A multilayer two-dimensional composite electrode, a preparation method, a 2.5d laminated packaging method and application

Abstract

The application discloses a multilayer two-dimensional composite electrode, a preparation method, a packaging method and application thereof. The multilayer two-dimensional composite electrode is a Si / Ag / boronene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus structure. The preparation method of the multilayer two-dimensional composite electrode comprises the following steps: 1) preparing a Si / Ag substrate; 2) preparing a Si / Ag / boronene / bismuthene electrode; 3) preparing a Si / Ag / boronene / bismuthene / MXene / TiO2 electrode; and 4) preparing a Si / Ag / boronene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrode. The average transient current density of the multilayer two-dimensional composite electrode is 129 muA cm-2 at 0.3 V (relative to saturated calomel electrode) bias under the condition that a 400-430 nm blue-violet laser with a power of 200-300 mW is used as a light source. ‑2 The 2.5D laminated packaging method of the composite detection chip reduces the overall volume of the chip and reduces the power consumption of the chip. The chip is composed of a sensor module, an optical device module, a microprocessor module, a power management module and a wireless transceiver module, simultaneously provides a new way for wearable smart monitoring capable of performing electromyographic sensing, and is expected to be applied to intelligent robots.

Description

Technical Field

[0001] The present invention relates to a multi-layer two-dimensional composite electrode and a preparation method thereof, and applications in a 2.5D stacked packaging chip and a bioelectric detection sensor, especially an electromyographic sensor, belonging to the technical field of intelligent electronic devices. Background Art

[0002] sEMG (surface electromyography) is a bioelectrical signal that is generated in biological tissues and organs. It is a bioelectrical signal generated by muscle contraction and is easily affected by electrode position, sleeping posture and skin resistance.

[0003] In the paper Synergistic enhancing photoelectrochemical response of Bi 10 O6S9with WO3 optical heterojunction in wide wavelength range (Appl.Surf.Sci.509(2020)144697) introduces a WO3 / Bi 10 O6S9 heterojunction photoelectrode. In situ growth of Bi on WO3 nanosheets based on chemical bath deposition 10 O6S9 nanosheets. A simple synergistic optical heterojunction structure was formed by coupling a multidimensional staggered heterojunction with a light-trapping structure. Results showed that at long wavelengths, the device exhibited accelerated interfacial charge transfer, enhanced light absorption, and improved separation and transfer efficiency of photoexcited electron-hole pairs. At -0.1 V (relative to a saturated calomel electrode), the photocurrent response was 1.16 mA cm -2 , pure WO3 electrode and pure Bi respectively 10 The optical heterojunction did not meet expectations, as there were three-dimensional holes on its surface that were not filled.

[0004] In the Chinese patent "A rehabilitation training device and model training method for hand motor function of hemiplegic patients" (publication number CN109498362A), the invention discloses a rehabilitation training device and model training method for hand motor function of hemiplegic patients. By assisting patients to continuously move their hands according to their will, rehabilitation training focuses more on improving their ability to take care of themselves in daily life. The system consists of a microprocessor module, a main body module, an array electromyographic signal acquisition module, a bridge module, a wireless communication module, a power management module, a wearable rehabilitation glove module, and a detection module. The rehabilitation training device for hand motor function of hemiplegic patients includes an array electromyographic signal acquisition module worn on the forearm of the healthy hand of the hemiplegic patient. This acquisition module collects electromyographic data from the brachioradialis and flexor digitorum superficialis muscles of the forearm during continuous movement of the healthy hand. The collected electromyographic data is sent to the microprocessor via the wireless communication module. The microprocessor classifies this continuous hand movement data into categories such as index finger extension, scissor hand, index finger and middle finger flexion, five-finger flexion, resting state, etc. The EMG data is labeled according to the hand movement category, resulting in EMG data with hand movement state labels. This data is then used to train a continuous hand movement recognition model, which is stored in the OMAP3530 microprocessor. Once the continuous hand movement recognition model is trained, the microprocessor no longer labels and classifies the EMG data from the healthy forearm of the hemiplegic patient. The EMG measurement described in the patent uses an array of EMG electrodes with a sampling frequency of 1000Hz. However, due to the small EMG signal, an external signal amplifier is required. Summary of the Invention

[0005] To address the problems of the prior art, the present invention provides a multi-layer two-dimensional composite electrode, a method for preparing the same, and a detection chip based on the composite electrode. These electrodes address the difficulties encountered in myoelectric signal acquisition, and utilize a composite detection device with bioelectricity, especially myoelectricity, sensing capabilities to enhance bioelectricity, especially myoelectricity, signal detection. To address these issues, the present invention employs the following technical solutions:

[0006] First, the present invention provides a multilayer two-dimensional composite electrode, wherein the electrode is a multilayer two-dimensional structure formed by Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus, and the multilayer two-dimensional composite electrode Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus is a working electrode;

[0007] Preferably, for the multi-layer two-dimensional composite electrode, there are three-dimensional hole defects on the Si surface, with 1 to 5 hole defects per square micron, and the area of ​​each hole defect is 100 to 1000 nm. 2, depth is 50-110nm; the upper surface of Si is an Ag layer, and there are three-dimensional hole defects on the surface of the Ag layer. There are 1-5 hole defects per square micron, and the area of ​​each hole defect is 100-1000nm 2 , with a depth of 50 to 120 nm; on the Ag layer is a boronene layer, which fills the three-dimensional hole defects of the Ag layer; on the boronene layer is a bismuthene layer, which continues to fill the three-dimensional hole defects of the Ag layer; the MXene layer evenly covers the upper surface of the bismuthene layer, and there are three-dimensional hole defects on its surface, with about 1 to 5 hole defects per square micron, and the area of ​​each hole defect is 100 to 200 nm 2 , with a depth of 80 to 120 nm; there is TiO2 on the two-dimensional MXene layer, and TiO2 is connected to MXene through Ti-O bonds; there is a black phosphorus layer on the MXene layer, and black phosphorus fills the three-dimensional hole defects on the surface of the MXene layer; and there is P2O3 at the interface between the MXene layer and the black phosphorus layer, and the black phosphorus layer is connected to TiO2 through PO-Ti bonds and to P2O3 through PO bonds.

[0008] Preferably, for the multilayer two-dimensional composite electrode, the thickness of Si is 480-520 μm, and the roughness is 20-30 nm; the thickness of Ag is 80-100 nm, and the roughness of the formed Si / Ag layer is 25-40 nm; the thickness of borophene is 130-150 nm, and the roughness of the formed Si / Ag / borophene layer is 90-110 nm; the thickness of bismuthene is 120-140 nm, and the roughness of the formed Si / Ag / borophene / bismuthene layer is 190-210 nm; the thickness of MXene is 540-570 nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 layer is 140-160 nm; the thickness of black phosphorus is 60-90 nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus layer is 150-170 nm.

[0009] Secondly, the present invention also provides a method for preparing the multilayer two-dimensional composite electrode, which may include the following steps:

[0010] 1) Fabrication of Si / Ag substrate: Deposition of Ag on the etched Si surface;

[0011] 2) Fabricating a Si / Ag / borophene / bismuthene electrode: spin-coating a borophene precursor solution on a Si / Ag substrate, vacuum drying, and then spin-coating a bismuthene precursor solution, vacuum drying, to obtain a Si / Ag / borophene / bismuthene electrode;

[0012] 3) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 electrode: Spin-coat the MXene precursor solution on the Si / Ag / borophene / bismuthene electrode. After spin coating, anneal the solution at a constant temperature of 200-350°C for 20-40 minutes, followed by ozone treatment for 20-50 minutes to grow TiO2 on the MXene layer.

[0013] 4) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrode: Spin-coat 1.2-1.5 mg mL onto the Si / Ag / borophene / bismuthene / MXene / TiO2 electrode. -1 of black phosphorus solution, and then annealed at a constant temperature of 200-350°C for 20-50min.

[0014] Preferably, in the above-mentioned preparation method, the concentration of the boron olefin precursor solution in step 2) is 0.9-1.0 g·mL -1 Preferably 0.948 to 0.950 g·mL -1 The concentration of the bismuthene precursor solution is 1.000-1.008 g·mL -1 Preferably 1.000-1.005 g·mL -1 ; Step 3) The concentration of MXene precursor solution is 1.0-2.0 mg·mL -1 Preferably 1.2–1.5 mg / mL -1 ; Step 4) The concentration of black phosphorus solution is 1.0-2.0 mg mL -1 Preferably 1.2–1.5 mg / mL -1 .

[0015] As a more preferred technical solution, the method for preparing the multilayer two-dimensional composite electrode of the present invention may specifically include the following steps:

[0016] 1) Fabrication of Si / Ag substrate: Depositing a layer of Ag on the clean Si surface after etching.

[0017] 2) Preparation of boronene and bismuthene solutions: 100 mg of boron powder was dispersed in 20 mL of DMF (N,N-dimethylformamide). The solution was ultrasonicated at 500-700 W for 4-6 hours and centrifuged at 2500-3000 rpm for 25-35 minutes to remove any loose boron particles. This yielded a boronene precursor solution (supernatant) with a density of 0.948-0.950 g mL -1 100 mg of bismuth powder was dispersed in 30 mL of deionized water and sonicated for 4 to 6 hours using a probe ultrasonicator at a frequency of 4 to 6 seconds, followed by a 4 to 6 second pause. The solution was then centrifuged at 4500 to 5000 rpm for 15 to 20 minutes to obtain a bismuthene precursor solution (supernatant) with a density of 1.000 to 1.002 g mL-1 .

[0018] 3) Fabricating a Si / Ag / borophene / bismuthene electrode: spin-coating the boropene precursor solution described in 2) on the prepared Si / Ag substrate at a temperature of 20-25° C. and a humidity of 35-85% RH at a speed of 2500-3000 rpm, with a 3-5 minute interval between each application, and performing two spin-coating cycles for 20-40 seconds each. After vacuum drying for 6-8 hours, spin-coating the bismuthene precursor solution described in 2) at a speed of 2500-3000 rpm, with a 3-5 minute interval between each application, and performing two spin-coating cycles for 20-40 seconds each. After spin coating, vacuum drying was performed for 6-8 hours to obtain a Si / Ag / borophene / bismuthene electrode.

[0019] 4) Preparation of MXene solution: Dissolve 1g LiF in 20mL HCl (9M) and stir for 9-11 minutes until completely dissolved. Add 1g Ti3AlC2 to the solution in 10 equal portions, stirring with magnetic force for 9-11 minutes each time until completely dissolved, and place in a water bath and maintain stirring at 33-37°C for 23-25 ​​hours. After the reaction is complete, transfer the reacted liquid to a centrifuge tube, add deionized water to (40-50)mL, and centrifuge at 3000-4000rpm for 3-5min, and repeat several times, taking the supernatant each time until the pH is close to 6. Pour the shaken liquid into a washing bottle and ultrasonicate under argon environment for 50-70min, while keeping the temperature below 35°C. Then centrifuge at 3000-4000rpm for 20-30min, remove the lower layer of precipitate, and finally dilute with water to obtain 1.2-1.5mg·mL -1 MXene precursor solution.

[0020] 5) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 Electrode: At 20-25°C and 35-85% RH, spin-coat the MXene precursor solution from 4) onto the prepared Si / Ag / borophene / bismuthene electrode to a MXene thickness of 530-570 nm. Spin coat the electrode at a speed of 2500-3000 rpm, with a 3-5 minute interval between each pass. Spin coat twice, each pass lasting 20-40 seconds. After spin coating, anneal the electrode at 200-350°C for 20-40 minutes in an argon glove box with a water content of 0-0.15 ppm and an oxygen content of 0-0.2 ppm. Ozone treatment is then performed for 20-40 minutes to grow TiO2 on the edges of the MXene layer.

[0021] 6) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes: Spin-coat 1.2-1.5 mg mL of MgSO4 on the prepared Si / Ag / borophene / bismuthene / MXene / TiO2 electrodes at a temperature of 20-25°C and a humidity of 35-85% RH. -1 The black phosphorus solution was prepared with a spin coater at a speed of 2500-3000 rpm. The spin coater was applied twice with an interval of 3-5 minutes, and each spin coat was 20-40 seconds. The product was then placed in an argon glove box with a water content of 0-0.15 ppm and an oxygen content of 0-0.2 ppm, and annealed at a constant temperature of 200-350°C for 20-40 minutes.

[0022] Thirdly, the present invention also provides a sensor module or sensor capable of sensing both electric field signals and optical signals, which includes the multilayer two-dimensional composite electrode of the present invention. When the multilayer two-dimensional composite electrode is used as a working electrode, the average transient current density is 129 μA·cm at a bias voltage of 0.3 V (relative to a saturated calomel electrode) when a (200-300) mW (400-430) nm blue-violet laser is used as a light source. -2 .

[0023] Fourthly, based on the above-mentioned multi-layer two-dimensional composite electrode of the present invention, the present invention also provides a composite detection chip, which adopts 2.5D packaging, including a sensor module, an optical device module, a microprocessor module, a power management module, and a wireless transceiver module. The chip structure is packaged using 2.5D packaging fan-out, through-silicon vias, rewiring, and flip-chip bonding packaging to reduce the chip volume. In the present invention, although each module is commonly used, it is not common to use a 2.5D packaging method for packaging, but a unique design of the present invention. Specifically, a unique multi-layer two-dimensional composite electrode is used to realize myoelectric enhancement detection by sensing both electric field signals and optical signals.

[0024] The composite detection chip described in the present invention includes the above-mentioned sensor module, optical device module, microprocessor module, power management module, wireless transceiver module and base; the sensor module and power management module are arranged on the base, the optical device module is arranged on the sensor module, the microprocessor module is arranged on the power management module, and the wireless transceiver module is arranged on the microprocessor module.

[0025] The sensor module is used to capture external electric field signals and optical signals and convert them into electrical signals. It includes a multi-layer two-dimensional composite electrode wrapped with hydrogel as an electrolyte. The sensor module has eight pins, namely power supply 1, ground 1, data input 1, data output 1, debug input 1, debug output 1, reset 1 and clock 1. The pins of power supply 1, ground 1 and clock 1 are flip-chip bonded to the pins of power supply 2, ground 2 and clock 2 of the upper optical device module through solder balls; reset 1, data input 1, data output 1, debug input 1 and debug output 1 are bonded to the reset 1, data input 1, data output 1, debug input 1 and debug output 1 pins of the base through solder balls and copper layers; reset 2, debug input 2 and debug output 2 pass through the sensor module through silicon vias and are bonded to the reset 2, debug input 2 and debug output 2 pins of the base through solder balls and copper layers.

[0026] The optical device module is used to provide a light source for the sensor module. It consists of two micro-LED devices that emit blue-violet light with a wavelength of 400-430nm. The power management module controls them to flash at a frequency of 80-120Hz. The optical device module has six pins: power supply 2, ground 2, debug input 2, debug output 2, reset 2, and clock 2.

[0027] The power management module is used to provide power for the optical device module, the sensor module, the microprocessor module, and the wireless transceiver module; the power management module has a total of six pins, namely power supply 3, ground 3, debug input 3, debug output 3, reset 3, and clock 3; the power supply 3, ground 3, and clock 3 pins are flip-chip bonded to the power supply 4, ground 4, and clock 4 pins of the upper optical device module through solder balls; reset 3, debug input 3, and debug output 3 are bonded to the reset 3, debug input 3, and debug output 3 pins of the base through solder balls and copper layers; reset 4, data input 4, data output 4, debug input 4, and debug output 4 pass through the power management module through silicon vias and are bonded to the reset 4, data output 1, data input 1, debug input 4, and debug output 4 pins of the base through solder balls and copper layers;

[0028] The microprocessor module is used to receive, record, and process signals input by the sensor module, and includes a preamplifier, a bandpass filter, and a digital signal processor. The microprocessor module has eight pins, namely, power supply 4, ground 4, data input 4, data output 4, debug input 4, debug output 4, reset 4, and clock 4. The power supply 4, ground 4, and clock 4 pins are flip-chip bonded to the power supply 5, ground 5, and clock 5 pins of the upper optical device module via solder balls. The data input pin 5 is bonded to the lower data output pin 4, and the data output pin 5 is bonded to the lower data input pin 4. The reset 5, debug input 5, and debug output 5 pass through the power management module and the microprocessor module via silicon through-hole vias, and are bonded to the reset 5, debug input 5, and debug output 5 pins of the base via solder balls and copper layers.

[0029] The wireless transceiver module is used to send the data and analysis results processed by the microprocessor module to an external device or receive control signals from an external device; it has a total of eight pins: power supply 5, ground 5, data input 5, data output 5, debug input 5, debug output 5, reset 5 and clock 5.

[0030] The base is used to support the module and form a packaging layer, and to lead out the internal pins. It has a total of 20 pins: power, ground, data input 1, data output 1, debug input 1, debug output 1, debug input 2, debug output 2, debug input 3, debug output 3, debug input 4, debug output 4, debug input 5, debug output 5, reset 1, reset 2, reset 3, reset 4, reset 5, and clock.

[0031] There is a layer of polyimide on the surface of the base for rewiring. The power supply 1, ground 1, and clock 1 pins of the sensor module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers respectively. The power supply 3, ground 3, and clock 3 pins of the power management module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers respectively.

[0032] Finally, a transparent resin is used as a light-transmitting window and placed above the optical device module. Its size is the same as that of the optical device module, with a thickness of 10 to 20 μm. Polyimide and / or resin are used to fill the gaps between the modules to form the chip packaging shell. The above-mentioned solder balls are made of tin and have a diameter of 2 to 4 μm. The internal filling material of the silicon through-hole is copper, and the diameter of the silicon through-hole is 1 to 5 μm.

[0033] Preferably, the microprocessor module is used to collect signals from the sensor module and the optical device module, and the signals are amplified by the preamplifier in the microprocessor module, filtered by the bandpass filter, analyzed and processed by the digital signal processor, and then output to the wireless transceiver module.

[0034] Preferably, the wireless transceiver module can send data and analysis results to external devices such as mobile phones, computers or wireless receivers, and can also receive control signals from external devices. It consists of a wireless transceiver chip and a pair of microwave antennas.

[0035] Fifthly, the present invention also provides an application of the above-mentioned composite detection chip in sensing and enhancing the detection of bioelectric signals, wherein the bioelectric signals are electrocardiogram signals, electroencephalogram signals, electromyography signals, gastric electrogram signals or retinal electrogram signals.

[0036] Preferably, when the bioelectric signal is an electromyographic signal, the composite detection chip is applied to the detection of the electromyographic signal, which may include the following detection steps:

[0037] S1. The chip is powered on for self-test. The optical device module provides a light field, and the microprocessor module detects the working electrode impedance and determines whether the reading is normal. If the reading is abnormal, a warning signal is sent through the wireless transceiver module. If the reading is normal, the chip enters normal working mode.

[0038] S2, the sensor module senses the electromyographic signal outside the chip;

[0039] S3, the light field enhances the electromyographic signal, and the sensor module sends the enhanced electromyographic signal to the microprocessor module;

[0040] S4, the microprocessor module receives and processes the input signal of the sensor module and sends the data to the wireless transceiver module;

[0041] S5. The wireless transceiver module sends the corrected data.

[0042] In the above application, the microprocessor module performs smoothing on the transient photocurrent response to remove unnecessary noise, and uses the Allometrical model to fit the photocurrent. The fitted function is C = 0.27*T -0.18 , where C is the photocurrent density after treatment and T is the response time, ranging from (29 to 59) s.

[0043] The preparation of the Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus working electrode and the principle of 3D hole defect repair of the present invention are as follows:

[0044] like Figure 1As shown, Si is etched with a strong base to form three-dimensional hole defects, and silver is evaporated and plated to form a Si / Ag substrate. The formed Si / Ag substrate has some three-dimensional hole defects; spin coating can make the coating evenly cover the surface. Since small-scale two-dimensional semiconductor materials can enter the interior of larger hole defects and are blocked and adsorbed by the hole defects during spin coating and thus remain inside the hole defects, the three-dimensional hole defects can be filled by spin coating of smaller two-dimensional semiconductor materials, and van der Waals junctions will be formed between the two-dimensional materials; therefore, borophene is used to fill the three-dimensional hole defects of the Si / Ag substrate by spin coating, and bismuthene is further used to continue to fill the three-dimensional holes of the Si / Ag substrate by spin coating. Then, by continuing to spin-coat MXene, the boron olefin, bismuth olefin and Si / Ag substrates are basically completely covered. However, some three-dimensional hole defects are still generated on the surface. The MXene layer is made stronger by annealing in argon. The electrode is treated with ozone to partially oxidize the Ti in the MXene to form TiO2. Finally, black phosphorus is filled in the three-dimensional holes of the MXene layer by spin coating. Since black phosphorus is extremely easy to oxidize, P2O3 exists on its surface. Annealing in argon makes the black phosphorus layer stronger.

[0045] The working principle of the Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus working electrode of the present invention is:

[0046] like Figure 2 As shown in the figure, at the black phosphorus / MXene interface, black phosphorus / TiO2 interface, TiO2 / MXene interface, and Si / Ag interface, in equilibrium, the Fermi level of the semiconductor is balanced and causes the energy bands of these semiconductors to bend at the interface. In the "light field on" state, electrons (photogenerated electrons) and holes (photogenerated holes) induced by the light field are formed in the black phosphorus, bismuthene, TiO2, and Si regions. The Ag layer, borophene, and MXene are conductive, and in black phosphorus, the holes (photogenerated holes) move upward along the valence band (i.e., migrate toward the positive electrode circuit, and react with OH in the electrolyte). - The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band to TiO2, through MXene to bismuthene, and through MXene, boron olefin, and Ag layer to the Si layer (i.e., migrate to the negative electrode circuit, and H in the electrolyte + The reaction generates H2); in TiO2, holes (photogenerated holes) migrate along the valence band toward the black phosphorus layer (i.e., toward the positive electrode circuit, and OH in the electrolyte - The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band through MXene to bismuthene and through MXene, boron olefin, and Ag layer to the Si layer (i.e., migrate to the negative electrode circuit, and H in the electrolyte + The reaction generates H2); in bismuthene, holes (photogenerated holes) migrate along the valence band through MXene to TiO2 and black phosphorus layer (i.e., migrate to the positive electrode circuit, and OH in the electrolyte -The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band through the boron olefin and Ag layers to the Si layer (i.e., migrate to the negative electrode circuit and react with H in the electrolyte). + The reaction generates H2); in Si, holes (photogenerated holes) migrate along the valence band through the Ag layer, borene to bismuthene, and through the Ag layer, borene, and MXene layer to TiO2 and black phosphorus layer (i.e., migrate to the positive electrode circuit, and OH in the electrolyte). - The reaction generates O2), and the electrons (photogenerated electrons) move down the conduction band (i.e., migrate to the negative electrode circuit and react with H in the electrolyte). + The reaction generates H2). In the "external electric field on" state, the electric field induced electrons (electrogenerated electrons) and holes (electrogenerated holes) are formed in the black phosphorus, MXene, and boron olefin regions. All electrons (electrogenerated electrons) migrate to the Si layer under the action of the external electric field (i.e., migrate to the negative electrode circuit and react with H2 in the electrolyte). + The reaction generates H2), and the holes (electrogenerated holes) migrate to the black phosphorus layer (i.e., migrate to the positive electrode circuit, and the OH in the electrolyte - The reaction generates O2). The applied electric field affects the charge transfer rate, promotes the separation of photogenerated electrons and holes, and inhibits their recombination. It can produce a superposition effect with the light field, thereby enhancing the photoelectrochemical performance in the electric and light fields.

[0047] Compared with the prior art, the present invention has the following beneficial effects:

[0048] 1) The composite detection chip of the present invention has both light field sensing and electric field sensing functions; the Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus working electrode is affected by the light field, generating photogenerated electron-hole pairs to form a photocurrent detection light field; the Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus working electrode is affected by the electric field, inducing electrogenerated electron-hole pairs to form a current detection electric field, and accelerating the separation of photogenerated electrons and holes, which can produce a superposition effect with the light field, thereby enhancing the photoelectrochemical performance in the electric field and light field.

[0049] 2) Compared with the existing technology, the integrated 2.5D chip packaging structure of the electromyographic sensor greatly reduces the overall volume of the chip.

[0050] 3) The composite detection chip for detecting myoelectric information of the present invention can be integrated into smart wearable devices, and thus applied to artificial intelligence technology equipment to achieve real-time monitoring and intelligent control of myoelectric signals, and is more likely to be used as an auxiliary for patients with hemiplegia or movement disorders. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 This is the multi-layer two-dimensional composite electrode manufacturing process and defect filling process of the present invention.

[0052] Figure 2 Schematic diagram of the multi-layer two-dimensional composite electrode structure and the direction of the applied electric field of the present invention.

[0053] Figure 3 This is a structural diagram of the 2.5D composite detection chip of the present invention, wherein the mark 000 is the base, the mark 100 is the sensor module, the mark 200 is the optical device module, the mark 300 is the power management module, the mark 400 is the microprocessor module, and the mark 500 is the wireless transceiver module.

[0054] Figure 4 This is a bottom view of the 2.5D composite detection chip package of the present invention. Mark 101 is the power button, mark 102 is the clock button, mark 103 is the ground button, mark 104 is the data input button, mark 105 is the data output button, mark 106 is the debug input button, mark 107 is the debug output button, mark 108 is the reset button, mark 201 is the power button twice, mark 202 is the clock button twice, mark 203 is the ground button twice, mark 204 is the debug input button twice, mark 205 is the debug output button twice, mark 206 is the reset button twice, mark 301 is the power button three times, mark 302 is The clock is three times, the mark 303 is the ground three times, the mark 304 is the debug input three times, the mark 305 is the debug output three times, the mark 306 is the reset three times, the mark 401 is the power four times, the mark 402 is the clock four times, the mark 403 is the ground four times, the mark 404 is the data input four times, the mark 405 is the data output four times, the mark 406 is the debug input four times, the mark 407 is the debug output four times, the mark 408 is the reset four times, the mark 501 is the power five times, the mark 502 is the clock five times, the mark 503 is the ground five times, the mark Mark 504 is data input five clicks, mark 505 is data output five clicks, mark 506 is debug input five clicks, mark 507 is debug output five clicks, mark 508 is reset five clicks, mark 001 is power on, mark 002 is clock on, mark 003 is ground on, mark 004 is data input once, mark 005 is data output once, mark 006 is debug input once, mark 007 is debug output once, mark 008 is debug input twice, mark 009 is debug output twice, mark 010 is debug input three times, Marker 011 is debug output three times, mark 012 is debug input four times, mark 013 is debug output four times, mark 014 is debug input five times, mark 015 is debug output five times, mark 016 is reset once, mark 017 is reset twice, mark 018 is reset three times, mark 019 is reset four times, mark 020 is reset five times, and marks 151, 152, 153, 351, 352, 353, 354, 355, 356, 357, 358, 451, 452, and 453 are under silicon vias.

[0055] Figure 5 This is a top view of the 2.5D composite detection chip package of the present invention. Mark 000 is the base, mark 100 is the sensor module, mark 200 is the optical device module, mark 300 is the power management module, mark 400 is the microprocessor module, mark 500 is the wireless transceiver module, mark 121 is the power supply one, mark 122 is the clock one, mark 123 is the ground one, mark 321 is the power supply three, mark 322 is the clock three, mark 323 is the ground three, mark 421 is the power supply four, mark 422 is the clock four, mark 423 is the ground four, mark 424 is the data input four, mark 425 is the data output four, mark 031 is the power supply, mark 032 is the clock, mark 033 is the ground, mark 034 is the data input one, mark 035 is the data output 1, label 036 is debug input 1 on, label 037 is debug output 1 on, label 038 is debug input 2 on, label 039 is debug output 2 on, label 040 is debug input 3 on, label 041 is debug output 3 on, label 042 is debug input 4 on, label 043 is debug output 4 on, label 044 is debug input 5 on, label 045 is debug output 5 on, label 046 is reset 1 on, label 047 is reset 2 on, label 048 is reset 3 on, label 049 is reset 4 on, label 050 is reset 5 on, and labels 161, 162, 163, 361, 362, 363, 364, 366, 366, 367, 368, 461, 461, and 462 are through-silicon vias.

[0056] Figure 6 This is a schematic diagram of the structure of the 2.5D composite detection chip after packaging.

[0057] Figure 7 This is a framework diagram of the module division of the present invention and the working relationship between the modules.

[0058] Figure 8 This is a schematic diagram of the array electrode patch composed of the composite detection chip of the present invention and its wearing.

[0059] Figure 9 SEM (scanning electron microscopy) images of (a) Si / Ag, (b) Si / Ag / borene, (c) Si / Ag / borene / bismuthene, (d) Si / Ag / borene / bismuthene / MXene / TiO2 and (e) Si / Ag / borene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes.

[0060] Figure 10 This is the XPS (X-ray photoelectron spectroscopy) spectrum of Ti 2p of the multilayer two-dimensional composite electrode, and the results show the existence of Ti-O bonds.

[0061] Figure 11This is the XPS spectrum of P 2p of the multilayer two-dimensional composite electrode, and the results show the existence of PO-Ti bonds and PO bonds.

[0062] Figure 12 is the transient current density of the multilayer two-dimensional composite electrode, from small to large: Si / Ag / borophene (B), Si / Ag / borophene / bismuthene (BBi), Si / Ag / borophene / bismuthene / MXene / TiO2 (BBiM) and Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus (BBiMP).

[0063] Figure 13 AFM (atomic force microscope) images of (a) Si / Ag / borophene, (b) Si / Ag / borophene / bismuthene, (c) Si / Ag / borophene / bismuthene / MXene / TiO2 and (d) Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes, 3D AFM images of (e) Si / Ag / borophene, (f) Si / Ag / borophene / bismuthene, (g) Si / Ag / borophene / bismuthene / MXene / TiO2 and (h) Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes.

[0064] Figure 14 This is a workflow diagram of the composite detection chip of the present invention. DETAILED DESCRIPTION

[0065] The following embodiments are further descriptions of the present invention to illustrate the technical content of the present invention, but the essential content of the present invention is not limited to the following embodiments. Ordinary technicians in this field can and should know that any simple changes or replacements based on the essential spirit of the present invention should fall within the scope of protection required by the present invention.

[0066] Example 1. Preparation of multilayer two-dimensional composite electrodes

[0067] 1) Fabrication of Si / Ag substrate: Depositing a layer of Ag film on the clean Si surface after etching.

[0068] 2) Preparation of boronene and bismuthene solutions: 100 mg of boron powder was dispersed in 20 mL of DMF. The solution was ultrasonicated at 700 W for 6 hours and centrifuged at 3000 rpm for 35 minutes to remove the detached boron particles. The resulting boronene precursor solution (supernatant) had a density of 0.950 g mL -1 100 mg of bismuth powder was dispersed in 30 mL of deionized water and sonicated for 6 hours using a probe ultrasonicator at a frequency of 6 seconds followed by a 4-second pause. The solution was then centrifuged at 5000 rpm for 20 minutes to obtain a bismuthene precursor solution (supernatant) with a density of 1.002 g mL -1 .

[0069] 3) Fabricating a Si / Ag / borophene / bismuthene electrode: At a temperature of 25°C and a humidity of 85% RH, the boropene precursor solution described in 2) was spin-coated on the prepared Si / Ag substrate at a speed of 3000 rpm for 5 minutes each, with the spin coating repeated twice for 40 seconds each time. After vacuum drying for 8 hours, the bismuthene precursor solution described in 2) was spin-coated at a speed of 3000 rpm for 5 minutes each, with the spin coating repeated twice for 40 seconds each time. After spin coating, the Si / Ag / borophene / bismuthene electrode was obtained by vacuum drying for 8 hours.

[0070] 4) Preparation of MXene solution: Dissolve 1g LiF in 20mL HCl (9M) and stir for 11 minutes until completely dissolved. Add 1g Ti3AlC2 to the solution in 10 equal portions, stir magnetically for 11 minutes each time until completely dissolved, and place in a water bath and maintain stirring at 37°C for 25 hours. After the reaction is complete, transfer the reacted liquid to a centrifuge tube, add deionized water to 50mL, and centrifuge at 4000rpm for 5min. Repeat several times, taking the supernatant each time until the pH is close to 6. Pour the shaken liquid into a washing bottle and ultrasonicate under argon for 70min, while keeping the temperature below 35°C. Then centrifuge at 4000rpm for 30min, remove the lower layer of precipitate, and finally dilute with water to obtain 1.5mg·mL -1 MXene precursor solution.

[0071] 5) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 Electrode: At 25°C and 85% RH, the MXene precursor solution from 4) was spin-coated onto the prepared Si / Ag / borophene / bismuthene electrode to a MXene thickness of 570 nm. Spin coating was performed twice, with a 5-minute interval between coats at 3000 rpm. After spin coating, the electrode was placed in an argon glove box with a water content of 0.15 ppm and an oxygen content of 0.2 ppm. Annealing was performed at 350°C on a hot plate for 40 minutes, followed by ozone treatment for 40 minutes to grow TiO2 on the edges of the MXene layer.

[0072] 6) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes: Spin-coat 1.5 mg mL of MgSO4 on the prepared Si / Ag / borophene / bismuthene / MXene / TiO2 electrodes at 25°C and 35-85% RH. -1The black phosphorus solution was prepared with a spin coater at a speed of 3000 rpm. The spin coater was applied twice with an interval of 5 minutes, and each spin coat was 40 seconds. The sample was then placed in an argon glove box with a water content of 0.15 ppm and an oxygen content of 0.2 ppm, and annealed at a constant temperature of 350°C for 40 minutes using a hot stage.

[0073] like Figure 9 The structure of the working electrode shown is as follows: there are three-dimensional hole defects on the Si surface, 5 hole defects per square micron, and the area of ​​each hole defect is 1000nm 2 , depth is 110nm; the upper surface of Si is an Ag layer, and there are three-dimensional hole defects on the surface of the Ag layer. There are 5 hole defects per square micron, and the area of ​​each hole defect is 1000nm 2 , with a depth of 120nm; on the Ag layer is a boronene layer, which fills the three-dimensional hole defects of the Ag layer; on the boronene layer is a bismuthene layer, which continues to fill the three-dimensional hole defects of the Ag layer; the MXene layer evenly covers the upper surface of the bismuthene layer, and there are three-dimensional hole defects on its surface. There are about 5 hole defects per square micron, and the area of ​​each hole defect is 200nm 2 , depth 120nm; TiO2 exists on the two-dimensional MXene layer, such as Figure 10 As shown, the peaks at 454.86, 458.34 and 463.99 eV are respectively related to Ti 3+ 2p 3 、Ti-C 2p 1 and Ti-O 2p 1 The corresponding bonds indicate that TiO2 is formed and TiO2 is connected to MXene through Ti-O bonds; black phosphorus fills the three-dimensional hole defects on the surface of the MXene layer; and P2O3 exists at the interface between the MXene layer and the black phosphorus layer, such as Figure 11 As shown, the peaks at 126.84, 127.78, 128.25, 132.76, and 134.35 eV correspond to P 2p 3 / 2 、P 2p 1 / 2 , P-Ti bond, PO-Ti bond and P x O y The black phosphorus layer is connected to TiO2 through PO-Ti bonds and to P2O3 through PO bonds.

[0074] The thickness of n-Si is 520 μm and the roughness is 30 nm; the thickness of the Ag layer is 100 nm, and the roughness of the formed Si / Ag layer is 40 nm; the thickness of borophene is 150 nm. Figure 13 As shown in (e), the roughness of the formed Si / Ag / borophene layer is 100nm; the thickness of bismuthene is 140nm. Figure 13As shown in (f), the roughness of the formed Si / Ag / borophene / bismuthene layer is 196nm; the thickness of MXene is 570nm, as shown in Figure 13 As shown in (g), the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 layer is 149nm; the thickness of black phosphorus is 90nm, as shown in Figure 13 As shown in (h), the roughness of the formed Si / Ag / borene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus layer is 156nm.

[0075] Example 2. Preparation of multilayer two-dimensional composite electrodes

[0076] 1) Fabrication of Si / Ag substrate: Depositing a layer of Ag on the clean Si surface after etching.

[0077] 2) Preparation of boronene and bismuthene solutions: 100 mg of boron powder was dispersed in 20 mL of DMF. The mixture was ultrasonicated at 500 W for 4 hours and centrifuged at 2500 rpm for 25 minutes to remove the detached boron particles. The resulting boronene precursor solution (supernatant) had a density of 0.948 g mL -1 100 mg of bismuth powder was dispersed in 30 mL of deionized water and sonicated for 4 hours using a probe ultrasonicator at a frequency of 4 seconds followed by a 6-second pause. The solution was then centrifuged at 4500 rpm for 15 minutes to obtain a bismuthene precursor solution (supernatant) with a density of 1.000 g mL -1 .

[0078] 3) Fabricating a Si / Ag / borophene / bismuthene electrode: At a temperature of 20°C and a humidity of 50% RH, the boropene precursor solution described in 2) was spin-coated on the prepared Si / Ag substrate at a speed of 2500 rpm for 3 minutes each, with the spin coating repeated twice for 20 seconds each time. After vacuum drying for 6 hours, the bismuthene precursor solution described in 2) was spin-coated at a speed of 2500 rpm for 3 minutes each, with the spin coating repeated twice for 20 seconds each time. After spin coating, the Si / Ag / borophene / bismuthene electrode was obtained by vacuum drying for 6 hours.

[0079] 4) Preparation of MXene solution: Dissolve 1g LiF in 20mL HCl (9M) and stir for 9 minutes until completely dissolved. Add 1g Ti3AlC2 to the solution in 10 equal portions, stir magnetically for 9 minutes each time until completely dissolved, and place in a water bath and maintain stirring at 33°C for 23 hours. After the reaction is complete, transfer the reacted liquid to a centrifuge tube, add deionized water to 40mL, and centrifuge at 3000rpm for 3min, and repeat several times, taking the supernatant each time until the pH is close to 6. Pour the shaken liquid into a washing bottle and ultrasonicate under argon for 50min, while keeping the temperature below 35°C. Then centrifuge at 3000rpm for 20min, remove the lower layer of precipitate, and finally dilute with water to obtain 1.2mg·mL -1 MXene precursor solution.

[0080] 5) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 Electrode: At 20°C and 50% humidity, the MXene precursor solution from 4) was spin-coated onto the prepared Si / Ag / borophene / bismuthene electrode to a MXene thickness of 530 nm. Spin coating was performed twice, with a 3-minute interval between each pass at a spin coater speed of 2500 rpm. After spin coating, the electrode was placed in an argon glove box with a water content of 0.1 ppm and an oxygen content of 0.1 ppm. Annealing was performed at 200°C on a hot plate for 20 minutes, followed by ozone treatment for 20 minutes to grow TiO2 on the edges of the MXene layer.

[0081] 6) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes: Spin-coat 1.2 mg mL of MgSO4 on the prepared Si / Ag / borophene / bismuthene / MXene / TiO2 electrodes at 20°C and 50% RH. -1 The black phosphorus solution was prepared at a spin coater speed of 2500 rpm, with a 3-min interval between each application, and the spin coating was repeated twice, with each application lasting 20 s. The sample was then placed in an argon glove box with a water content of 0.1 ppm and an oxygen content of 0.1 ppm, and annealed at a constant temperature of 200°C for 20 min using a hot plate.

[0082] The thickness of n-Si is 480μm and the roughness is 20nm; the thickness of the Ag layer is 80nm, and the roughness of the formed Si / Ag layer is 25nm; the thickness of borophene is 130nm, and the roughness of the formed Si / Ag / borophene layer is 90nm; the thickness of bismuthene is 120nm, and the roughness of the formed Si / Ag / borophene / bismuthene layer is 190nm; the thickness of MXene is 540nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 layer is 140nm; the thickness of black phosphorus is 60nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus layer is 150nm.

[0083] Comprehensive examples 1 and 2, according to Figure 12 The transient current density of the multilayer two-dimensional composite electrode is 129 μA cm-1 at a bias voltage of 0.3 V (relative to a saturated calomel electrode) when the Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrode is provided by a (200-300) mW (400-430) nm blue-violet laser. -2 , is a Si / Ag / borophene electrode (10μAcm -2 ) is 12.9 times that of Si / Ag / borophene / bismuthene electrode (40μAcm -2 ) is 3.22 times that of Si / Ag / borophene / bismuthene / MXene / TiO2 electrode (63μAcm -2 ) is 2.05 times.

[0084] Example 3. 2.5D packaging of composite detection chip

[0085] like Figure 3 and Figure 6 Figure 1 shows a schematic diagram of a 2.5D composite detection chip. Below the light-transmitting window, from bottom to top, are the sensor module and the optical device module. On the other side, from bottom to top, are the power management module, the microprocessor module, and the wireless transceiver module.

[0086] The sensor module is used to capture external electric field signals and optical signals and convert them into electrical signals. It is composed of a multilayer two-dimensional composite electrode wrapped with hydrogel as an electrolyte; the optical device module is used to provide a light source for the sensor module. It is composed of two micro-LED devices with an emission wavelength of 420nm blue-violet light, which are controlled by the power management module to flash at a frequency of 100Hz; the power management module is used to provide power for the optical device module, sensor module, microprocessor module, and wireless transceiver module; the wireless transceiver module is used to send the data and analysis results processed by the microprocessor module to an external device or receive control signals from an external device; the microprocessor module is used to receive, record, and process the signals input by the sensor module. It includes a preamplifier, a bandpass filter, and a digital signal processor. The microprocessor module smoothes the transient photocurrent response to remove unnecessary noise, and uses the Allometrical model to fit the photocurrent. The fitting function is C=0.27*T -0.18 , where C is the photocurrent density after treatment and T is the response time, ranging from (29 to 59) s.

[0087] like Figure 7 The diagram shows the module division and the working relationships between them. The power management module is connected to the power ports of the sensor module, optical device module, microprocessor module, and wireless transceiver module. The data input of the microprocessor module is connected to the data output of the sensor module and the wireless transceiver module, while the data output of the microprocessor module is connected to the data input of the sensor module and the wireless transceiver module. The optical device module provides a light field for the sensor module.

[0088] The sensor module has eight pins: power 1, ground 1, data input 1, data output 1, debug input 1, debug output 1, reset 1, and clock 1. The optical device module has six pins: power 2, ground 2, debug input 2, debug output 2, reset 2, and clock 2. The power management module has six pins: power 3, ground 3, debug input 3, debug output 3, reset 3, and clock 3. The microprocessor module has eight pins: power 4, ground 4, data input 4, data output 4, debug input 4, debug output 4, reset 4, and clock 4. The wireless transceiver module has eight pins: power 5, ground 5, data input 5, data output 5, debug input 5, debug output 5, reset 5, and clock 5. The base has twenty pins: power 1, ground, data input 1, data output 1, debug input 1, debug output 1, debug input 2, debug output 2, debug input 3, debug output 3, debug input 4, debug output 4, debug input 5, debug output 5, reset 1, reset 2, reset 3, reset 4, reset 5, and clock.

[0089] Between the sensor module and the optical device module: the power supply 1, ground 1, and clock 1 pins are flip-chip bonded to the power supply 2, ground 2, and clock 2 pins of the upper optical device module through solder balls; the reset 1, data input 1, data output 1, debug input 1, and debug output 1 are bonded to the reset 1, data input 1, data output 1, debug input 1, and debug output 1 pins of the base through solder balls and copper layers; the reset 2, debug input 2, and debug output 2 pass through the sensor module through silicon vias, through solder balls, and through copper layers to the reset 2, debug input 2, and debug output 2 pins of the base;

[0090] Between the power management module and the microprocessor module: the power supply 3, ground 3, and clock 3 pins are flip-chip bonded to the power supply 4, ground 4, and clock 4 pins of the upper optical device module through solder balls; reset 3, debug input 3, and debug output 3 are bonded to the reset 3, debug input 3, and debug output 3 pins of the base through solder balls and copper layers; reset 4, data input 4, data output 4, debug input 4, and debug output 4 pass through the power management module through silicon vias, through solder balls, and through copper layers to the reset 4, data output 1, data input 1, debug input 4, and debug output 4 pins of the base;

[0091] Between the microprocessor module and the wireless transceiver module: the power supply 4, ground 4, and clock 4 pins are flip-chip bonded to the power supply 5, ground 5, and clock 5 pins of the upper optical device module through solder balls; the data input pin 5 is bonded to the lower data output pin 4, and the data output 5 is bonded to the lower data input pin 4; the reset 5, debug input 5, and debug output 5 pass through the power management module and the microprocessor module through silicon vias, and are bonded to the reset 5, debug input 5, and debug output 5 pins of the base through solder balls and copper layers;

[0092] On the base: rewiring is performed through a layer of polyimide. The power supply 1, ground 1, and clock 1 pins of the sensor module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers. The power supply 3, ground 3, and clock 3 pins of the power management module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers.

[0093] Finally, a transparent resin window is placed above the optical device module. Its dimensions are the same as the module's, with a thickness of 15μm. Polyimide, resin, and other materials are used to fill the gaps between the modules, forming the chip's package. The solder balls are made of tin and have a diameter of 3μm. The through-silicon vias (TSVs) are filled with copper and have a diameter of 3μm.

[0094] like Figure 4As shown, a bottom view of a composite detection chip 2.5D package, mark 101 is a power supply, mark 102 is a clock, mark 103 is a ground, mark 104 is a data input, mark 105 is a data output, mark 106 is a debug input, mark 107 is a debug output, mark 108 is a reset, mark 201 is a power supply, mark 202 is a clock, mark 203 is a ground, mark 204 is a debug input, mark 205 is a debug output, mark 206 is a reset, mark Mark 301 is power three times, mark 302 is clock three times, mark 303 is ground three times, mark 304 is debug input three times, mark 305 is debug output three times, mark 306 is reset three times, mark 401 is power four times, mark 402 is clock four times, mark 403 is ground four times, mark 404 is data input four times, mark 405 is data output four times, mark 406 is debug input four times, mark 407 is debug output four times, mark 408 is reset four times, mark 501 is power five times, mark 502 is clock five times, mark Mark 503 is grounded five times, mark 504 is data input five times, mark 505 is data output five times, mark 506 is debug input five times, mark 507 is debug output five times, mark 508 is reset five times, mark 001 is power on, mark 002 is clock on, mark 003 is grounded, mark 004 is data input once, mark 005 is data output once, mark 006 is debug input once, mark 007 is debug output once, mark 008 is debug input twice, mark 009 is debug output twice, mark 010 is debug Try input three times, mark 011 is debug output three times, mark 012 is debug input four times, mark 013 is debug output four times, mark 014 is debug input five times, mark 015 is debug output five times, mark 016 is reset once, mark 017 is reset twice, mark 018 is reset three times, mark 019 is reset four times, mark 020 is reset five times, marks 151, 152, 153, 351, 352, 353, 354, 355, 356, 357, 358, 451, 452, 453 are under silicon via.

[0095] like Figure 5As shown, a top view of a composite detection chip 2.5D package, mark 000 is the base, mark 100 is the sensor module, mark 200 is the optical device module, mark 300 is the power management module, mark 400 is the microprocessor module, mark 500 is the wireless transceiver module, mark 121 is the power supply one, mark 122 is the clock one, mark 123 is the ground one, mark 321 is the power supply three, mark 322 is the clock three, mark 323 is the ground three, mark 421 is the power supply four, mark 422 is the clock four, mark 423 is the ground four, mark 424 is the data input four, mark 425 is the data output four, mark 031 is the power supply, mark 032 is the clock, mark 033 is the ground, mark 034 is the data input one, Marker 035 indicates data output one, marker 036 indicates debug input one, marker 037 indicates debug output one, marker 038 indicates debug input two, marker 039 indicates debug output two, marker 040 indicates debug input three, marker 041 indicates debug output three, marker 042 indicates debug input four, marker 043 indicates debug output four, marker 044 indicates debug input five, marker 045 indicates debug output five, marker 046 indicates reset one, marker 047 indicates reset two, marker 048 indicates reset three, marker 049 indicates reset four, marker 050 indicates reset five, and marks 161, 162, 163, 361, 362, 363, 364, 366, 366, 367, 368, 461, 461, and 462 indicate through-silicon vias.

[0096] like Figure 2 As shown in the figure, at the black phosphorus / MXene interface, black phosphorus / TiO2 interface, TiO2 / MXene interface, and Si / Ag interface, in equilibrium, the Fermi level of the semiconductor is balanced and causes the energy bands of these semiconductors to bend at the interface. In the "light field on" state, electrons (photogenerated electrons) and holes (photogenerated holes) induced by the light field are formed in the black phosphorus, bismuthene, TiO2, and Si regions. The Ag layer, borophene, and MXene are conductive, and in black phosphorus, the holes (photogenerated holes) move upward along the valence band (i.e., migrate toward the positive electrode circuit, and react with OH in the electrolyte). - The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band to TiO2, through MXene to bismuthene, and through MXene, boron olefin, and Ag layer to the Si layer (i.e., migrate to the negative electrode circuit, and H in the electrolyte + The reaction generates H2); in TiO2, holes (photogenerated holes) migrate along the valence band toward the black phosphorus layer (i.e., toward the positive electrode circuit, and OH in the electrolyte - The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band through MXene to bismuthene and through MXene, boron olefin, and Ag layer to the Si layer (i.e., migrate to the negative electrode circuit, and H in the electrolyte +The reaction generates H2); in bismuthene, holes (photogenerated holes) migrate along the valence band through MXene to TiO2 and black phosphorus layer (i.e., migrate to the positive electrode circuit, and OH in the electrolyte - The reaction generates O2), and the electrons (photogenerated electrons) migrate along the conduction band through the boron olefin and Ag layers to the Si layer (i.e., migrate to the negative electrode circuit and react with H in the electrolyte). + The reaction generates H2); in Si, holes (photogenerated holes) migrate along the valence band through the Ag layer, borene to bismuthene, and through the Ag layer, borene, and MXene layer to TiO2 and black phosphorus layer (i.e., migrate to the positive electrode circuit, and OH in the electrolyte). - The reaction generates O2), and the electrons (photogenerated electrons) move down the conduction band (i.e., migrate to the negative electrode circuit and react with H in the electrolyte). + The reaction generates H2). In the "external electric field on" state, the electric field induced electrons (electrogenerated electrons) and holes (electrogenerated holes) are formed in the black phosphorus, MXene, and boron olefin regions. All electrons (electrogenerated electrons) migrate to the Si layer under the action of the external electric field (i.e., migrate to the negative electrode circuit and react with H2 in the electrolyte). + The reaction generates H2), and the holes (electrogenerated holes) migrate to the black phosphorus layer (i.e., migrate to the positive electrode circuit, and the OH in the electrolyte - The reaction generates O2). The applied electric field affects the charge transfer rate, promotes the separation of photogenerated electrons and holes, and inhibits their recombination. It can produce a superposition effect with the light field, thereby enhancing the photoelectrochemical performance in the electric and light fields.

[0097] The composite detection chip in this embodiment can be designed as an array electrode patch and worn on the biceps of the human arm, such as Figure 8 As shown, Figure 8 The lower figure is an enlarged view of the array electrode patch, which includes 10 composite detection chips of the present invention.

[0098] Example 4. Working method of the composite detection chip

[0099] like Figure 14 As shown, a chip working method includes the following steps:

[0100] S1. The chip is powered on for self-test. The optical device module provides a light field, and the microprocessor module detects the working electrode impedance and determines whether the reading is normal. If the reading is abnormal, a warning signal is sent through the wireless transceiver module. If the reading is normal, the chip enters normal working mode.

[0101] S2, the sensor module senses the electromyographic signal outside the chip;

[0102] S3, the light field enhances the electromyographic signal, and the sensor module sends the enhanced electromyographic signal to the microprocessor module;

[0103] S4, the microprocessor module receives and processes the input signal of the sensor module and sends the data to the wireless transceiver module;

[0104] S5. The wireless transceiver module sends the corrected data.

[0105] The microprocessor module smoothes the transient photocurrent response to remove unnecessary noise and uses the Allometrical model to fit the photocurrent. The fitted function is C = 0.27*T -0.18 , where C is the photocurrent density after treatment and T is the response time, ranging from (29 to 59) s.

Claims

1. A multi-layer two-dimensional composite electrode, characterized in that: It is a multilayer two-dimensional structure formed by Si / Ag / borene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus. There are three-dimensional hole defects on the Si surface, with 1 to 5 hole defects per square micron, and the area of ​​each hole defect is 100 to 1000nm. 2 , depth is 50-110nm; the upper surface of Si is an Ag layer, and there are three-dimensional hole defects on the surface of the Ag layer. There are 1-5 hole defects per square micron, and the area of ​​each hole defect is 100-1000nm 2 , with a depth of 50 to 120 nm; on the Ag layer is a boronene layer, which fills the three-dimensional hole defects of the Ag layer; on the boronene layer is a bismuthene layer, which continues to fill the three-dimensional hole defects of the Ag layer; the MXene layer evenly covers the upper surface of the bismuthene layer, and there are three-dimensional hole defects on its surface, with about 1 to 5 hole defects per square micron, and the area of ​​each hole defect is 100 to 200 nm 2 , with a depth of 80 to 120 nm; there is TiO2 on the two-dimensional MXene layer, and TiO2 is connected to MXene through Ti-O bonds; there is a black phosphorus layer on the MXene layer, and black phosphorus fills the three-dimensional hole defects on the surface of the MXene layer; and there is P2O3 at the interface between the MXene layer and the black phosphorus layer, and the black phosphorus layer is connected to TiO2 through PO-Ti bonds and to P2O3 through PO bonds.

2. The multilayer two-dimensional composite electrode according to claim 1, wherein the thickness of Si is 480-520 μm and the roughness is 20-30 nm; the thickness of Ag is 80-100 nm, and the roughness of the formed Si / Ag layer is 25-40 nm; the thickness of borophene is 130-150 nm, and the roughness of the formed Si / Ag / borophene layer is 90-110 nm; the thickness of bismuthene is 120-140 nm, and the roughness of the formed Si / Ag / borophene / bismuthene layer is 190-210 nm; the thickness of MXene is 540-570 nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 layer is 140-160 nm; the thickness of black phosphorus is 60-90 nm, and the roughness of the formed Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus layer is 150-170 nm.

3. A method for preparing the multilayer two-dimensional composite electrode according to claim 1 or 2, comprising the following steps: 1) Fabrication of Si / Ag substrate: Depositing a layer of Ag on the clean Si surface after etching; 2) Preparation of borophene and bismuthene precursor solutions: Disperse boron powder in DMF to obtain a supernatant borophene precursor solution with a density of 0.9-1.0 g·mL -1 Disperse bismuth powder in deionized water to obtain a supernatant bismuthene precursor solution with a density of 1.000-1.005 g·mL -1 ; 3) Fabrication of a Si / Ag / borophene / bismuthene electrode: At a temperature of 20-25°C and a humidity of 35-85% RH, spin-coat the boropene precursor solution described in 2) onto the prepared Si / Ag substrate at a speed of 2500-3000 rpm, with a 3-5 minute interval between each application, for two spin-coating cycles of 20-40 seconds. After vacuum drying for 6-8 hours, spin-coat the bismuthene precursor solution described in 2) at a speed of 2500-3000 rpm, with a 3-5 minute interval between each application, for two spin-coating cycles of 20-40 seconds. After spin coating, vacuum dry the substrate for 6-8 hours to obtain a Si / Ag / borophene / bismuthene electrode. 4) Preparation of MXene precursor solution: 1.2-1.5 mg mL -1 MXene precursor solution; 5) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 electrodes: Spin-coat the MXene precursor solution prepared in 4) onto the prepared Si / Ag / borophene / bismuthene electrodes at a temperature of 20-25°C and a humidity of 35-85% RH. Spin-coat the electrodes at a speed of 2500-3000 rpm, with a 3-5 minute interval between each pass. Spin-coat the electrodes twice, each pass for 20-40 seconds. After spin-coating, anneal the electrodes at 200-350°C for 20-40 minutes in an argon glove box containing 0-0.15 ppm water and 0-0.2 ppm oxygen. Then, anneal the electrodes in an ozone atmosphere for 20-40 minutes to grow TiO2 on the edges of the MXene layer. 6) Fabrication of Si / Ag / borophene / bismuthene / MXene / TiO2 / P2O3 / black phosphorus electrodes: Spin-coat 1.2-1.5 mg mL of MgSO4 on the prepared Si / Ag / borophene / bismuthene / MXene / TiO2 electrodes at a temperature of 20-25°C and a humidity of 35-85% RH. -1 The black phosphorus solution was prepared with a spin coater at a speed of 2500-3000 rpm. The spin coater was applied twice with an interval of 3-5 minutes, and each spin coat was 20-40 seconds. The product was then placed in an argon glove box with a water content of 0-0.15 ppm and an oxygen content of 0-0.2 ppm, and annealed at a constant temperature of 200-350°C for 20-40 minutes.

4. A sensor module capable of sensing both electric field signals and optical signals, comprising a multilayer two-dimensional composite electrode as described in any one of claims 1 to 2 or obtained by the preparation method of claim 3, wrapped with hydrogel as an electrolyte.

5. A composite detection chip, comprising the sensor module, optical device module, microprocessor module, power management module, wireless transceiver module and base according to claim 4; the sensor module and power management module are arranged on the base, the optical device module is arranged on the sensor module, the microprocessor module is arranged on the power management module, and the wireless transceiver module is arranged on the microprocessor module.

6. The composite detection chip according to claim 5, wherein: The sensor module is used to capture external electric field signals and optical signals and convert them into electrical signals; The optical device module is used to provide a light source for the sensor module. It consists of two micro-LED devices that emit blue-violet light with a wavelength of 400 to 430 nm, and is controlled by the power management module to flash at a frequency of 80 to 120 Hz. The power management module is used to provide power to the optical device module, sensor module, microprocessor module, and wireless transceiver module; The microprocessor module is used to receive, record, and process signals input by the sensor module, and includes a preamplifier, a bandpass filter, and a digital signal processor. The microprocessor module collects signals from the sensor module, amplifies them through the preamplifier in the microprocessor module, filters them through the bandpass filter, and analyzes and processes them through the digital signal processor before outputting them to the wireless transceiver module. The wireless transceiver module is used to send the data and analysis results processed by the microprocessor module to an external device or receive control signals from an external device; The base is used to support the modules and form a packaging layer, and to lead out internal pins.

7. The packaging and manufacturing method of the composite detection chip according to claim 5 or 6, adopting 2.5D packaging, using fan-out, through silicon via, redistribution wiring, and flip-chip bonding packaging processes, specifically: Between the sensor module and the optical device module: the power supply 1, ground 1, and clock 1 pins of the sensor module are flip-chip bonded to the power supply 2, ground 2, and clock 2 pins of the upper optical device module through solder balls; the reset 1, data input 1, data output 1, debug input 1, and debug output 1 of the sensor module are bonded to the reset 1, data input 1, data output 1, debug input 1, and debug output 1 pins of the base through solder balls and copper layers; the reset 2, debug input 2, and debug output 2 of the optical device module pass through the sensor module through silicon vias, through solder balls, and through copper layers to the reset 2, debug input 2, and debug output 2 pins of the base; Between the power management module and the microprocessor module: the power supply 3, ground 3, and clock 3 pins of the power management module are flip-chip bonded to the power supply 4, ground 4, and clock 4 pins of the upper microprocessor module through solder balls; The reset 3, debug input 3 and debug output 3 of the power management module are bonded to the reset 3, debug input 3 and debug output 3 pins of the base through the copper layer via solder balls. The reset pin 4, data input pin 4, data output pin 4, debug input pin 4, and debug output pin 4 of the microprocessor module pass through the power management module through through-silicon vias, and are bonded to the reset pin 4, data output pin 1, data input pin 1, debug input pin 4, and debug output pin 4 of the base through the solder balls and the copper layer respectively; Between the microprocessor module and the wireless transceiver module: the power supply pin 4, ground pin 4, and clock pin 4 of the microprocessor module are flip-chip bonded to the power supply pin 5, ground pin 5, and clock pin 5 of the upper wireless transceiver module through solder balls; the data input pin 5 of the wireless transceiver module is bonded to the data output pin 4 of the lower microprocessor module, and the data output 5 of the wireless transceiver module is bonded to the data input pin 4 of the lower microprocessor module; the reset pin 5, debug input pin 5, and debug output pin 5 of the wireless transceiver module pass through the power management module and the microprocessor module through silicon vias, through solder balls, and through the copper layer to the reset pin 5, debug input pin 5, and debug output pin 5 of the base; On the base: Rewiring is performed through a layer of polyimide. The power supply 1, ground 1, and clock 1 pins of the sensor module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers. The power supply 3, ground 3, and clock 3 pins of the power management module are bonded to the power supply, ground, and clock pins of the base through solder balls and copper layers. Finally, a transparent resin is used as a light-transmitting window and placed above the optical device module. Its size is the same as that of the optical device module, with a thickness of 10~20μm. Polyimide and / or resin are used to fill the gaps between the modules to form the chip packaging shell. The above-mentioned solder balls are made of tin and have a diameter of 2~4μm. The internal filling material of the silicon via is copper, and the diameter of the silicon via is 1~5μm.

8. Use of the composite detection chip according to claim 5 or 6 in sensing and enhancing bioelectric signal detection, wherein the bioelectric signal is an electrocardiogram signal, an electroencephalogram signal, an electromyogram signal, an electrogastric signal or a retinal signal.

9. The use according to claim 8, characterized in that The bioelectric signal is an electromyographic signal.

10. The use according to claim 9, characterized in that The following detection steps are included: S1. The chip is powered on for self-test. The optical device module provides a light field, and the microprocessor module detects the working electrode impedance and determines whether the reading is normal. If the reading is abnormal, a warning signal is sent through the wireless transceiver module. If the reading is normal, the chip enters normal working mode. S2, the sensor module senses the electromyographic signal outside the chip; S3, the light field enhances the electromyographic signal, and the sensor module sends the enhanced electromyographic signal to the microprocessor module; S4. The microprocessor module receives and processes the input signal of the sensor module and sends the data to the wireless transceiver module. The microprocessor module smoothes the transient photocurrent response to remove unnecessary noise and uses the Allometrical model to fit the photocurrent. The fitted function is C=0.27*T -0.18 , where C is the photocurrent density after treatment, T is the response time, ranging from 29 to 59 s; S5. The wireless transceiver module sends the corrected data.

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