CN113176319B - PH sensor and preparation method thereof - Google Patents

PH sensor and preparation method thereof Download PDF

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CN113176319B
CN113176319B CN202110459322.2A CN202110459322A CN113176319B CN 113176319 B CN113176319 B CN 113176319B CN 202110459322 A CN202110459322 A CN 202110459322A CN 113176319 B CN113176319 B CN 113176319B
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substrate
sensitive layer
silk
based carbon
sensor
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CN113176319A (en
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王凤霞
黄婷
杨湛
孙立宁
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Suzhou University
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/414Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS
    • 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 relates to a PH sensor and a preparation method thereof, wherein the PH sensor comprises: the semiconductor device comprises a substrate, a sensitive layer, a packaging layer and a metal oxide field effect transistor. The substrate comprises a substrate middle area positioned in the middle of the substrate, and substrate side areas arranged on two sides of the substrate middle area; the sensitive area is arranged on the upper surface of the middle area of the substrate, and the sensitive layer comprises a sensitive layer middle area and sensitive layer side areas positioned at two sides of the sensitive layer middle area; the packaging layer covers the upper surface and the side surface of the side area of the substrate and covers the upper surface and the side surface of the side area of the sensitive layer; the metal oxide field effect transistor comprises a grid electrode, and one side of the grid electrode is connected with one side of the sensitive layer through a metal wire.

Description

PH sensor and preparation method thereof
Technical Field
The invention belongs to the technical field of PH sensing, and particularly relates to a PH sensor and a preparation method thereof.
Background
The pH value describes the degree of acid-base strength of an aqueous solution, and is also an important observation index for maintaining the health balance of a biological environment, and the interference and the change of the pH value can be the cause of diseases and dysfunction in a biological system. The PH sensor is mainly used for detecting the concentration of hydrogen ions in a detected object and converting the concentration of hydrogen ions into a corresponding usable output signal. Since the PH value plays an important role in cells and plays an important role in understanding physiological and pathological processes in organisms, PH sensors applied to biomedicine are increasingly receiving attention of various scholars and have been developed remarkably in recent years.
The PH sensor can be classified into a PH probe, a field effect transistor-based PH sensor, and a PH fluorescence sensor by a principle difference. However, the PH probe device has larger overall size, is not beneficial to measurement in micro-environments such as cells, and is easy to damage the cells during movement; the PH fluorescence sensor signal needs special complex instrument to process for use, and the cell based on the field effect tube has the advantages of stable detection, high sensitivity and the like, but the existing PH fluorescence sensor based on the field effect tube has the problems of poor biocompatibility and the like, and limits the development of the PH fluorescence sensor in the cell field.
Disclosure of Invention
Based on this, it is necessary to provide a new PH sensor and a method for manufacturing the same.
The invention adopts the following technical scheme:
a PH sensor, comprising:
the substrate comprises a substrate middle area positioned in the middle of the substrate and substrate side areas arranged on two sides of the substrate middle area, wherein the substrate middle area is provided with an upper surface positioned above the substrate middle area, and the substrate side areas are provided with an upper surface positioned above the substrate side areas and side surfaces positioned on two sides of the upper surface;
the sensitive layer is arranged on the upper surface of the substrate middle region, the sensitive layer comprises a sensitive layer middle region and sensitive layer side regions positioned at two sides of the sensitive layer middle region, and the sensitive layer side regions comprise an upper surface positioned above the sensitive layer side regions and side surfaces positioned at two sides of the sensitive layer side regions;
the packaging layer covers the upper surface and the side surface of the substrate side area and covers the upper surface and the side surface of the sensitive layer side area;
the metal oxide field effect transistor comprises a grid electrode, and one side of the grid electrode is connected with one side of the sensitive layer through a metal wire.
Further, the metal wire penetrates through the packaging layer from outside to inside so as to be connected with one side of the sensitive layer.
Further, the material of the sensitive layer comprises composite silk-based carbon nanofibers.
Further, the composite silk-based carbon nanofiber comprises silk-based carbon nanofibers and nickel nanoparticles distributed on the surfaces of the silk-based carbon nanofibers;
further, the substrate comprises a quartz base.
Further, the material of the encapsulation layer comprises epoxy resin.
According to the PH sensor, the gate-expanding type field effect transistor with the nano structure is adopted for sensing, the metal oxide field effect transistor is separated from the sensitive layer through the gate-expanding structure, the sensitive layer is immersed in the solution, and the metal oxide field effect transistor is isolated from the chemical environment, so that the long-term stability is enhanced.
The metal oxide field effect transistor is a commercial transistor (HEF 4007 UBD), and the sensitive layer adopts a nano structure, so that the size of the metal oxide field effect transistor is tiny, and the metal oxide field effect transistor is favorable for providing pH value sensing of a cell microenvironment when a micro-nano robot performs cell level operation.
The sensitive layer adopts silk-based carbon nanofiber, so that the biocompatibility is good, and the toxicity to cells is avoided, so that the survival rate of the cells is affected; and the sensitivity is high, and the method is more suitable for feeding back in micro pH value changes of microenvironments such as cells.
The invention can also adopt the following technical scheme: a method for preparing a PH sensor, comprising the steps of:
providing a composite silk-based carbon nanofiber;
transferring the composite silk-based carbon nanomaterial to a substrate to form a sensitive layer;
one end of the sensitive layer is connected with a metal wire through silver paste, and the other end of the metal wire is connected with the grid electrode of the metal oxide field effect tube;
and packaging the two ends of the sensitive layer and the two sides of the substrate through epoxy resin to form a packaging layer.
Further, the composite silk-based carbon nanofiber is obtained by the following steps:
degumming silk by alkali liquor;
preparing deep eutectic solution to microfibrillate the degummed silk fiber to form silk nanofiber;
performing heat treatment on the silk nanofiber to form a silk-based carbon nanofiber;
nickel nanoparticles are modified on the surface of the silk-based carbon nanofibers by electrochemical deposition.
Further, before the step of transferring the composite silk-based carbon nanofiber onto the substrate, the method further comprises:
the substrate is firstly washed by ethanol under ultrasonic, then washed by water under ultrasonic, and then dried.
Further, the method further comprises the following steps: and the packaging layer is dripped and dried through a die to form a patterned structure.
According to the preparation method of the PH sensor, the obtained PH sensor adopts the biochar as a sensitive material, so that the biocompatibility is good, the one-dimensional nano structure has a high specific surface area, the sensitivity of the device is ensured, the whole sensor adopts a gate-expanding structure to separate the metal oxide field effect tube from the sensitive layer, the stability and the repeatability of the device are improved, stable PH value sensing can be carried out in a complex cell environment, and the novel PH sensor facing cell monitoring is small in size, so that the novel PH sensor is more suitable for being combined with a micro-nano robot, and feeds back the tiny PH value change during cell level operation.
Drawings
FIG. 1 is a schematic diagram of a PH sensor according to an embodiment of the invention.
Fig. 2 is a schematic structural diagram of the sensitive layer in fig. 1.
FIG. 3 is a graph of the pH response of the sensitive layer of FIG. 1.
In the figure, the substrate comprises a 1-substrate, a 14-substrate middle region, a 15-substrate side region, a 2-sensitive layer, a 24-sensitive layer middle region, a 25-sensitive layer side region, a 3-packaging layer, a 4-metal oxide field effect transistor, a 5-grid electrode, a 6-metal wire, a 21-wire-based carbon nanofiber and 22-nickel nanoparticles.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the detailed description is presented by way of example only and is not intended to limit the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Referring to FIGS. 1-2, a PH sensor is disclosed in an embodiment of the invention, which is a novel PH sensor facing cell monitoring, comprising:
the substrate 1, the substrate 1 includes the substrate middle area 14 located in its middle part, and the substrate side areas 15 set up in the both sides of the substrate middle area 14, the substrate middle area 14 has upper surface located above it, the substrate side area 15 has upper surface located above it and sides located in both sides of upper surface;
the sensitive layer 2 is arranged on the upper surface of the substrate middle region 14, the sensitive layer 2 comprises a sensitive layer middle region 24 and sensitive layer side regions 25 positioned on two sides of the sensitive layer middle region 24, and the sensitive layer side regions comprise an upper surface positioned above the sensitive layer side regions and side surfaces positioned on two sides of the sensitive layer side regions.
The packaging layer 3 covers the upper surface and the side surface of the substrate side area 15 and covers the upper surface and the side surface of the sensitive layer side area 25;
a metal oxide field effect transistor (MOSFET) 4, the metal oxide field effect transistor 4 comprising a gate 5, one side of the gate 5 being connected to one side of the sensitive layer 2 by a metal wire 6. The metal wire 6 penetrates the encapsulation layer 3 from outside to inside to be connected with one side of the sensitive layer 2.
The material of the sensitive layer 2 comprises composite silk-based carbon nanofibers, wherein the composite silk-based carbon nanofibers comprise silk-based carbon nanofibers 21 and nickel nanoparticles 22 distributed on the surface of the silk-based carbon nanofibers 21.
The novel PH sensor working principle facing cell monitoring of this application is: the material of the sensitive layer 2 is composite silk-based carbon nanofiber, silk-based carbon fiber is immersed in an acidic or alkaline solution, hydrogen ions or hydroxyl ions can interact with carboxyl groups on the surface of the carbon fiber, and protonizing and deprotonating processes occur on the surface of the carbon fiber, so that the surface potential of the sensitive layer is changed, and the pH value of the solution is detected by detecting the threshold voltage of a novel PH sensor facing cell monitoring.
The primary function of the substrate is, among other things, to provide support for the other layers.
For ease of illustration, the flexible substrate 1 is divided into a substrate middle region 14, and two substrate side regions 15 located on either side of the middle region. Wherein the substrate intermediate region 14 corresponds to the sensitive layer 2; the two substrate-side regions 15 correspond to the encapsulation layer 3.
Wherein the sensitive layer 2 is the core component of the flexible temperature sensor. The material of the sensitive layer 2 is composite silk-based carbon nanofiber. The silk-based carbon nanofiber has conductivity due to the local graphite structure, the content of pyrrole nitrogen and the additional carboxylic acid types in the carbon nanofiber determine the protonation and deprotonation of hydrogen ions to a great extent, and nickel (Ni) nanoparticles can further increase the defect state of the surface of the silk-based carbon nanofiber, so that the sensitivity of the novel PH sensor facing cell monitoring is further improved.
The composite silk-based carbon nanofiber is a one-dimensional material. The one-dimensional composite silk-based carbon nanofiber serving as the sensitive layer 2 has better performance in terms of crystallinity, electrical performance and flexibility than a two-dimensional-based field effect tube; when the detection of the cell microenvironment is carried out, the one-dimensional composite material is adopted to provide a better specific surface area, so that the novel PH sensor for cell monitoring has higher sensitivity and smaller device size, is favorable for the structure of the micro-robot, and provides PH value sensing of the cell microenvironment when the cell level operation is carried out.
Wherein, optionally, the substrate 1 is a quartz base. Of course, it is understood that the substrate of the present application is not limited to a quartz base, but may be made of other materials as deemed appropriate by those skilled in the art.
Wherein, preferably, the material of the encapsulation layer 3 is epoxy resin. The epoxy resin provides conformal coverage for the nano structure of the sensitive layer, improves the overall stability of the device, and prolongs the service life of the device in complex environment.
The invention also provides a preparation method of the PH sensor.
A method for preparing a novel PH sensor for cell monitoring, comprising the steps of:
providing a composite silk-based carbon nanofiber;
transferring the composite silk-based carbon nanomaterial onto a substrate 1 to form a sensitive layer 2;
one end of the sensitive layer 2 is connected with a metal wire 6 through silver paste, and the other end of the metal wire 6 is connected with a grid electrode 5 of the metal oxide field effect tube 4;
and packaging the two ends of the sensitive layer 2 and the two sides of the substrate through epoxy resin to form a packaging layer.
Optionally, in order to make the substrate 1 cleaner and avoid the influence of other impurities, before the step of transferring the composite silk-based carbon nanofiber onto the substrate, the method further comprises:
the substrate 1 is first washed with ethanol under ultrasound, then with water under ultrasound, and then dried.
Wherein, alternatively, the composite silk-based carbon nanofiber can be obtained by the following steps:
degumming silk by alkali liquor, preparing deep eutectic solution, microfibrillating the degummed silk fiber to obtain silk nanofiber, performing heat treatment on the silk nanofiber to form silk-based carbon nanofiber, and modifying nickel nanoparticles on the surface of the silk-based carbon nanofiber by electrochemical deposition. Through the mode, the nickel nano particles can be randomly distributed on the surface of the silk-based carbon nano fiber, and the size and the morphology of the nickel nano particles can be effectively controlled by controlling the electrodeposition time. The silk nanofiber is adopted to make the device, and the biocompatibility of the device is better. Wherein, optionally, the composite silk-based carbon nanofibers are transferred onto the flexible substrate 1 by a Scanning Electron Microscope (SEM) four-hand nano-manipulation system, the orientation of the plurality of composite silk-based nanofibers is uniform.
Optionally, the encapsulation layer 3 is dried by die drop coating to form a patterned structure.
According to the preparation method of the novel PH sensor facing cell monitoring, the novel PH sensor facing cell monitoring is prepared by adopting biochar as a sensitive material, so that the biocompatibility is good, a one-dimensional nano structure has a high specific surface area, the sensitivity of a device is ensured, the whole sensor adopts a gate-expanding structure to separate a metal oxide field effect transistor (MOSFET) from a sensitive layer, the stability and repeatability of the device are improved, stable PH value sensing can be performed in a complex cell environment, and the novel PH sensor facing cell monitoring is small in size, so that the novel PH sensor is more suitable for being combined with a micro-nano robot, and feeds back tiny PH value change during cell level operation.
The PH sensor obtained by the novel preparation method of the PH sensor facing cell monitoring has the advantages of good biocompatibility, high sensitivity, good stability and repeatability, small size of the device and capability of conducting stable PH value sensing under severe cell microenvironment, and the performance of a sensitive layer is shown in figure 3.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (7)

1. A PH sensor, comprising:
the substrate comprises a substrate middle area positioned in the middle of the substrate and substrate side areas arranged on two sides of the substrate middle area, wherein the substrate middle area is provided with an upper surface positioned above the substrate middle area, and the substrate side areas are provided with an upper surface positioned above the substrate side areas and side surfaces positioned on two sides of the upper surface;
the sensitive layer is arranged on the upper surface of the substrate middle region, the sensitive layer comprises a sensitive layer middle region and sensitive layer side regions positioned at two sides of the sensitive layer middle region, the sensitive layer side regions comprise an upper surface positioned above the sensitive layer side regions and side surfaces positioned at two sides of the sensitive layer side regions, the material of the sensitive layer comprises composite silk-based carbon nano fibers, and the composite silk-based carbon nano fibers comprise silk-based carbon nano fibers and nickel nano particles distributed on the surfaces of the silk-based carbon nano fibers;
the packaging layer covers the upper surface and the side surface of the substrate side area and covers the upper surface and the side surface of the sensitive layer side area;
the metal oxide field effect transistor comprises a grid electrode, and one side of the grid electrode is connected with one side of the sensitive layer through a metal wire.
2. The PH sensor of claim 1, wherein the metal wire penetrates the encapsulation layer from outside to inside to connect with one side of the sensing layer.
3. The PH sensor of claim 1 or 2, wherein the substrate comprises a quartz base.
4. The PH sensor of claim 1 or 2, wherein the material of the encapsulation layer comprises an epoxy.
5. A method for manufacturing a PH sensor, comprising the steps of:
providing a composite silk-based carbon nanofiber; the composite silk-based carbon nanofiber is obtained through the following steps:
degumming silk by alkali liquor;
preparing deep eutectic solution to microfibrillate the degummed silk fiber to form silk nanofiber;
performing heat treatment on the silk nanofiber to form a silk-based carbon nanofiber;
modifying nickel nano particles on the surface of the silk-based carbon nano fiber through electrochemical deposition;
transferring the composite silk-based carbon nanomaterial to a substrate to form a sensitive layer;
one end of the sensitive layer is connected with a metal wire through silver paste, and the other end of the metal wire is connected with the grid electrode of the metal oxide field effect tube;
and packaging the two ends of the sensitive layer and the two sides of the substrate through epoxy resin to form a packaging layer.
6. The method of preparing as claimed in claim 5, further comprising, before the step of transferring the composite silk-based carbon nanofiber onto a substrate:
the substrate is firstly washed by ethanol under ultrasonic, then washed by water under ultrasonic, and then dried.
7. The method of manufacturing according to claim 5, further comprising: and the packaging layer is dripped and dried through a die to form a patterned structure.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
CN1865501A (en) * 2006-06-22 2006-11-22 上海交通大学 Process for preparing nano noble metal reinforced silk fiber-base composite materials
CN108802124A (en) * 2018-08-28 2018-11-13 长沙理工大学 A kind of detection method and sensor of the l-cysteine based on glutathione composite membrane grid gold electrode
CN208860792U (en) * 2018-08-28 2019-05-14 长沙理工大学 A kind of sensor detecting l-cysteine
CN111599920A (en) * 2020-05-21 2020-08-28 苏州大学 Flexible temperature sensor and preparation method and application thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1865501A (en) * 2006-06-22 2006-11-22 上海交通大学 Process for preparing nano noble metal reinforced silk fiber-base composite materials
CN108802124A (en) * 2018-08-28 2018-11-13 长沙理工大学 A kind of detection method and sensor of the l-cysteine based on glutathione composite membrane grid gold electrode
CN208860792U (en) * 2018-08-28 2019-05-14 长沙理工大学 A kind of sensor detecting l-cysteine
CN111599920A (en) * 2020-05-21 2020-08-28 苏州大学 Flexible temperature sensor and preparation method and application thereof

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Title
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