CN110806429A - Resistance-type flexible gas sensor with resistance compensation function in bending state and preparation method thereof - Google Patents
Resistance-type flexible gas sensor with resistance compensation function in bending state and preparation method thereof Download PDFInfo
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- CN110806429A CN110806429A CN201910730078.1A CN201910730078A CN110806429A CN 110806429 A CN110806429 A CN 110806429A CN 201910730078 A CN201910730078 A CN 201910730078A CN 110806429 A CN110806429 A CN 110806429A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/126—Composition of the body, e.g. the composition of its sensitive layer comprising organic polymers
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/041—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
Abstract
The invention relates to the field of sensors, and discloses a resistance-type flexible gas sensor with a resistance compensation function in a bending state and a preparation method thereof, wherein the sensor comprises an insulating flexible substrate, and at least one sensing unit is respectively arranged on the upper surface and the lower surface of the insulating flexible substrate; each sensing unit comprises a pair of electrodes and a gas sensitive material film arranged between the electrodes, and the electrodes and the gas sensitive material film are arranged on the surface of the insulated flexible substrate. The electrodes and the gas sensitive material films (namely the sensing units) are arranged on the upper surface and the lower surface of the flexible material, and when the flexible material is bent and deformed, the two sensing units are subjected to opposite strain effects to generate opposite resistance value changes, so that the resistance change caused by strain is compensated. Compared with the strain immunity obtained based on the structural design of materials or devices at present, the compensation method for the resistance change caused by the bending strain has the advantages of more universality, more simplicity, convenience and lower cost.
Description
Technical Field
The invention relates to the field of sensors, in particular to a resistance-type flexible gas sensor with a resistance compensation function in a bending state and a preparation method thereof.
Background
Flexible electronic devices are an area of intense research that has emerged in recent years. The resistance-type flexible device, especially a flexible sensor, can be widely applied to intelligent robots, wearable and unmanned equipment and the like. Flexible electronic devices are typically built on flexible/ductile substrates. Compared with traditional electronics, the flexible electronics have higher flexibility, can adapt to different working environments to a certain extent, and meet the deformation requirement of equipment. But the corresponding technical requirements also restrict the development of flexible electronics. It is important that flexible electronics provide new challenges and requirements for the materials used to fabricate the circuits, in terms of their flexibility and stretchability without compromising their electronic performance.
Specifically, for example, in a resistive flexible sensor, a sensitive material is attached to a surface of a flexible substrate in a form of a thin film, and when a device is bent by an external force, a resistance value of the sensitive material inevitably changes, and the change inevitably interferes with the sensor in a working state. One approach to this problem has been to develop sensitive materials with some strain "immunity" function. For example, the Takao Someya research team has produced an ultra-thin resistive pressure sensor that is nearly "immune" to device bending deformation, yet extremely sensitive to positive pressure (DOI: 10.1038/nnano.2015.324); the Steve Park team invented a touch sensor using multi-walled carbon nanotubes as sensitive materials, which realizes the decoupling of tensile stress and compressive stress, can realize high-sensitivity response to tensile stress, and is insensitive to positive pressure (DOI: 10.1021/acsano.8b03488).
However, only a few sensitive materials have such an "immune" function, and most of the sensitive materials have a significant change in resistance when deformed due to external force bending, so that it is still very challenging to implement bending strain "immune" on a flexible electronic device universally. In the field of flexible gas sensors, in most cases, bending of the device will undoubtedly result in a corresponding change in the resistance value, which will cause the response signal of the device to be severely disturbed. It is particularly necessary to compensate for resistance changes caused by bending.
There is therefore a need in the art for a simple, practical and versatile method for eliminating or compensating for changes in the resistance of a flexible electronic device caused by bending due to an external force.
Disclosure of Invention
In order to solve the technical problems, the invention provides a resistance-type flexible gas sensor with a resistance compensation function in a bending state.
The specific technical scheme of the invention is as follows: a resistance-type flexible gas sensor with a resistance compensation function in a bending state comprises an insulating flexible substrate. The upper surface and the lower surface of the insulating flexible substrate are respectively provided with at least one sensing unit; each sensing unit comprises a pair of electrodes and a gas sensitive material film arranged between the electrodes, and the electrodes and the gas sensitive material film are arranged on the surface of the insulated flexible substrate.
In the scheme of the invention, the upper surface and the lower surface of the insulating flexible substrate are respectively provided with the sensing units, and the two sensing units are opposite in strain and opposite in resistance change trend under the condition that the device is bent. Assuming that the initial resistances of the gas sensitive material films of the upper and lower surfaces are R1 and R2, respectively, the series resistance is R1+ R2. When the device is subjected to bending deformation as shown in fig. 2, it can be known from the knowledge of material mechanics that the gas sensitive material films on the upper and lower surfaces are subjected to tensile and compressive strain, respectively, thereby causing opposite changes in R1 and R2. At this time, assuming that the resistance values are changed to R1+ Δ R1 and R2 to Δ R2, respectively, the device resistance due to bending is changed to Δ R1 to Δ R2. In general, the present invention provides compensation for variations in resistance of-ar 2 when bent, as compared to when only the upper surface of the substrate is provided with a thin film of gas sensitive material.
Further, the strain response values of the upper and lower surface sensing units can be made close to or equal by selecting, i.e. Δ R1- Δ R2 ≈ 0. Therefore, the resistance change of the flexible sensor when being bent can be compensated. Obviously, when the two sensing units are subjected to bending strain, the closer the absolute value of the resistance value variation is, the better the compensation effect is. And the compensation effect is related to the response characteristics of the resistance values of the two sensing units to strain. The response characteristics of the resistance values of the two sensing units to strain can be regulated and controlled from the aspects of electrode structure, shape, size and material, the type and microstructure of the gas-sensitive material and the like.
In summary, the invention adopts a scheme that the electrodes and the gas sensitive material thin films (i.e. the sensing units) are arranged on the upper surface and the lower surface of the flexible material, when the flexible material is bent and deformed, the two sensing units are subjected to opposite strain effects to generate opposite resistance value changes, so that the effect of compensating the resistance change caused by strain is achieved. Compared with the strain immunity obtained based on the structural design of materials or devices at present, the compensation method for the resistance change caused by the bending strain has the advantages of more universality, more simplicity, convenience and lower cost.
Preferably, the gas sensitive material films on the upper surface and the lower surface of the insulating flexible substrate are the same or different in shape, size and material.
Preferably, the electrodes on the upper and lower surfaces of the insulating flexible substrate are the same or different in shape, size and material.
Preferably, the raw material of the gas sensitive material film comprises Pd, Ag and SnO2ZnO, carbon nanotube, graphene, MoS2Polypyrrole, poly (3, 4-ethylenedioxythiophene), and the like.
Preferably, the material of the lead is copper.
Preferably, the insulating flexible substrate is polyethylene terephthalate.
A preparation method of the resistance-type flexible gas sensor comprises the following steps:
1) preparing an insulating flexible substrate;
2) preparing an electrode: preparing electrodes on two sides of an insulating flexible substrate respectively;
3) preparing a gas sensitive material film: respectively depositing gas sensitive materials between two electrodes on the same surface by adopting a nanoparticle beam deposition technology;
4) resistance detection: and connecting the electrodes on the upper surface and the lower surface by using a lead matched with conductive silver paste to form a series structure, and further serially connecting a signal monitoring device in the series structure to finally carry out resistance detection.
Preferably, in step 2), the electrode is prepared specifically by: arranging a mask plate on the insulating flexible substrate for shielding; and then heating the evaporation boat to volatilize the metal raw materials in the thermal evaporation boat to form atomic vapor which is deposited on the surface of the insulating flexible substrate to form an electrode.
Preferably, the mask plate is made of molybdenum.
Compared with the prior art, the invention has the beneficial effects that: the invention adopts the scheme that the electrodes and the gas sensitive material films (namely the sensing units) are arranged on the upper surface and the lower surface of the flexible material, when the flexible material is bent and deformed, the two sensing units are subjected to opposite strain effects to generate opposite resistance value changes, thereby playing the role of compensating the resistance change caused by strain. Compared with the strain immunity obtained based on the structural design of materials or devices at present, the compensation method for the resistance change caused by the bending strain has the advantages of more universality, more simplicity, convenience and lower cost.
Drawings
FIG. 1 is a schematic structural view of a resistive flexible gas sensor according to the present invention in a normal state;
FIG. 2 is a schematic diagram of resistance compensation of the resistive flexible gas sensor according to the present invention in a bent state;
FIG. 3 is a flow chart of the process for manufacturing the resistive flexible gas sensor according to the present invention;
FIG. 4 is a schematic view showing the arrangement of upper and lower surface electrodes in example 1;
fig. 5 is a diagram illustrating resistance values of the upper and lower surface sensing units and a change in series resistance of the upper and lower surface sensing units when the resistive flexible gas sensor according to embodiment 1 of the present invention is subjected to a bending action;
fig. 6 is a schematic view of the arrangement of the lower surface electrodes in example 2.
The reference signs are: the device comprises an insulating flexible substrate 101, an electrode 102, a gas sensitive material film 103, a lead 104, a signal monitoring device 105, a mask plate 201, a metal raw material 202 and an evaporation boat 203.
Detailed Description
The present invention will be further described with reference to the following examples.
General examples
As shown in fig. 1, a resistance-type flexible gas sensor with a resistance compensation function in a bent state includes an insulating flexible substrate 101, where at least one sensing unit is disposed on an upper surface and a lower surface of the insulating flexible substrate respectively; each sensing unit comprises a pair of electrodes 102 and a gas sensitive material film 103 arranged between the electrodes, wherein the electrodes and the gas sensitive material film are arranged on the surface of the insulated flexible substrate.
The gas sensitive material films on the upper surface and the lower surface of the insulating flexible substrate are the same or different in shape, size and material. The electrodes on the upper surface and the lower surface of the insulated flexible substrate are the same or different in shape, size and material.
A preparation method of the resistance-type flexible gas sensor comprises the following steps:
1) preparing an insulating flexible substrate;
2) preparing electrodes on two sides of an insulating flexible substrate respectively: arranging a mask plate on the insulating flexible substrate for shielding; and then heating the evaporation boat to volatilize the metal raw materials in the thermal evaporation boat to form atomic vapor which is deposited on the surface of the insulating flexible substrate to form an electrode.
3) Preparing a gas sensitive material film: respectively depositing gas sensitive materials between two electrodes on the same surface by adopting a nanoparticle beam deposition technology; the raw materials of the gas sensitive material film comprise Pd, Ag and SnO2ZnO, carbon nanotube, graphene, MoS2Polypyrrole, poly (3, 4-ethylenedioxythiophene), and the like.
4) Resistance detection: and connecting the electrodes on the upper surface and the lower surface by using a lead matched with conductive silver paste to form a series structure, and further serially connecting a signal monitoring device in the series structure to finally carry out resistance detection.
Example 1
A resistance-type flexible gas sensor with a resistance compensation function in a bending state comprises an insulating flexible substrate (made of a PET material). The upper surface and the lower surface of the insulating flexible substrate are respectively provided with a sensing unit; each sensing unit comprises a pair of electrodes and a gas sensitive material film arranged between the electrodes, and the electrodes and the gas sensitive material film are arranged on the surface of the insulated flexible substrate.
As shown in fig. 2, the preparation method is as follows:
1) polyethylene terephthalate (PET) having a thickness of 0.5mm was used as the insulating flexible substrate 101 and the area was 20 × 40 mm.
2) As shown in fig. 3(a), parallel metal electrodes are prepared on the insulating flexible substrate by a mask plate 201 shielding thermal evaporation coating process, and the arrangement directions of the electrodes on the upper and lower surfaces are the same, as shown in fig. 4. The electrode 102 is formed by heating the evaporation boat 203 so that the metal raw material 202 in the thermal evaporation boat 203 is volatilized to form vapor of atoms which is deposited on the surface of the insulating flexible substrate. The metal raw material is gold which has good conductivity and is not easy to be oxidized. In order to obtain a metal electrode having a specific shape, the mask plate 201 is used as a mask. The mask plate 201 is made by wet etching using molybdenum as a material.
3) As shown in fig. 3(b), after preparing an electrode on one surface of an insulating flexible substrate, an electrode is prepared on the other surface of the insulating flexible substrate in the same manner as in step 2).
4) And (3) respectively depositing the Pd nanoparticles between the two pairs of electrodes prepared in the step 3) by adopting a nanoparticle beam deposition technology, so that a tunneling conducting path can be formed between the electrodes (the specific preparation method is shown in Chinese patent ZL200910028487.3), and finally obtaining the gas sensitive material films 103 (Pd nanoparticle films) with the initial resistance values of 5M omega on the upper surface and the lower surface of the insulating flexible substrate, as shown in fig. 3 (d).
5) As shown in fig. 3(c), the electrodes on the upper and lower surfaces are connected by 0.05mm wires 104 (copper wires) and conductive silver paste to form a series structure (connected in series with a signal detection device 105). The resistance value of the Pd nanoparticle film with the upper surface and the lower surface connected in series is measured to be 10M omega. The device is a flexible hydrogen sensor and can detect the concentration of the hydrogen in the environment in real time.
The results of measuring the resistance between the upper and lower surface electrodes and the change in the resistance after the series connection when the insulating flexible substrate was bent are shown in fig. 5. It can be seen that, at 2500 seconds, the Pd nanoparticle film on the upper surface of the device was stretched by bending the device, and the resistance value was increased. And the lower surface is squeezed, so that the resistance is reduced. The sum of the resistances of the two was measured, and it was found that the resistance value did not change significantly even after the bending action was received, and remained at 10M Ω. This shows that by preparing gas sensing cells on both surfaces of the substrate and by connecting them in series, the resistance change caused by bending can be compensated, so that the flexible gas sensor responds only to gas, but not to strain generated by bending.
In summary, the present invention provides a method for compensating for resistance change caused by bending of a resistive flexible gas sensor. The resistance of the flexible gas sensor prepared by the method is not affected by the bending of the device. The sensor is expected to be widely applied in the fields of industry and scientific research. The foregoing has outlined rather broadly the features and technical advantages of the present invention in order that the detailed description of the invention that follows may be better understood.
Example 2
The present embodiment is different from embodiment 1 in the sensor structure in that: the arrangement of the electrodes on the lower two surfaces is different. In this example, the top surface electrode position was the same as in example 1, but as shown in fig. 6, the bottom surface electrode was disposed at 90 degrees to the top surface electrode direction. In this case, if different types of sensitive materials are used for the upper and lower surfaces, the amount of change in the resistance value will be greatly different due to the anisotropy of the sensitive material between the electrodes when the sensitive material is bent. In fact, the closer the absolute value of the resistance value variation, the better the compensation effect, and vice versa. Therefore, in the electrode structure, if the upper and lower surface sensitive materials are different, the arrangement of the upper and lower surface electrodes is different, which results in poor compensation effect. However, this electrode arrangement is suitable for different kinds of sensitive materials. In specific application, different suitable sensitive materials can be selected according to actual requirements, so that the resistance value of the sensor can be kept basically unchanged when the sensor is bent.
Comparative example 1
This comparative example differs from example 1 in that: the sensitive materials used on the upper surface and the lower surface are Pd nano particles and Ag nano particles respectively. Generally, the amount of resistance change produced by Pd nanoparticles and Ag nanoparticles will be significantly different when subjected to bending. Therefore, in this case, the compensation effect is not ideal.
Comparative example 2
The comparative example is different from example 1 in the preparation processes of the sensitive materials on the upper and lower surfaces. The upper surface was deposited with Pd nanoparticles to a resistance of 5M Ω and the lower surface was deposited to a resistance of 5k Ω. In this case, when the bending occurs, the resistance variation of the upper surface is much larger than that of the lower surface, resulting in poor compensation effect.
From the above four embodiments/comparative examples, it can be seen that the principle of achieving the ideal compensation effect is to make the resistance changes of the sensing units on the upper and lower surfaces as close as possible when the sensing units are bent.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (9)
1. The utility model provides a flexible gas sensor of resistance-type that has resistance compensation function under state of buckling, includes insulating flexible substrate, its characterized in that: the upper surface and the lower surface of the insulating flexible substrate are respectively provided with at least one sensing unit; each sensing unit comprises a pair of electrodes and a gas sensitive material film arranged between the electrodes, and the electrodes and the gas sensitive material film are arranged on the surface of the insulated flexible substrate.
2. The resistive flexible gas sensor of claim 1, wherein the gas sensitive material films on the upper and lower surfaces of the insulating flexible substrate are the same or different in shape, size, and material.
3. The resistive flexible gas sensor of claim 1 or 2, wherein the electrodes on the upper and lower surfaces of the insulating flexible substrate are the same or different in shape, size and material.
4. The resistive flexible gas sensor of claim 1, wherein the gas sensitive material film comprises Pd, Ag, SnO as a raw material2ZnO, carbon nanotube, graphene, MoS2One or more of polypyrrole and poly (3, 4-ethylenedioxythiophene).
5. The resistive flexible gas sensor of claim 1, wherein the wire is copper.
6. The resistive flexible gas sensor of claim 1, wherein the insulating flexible substrate is polyethylene terephthalate.
7. A method for preparing a resistive flexible gas sensor according to any of claims 1 to 6, comprising the steps of:
1) preparing an insulating flexible substrate;
2) preparing an electrode: preparing electrodes on two sides of an insulating flexible substrate respectively;
3) preparing a gas sensitive material film: respectively depositing gas sensitive materials between two electrodes on the same surface by adopting a nanoparticle beam deposition technology;
4) resistance detection: and connecting the electrodes on the upper surface and the lower surface by using a lead matched with conductive silver paste to form a series structure, and further serially connecting a signal monitoring device in the series structure to finally carry out resistance detection.
8. The method according to claim 7, wherein in step 2), the electrode is prepared by: arranging a mask plate on the insulating flexible substrate for shielding; and then heating the evaporation boat to volatilize the metal raw materials in the thermal evaporation boat to form atomic vapor which is deposited on the surface of the insulating flexible substrate to form an electrode.
9. The method according to claim 7, wherein the mask plate is made of molybdenum.
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Application publication date: 20200218 |