrate after a through-hole is made with the solder balls facing upwards; label 613 indicates the ammonium ion detection module reset point 1 on the substrate after a through-hole is made with the solder balls facing upwards; label 618 indicates the ammonium ion detection module debugging point 1 on the substrate after a through-hole is made with the solder balls facing upwards; label 626 indicates the ammonium ion detection module debugging point 2 on the substrate after a through-hole is made with the solder balls facing upwards; label 630 indicates the ammonium ion detection module reference electrode point 1 on the substrate after a through-hole is made with the solder balls facing upwards. Marker 609 indicates a via with the solder ball facing upwards on the substrate, placed on the power supply of the ammonium ion detection module. Marker 607 indicates a via with the solder ball facing upwards on the substrate, placed on the clock of the ammonium ion detection module. Marker 608 indicates a via with the solder ball facing upwards on the substrate, placed on the working electrode of the ammonium ion detection module. Marker 637 indicates a via with the solder ball facing upwards on the substrate, placed on the temperature of the ammonium ion detection module. Marker 640 indicates a via with the solder ball facing upwards on the substrate, placed on the counter electrode of the ammonium ion detection module.

[0126] Identifier 610 indicates a through-hole on the substrate with solder balls facing upwards, used for grounding the storage module on the substrate; Identifier 614 indicates a through-hole on the substrate with solder balls facing upwards, used for resetting the storage module on the substrate; Identifier 621 indicates a through-hole on the substrate with solder balls facing upwards, used for debugging the storage module on the substrate; Identifier 631 indicates a through-hole on the substrate with solder balls facing upwards, used for debugging the storage module on the substrate; Identifier 4099 indicates a through-hole on the substrate with solder balls facing upwards, used for power supply the storage module on the substrate; Identifier 603 indicates a through-hole on the substrate with solder balls facing upwards, used for clocking the storage module on the substrate.

[0127] Marker 610 indicates a wireless transceiver module grounding connection after a through-hole is made with the solder balls facing upwards. Marker 615 indicates a wireless transceiver module reset connection after a through-hole is made with the solder balls facing upwards. Marker 624 indicates a wireless transceiver module debugging connection after a through-hole is made with the solder balls facing upwards. Marker 636 indicates a wireless transceiver module debugging connection after a through-hole is made with the solder balls facing upwards. Marker 609 indicates a wireless transceiver module power supply connection after a through-hole is made with the solder balls facing upwards. Marker 607 indicates a wireless transceiver module clock connection after a through-hole is made with the solder balls facing upwards. Marker 639 indicates a wireless transceiver module output connection after a through-hole is made with the solder balls facing upwards.

[0128] Identifier 708 indicates grounding the wireless transceiver module; Identifier 707 indicates resetting the wireless transceiver module; Identifier 706 indicates debugging the wireless transceiver module; Identifier 705 indicates debugging the wireless transceiver module twice; Identifier 704 indicates powering on the wireless transceiver module; Identifier 703 indicates clocking the wireless transceiver module; Identifier 702 indicates data input for the wireless transceiver module; Identifier 701 indicates data input for the wireless transceiver module.

[0129] Identifier 729 indicates the analog-to-digital converter (ADC) clock cycle; Identifier 731 indicates the ADC reset cycle; Identifier 728 indicates the ADC data input cycle; Identifier 727 indicates the ADC data output cycle; Identifier 730 indicates the ADC power supply cycle; Identifier 732 indicates the ADC grounding cycle; Identifier 709 indicates the ADC debugging cycle; Identifier 710 indicates the ADC debugging cycle.

[0130] Identifier 725 indicates the storage module is grounded once; Identifier 723 indicates the storage module is reset once; Identifier 721 indicates the storage module is debugged once; Identifier 5019 indicates the storage module is debugged twice; Identifier 726 indicates the storage module is powered once; Identifier 5012 indicates the storage module is clocked once; Identifier 714 indicates the storage module is input once; Identifier 716 indicates the storage module is output once.

[0131] Identifier 724 indicates that after the wireless transceiver module has a through-hole facing downwards, the clock signal is applied once under the storage module. Identifier 722 indicates that after the wireless transceiver module has a through-hole facing downwards, the reset signal is applied once under the storage module. Identifier 720 indicates that after the wireless transceiver module has a through-hole facing downwards, the data input signal is applied once under the storage module. Identifier 718 indicates that after the wireless transceiver module has a through-hole facing downwards, the data output signal is applied once under the storage module. Identifier 711 indicates that after the wireless transceiver module has a through-hole facing downwards, the power supply signal is applied once under the storage module. Identifier 713 indicates that after the wireless transceiver module has a through-hole facing downwards, the ground signal is applied once under the storage module. Identifier 715 indicates that after the wireless transceiver module has a through-hole facing downwards, the debugging signal is applied once under the storage module. Identifier 717 indicates that after the wireless transceiver module has a through-hole facing downwards, the debugging signal is applied twice under the storage module.

[0132] Identifier 846 indicates the microprocessor module clock signal is applied once; Identifier 845 indicates the microprocessor module reset signal is applied once; Identifier 844 indicates the microprocessor module data input signal is applied once; Identifier 843 indicates the microprocessor module data output signal is applied once; Identifier 805 indicates the microprocessor module power supply signal is applied once; Identifier 806 indicates the microprocessor module ground signal is applied once; Identifier 807 indicates the microprocessor module debugging signal is applied once; Identifier 808 indicates the microprocessor module debugging signal is applied twice.

[0133] Identifier 813 indicates the power management module clock cycle; Identifier 814 indicates the power management module reset cycle; Identifier 815 indicates the power management module data input cycle; Identifier 816 indicates the power management module data output cycle; Identifier 809 indicates the power management module power supply cycle; Identifier 810 indicates the power management module grounding cycle; Identifier 811 indicates the power management module debugging cycle; Identifier 812 indicates the power management module debugging cycle.

[0134] Identifier 848 indicates the filter module clock cycle; Identifier 849 indicates the filter module reset cycle; Identifier 847 indicates the filter module data input cycle; Identifier 804 indicates the filter module data output cycle; Identifier 852 indicates the filter module power supply cycle; Identifier 855 indicates the filter module grounding cycle; Identifier 5088 indicates the filter module debugging cycle; Identifier 801 indicates the filter module debugging cycle.

[0135] The following symbols indicate the sequence of events: 850 indicates the analog-to-digital converter (ADC) module has a through-hole at the bottom, which is then connected to the filter module for a clock cycle; 853 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a reset cycle; 858 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a data input cycle; 803 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a data output cycle; 851 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a power supply cycle; 854 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a ground cycle; 857 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a debugging cycle; and 802 indicates the ADC module has a through-hole at the bottom, which is then connected to the filter module for a second debugging cycle.

[0136] Identifier 839 indicates grounding the ammonium ion detection module; Identifier 834 indicates resetting the ammonium ion detection module; Identifier 829 indicates debugging the ammonium ion detection module; Identifier 824 indicates debugging the ammonium ion detection module a second time; Identifier 820 indicates the reference electrode of the ammonium ion detection module; Identifier 842 indicates the power supply of the ammonium ion detection module; Identifier 838 indicates the clock input of the ammonium ion detection module; Identifier 830 indicates the working electrode of the ammonium ion detection module; Identifier 822 indicates the temperature of the ammonium ion detection module; Identifier 818 indicates the counter electrode of the ammonium ion detection module; Identifier 837 indicates grounding the ammonium ion module after making a through hole downwards in the storage module; Identifier 833 indicates resetting the ammonium ion module after making a through hole downwards in the storage module.

[0137] Indicated by label 827: After making a through-hole in the storage module, debug it under the ammonium ion module. Indicated by label 823: After making a through-hole in the storage module, debug it twice under the ammonium ion module. Indicated by label 841: After making a through-hole in the storage module, power it under the ammonium ion module. Indicated by label 835: After making a through-hole in the storage module, ground it under the ammonium ion module. Indicated by label 828: After making a through-hole in the storage module, input data under the ammonium ion module. Indicated by label 819: After making a through-hole in the storage module, output data under the ammonium ion module.

[0138] Identifier 836 indicates that the wireless transceiver module is grounded once under the ammonium ion module after making a through hole downwards; Identifier 831 indicates that the wireless transceiver module is reset once under the ammonium ion module after making a through hole downwards; Identifier 825 indicates that the wireless transceiver module is debugged once under the ammonium ion module after making a through hole downwards; Identifier 821 indicates that the wireless transceiver module is debugged twice under the ammonium ion module after making a through hole downwards; Identifier 840 indicates that the wireless transceiver module is powered once under the ammonium ion module after making a through hole downwards; Identifier 832 indicates that the wireless transceiver module is grounded once under the ammonium ion module after making a through hole downwards; Identifier 826 indicates that the wireless transceiver module is input once under the ammonium ion module after making a through hole downwards; Identifier 817 indicates that the wireless transceiver module is output once under the ammonium ion module after making a through hole downwards.

[0139] Mark 901 indicates that after the microprocessor module has a through-hole drilled downwards, a clock signal is applied once under PI glue. Mark 904 indicates that after the microprocessor module has a through-hole drilled downwards, a reset signal is applied once under PI glue. Mark 907 indicates that after the microprocessor module has a through-hole drilled downwards, a data input signal is applied once under PI glue. Mark 949 indicates that after the microprocessor module has a through-hole drilled downwards, a power signal is applied once under PI glue. Mark 902 indicates that after the microprocessor module has a through-hole drilled downwards, a ground signal is applied once under PI glue. Mark 903 indicates that after the microprocessor module has a through-hole drilled downwards, a debugging signal is applied once under PI glue. Mark 905 indicates that after the microprocessor module has a through-hole drilled downwards, a debugging signal is applied twice under PI glue.

[0140] Mark 911 indicates that the power management module is clocked once under PI glue after making a through hole downwards; Mark 912 indicates that the power management module is reset once under PI glue after making a through hole downwards; Mark 913 indicates that the power management module is input once under PI glue after making a through hole downwards; Mark 906 indicates that the power management module is powered once under PI glue after making a through hole downwards; Mark 908 indicates that the power management module is grounded once under PI glue after making a through hole downwards; Mark 909 indicates that the power management module is debugged once under PI glue after making a through hole downwards; Mark 910 indicates that the power management module is debugged twice under PI glue after making a through hole downwards.

[0141] Mark 938 indicates that after the filter module has a through hole made downwards, clock it once under the PI glue; Mark 937 indicates that after the filter module has a through hole made downwards, reset it once under the PI glue; Mark 943 indicates that after the filter module has a through hole made downwards, power it once under the PI glue; Mark 944 indicates that after the filter module has a through hole made downwards, ground it once under the PI glue; Mark 946 indicates that after the filter module has a through hole made downwards, adjust it once under the PI glue; Mark 947 indicates that after the filter module has a through hole made downwards, adjust it twice under the PI glue.

[0142] Mark 940 indicates that after making a through hole downwards for the analog-to-digital converter module, clock it once under PI glue; Mark 939 indicates that after making a through hole downwards for the analog-to-digital converter module, reset it once under PI glue; Mark 942 indicates that after making a through hole downwards for the analog-to-digital converter module, power it once under PI glue; Mark 941 indicates that after making a through hole downwards for the analog-to-digital converter module, ground it once under PI glue; Mark 945 indicates that after making a through hole downwards for the analog-to-digital converter module, adjust it once under PI glue; Mark 948 indicates that after making a through hole downwards for the analog-to-digital converter module, adjust it twice under PI glue.

[0143] Mark 933 indicates that the ammonium ion detection module is grounded under PI glue after a through hole is made downwards; Mark 928 indicates that the ammonium ion detection module is reset under PI glue after a through hole is made downwards; Mark 923 indicates that the ammonium ion detection module is adjusted under PI glue after a through hole is made downwards; Mark 920 indicates that the ammonium ion detection module is adjusted twice under PI glue after a through hole is made downwards; Mark 917 indicates that the reference electrode is applied under PI glue after a through hole is made downwards; Mark 936 indicates that the power supply is applied under PI glue after a through hole is made downwards; Mark 931 indicates that the clock is applied under PI glue after a through hole is made downwards; Mark 924 indicates that the working electrode is applied under PI glue after a through hole is made downwards; Mark 916 indicates that the temperature is applied under PI glue after a through hole is made downwards; Mark 915 indicates that the counter electrode is applied under PI glue after a through hole is made downwards.

[0144] Identifier 922 indicates that after the storage module has a through-hole, it is grounded once under the PI glue module; Identifier 927 indicates that after the storage module has a through-hole, it is reset once under the PI glue module; Identifier 922 indicates that after the storage module has a through-hole, it is debugged once under the PI glue module; Identifier 919 indicates that after the storage module has a through-hole, it is debugged twice under the PI glue module; Identifier 935 indicates that after the storage module has a through-hole, it is powered once under the PI glue module; Identifier 929 indicates that after the storage module has a through-hole, it is clocked once under the PI glue module; Identifier 914 indicates that after the storage module has a through-hole, it is data output once under the PI glue module.

[0145] Mark 930 indicates that after making a through hole downwards, the wireless transceiver module is grounded once under PI glue; Mark 925 indicates that after making a through hole downwards, the wireless transceiver module is reset once under PI glue; Mark 921 indicates that after making a through hole downwards, the wireless transceiver module is adjusted once under PI glue; Mark 918 indicates that after making a through hole downwards, the wireless transceiver module is adjusted twice under PI glue; Mark 934 indicates that after making a through hole downwards, the wireless transceiver module is powered once under PI glue; Mark 926 indicates that after making a through hole downwards, the wireless transceiver module is grounded once under PI glue.

[0146] Identifier 762 is the base solder ball for grounding of the ammonium ion detection module; Identifier 763 is the base solder ball for reset of the ammonium ion detection module; Identifier 758 is the base solder ball for debugging of the ammonium ion detection module; Identifier 755 is the base solder ball for debugging of the ammonium ion detection module; Identifier 754 is the base solder ball for reference electrode of the ammonium ion detection module; Identifier 761 is the base solder ball for power supply of the ammonium ion detection module; Identifier 765 is the base solder ball for clock of the ammonium ion detection module; Identifier 764 is the base solder ball for working electrode of the ammonium ion detection module; Identifier 748 is the base solder ball for temperature of the ammonium ion detection module; Identifier 751 is the base solder ball for counter electrode of the ammonium ion detection module.

[0147] Identifier 762 is the base solder ball for storage module grounding one, Identifier 759 is the base solder ball for storage module reset one, Identifier 756 is the base solder ball for storage module debugging one, Identifier 753 is the base solder ball for storage module debugging two, Identifier 761 is the base solder ball for storage module power supply one, and Identifier 767 is the base solder ball for storage module clock one.

[0148] Identifier 762 is the base solder ball for grounding of wireless transceiver module one; Identifier 760 is the base solder ball for reset of wireless transceiver module one; Identifier 755 is the base solder ball for debugging of wireless transceiver module one; Identifier 747 is the base solder ball for debugging of wireless transceiver module two; Identifier 761 is the base solder ball for power supply of wireless transceiver module one; Identifier 766 is the base solder ball for clock of wireless transceiver module one; and Identifier 750 is the base solder ball for data output of wireless transceiver module one.

[0149] Identifier 776 is the base solder ball for microprocessor module clock one, Identifier 741 is the base solder ball for microprocessor module reset one, Identifier 743 is the base solder ball for microprocessor module data output one, Identifier 733 is the base solder ball for microprocessor module power supply one, Identifier 734 is the base solder ball for microprocessor module ground one, Identifier 735 is the base solder ball for microprocessor module debugging one, and Identifier 736 is the base solder ball for microprocessor module debugging two.

[0150] Identifier 744 is the base solder ball of power management module clock one, Identifier 745 is the base solder ball of power management module reset one, Identifier 742 is the base solder ball of power management module data input one, Identifier 737 is the base solder ball of power management module power supply one, Identifier 738 is the base solder ball of power management module ground one, Identifier 739 is the base solder ball of power management module debugging one, and Identifier 740 is the base solder ball of power management module debugging two.

[0151] Identifier 771 is the base solder ball of filter module clock one, Identifier 772 is the base solder ball of filter module reset one, Identifier 773 is the base solder ball of filter module power supply one, Identifier 770 is the base solder ball of filter module ground one, Identifier 774 is the base solder ball of filter module debugging one, and Identifier 777 is the base solder ball of filter module debugging two.

[0152] Identifier 768 is the base solder ball for the clock of the analog-to-digital converter module 1; Identifier 769 is the base solder ball for the reset of the analog-to-digital converter module 1; Identifier 743 is the base solder ball for the data output of the analog-to-digital converter module 1; Identifier 773 is the base solder ball for the power supply of the analog-to-digital converter module 1; Identifier 770 is the base solder ball for the ground of the analog-to-digital converter module 1; Identifier 775 is the base solder ball for the debugging of the analog-to-digital converter module 1; and Identifier 778 is the base solder ball for the debugging of the analog-to-digital converter module 2.

[0153] Example 4. Working method of sweat monitoring chip

[0154] like Figure 12 As shown, firstly, the chip performs a power-on self-test. The microprocessor module reads the no-load readings of the ammonium ion detection electrode and temperature sensor of the ammonium ion detection module and determines whether the readings are normal. If the readings are abnormal, a warning signal is issued; otherwise, it enters the normal operation mode. The ammonium ion detection module applies a bias voltage to the external electrochemical electrode and receives the ammonium ion concentration electrical signal and the temperature electrical signal, converting them into electrical signals and transmitting them to the filtering module. The filtering module performs low-pass filtering on the input signal and sends the data to the analog-to-digital conversion module. The analog-to-digital conversion module performs analog-to-digital conversion on the input signal and sends the data to the microprocessor module. When the temperature is between -30 and 5°C or between 25 and 150°C, the microprocessor module performs temperature compensation on the ammonium ion concentration electrical signal based on the temperature signal; otherwise, the data is directly sent to the storage module. Subsequently, the storage module stores the corrected data. Finally, the wireless transmission module transmits the signal to the receiving terminal via the wireless transmitting antenna.

[0155] The sweat monitoring chip in this implementation example can be designed as a wearable device, worn on the arm of the wearer, such as... Figure 10 As shown.

[0156] Example 5: A method for temperature compensation

[0157] The output signal of the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode in the ammonium ion detection module drifts with temperature changes. To reduce the impact of temperature drift, a temperature compensation method is employed. The temperature compensation of this sweat monitoring chip involves both the ammonium ion detection module and the microprocessor module, with an effective temperature compensation range of (-30~5)℃ and (25~150)℃. Figure 12 The flowchart of the two-dimensional-three-dimensional composite electrode sweat monitoring chip of the present invention is shown. When the ammonium ion detection module detects that the temperature is between -30 and 5°C or between 25 and 150°C, the ammonium ion detection module sends the temperature information and the ion concentration electrical signal to the microprocessor module. The microprocessor module performs error compensation on the data according to the temperature compensation formula. The temperature compensation formula for the temperature between -30 and 5°C is I = I0 * [1 + a * (5 - t)], and the temperature compensation formula for the temperature between 25 and 150°C is I = I0 * [1 + a * (t - 25)], where I is the temperature compensation result, I0 is the actual value of the current, a is the temperature compensation coefficient, and t is the current temperature.

Claims

1. A two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene, characterized in that, The composite electrode is based on a Si wafer. On the surface of the Si wafer, an Ag layer, a Zn layer, a ZIF-8 layer, and a Cu3(HHTP)2-MXene composite layer are sequentially formed. Above the smooth and flat Si / Ag layer is a thin Zn layer. Above the Zn layer is a three-dimensional ZIF-8 layer with a nano-dodecahedral structure. Above the ZIF-8 layer is a composite layer consisting of a three-dimensional Cu3(HHTP)2 layer with a nano-needle structure and a two-dimensional MXene layer. The thickness of the Ag layer is 30-80 nm; the thickness of the Zn layer is 30-60 nm; the thickness of the ZIF-8 layer is 200-400 nm; and the thickness of the Cu3(HHTP)2-MXene composite layer is 240-390 nm.

2. A method for preparing the two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene as described in claim 1, characterized in that, Includes the following steps: 1) Preparation of Si / Ag structure: Cut the clean Si wafer into electrodes of the required size, wash and dry them, and then treat them with ultraviolet ozone for 10~20 minutes; Deposit an Ag layer on a Si wafer; 2) Preparation of Si / Ag / Zn structure: Deposit a Zn layer on the surface of the Ag layer; 3) Preparation of Cu3(HHTP)2: Dissolve 12-19 g of copper acetate and 10-15 g of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) powder in 1-3 mL of N,N-dimethylformamide solution. After reaction, centrifugation and drying, Cu3(HHTP)2 powder is obtained. 4) Preparation of MXene: Dissolve 1-2 g of lithium fluoride in 15-25 mL of 5-10 M hydrochloric acid solution. Heat in a water bath at 30-50°C with continuous stirring. Add 1-2 g of titanium aluminum carbide powder every 2-4 minutes, repeating 5-10 times. After centrifugation at 3000-5000 rpm, collect the precipitate and wash it several times with deionized water to obtain a concentration of 0.1-0.3 g / mL. -1 MXene solution; 5) Preparation of the composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene: Dissolve 8-9g of 2-methylimidazole and 10-11g of triethylamine in 90-110mL of deionized water to obtain a mixed solution; then, take 2-4mL of the above mixed solution and mix it with 5-8mL of deionized water and 0.2-0.6mL of hydrogen peroxide with a concentration of 20wt%-40wt% to prepare a reaction solution; next, add 30-60mg of Cu3(HHTP)2 powder and 3-6mL of MXene solution to it, and react fully in a water bath at 60-70℃ for 0.5-1 hour with magnetic stirring; finally, add the prepared Si / Ag / Zn structure substrate, continue the reaction for 0.5-1 hour, and after the reaction is completed, wash and dry at 40-80℃ to obtain the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene electrode.

3. An electrode system for detecting ammonium ion-containing systems, characterized in that, This includes the two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene as described in claim 1, or the two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene obtained by the preparation method described in claim 2.

4. The electrode system for detecting ammonium ion-containing systems as described in claim 3, characterized in that, A three-electrode electrochemical detection electrode was formed by using a two-dimensional-three-dimensional composite electrode Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene as the working electrode, combined with a reference electrode, a counter electrode, and PBS buffer.

5. The electrode system for detecting ammonium ion-containing systems as described in claim 3, characterized in that, The ammonium ion-containing system includes sweat and blood.

6. An ammonium ion monitoring chip based on an electrode system for detecting ammonium ion-containing systems as described in any one of claims 3-5, characterized in that, It includes an ammonium ion detection module, a filtering module, an analog-to-digital conversion module, a storage module, a wireless transceiver module, a microprocessor module, and a power management module; the ammonium ion detection module includes an ammonium ion detection electrode system and a temperature sensor; The ammonium ion detection module is used to receive the electrical signal collected by the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode of the ammonium ion detection electrode and the temperature signal collected by the temperature sensor, and to apply a bias voltage to the ammonium ion detection electrode. The filtering module is used to filter the Si / Ag / Zn / ZIF-8 / Cu3(HHTP)2-MXene working electrode signal collected by the ammonium ion detection module. After the input signal is filtered by the second-order Butterworth low-pass filter built into the filtering module, the signal is output. Its function is to remove high-frequency noise and interference in the signal and retain the low-frequency components in the signal, so as to achieve the purpose of clear and accurate signal. The analog-to-digital converter module is used to convert the analog signal after filtering by the filtering module into a digital signal; the input analog signal is converted into a discrete digital signal after sampling, quantization and encoding steps. The storage module is responsible for storing the digital signal after analog-to-digital conversion; The wireless transceiver module is used to send data results to external terminal devices or receive control signals from external terminal devices; the input signal is encoded and modulated, amplified and filtered, amplified and filtered to generate a radio frequency signal; finally, the amplified radio frequency signal is transmitted through a wireless antenna. The microprocessor module is used to issue instructions to the ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, and power management module, and to control the operation of each module. The power management module is used to supply power to the ammonium ion detection module, filtering module, analog-to-digital conversion module, storage module, wireless transceiver module, and microprocessor module.

7. The ammonium ion monitoring chip as described in claim 6, characterized in that, The device employs a 2.5D chip package. The ammonium ion detection module, filter module, microprocessor module, and power management module are all located on PI adhesive, which is situated on a silicon interposer. The ammonium ion detection module, storage module, and wireless transceiver module are stacked together, with the ammonium ion detection module at the bottom, the wireless transceiver module at the top, and the storage module between them. The filter module and analog-to-digital converter module are also stacked together, with the filter module located below the analog-to-digital converter module. Between the ammonium ion detection module and the filter module: The working electrode pin of the ammonium ion detection module is connected to the data input pin of the filter module through copper wires printed on the PI adhesive; Between the filtering module and the analog-to-digital converter module: The data input pin of the analog-to-digital converter module passes through the filtering module via a through-silicon via and is connected to the solder ball of the data output pin of the filtering module via a copper wire printed on the PI adhesive; Between the analog-to-digital conversion module and the storage module: The data output pin of the analog-to-digital conversion module passes through the filter module via a through-silicon via and is connected to the solder ball below. The data input pin of the storage module passes through the ammonium ion detection module via a through-silicon via and is connected to the solder ball below. The two solder balls are connected by copper wires printed on the PI adhesive. Between the storage module and the wireless transceiver module: the data output pin of the storage module passes through a through-silicon via (TSV) through the ammonium ion detection module and connects to the solder ball below. The data input pin of the wireless transceiver module passes through both the storage module and the ammonium ion detection module and connects to the solder ball below. The two solder balls are connected by copper wires printed on PI adhesive.

8. The operating method of the ammonium ion monitoring chip according to claim 7, characterized in that, First, the chip performs a power-on self-test. The microprocessor module reads the no-load readings of the ammonium ion detection electrode and temperature sensor from the ammonium ion detection module and determines whether the readings are normal. If the readings are abnormal, a warning signal is issued; otherwise, it enters normal operation mode. The ammonium ion detection module applies a bias voltage to the external electrochemical electrode and receives the ammonium ion concentration and temperature electrical signals, converting them into electrical signals and transmitting them to the filtering module. The filtering module performs low-pass filtering on the input signals and sends the data to the analog-to-digital converter module. The analog-to-digital converter module performs analog-to-digital conversion on the input signals and sends the data to the microprocessor module. When the temperature is between -30 and 5 ℃ or between 25 and 150 ℃, the microprocessor module performs temperature compensation on the ammonium ion concentration electrical signal based on the temperature signal; otherwise, the data is directly sent to the storage module. Subsequently, the storage module stores the corrected data. Finally, the wireless transceiver module transmits the signal to the receiving terminal via the wireless transmitting antenna.

Citation Information

Patent Citations

  • Ammonium ion sensor and preparation method thereof

    CN115856035A