CN115561295B - Silicon nanowire field effect glucose sensor and preparation method thereof - Google Patents

Silicon nanowire field effect glucose sensor and preparation method thereof Download PDF

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CN115561295B
CN115561295B CN202211555174.5A CN202211555174A CN115561295B CN 115561295 B CN115561295 B CN 115561295B CN 202211555174 A CN202211555174 A CN 202211555174A CN 115561295 B CN115561295 B CN 115561295B
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silicon nanowire
glucose
solution
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sensor
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CN115561295A (en
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魏千惠
魏峰
李港荣
朱艳
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Youyan Guangdong New Material Technology Research Institute
GRIMN Engineering Technology Research Institute Co Ltd
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Youyan Guangdong New Material Technology Research Institute
GRIMN Engineering Technology Research Institute Co Ltd
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    • G01N27/4145Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS specially adapted for biomolecules, e.g. gate electrode with immobilised receptors
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    • G01N27/4146Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS involving nanosized elements, e.g. nanotubes, nanowires
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Abstract

The invention belongs to the technical field of glucose biosensors, and discloses a silicon nanowire field effect glucose sensor and a preparation method thereof. The glucose sensor adopts a silicon nanowire field effect sensor compatible with a CMOS process, a self-assembled catalytic layer is functionally mixed on the surface of a silicon nanowire, an amino end cap is formed by modifying the silicon nanowire field effect sensor by a mixed solution of 3-aminopropyl trimethoxy silane and polyethylene glycol, then glucose oxidase is fixed on the surface of the silicon nanowire, the modification density of probe molecule glucose oxidase is regulated, the dielectric property of a high-ionic strength solution is obviously changed, the Debye length is increased, the glucose is subjected to enzymatic reaction, and effective charge is detected, so that the sensitivity of the sensor is improved. The glucose sensor has the advantages of easy miniaturization, no marking, commercialization, large-scale application, large-scale production and the like.

Description

Silicon nanowire field effect glucose sensor and preparation method thereof
Technical Field
The invention belongs to the technical field of glucose biosensors, and particularly relates to a silicon nanowire field effect glucose sensor and a preparation method thereof.
Background
For the last decade, field effect biosensors compatible with Complementary Metal Oxide Semiconductors (CMOS) have attracted attention from many researchers because of their sensitivity, selectivity, rapidity, economy, simplicity, etc., and in field effect biosensor-based fabrication, one-dimensional nanomaterials (e.g., carbon nanotubes, silicon nanowires, etc.) have been widely used as conductive channels for detecting various disease biomarkers, such as viruses, proteins, DNA, antigens, small molecules, etc., by monitoring current changes. Silicon nanowire field effect (SiNW-FET) biosensors have proven to be an ultra-sensitive detection platform that can provide real-time, rapid and label-free detection of biological samples, with commercialization and large-scale applications benefiting from the development of the semiconductor industry as compared to other types of nanostructured biosensors.
However, siNW-FETs are limited to detecting analytes with a certain charge, while detecting weakly charged or uncharged analytes such as glucose remains a challenge. On the other hand, when the SiNW-FET biosensor works under the condition of high ionic strength, the biosensor is greatly limited in various aspects such as sensitivity due to the influence of the Debye shielding effect, so that the improvement of the performance of the SiNW-FET glucose sensor is critical by optimizing the modification process.
Therefore, siNW-FET glucose sensors that are fast in development, highly specific, highly sensitive, low in manufacturing cost, and capable of directly detecting glucose in physiological solutions are of great importance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a silicon nanowire field effect glucose sensor and a preparation method thereof, which can detect glucose molecules in a high-ionic strength solution in real time with high specificity and high sensitivity, and the biosensor has the advantages of portability, no marking, commercialization, large-scale application, mass production and the like.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a silicon nanowire field effect glucose sensor adopts a silicon nanowire field effect (SiNW-FET) sensor compatible with a CMOS process, a mixed self-assembly catalytic layer is modified on the surface of a silicon nanowire, polyethylene glycol (PEG) and Glucose Oxidase (GOD) in the catalytic layer are modified at intervals, and enzymatic reaction occurs when a target glucose molecule exists, so that charge is detected.
Preferably, the mixed self-assembled catalytic layer is formed by modifying a SiNW-FET sensor by a mixed solution of 3-aminopropyl trimethoxy silane (APTMS) and PEG to form an amino end cap, and Glucose Oxidase (GOD) is immobilized on the surface of the silicon nanowire through an amide bond by using Glutaraldehyde (GA) crosslinking agent, so that an enzymatic reaction is triggered when a target glucose molecule exists.
Because PEG in the mixed self-assembled catalytic layer can obviously change the dielectric property of the high-ionic strength solution to increase the Debye length on the one hand, and can be used as a spacer molecule to regulate the modification density of the probe molecule glucose oxidase on the other hand, when the glucose molecule exists, enzymatic reaction occurs so as to detect effective charge, thereby improving the sensitivity of the sensor.
The invention also aims to provide a preparation method of the silicon nanowire field effect glucose sensor, which comprises the following steps:
s1, surface pretreatment of a silicon nanowire is carried out to enable the surface of the silicon nanowire to be hydroxylated;
s2, soaking the silicon nanowire with the surface blocked by the hydroxyl group obtained in the step S1 in a mixed ethanol solution containing APTMS and PEG, then washing with ethanol, drying in an oven to enable the surface of the SiNW-FET to form an amino group blocked, then incubating in glutaraldehyde solution, washing with PBS solution, and enabling the surface of the SiNW-FET to form an amino aldehyde group blocked;
s3, incubating the sensor obtained in the step S2 with GOD solution overnight, and drying after washing;
and S4, incubating the sensor obtained in the step S3 with a Bovine Serum Albumin (BSA) solution for end capping.
Preferably, the pretreatment in step S1 includes cleaning the surface of the silicon nanowire with acetone, absolute ethanol, removing impurities, and then cleaning the surface of the silicon nanowire with oxygen plasma to hydroxylate the surface thereof.
Preferably, the concentration ratio of 3-aminopropyl trimethoxysilane (APTMS) to PEG in step S2 is 10:1 to 1:10.
More preferably, the concentration of APTMS in the step S2 is 0.01 mmol/L-1 mmol/L, the concentration of PEG solution is 0.01 mmol/L-3 mmol/L, and the molecular weight of polyethylene glycol is 1KDa-30KDa.
Preferably, the glutaraldehyde solution concentration in step S2 is 0.5% -10%.
Preferably, the GOD solution in step S3 has a concentration of 0.1. Mu.g/mL-10 mg/mL.
Preferably, the concentration of the bovine serum albumin solution in the step S4 is 0.01-20 mg/mL.
More specifically, in the present invention, the process for preparing the silicon nanowire field effect transistor sensor may refer to patent CN 113960128A, and includes the following steps:
(1) Preparing a substrate: deposition of 145nm SiO on 200mm silicon wafer 2 And 40nm polysilicon;
(2) Sequentially depositing SiO on the SOI silicon wafer by chemical vapor deposition 2 An amorphous silicon (alpha-Si)/SiNx film is subjected to gluing, pre-baking, ultraviolet exposure, post-baking, developing light and development to form rectangular patterns, and the SiNx and the alpha-Si are etched by using a dry etching process to form a side wall approaching 90 degrees of abruptness;
(3) By heating at 140℃H 3 PO 4 Solution removing the top SiNx Hard Mask (HMs), depositing a SiNx film using plasma enhanced chemical vapor deposition, and then performing a corresponding silicon nitride Reactive Ion Etch (RIE) to form two back-to-back wedge-shaped Si on both sides of the rectangular alpha-Si 3 N 4 Side wall, removing alpha-Si by tetramethyl ammonium hydroxide, and removing SiO 2 The top of the film left Si on nano scale 3 N 4 The side wall HMs array is then etched by using the nano-scale side wall as a mask to etch SiO at the bottom 2 And a single crystal Si layer with heat H 3 PO 4 And removing the SiNx mask and HMs on the top by using a diluted hydrofluoric acid solution to obtain a silicon nanowire array with good uniformity and consistency;
(4) Forming metal silicide in source and drain regions using nickel-platinum alloy to reduce parasitic resistance of silicon nanowire, and then implanting high dose low energy BF 2+ Ions, then activating the injected ions through low-temperature annealing to form a Schottky barrier source electrode and a Schottky barrier drain electrode;
(5) For better bonding, an aluminum electrode is prepared by a sputtering process and an RIE process is performed, followed by deposition of a layer of SiO thick 2 Beating by photolithography and etching processesAn open source drain contact hole;
(6) Finally, defining grids with different channel lengths by photoetching technology, realizing an open grid channel of the sensor by RIE process to expose a sensitive area, and depositing a layer of HfO on the surface of the device to meet the liquid detection environment 2
In using the glucose sensor prepared according to the present invention, when the sensor is placed in a high ionic strength solution and a target glucose molecule is detected, glucose is converted into gluconolactone and hydrogen peroxide (H) under the catalysis of GOD 2 O 2 ) Then H 2 O 2 Further dissociates and generates hydrogen ions (H) + ) And electrons (e) - ) The GOD is brought closer to the SiNW-FET surface due to the linking effect of GA, H generated by enzymatic reaction + Gradually increasing and accumulating at the interface of the SiNW channel layer and the solution, resulting in a local pH decrease, inducing an effect on the channel layer, the SiNW-FET behaves as a p-type semiconductor at the gate voltage (-3V). Thus, at H + The number of carriers (holes) in the SiNW-FET channel layer decreases, resulting in a decrease in conductance, and the current value of the SiNW-FET changes as glucose increases from low concentration to high concentration.
Compared with the prior art, the invention has the beneficial effects that:
1. the glucose sensor provided by the invention can detect glucose molecules in a high-ionic strength solution in real time with high specificity and high sensitivity by modifying the mixed self-assembly catalytic layer on the surface of the SiNW-FET.
2. By monitoring the change of the threshold voltage, the glucose concentration is reflected, and the direct detection of glucose molecules in the high-ionic strength solution is realized.
3. The sensitivity of the SiNW-FET biosensor modified by the mixed self-assembled catalytic layer is tested by glucose solutions with different concentrations, the SiNW-FET has quick response to glucose detection, the detection limit is less than 8 nM, and glucose can be detected in a complex background with high sensitivity.
Drawings
FIG. 1 is a schematic diagram of a hybrid self-assembled modified silicon nanowire field effect glucose sensor of the present invention for detecting glucose.
FIG. 2 is a graph showing the variation of threshold voltage with glucose solution when glucose sensors prepared in examples 1-3 of the present invention were each added with glucose solutions of different concentrations.
FIG. 3 is a graph showing the variation of threshold voltage with glucose solution when glucose sensors prepared in example 1 and comparative example 1 of the present invention were respectively dropped with glucose solutions of different concentrations.
FIG. 4 is a graph showing the current change with time when glucose solutions of different concentrations were respectively added dropwise to the glucose sensor prepared in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test methods used in the embodiment of the invention are all conventional methods unless specified otherwise; the materials, reagents and the like used, unless otherwise specified, are those commercially available.
As shown in FIG. 1, the glucose sensor of the invention adopts a CMOS compatible 'top-down' method to prepare a silicon nanowire field effect sensor, and then a mixed self-assembly catalytic layer is modified on the surface of the silicon nanowire. The method specifically comprises the following steps: respectively depositing 145nm SiO on 200mm silicon wafer 2 And 40nm of polysilicon; then forming a SiNW pattern by adopting a self-aligned side wall technology, and etching a SiNW array; then preparing SiNW biosensor electrode, and depositing to form insulating medium isolation layer by atomic layer deposition process; cleaning the SiNW surface by oxygen plasma to hydroxylate the SiNW surface; then soaking SiNW with the surface full of hydroxyl groups in an ethanol solution containing APTMS and silane-PEG to form an amino terminal; then incubated with Glutaraldehyde (GA) solution at room temperature. Finally, the step of obtaining the product,incubation with GOD solution, rinsing with a small amount of PBS solution, drying at room temperature, and blocking the device obtained above by incubation in BSA solution to prevent nonspecific adsorption.
In a specific embodiment of the invention, a process of a silicon nanowire field effect glucose sensor comprises the steps of preparing the silicon nanowire field effect transistor sensor and modifying the SiNW-FET glucose sensor by a mixed self-assembled catalytic layer.
The preparation of the silicon nanowire field effect transistor sensor (SiNW-FET) can refer to the preparation process of the biosensor in the patent CN 113960128A, and comprises the following steps:
(1) Preparing a substrate: respectively depositing 145nm SiO on 200mm silicon wafer 2 And 40nm of polysilicon;
(2) Sequentially depositing SiO on the SOI silicon wafer by chemical vapor deposition 2 Forming rectangular patterns on an amorphous silicon (alpha-Si)/SiNx film through the steps of gluing, pre-baking, ultraviolet exposure, post-baking, developing light, developing and the like, and etching the SiNx film and the alpha-Si film by using a dry etching process to form a side wall approaching 90 degrees of abruptness;
(3) By heating at 140℃H 3 PO 4 The solution removes the top SiNx Hard Mask (HMs) and a layer of SiNx film is deposited using plasma enhanced chemical vapor deposition. Then, a corresponding Reactive Ion Etching (RIE) of silicon nitride is carried out to form two wedge-shaped Si bodies back to back on two sides of the rectangular alpha-Si 3 N 4 Side wall, removing alpha-Si with tetramethyl ammonium hydroxide (TMAH), removing alpha-Si with SiO 2 The top of the film left Si on nano scale 3 N 4 And a side wall hard mask array. Etching the SiO at the bottom by using the nano-scale side wall as a mask 2 And a single crystal Si layer with heat H 3 PO 4 And removing the SiNx mask and HMs on the top by using a diluted hydrofluoric acid solution to obtain a silicon nanowire array with good uniformity and consistency;
(4) Forming metal silicide in source and drain regions using nickel-platinum alloy to reduce parasitic resistance of silicon nanowire, and then implanting high dose low energy BF 2+ Ions, followed by activation of the implanted ions by low temperature annealing, form schottky barrier source and drainA pole;
(5) For better bonding, an aluminum electrode was prepared by a sputtering process, and an RIE process was performed. Then deposit a layer of SiO 1-5 μm thick 2 The source and drain contact holes are opened by utilizing photoetching and etching processes;
(6) Finally, defining grids with different channel lengths by photoetching technology, realizing an open grid channel of the sensor by RIE process to expose a sensitive area, and depositing a layer of HfO on the surface of the device to meet the liquid detection environment 2 A SiNW-FET is obtained.
Example 1
A silicon nanowire field effect glucose sensor is prepared by the following steps:
(1) Cleaning the surface of the SiNW-FET by using acetone and absolute ethyl alcohol to remove impurities, and then cleaning the surface of the silicon nanowire by using an oxygen plasma photoresist remover to hydroxylate the surface of the silicon nanowire;
(2) Silicon nanowires with hydroxyl-terminated surfaces were immersed in a solution containing 3-aminopropyl trimethoxysilane (APTMS) (0.4 mmol/L) in a concentration ratio of 2:1: polyethylene glycol (PEG) (0.2 mmol/L, m=10kda) in mixed ethanol solution were incubated with shaking for 20 min, then the device was rinsed with absolute ethanol to remove the residue and treated at oven 100 ℃ for 15 min to ensure amine-terminated SiNW-FET surfaces;
(3) Then incubated with 1% Glutaraldehyde (GA) solution for 30 min at room temperature and rinsed several times with PBS solution to remove residual GA to ensure that the SiNW-FET surface forms amine aldehyde-terminated;
(4) 0.5 mg/mL Glucose Oxidase (GOD) solution was formulated with 1 XPBS solution and incubated overnight at 4deg.C, after incubation, the FET was rinsed several times with a small amount of PBS solution to remove residual GOD and dried at room temperature for 20 minutes;
(5) To prevent non-specific adsorption, the devices obtained above were capped by incubating 0.5 mg/mL BSA solution in 1×pbs solution for 1 hour at 4 ℃, after which the FETs were rinsed several times with a small amount of PBS solution.
Example 2
A silicon nanowire field effect glucose sensor is prepared by the following steps:
(1) Cleaning the surface of the SiNW-FET by using acetone and absolute ethyl alcohol to remove impurities, and then cleaning the surface of the silicon nanowire by using an oxygen plasma photoresist remover to hydroxylate the surface of the silicon nanowire;
(2) The silicon nanowire with the surface blocked by hydroxyl groups is soaked in APTMS (0.2 mmol/L) with the concentration ratio of 1:2: shaking incubation in a mixed ethanol solution of PEG (0.4 mmol/L, m=10kda) for 20 min, then washing the device with absolute ethanol to remove the residue, and treating at oven 100 ℃ for 15 min to ensure amine-terminated SiNW-FET surface formation;
(3) Then incubated with 1% Glutaraldehyde (GA) solution for 30 min at room temperature and rinsed several times with PBS solution to remove residual GA to ensure that the SiNW-FET surface forms amine aldehyde-terminated;
(4) 0.5 mg/mL GOD solution in 1 XPBS solution was incubated overnight at 4deg.C, after incubation, the FET was rinsed several times with a small amount of PBS solution to remove residual GOD and dried at room temperature for 20 minutes;
(5) To prevent non-specific adsorption, the devices obtained above were capped by incubating 0.5 mg/mL BSA solution in 1×pbs solution for 1 hour at 4 ℃, after which the FETs were rinsed several times with a small amount of PBS solution.
Example 3
A silicon nanowire field effect glucose sensor is prepared by the following steps:
(1) Cleaning the surface of the SiNW-FET by using acetone and absolute ethyl alcohol to remove impurities, and then cleaning the surface of the silicon nanowire by using an oxygen plasma photoresist remover to hydroxylate the surface of the silicon nanowire;
(2) The silicon nanowire with the surface blocked by hydroxyl groups is soaked in APTMS (0.2 mmol/L) with the concentration ratio of 1:1: shaking incubation in a mixed ethanol solution of PEG (0.2 mmol/L, m=10kda) for 20 min, then washing the device with absolute ethanol to remove the residue, and treating at oven 100 ℃ for 15 min to ensure amine-terminated SiNW-FET surface formation;
(3) Then incubated with 1% Glutaraldehyde (GA) solution for 30 min at room temperature and rinsed several times with PBS solution to remove residual GA to ensure that the SiNW-FET surface forms amine aldehyde-terminated;
(4) 0.5 mg/mL GOD solution in 1 XPBS solution was incubated overnight at 4deg.C, after incubation, the FET was rinsed several times with a small amount of PBS solution to remove residual GOD and dried at room temperature for 20 minutes;
(5) To prevent non-specific adsorption, the devices obtained above were capped by incubating 0.5 mg/mL BSA solution in 1×pbs solution for 1 hour at 4 ℃, after which the FETs were rinsed several times with a small amount of PBS solution.
Comparative example 1
Preparation of a single modified SiNW-FET glucose sensor based on glucose oxidase comprising the steps of:
(1) Cleaning the surface of the SiNW-FET by using acetone and absolute ethyl alcohol to remove impurities, and then cleaning the surface of the silicon nanowire by using an oxygen plasma photoresist remover to hydroxylate the surface of the silicon nanowire;
(2) Soaking the silicon nanowire with the surface blocked by hydroxyl groups in an APTMS (0.4 mmol/L) ethanol solution for shaking incubation for 20 minutes, then washing the device with absolute ethanol to remove residues, and treating at the temperature of 100 ℃ in an oven for 15 minutes to ensure that the SiNW-FET surface forms amine groups to be blocked;
(3) Then incubated with 1% Glutaraldehyde (GA) solution for 30 min at room temperature and rinsed several times with PBS solution to remove residual GA to ensure that the SiNW-FET surface forms amine aldehyde-terminated;
(4) 0.5 mg/mL GOD solution in 1 XPBS solution was incubated overnight at 4deg.C, after incubation, the FET was rinsed several times with a small amount of PBS solution to remove residual GOD and dried at room temperature for 20 minutes;
(5) To prevent non-specific adsorption, the devices obtained above were capped by incubating 0.5 mg/mL BSA solution in 1×pbs solution for 1 hour at 4 ℃, after which the FETs were rinsed several times with a small amount of PBS solution.
Experimental example
1. The SiNW-FET biosensor modified by the mixed self-assembled catalytic layer shown in the figure 1 and prepared in the examples 1-3 was used to monitor the change of the threshold voltage with the glucose solution when glucose solutions with different concentrations were added dropwise.
As shown in fig. 2 and 3: comparison curves show that the SiNW-FET glucose sensors modified by three different APTMS and PEG ratios can recognize glucose in the range of 100 nM-10 mM and respond linearly to a certain extent. The sensor threshold voltage change curves of comparative example 1 and comparative example 1, the responsiveness of the PEG-modified glucose sensor was much greater than that of the glucose oxidase alone modified sensor.
2. Glucose solutions at concentrations of 8 nM, 10 nM, 50 nM, 100 nM, 1 μM, 10 μM, 100 μM, 1 mM, and 10 mM were prepared using 1×pbs solution, 1 μl of the different glucose solutions were added dropwise to the sensor-sensitive grid sites, and the electrical signals were recorded using a Keithley 4200 semiconductor analyzer.
As shown in FIG. 4, the obtained electric signals are time response curves with glucose concentration of 8 nM to 10 mM from bottom to top, and the absolute value of the source-drain current gradually decreases with the increase of the glucose concentration, because H is generated by the enzymatic reaction + The p-type SiNW-FET biosensor is induced to reduce the number of conducting channel carriers, thereby affecting the magnitude of the source leakage current.
The measurement results show that when the glucose solution is added to the surface of the SiNW-FET for less than 8a s a current signal is generated that stabilizes, indicating that the SiNW-FET has a rapid response to glucose detection. The glucose solution with response signal of 8 nM has detection limit less than 8 nM and far less than human blood glucose concentration. Background solution 1 XPBS and serum have the same ionic strength as whole blood solutions, and the sensor provided herein can detect glucose with high sensitivity in complex backgrounds.
It should be understood that the foregoing description of the specific embodiments is merely illustrative of the invention, and is not intended to limit the invention, and that any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.

Claims (6)

1. The silicon nanowire field effect glucose sensor is characterized in that the glucose sensor adopts a silicon nanowire field effect transistor sensor compatible with CMOS, a mixed self-assembly catalytic layer is modified on the surface of a silicon nanowire, polyethylene glycol and glucose oxidase are adopted in the mixed self-assembly catalytic layer for interval modification, and when a target glucose molecule exists, enzymatic reaction occurs so as to detect charges;
the preparation process of the silicon nanowire field effect transistor sensor comprises the following steps:
(1) Preparing a substrate: siO deposited separately on silicon wafers 2 And polysilicon;
(2) Sequentially depositing SiO on the SOI silicon wafer by chemical vapor deposition 2 The amorphous silicon/SiNx film is subjected to gluing, pre-baking, ultraviolet exposure, post-baking, developing light and development to form rectangular patterns, and the SiNx and alpha-Si are etched by using a dry etching process to form side walls approaching 90 degrees of abruptness;
(3) By heat H 3 PO 4 Removing the SiNx hard mask at the top by using the solution, depositing a SiNx film by using plasma enhanced chemical vapor deposition, and then performing corresponding silicon nitride reactive ion etching to form two wedge-shaped Si on two sides of the rectangular alpha-Si in a back-to-back manner 3 N 4 Side wall, removing alpha-Si by tetramethyl ammonium hydroxide, and removing SiO 2 The top of the film left Si on nano scale 3 N 4 The side wall HMs array is then etched by using the nano-scale side wall as a mask to etch SiO at the bottom 2 And a single crystal Si layer with heat H 3 PO 4 And removing the SiNx mask and HMs on the top by using a diluted hydrofluoric acid solution to obtain a silicon nanowire array with good uniformity and consistency;
(4) Forming metal silicide in source and drain regions using nickel-platinum alloy, and then implanting BF 2+ Activating the injected ions through low-temperature annealing to form a Schottky barrier source electrode and a Schottky barrier drain electrode;
(5) Aluminum electrodes were prepared and subjected to an RIE process, followed by deposition of SiO 2 Opening the source-drain contact holes by utilizing photoetching and etching processes;
(6) Defining grid electrodes with different channel lengths by photoetching technology, realizing an open grid channel of a sensor by RIE process to expose a sensitive area, and depositing a layer of HfO on the surface of the device to meet the liquid detection environment 2
The process for modifying the surface of the silicon nanowire by the mixed self-assembled catalytic layer comprises the following steps of:
s1, surface pretreatment of a silicon nanowire is carried out to enable the surface of the silicon nanowire to be hydroxylated;
s2, soaking the silicon nanowire with the surface blocked by the hydroxyl group obtained in the step S1 in a mixed ethanol solution containing 3-aminopropyl trimethoxy silane and polyethylene glycol for incubation, cleaning and drying to enable the surface of the silicon nanowire to form an amino group blocked, and then incubating in glutaraldehyde solution to enable the surface of the silicon nanowire to form an amine aldehyde group blocked;
s3, incubating the sensor obtained in the step S2 with glucose oxidase solution overnight, and drying after cleaning;
s4, incubating the sensor obtained in the step S3 with a bovine serum albumin solution for end sealing;
the ratio of the 3-aminopropyl trimethoxysilane to the polyethylene glycol in the step S2 is 10:1-1:10.
2. The silicon nanowire field effect glucose sensor of claim 1, wherein the pretreatment of step S1 comprises cleaning the surface of the silicon nanowire with acetone, absolute ethanol, removing impurities, and then cleaning the surface of the silicon nanowire with oxygen plasma to hydroxylate the surface.
3. The silicon nanowire field effect glucose sensor of claim 1, wherein the concentration of the 3-aminopropyl trimethoxysilane solution is 0.01 mmol/L-1 mmol/L, the concentration of the polyethylene glycol solution is 0.01 mmol/L-3 mmol/L, and the molecular weight of the polyethylene glycol is 1kDa-30kDa.
4. The silicon nanowire field effect glucose sensor of claim 1, wherein the glutaraldehyde solution concentration in step S2 is 0.5% -10%.
5. The silicon nanowire field effect glucose sensor of claim 1, wherein the glucose oxidase solution concentration in step S3 is 0.1 μg/mL to 10 mg/mL.
6. The silicon nanowire field effect glucose sensor of claim 1, wherein the concentration of the bovine serum albumin solution in step S4 is 0.01-20 mg/mL.
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