CN106814110B - Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof - Google Patents
Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof Download PDFInfo
- Publication number
- CN106814110B CN106814110B CN201710007556.7A CN201710007556A CN106814110B CN 106814110 B CN106814110 B CN 106814110B CN 201710007556 A CN201710007556 A CN 201710007556A CN 106814110 B CN106814110 B CN 106814110B
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- gas sensor
- insulating substrate
- gas
- flexible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a stretchable semiconductor resistance type flexible gas sensor with a micro-fold film structure and a preparation method thereof. Adopting a stretchable insulating substrate-polyacrylate double-sided foam adhesive tape (VHB) to fix the adhesive tape on a rigid substrate in a pre-stretched manner to a certain extent in a single direction; and preparing a patterned graphene electrode and a colloidal quantum dot film on the VHB substrate in a pre-stretched state, and then slowly retracting the VHB substrate to complete the preparation of the sensor. The gas sensor prepared by the method has the gas sensitive layer with the micro-fold film structure and the patterned graphene electrode, has the stretchable flexible characteristic, the manufacturing temperature and the working temperature of the sensor can be lowered to room temperature, the instantaneous or micro-change of the gas concentration can be detected at the room temperature, the response recovery speed is high, the sensitivity is high, and meanwhile, the gas sensor has the characteristic of environmental humidity interference resistance and has better long-term stability.
Description
Technical Field
The invention belongs to the technical field of gas sensitive materials and elements, and particularly relates to a stretchable semiconductor resistance type flexible gas sensor with a film microcosmic fold film structure and taking colloidal quantum dots as a gas sensitive material and a preparation method thereof.
Background
Because the traditional gas sensor is manufactured at higher temperature, high heat-resistant rigid materials such as ceramics, quartz, silicon and the like are generally adopted as a substrate, with the development of a low-temperature or even room-temperature deposition process of nano materials, the latest gas sensor research can adopt modes such as spin coating, lifting, printing and the like to coat gas-sensitive materials on plastic (such as PET polyester, polyimide PI) or even flexible substrates such as paper and the like with required patterns to manufacture a novel flexible sensor, has the characteristics of light weight, thin appearance, good flexibility, convenient processing and easy scale production, is expected to be directly attached to curved surfaces such as gas storage equipment, various foods and biological skin surfaces and the like for use, has incomparable advantages compared with the traditional rigid sensor in the fields of environmental protection, food industry, medical health and the like, and is easy to pattern and integrate, compared with a rigid device, the flexible gas sensor is easier to integrate into systems such as a multi-sensor array, an electronic nose, an intelligent textile, an RFID (radio frequency identification) radio frequency tag and the like to realize brand new applications, and accords with the development trend of miniaturization, intelligence and multiple functions of the gas sensor.
In view of the attractive application prospect of flexible devices, the development of devices based on flexible substrates is a new development direction of gas sensors in recent years. However, most of gas sensitive layers in the current flexible gas sensor are organic materials, for example, 2011, Suzhou university and national nanometer scientific center collaboratively research a room-temperature flexible gas sensor taking conductive polymer PANI nanowires as gas sensitive materials and PET polyester plastics as substrates, and the room-temperature flexible gas sensor can be used for 100ppmH at room temperature2The gas response time and the recovery time are about 100 seconds and 250 seconds respectively, while the inorganic material with better electrical property is generally higher in deposition temperature and poorer in compatibility of a device manufacturing process and a flexible substrate, so that the development of an inorganic gas-sensitive material capable of forming a film at low temperature even at room temperature is urgently needed, and the inorganic gas-sensitive material can be deposited on the flexible substrate to manufacture a device.
On the other hand, from the level of gas-sensitive performance reported in research, the current flexible gas sensor has the problems of low sensitivity and undesirable response-recovery characteristics, and the reports concerning flexibility of the gas sensor are less. For example, in 2010, korean researchers have used carbon nanotube/reduced graphene composite film as gas sensitive material to fabricate flexible gas sensor on polyimide PI substrate, which is sensitive to 10ppm NO at room temperature2The gas sensitivity was only 1.2; the Rowell division of the university of Massachusetts 2012, USA, ink-jet prints carbon nanotubes on paper to form a film with 100ppm NO at room temperature2And Cl2Respectively, sensitivity of 2.4 and 2.7, response time of 3 minutes and 5 minutes, respectively, and recovery time of up to 12 minutes and 5 minutes, respectivelyFor 7 minutes.
In addition, patent CN103675034B discloses a semiconductor resistance type gas sensor and a method for manufacturing the same, wherein the substrate is an alumina ceramic rigid base, which has no flexibility and stretchability, and microstructure films with different morphologies cannot be constructed by deformation of the base; the university of science and technology in china reports that a PbS colloidal quantum dot flexible gas sensor (adv. mater.2014,26, 2718-. Therefore, reports aiming at flexible substrate optimization, film microstructure regulation and control and stretchable sensor gas-sensitive performance which are special for flexible gas sensors are not found at present.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides a stretchable semiconductor resistive flexible gas sensor with a micro-wrinkled film structure and a method for manufacturing the same, which aims to solve the technical problems of low gas sensitivity response, slow response/recovery time and limitation of development on flexible electronic devices caused by poor flexibility of a rigid substrate and incompatibility of a film forming process and a flexible substrate in the prior art.
The invention provides a stretchable semiconductor resistance type flexible gas sensor, which comprises: the flexible graphene electrode comprises a flexible insulating substrate, a patterned graphene electrode and a colloid quantum dot gas-sensitive layer.
The flexible insulating substrate has the characteristics of stretching/retracting, rough surface and certain adhesion, and is favorable for adhesion transfer of the graphene electrode and firm film formation of the colloidal quantum dots on the surface of the flexible insulating substrate. The material is polyacrylate double-sided foam adhesive tape (VeryHighBond, VHB).
The patterned graphene electrode is prepared on filter paper by a suction filtration method, the graphene paper is uniform in thickness, and the adhesion force of the graphene paper on the filter paper is smaller than that of a VHB substrate, so that the patterned graphene electrode can be transferred to the VHB substrate after patterning to prepare the patterned graphene electrode serving as a working electrode of a gas sensor.
The colloid quantum dot gas-sensitive layer can effectively adsorb target gas and generate electron transfer as a gas-sensitive layer, so that the resistance of the material is changed, and then the change of a resistance signal is detected through the transmission of a graphene electrode, so that the purpose of detecting gas is achieved. The gas-sensitive layer of the colloidal quantum dot is sulfide or oxide semiconductor (PbS, SnO)2、ZnO、WO3Quantum dots).
The gas sensor provided by the invention has a microscopic film fold structure, can detect the instant or micro change of gas concentration at room temperature, has high response recovery speed and high sensitivity, and simultaneously has stretchable gas-sensitive performance for 0.5-100 ppm of NO under different stretching degrees2The gas has quick response and recovery capability; in addition, the microscopic fold structure has the humidity interference resistance and can stably work for a long time under different humidity conditions. The gas sensor is simple in manufacturing process, low in cost, safe and portable, and meanwhile, the gas sensor can be applied to wearable equipment and has a good market prospect.
The invention provides a preparation method of a stretchable semiconductor resistance type gas sensor, which comprises the following steps: (1) VHB is uniaxially prestretched to some extent 0-200% (L-L)0)/L0，L0The original length of VHB, L is the length of VHB after being pre-stretched) is fixed on a rigid substrate (can be selected randomly); (2) preparing graphene paper on cellulose filter paper by a vacuum filtration method, and transferring the graphene paper prepared by the vacuum filtration method to a VHB (very high frequency) to prepare a patterned graphene electrode by using the graphene paper as a sensor electrode; (3) coating a colloid quantum dot solution prepared by a colloid chemical method on a VHB substrate attached with a patterned graphene electrode, and uniformly forming a film on the VHB substrate by adopting processes such as spin coating; (4) treating the colloidal quantum dot film with a short-chain salt solution ligand to remove the surface-coated long-chain oleic acid oleylamine ligand; (5) removing residual short-chain ligand and byproducts thereof by using methanol; (6) the pre-stretched VHB substrate was retracted at a rate of 0.5-2cm/s, resulting in a stretchable semiconductor resistive gas sensor with a micro-pleated structure.
Preferably, the degree of VHB uniaxial tension is 0-200%; considering the strain capacity of VHB, when the degree of stretching exceeds 200%, the VHB substrate is susceptible to fracture.
Preferably, the graphene electrode is prepared by adopting a suction filtration method, and the concentration of a graphene solution used in the suction filtration is 5-10mg/100 mL; the graphene with proper concentration is beneficial to the preparation of graphene electrodes with uniform thickness and can keep good tensile property. When the concentration is too small, the continuity of the graphene electrode is poor, so that the conductivity is poor, and when the concentration is too high, the thickness of the prepared graphene electrode is not uniform, so that the graphene electrode is not beneficial to being transferred onto the VHB substrate, and the graphene electrode is easy to break in the stretching process of the VHB substrate.
Preferably, the colloidal quantum dots are prepared by a colloidal method, the surfaces of the colloidal quantum dots are wrapped by long-chain ligands such as oleic acid, oleylamine and the like, and the colloidal quantum dots can be treated by a solution, and comprise PbS colloidal quantum dots dispersed in n-octane and SnO dispersed in toluene2、ZnO、WO3(ii) a The colloid method can prepare colloid quantum dots with uniform particle size, and the size and the dimension of the quantum dots can be accurately and finely regulated and controlled by the method.
Preferably, the short-chain ligand solution is CuCl2、ZnCl2、AgNO3、Cu(NO3)2、NH4Cl and NaNO2Or the mixed solution thereof, because long-chain ligands such as oleic acid oleylamine are introduced in the synthesis process of the colloidal quantum dots to regulate the size of the quantum dots, the surface long-chain ligands can be effectively removed through the treatment of short-chain ligands, so that the contact between the quantum dot material and target gas is enhanced, and the gas-sensitive response performance is improved.
Preferably, the pre-stretched VHB substrate is retracted at a rate of 1 cm/s; the proper retraction rate is a key factor for preparing a folded structure with a good film, but when the retraction rate is too high, the stress between the films cannot be effectively released, and the folded structure is easy to distort and collapse due to the existence of the internal stress of the films.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the instantaneous or micro-change of the gas concentration can be detected at a lower working temperature even at normal temperature. The stretchable gas sensor with different film micro-folds can be constructed through the pre-stretching degree of the flexible insulating substrate VHB and the film forming process, the gas-sensitive response characteristic can be adjusted accordingly, and meanwhile, the gas-sensitive characteristic can be further improved through adjusting and controlling short-chain salt solution to carry out ligand treatment on the film;
(2) the flexible stretchable semiconductor resistance type gas sensor is prepared on a flexible insulating substrate VHB substrate, a film with different micro-fold structures is constructed on the VHB substrate through the unidirectional pre-stretching characteristic of the VHB, the gas sensor not only has the stretchable gas-sensitive response characteristic, but also has certain humidity interference resistance in the micro structure, the environment interference resistance of the gas sensor can be improved, the long-term stability is enhanced, and the actual detection requirement is met;
(3) the stretchable semiconductor resistance-type gas sensor has the advantages of high room temperature response recovery speed, quick recovery without illumination or heating, high sensitivity, good selectivity, contribution to real-time monitoring, simple manufacturing process, hopeful direct sticking on curved surfaces such as gas storage equipment, various food and biological skin surfaces and the like, and good application prospect.
Drawings
Fig. 1 is a schematic diagram of a method for manufacturing a stretchable semiconductor resistive gas sensor with a film micro-corrugated structure according to an embodiment of the present invention.
FIG. 2 is a Scanning Electron Micrograph (SEM) of a stretchable semiconductor gas sensor with different membrane micro-corrugated structures prepared in examples 1, 2, 3, 4 and 5; in FIG. 2, (a), (b), (c), (d), and (e) represent the morphology of the stretchable gas sensor film prepared at pre-stretching levels of 0, 80%, 120%, 160%, and 200%, respectively. As can be seen, the film wrinkle structure becomes more pronounced as the degree of pretension increases. The degree of wrinkling is shown in wavelength in table 1.
FIG. 3 shows the tensile strength of 0, 80%, 120%, 160%, 200% in dry N for tensile semiconductor resistive gas sensors of examples 1, 2, 3, 4, 52And a room temperature response curve to 50ppm nitrogen dioxide at a relative humidity of 55%; in FIG. 3, (a), (b), (c), (d), (e) are shownRepresenting pre-stretching levels of 0, 80%, 120%, 160%, 200% of the devices started at dry N2Initial resistance and response recovery curves in (1); the initial resistance change and response recovery curve of the device was then changed to 55% humidity. The initial resistance and sensitivity and variation under different humidity conditions are shown in table 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The stretchable semiconductor resistive gas sensor of the present invention comprises: the graphene electrode structure comprises a flexible insulating substrate, a graphene electrode with a folded structure and a gas-sensitive layer. The gas sensitive layer is semiconductor colloidal quantum dot film, specifically PbS colloidal quantum dot film or SnO2A colloidal quantum dot film; the gas sensor has the stretchable characteristic, can still keep the continuity of a film in a limited stretching range, has good response recovery characteristic to target gas, and can be applied to flexible wearable equipment.
The flexible insulating substrate has flexibility and tensile properties, and includes VHB, Polydimethylsiloxane (PDMS), and the like.
The stretchable semiconductor resistance type gas sensor with the film micro-fold structure and the preparation method thereof provided by the embodiment of the invention are shown in figure 1 and specifically comprise the following steps:
(1) fixing the flexible insulating substrate VHB on a rigid base in a unidirectional pre-stretching way by 0-200% (optional);
(2) transferring the graphene paper prepared by the suction filtration method to a VHB (very high frequency) by using a sensor electrode to prepare a patterned graphene electrode;
(3) coating the colloid quantum dot solution on a VHB substrate attached with a patterned graphene electrode to uniformly form a film, wherein the film forming mode comprises spin coating, drip coating, spray coating, printing and the like;
(4) treating the quantum dot film by using a short-chain salt solution ligand to replace a long-chain oleic acid oleylamine ligand coated on the surface of the film, so that target gas molecules can be more easily contacted with the colloidal quantum dot film, and the gas-sensitive response is enhanced;
(5) removing residual short-chain ligand and byproducts thereof on the surface of the film by using methanol;
(6) and after the film is dried, retracting the stretched VHB substrate at the rate of 1cm/s to obtain the stretchable semiconductor resistance type gas sensor with the film (graphene electrode and gas-sensitive layer) micro-fold structure.
In order to make the present invention better understood by those skilled in the art, the following will describe the preparation method of the colloidal quantum dot thin film gas sensor in detail with reference to specific examples.
Example 1: the preparation method of the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 0 specifically comprises the following steps:
(1) and preparing a PbS colloidal quantum dot solution. PbO is used as a lead source, bis-Trimethylsilylthioalkane (TMS) is used as a sulfur source, and the reaction is carried out by adopting a colloid chemical method.
Specifically, 0.9g (4mmol) of PbO was dissolved in 3mL of Oleic Acid (OA) and 17mL of Octadecene (ODE) under a nitrogen atmosphere and heated to 90 ℃ to prepare a precursor of lead oleate as a lead source. After evacuation for 8 hours, the precursor temperature was raised to 120 ℃. mu.L (1mmol) of TMS was dissolved in 10mL of ODE as a sulfur source. The sulfur source was rapidly injected into the lead source at 120 c and after the reaction system had completely darkened (approximately 15s) the solution was placed in cold water to rapidly cool to room temperature. And adding a proper amount of acetone into the cooled solution, centrifugally stirring, removing the supernatant, and then dispersing by toluene and centrifuging by acetone for multiple times until the supernatant is pure white. And drying the final product into powder and dispersing the powder in n-octane to obtain a 50mg/mL lead sulfide quantum dot solution. And measuring the position of an absorption peak of the colloidal quantum dot at 1178nm by ultraviolet-visible absorption spectroscopy.
(2) Preparing graphene paper by adopting a vacuum filtration method: preparing a graphene aqueous solution, dispersing 7mg of graphene in 100mL of water, performing ultrasonic dispersion, pouring the prepared solution into a filter flask paved with cellulose filter paper, performing suction filtration for 1-2 hours, taking out the filter paper, and performing vacuum drying at 60 ℃ for later use;
(3) fixing a VHB substrate which is not prestretched (namely, the prestretching degree is 0) on a glass substrate;
(4) cutting a strip-shaped graphene electrode, transferring the graphene electrode to a VHB substrate, uniformly dripping a PbS colloidal quantum dot solution on the VHB substrate attached with the graphene electrode, and spin-coating at the speed of 2500rpm for 20 s;
(5) adopting short-chain ligand to make the volume ratio of 10mg/mL be 1:3NaNO2And NH4C, paving the whole colloidal quantum dot film with a mixed methanol solution of Cl, soaking for 45s, spin-drying, and repeating twice;
(6) washing off residual particles and reaction byproducts on the surface of the film by using anhydrous methanol, soaking for 5s, spin-drying, and repeating for three times; all the steps described above are repeated twice,
(7) and placing the film in the air for 30-45s, and drying the colloidal quantum dot film to obtain the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 0.
The gas sensor prepared in example 1 of the present invention was tested for its degree of wrinkling and its response sensitivity to 50ppm nitrogen dioxide at room temperature under various humidity conditions.
Example 2: the preparation method of the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 80% comprises the following steps:
the steps (1), (2), (4), (5) and (6) are carried out in the same manner as in example 1, and the specific steps (3) and (7) are carried out as follows:
(3) fixing the VHB substrate on a glass substrate by 80% of unidirectional pre-stretching;
(7) and (3) placing the substrate in air for 30-45s, and after the quantum dot film is dried, slowly retracting the VHB substrate at the speed of 1cm/s to obtain the semiconductor resistance type gas sensor with the film micro-fold structure and the tensile property.
The gas sensor prepared in example 2 of the present invention was tested for its degree of wrinkling and its response sensitivity to 50ppm nitrogen dioxide at room temperature under various humidity conditions.
Example 3: the preparation method of the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 120% specifically comprises the following steps:
except the implementation step (3) is as follows: fixing the VHB substrate on a glass substrate by means of uniaxial tension of 120%; the steps (1), (2), (4), (5), (6) and (7) were carried out in the same manner as in example 2.
The gas sensor prepared in example 3 of the present invention was tested for its degree of wrinkling and room temperature response sensitivity to 50ppm nitrogen dioxide at different humidity at room temperature.
Example 4: the preparation method of the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 160% specifically comprises the following steps:
except the implementation step (3) is as follows: fixing the VHB substrate on a glass substrate by unidirectionally stretching 160%; the steps (1), (2), (4), (5), (6) and (7) were carried out in the same manner as in example 2.
The gas sensor prepared in example 4 of the present invention was tested for its degree of wrinkling and its response sensitivity to 50ppm nitrogen dioxide at room temperature under various humidity conditions.
Example 5: the preparation method of the stretchable semiconductor resistance type gas sensor with the pre-stretching degree of 200% specifically comprises the following steps:
except the implementation step (3) is as follows: fixing the VHB substrate on a glass substrate by uniaxial tension of 200%; the steps (1), (2), (4), (5), (6) and (7) were carried out in the same manner as in example 2.
The gas sensor prepared in example 5 of the present invention was tested for its degree of wrinkling and its response sensitivity to 50ppm nitrogen dioxide at room temperature under various humidity conditions.
The microstructure of the film of the stretchable semiconductor resistive gas sensor with a micro-corrugated structure prepared in examples 1, 2, 3, 4, 5 is shown in fig. 2. As can be seen, as the degree of prestretching increases (0-200%), the degree of wrinkling of the film gradually increases, and the degree of wrinkling can be defined by wavelength and is shown in Table 1.
Examples 1, 2, 3, 4, 5 stretchable semiconductor resistive gas sensor with micro-corrugated structure prepared in accordance with examples 1, 2, 3, 4, 52The gas response diagram is shown in FIG. 3, and the initial resistance and sensitivity changes are shown in Table 1 (Table 1 shows examples 1,2. 3, 4, and 5, the pre-stretching degree is 0, 80%, 120%, 160%, and 200%, and the initial resistance value and the sensitivity change value under different humidity conditions), it is known that the VHB has a better response sensitivity and an anti-environmental humidity capability under the pre-stretching degree of 160%.
TABLE 1
Example 6: the stretchable semiconductor resistive gas sensor with the pre-stretching degree of 120% is prepared at the retraction rate of 0.5cm/s, and specifically comprises the following steps:
after the quantum dot film is dried after being placed in the air for 30-45s in the step (7), the VHB substrate is slowly retracted at the rate of 0.5cm/s, and the semiconductor resistance type gas sensor with the film micro-fold structure and the stretching characteristic is obtained; steps (1), (2), (4), (5) and (6) were carried out in the same manner as in example 3.
Example 7: preparing a stretchable semiconductor resistive gas sensor with a pre-stretching degree of 120% at a retraction rate of 2cm/s, comprising the following steps:
after the quantum dot film is dried after being placed in the air for 30-45s in the step (7), slowly retracting the VHB substrate at the speed of 2cm/s to obtain the semiconductor resistance type gas sensor with the film micro-fold structure and the stretching characteristic; steps (1), (2), (4), (5) and (6) were carried out in the same manner as in example 3. Other gas sensors with different pre-stretching degrees (80%, 160%, 200%) with semiconductor resistance values could also meet such a retraction rate of 0.5cm/s to 2 cm/s.
Example 8: based on SnO2The method for preparing the stretchable semiconductor resistance type gas sensor with different film micro-fold structures by using the colloidal quantum dots specifically comprises the following steps:
(1) preparation of SnO2Colloidal amountAnd (4) sub-point solution.
Adding a certain proportional amount of SnCl4·5H2Heating O, oleic acid and oleylamine to 100 ℃, carrying out vacuum drying reaction until the mixture is clear, cooling to 60 ℃, taking out a certain amount of ethanol, mixing the ethanol uniformly, adding the mixture into a stainless steel autoclave, and putting the stainless steel autoclave into an oven at 180 ℃ for reaction for 3 hours. And taking out after the reaction is finished, taking out the solution in the autoclave when the solution is cooled to room temperature, mixing the solution with ethanol, precipitating and centrifuging, dispersing the precipitated product in a solvent, and performing ethanol centrifugal washing again. And dispersing the dried product in toluene according to the required concentration to obtain the colloidal quantum dot solution.
(2) The obtained colloidal quantum dot solution can be prepared into the SnO-based colloidal quantum dot film gas sensor according to the preparation method of the PbS colloidal quantum dot film gas sensor2The colloidal quantum dots can stretch the semiconductor resistive gas sensor.
The gas sensor prepared by the embodiments of the invention has a micro-fold structure, the gas-sensitive performance is less interfered by the ambient humidity, a certain moisture-resistant characteristic is shown, and the long-term stability of the device is improved. Compared with the existing room-temperature flexible gas sensor, the flexible gas sensor has the advantages that the response time and the recovery time are greatly shortened while the sensitivity is ensured, the flexible gas sensor not only has the flexible characteristic of the flexible gas sensor, but also shows the stretchable characteristic, and the flexible gas sensor still has good response recovery capability under a certain stretching degree.
The stretchable semiconductor resistive gas sensor and the method of manufacturing the same according to the present invention are not limited to the above-described embodiments, and particularly, the colloidal quantum dot film in the gas sensor is not limited to PbS colloidal quantum dot film or SnO2The colloid quantum dot film can be other semiconductor colloid quantum dot films; the colloidal quantum dot solution in the preparation method is not limited to PbS colloidal quantum dot solution or SnO2The colloidal quantum dot solution can also be other semiconductor colloidal quantum dots such as ZnO, WO3Etc.; short-chain ligand solutions are not limited to NH4Cl or NaNO2The solution can also be other short-chain inorganic or organic ligand solution, such as CuCl2、ZnCl2、AgNO3、Cu(NO3)2Solutions, etc., the electrodes and patterns used are not limited toGraphene electrodes and strips, including thin film gold electrodes, interdigitated patterns, and the like.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A stretchable semiconductor resistive flexible gas sensor, comprising: the flexible insulating substrate is attached to a patterned graphene electrode on the flexible insulating substrate and a colloidal quantum dot gas-sensitive layer with a micro-fold film structure;
the flexible insulating substrate has the characteristics of stretching and retracting, the surface of the flexible insulating substrate is rough and has adhesive force, and the adhesion transfer of a graphene electrode and firm film formation of colloidal quantum dot solution on the surface of the flexible insulating substrate are facilitated;
the patterned graphene electrode is used as a working electrode of a gas sensor and is transferred to a flexible insulating substrate;
firstly, a flexible insulating substrate is pre-stretched in a one-way mode to a certain degree, then a colloidal quantum dot solution is coated on the surface of the flexible insulating substrate to form a colloidal quantum dot gas-sensitive layer, and then retraction treatment is carried out on the flexible insulating substrate;
the colloid quantum dot gas-sensitive layer forms a film structure with microscopic folds depending on the stretching and retracting characteristics of the flexible insulating substrate, the gas-sensitive layer adsorbs target gas to cause electron transfer so that the resistance of the gas-sensitive layer is changed, and the change of a resistance signal is detected through the graphene electrode, so that gas detection is realized.
2. The stretchable semiconductor resistive flexible gas sensor of claim 1, wherein the material of the flexible insulating substrate is polyacrylate double-sided foam tape.
3. The stretchable semiconducting resistive flexible gas sensor of claim 1 or 2, wherein the colloidal quantum dot solution is a sulfide semiconducting quantum dot solution or an oxide semiconducting quantum dot solution.
4. The stretchable semiconducting resistive flexible gas sensor of claim 3, wherein the sulfide semiconductor quantum dot solution is a PbS quantum dot solution and the oxide semiconductor quantum dot solution is SnO2ZnO or WO3A quantum dot solution.
5. A method of making a stretchable semiconductor resistive flexible gas sensor according to claim 1, comprising the steps of:
(1) pre-stretching a polyacrylate double-sided foam adhesive tape in a single direction to a certain degree and fixing the polyacrylate double-sided foam adhesive tape on a rigid substrate to form a flexible insulating substrate;
(2) preparing graphene paper on cellulose filter paper by adopting a vacuum filtration method, and transferring the graphene paper serving as a sensor electrode onto a flexible insulating substrate to prepare a patterned graphene electrode;
(3) coating the colloidal quantum dot solution on a pre-stretched flexible insulating substrate attached with a patterned graphene electrode to form a colloidal quantum dot film on the flexible insulating substrate;
(4) treating the colloidal quantum dot film by using a short-chain ligand solution to remove the surface-coated long-chain oleic acid oleylamine ligand, and removing residual short-chain ligand and byproducts thereof by using methanol;
(5) and (4) performing retraction treatment on the flexible insulating substrate processed in the step (4) to obtain the stretchable semiconductor resistance type flexible gas sensor with the micro-wrinkled film structure.
6. The method of claim 5, wherein the polyacrylate double sided foam tape has a degree of uniaxial tension of 0 to 200%.
7. The preparation method according to claim 5 or 6, wherein in the step (2), the graphene electrode is prepared by a suction filtration method, and the concentration of the graphene solution used in the suction filtration is 5-10mg/100 mL.
8. The method of claim 5, wherein in step (4), the short-chain ligand solution is CuCl2、ZnCl2、AgNO3、Cu(NO3)2、NH4Cl or NaNO2Solution, or NH4Cl、NaNO2The mixed solution of (1).
9. The production method according to claim 5, wherein in the step (5), the retracting treatment is performed at a rate of 0.5cm/s to 2 cm/s.
10. The method of claim 9, wherein the retraction treatment is performed at a rate of 1 cm/s.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710007556.7A CN106814110B (en) | 2017-01-05 | 2017-01-05 | Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710007556.7A CN106814110B (en) | 2017-01-05 | 2017-01-05 | Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106814110A CN106814110A (en) | 2017-06-09 |
| CN106814110B true CN106814110B (en) | 2020-11-06 |
Family
ID=59109434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710007556.7A Active CN106814110B (en) | 2017-01-05 | 2017-01-05 | Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106814110B (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108007810B (en) * | 2017-11-10 | 2021-06-11 | 华中科技大学 | QCM chemical sensor and preparation method thereof |
| CN108333227B (en) * | 2018-01-12 | 2021-03-23 | 五邑大学 | Flexible gas sensor and preparation method thereof |
| CN108898953B (en) * | 2018-07-04 | 2020-12-22 | 京东方科技集团股份有限公司 | Preparation method of flexible display panel, flexible display panel and display device |
| CN111351773B (en) * | 2018-12-21 | 2022-12-20 | 中国科学院苏州纳米技术与纳米仿生研究所 | Gas sensor based on swelling dynamic response and preparation method thereof |
| CN109781947B (en) * | 2019-02-27 | 2021-01-19 | 华中科技大学 | Electronic nose chip based on quantum dots and design method thereof |
| CN110081810B (en) * | 2019-05-24 | 2024-03-01 | 清华大学深圳研究生院 | Flexible tensile strain sensor and preparation method thereof |
| CN110095211B (en) * | 2019-05-24 | 2023-12-19 | 清华大学深圳研究生院 | Stretchable touch sensor array and preparation method thereof |
| CN110284210B (en) * | 2019-06-17 | 2022-04-05 | 深圳第三代半导体研究院 | Flexible stretchable fiber with internal microstructure and preparation method and application thereof |
| CN110702147A (en) * | 2019-09-09 | 2020-01-17 | 江苏大学 | Flexible stretchable sensor and preparation method and application thereof |
| CN110579511A (en) * | 2019-09-30 | 2019-12-17 | 上海纳米技术及应用国家工程研究中心有限公司 | method for constructing high-sensitivity nitrogen dioxide gas sensor based on Van der Waals junction film |
| CN110702744B (en) * | 2019-10-17 | 2020-06-19 | 山东交通学院 | Special treatment device and sensing system for ship tail gas |
| CN111537575A (en) * | 2020-06-19 | 2020-08-14 | 河北工业大学 | Self-heatable laser-induced graphene flexible NO2Preparation method of gas sensor |
| WO2022014134A1 (en) * | 2020-07-16 | 2022-01-20 | 国立大学法人信州大学 | Gas sensor member and production method thereof, gas sensor, gas detection method, and micro amount gas detection method |
| CN112358874A (en) * | 2020-11-13 | 2021-02-12 | 浙江理工大学 | Preparation method of composite material with surface patterned quantum dots |
| CN113552295A (en) * | 2021-08-19 | 2021-10-26 | 电子科技大学 | Controllable growth lead sulfide composite film gas sensor and preparation method thereof |
| CN113834862B (en) * | 2021-09-17 | 2023-05-30 | 电子科技大学 | Method for regulating/enhancing sensitivity of self-driven flexible gas sensor by interface stress |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137900A (en) * | 2005-01-24 | 2008-03-05 | 住友电气工业株式会社 | Method of manufacturing sensor chip, and the sensor chip |
| CN103033537A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of gas sensor sensitive film based on flexible substrate |
| CN103033538A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of sensitive film based on flexible substrate for detecting gas at normal temperature |
| CN103308560A (en) * | 2013-06-04 | 2013-09-18 | 中国科学院微电子研究所 | Room temperature detection NH3Method for manufacturing gas sensor |
| CN103336027A (en) * | 2013-06-05 | 2013-10-02 | 中国科学院微电子研究所 | NO for room temperature detection2Method for manufacturing gas sensor |
| CN103969308A (en) * | 2014-05-05 | 2014-08-06 | 上海师范大学 | Printed NO2 gas sensitive element capable of working at room temperature and preparation method thereof |
| CN103995025A (en) * | 2014-05-16 | 2014-08-20 | 上海师范大学 | Printed type graphene-based NO2 gas-sensitive element and preparation method thereof |
| CN104391006A (en) * | 2014-11-13 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Preparation method of gas sensor |
| CN104502412A (en) * | 2014-12-08 | 2015-04-08 | 中国石油大学(华东) | Graphene-based ammonia sensitive material and preparation method thereof |
| CN104614413A (en) * | 2015-02-09 | 2015-05-13 | 华中科技大学 | Electrodeless semiconductor gas sensor and preparation method thereof |
| CN104764779A (en) * | 2015-04-09 | 2015-07-08 | 山东师范大学 | Preparation method of flexible gas-sensitive sensor with spongy graphene/zinc oxide mixed structure |
| CN105067682A (en) * | 2015-08-19 | 2015-11-18 | 东南大学 | Flexible capacitive humidity sensor and preparation method thereof |
| CN105319241A (en) * | 2014-07-04 | 2016-02-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible gas-sensitive sensor and making method thereof |
| CN105699426A (en) * | 2014-11-26 | 2016-06-22 | 中航商用航空发动机有限责任公司 | Method and apparatus for preparing gas sensor |
| CN105758909A (en) * | 2016-02-26 | 2016-07-13 | 武汉大学 | Gold nanotube based flexible stretchable electrode and preparation method and application thereof |
| GB2534808A (en) * | 2013-10-22 | 2016-08-03 | Jentek Sensors Inc | Method and apparatus for measurement of material condition |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11366077B2 (en) * | 2010-09-10 | 2022-06-21 | The Trustees Of Dartmouth College | Systems, sensing devices and methods for detection of airborne contaminants |
| CA2833897C (en) * | 2011-05-09 | 2020-05-19 | Advanced Liquid Logic, Inc. | Microfluidic feedback using impedance detection |
| US11371951B2 (en) * | 2012-09-27 | 2022-06-28 | Sensirion Ag | Gas sensor comprising a set of one or more sensor cells |
| CN103323498B (en) * | 2013-07-09 | 2015-03-25 | 山东师范大学 | Resistance type relative humidity sensor based on graphene carbon nanotube composite material |
| CN103675034B (en) * | 2013-11-29 | 2016-05-25 | 华中科技大学 | A kind of semi-conductor electricity resistive gas sensor and preparation method thereof |
| CN104569078A (en) * | 2015-01-29 | 2015-04-29 | 重庆墨希科技有限公司 | Flexible graphene nano wall resistance-type humidity sensor and preparation method thereof |
| CN104807861B (en) * | 2015-04-09 | 2017-05-24 | 山东师范大学 | Preparation method of spongy graphene-based stretchable gas sensor |
| CN106290507A (en) * | 2016-07-31 | 2017-01-04 | 西南大学 | Use novel can spray printing titanium carbide/graphene oxide composite material method of preparing hydrogen peroxide electrochemical sensor |
-
2017
- 2017-01-05 CN CN201710007556.7A patent/CN106814110B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137900A (en) * | 2005-01-24 | 2008-03-05 | 住友电气工业株式会社 | Method of manufacturing sensor chip, and the sensor chip |
| CN103033537A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of gas sensor sensitive film based on flexible substrate |
| CN103033538A (en) * | 2012-12-20 | 2013-04-10 | 中国科学院微电子研究所 | Preparation method of sensitive film based on flexible substrate for detecting gas at normal temperature |
| CN103308560A (en) * | 2013-06-04 | 2013-09-18 | 中国科学院微电子研究所 | Room temperature detection NH3Method for manufacturing gas sensor |
| CN103336027A (en) * | 2013-06-05 | 2013-10-02 | 中国科学院微电子研究所 | NO for room temperature detection2Method for manufacturing gas sensor |
| GB2534808A (en) * | 2013-10-22 | 2016-08-03 | Jentek Sensors Inc | Method and apparatus for measurement of material condition |
| CN103969308A (en) * | 2014-05-05 | 2014-08-06 | 上海师范大学 | Printed NO2 gas sensitive element capable of working at room temperature and preparation method thereof |
| CN103995025A (en) * | 2014-05-16 | 2014-08-20 | 上海师范大学 | Printed type graphene-based NO2 gas-sensitive element and preparation method thereof |
| CN105319241A (en) * | 2014-07-04 | 2016-02-10 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible gas-sensitive sensor and making method thereof |
| CN104391006A (en) * | 2014-11-13 | 2015-03-04 | 无锡信大气象传感网科技有限公司 | Preparation method of gas sensor |
| CN105699426A (en) * | 2014-11-26 | 2016-06-22 | 中航商用航空发动机有限责任公司 | Method and apparatus for preparing gas sensor |
| CN104502412A (en) * | 2014-12-08 | 2015-04-08 | 中国石油大学(华东) | Graphene-based ammonia sensitive material and preparation method thereof |
| CN104614413A (en) * | 2015-02-09 | 2015-05-13 | 华中科技大学 | Electrodeless semiconductor gas sensor and preparation method thereof |
| CN104764779A (en) * | 2015-04-09 | 2015-07-08 | 山东师范大学 | Preparation method of flexible gas-sensitive sensor with spongy graphene/zinc oxide mixed structure |
| CN105067682A (en) * | 2015-08-19 | 2015-11-18 | 东南大学 | Flexible capacitive humidity sensor and preparation method thereof |
| CN105758909A (en) * | 2016-02-26 | 2016-07-13 | 武汉大学 | Gold nanotube based flexible stretchable electrode and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "A novel flexible acetylene gas sensor based on PI/PTFE-supported Ag-loaded vertical ZnO nanorods array";A.S.M.Iftekhar Uddin et al.;《Sensors and Actuators B: Chemical》;20150828;第222卷;第536-543页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106814110A (en) | 2017-06-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106814110B (en) | Stretchable semiconductor resistance type flexible gas sensor and preparation method thereof | |
| Zhang et al. | PEDOT: PSS: From conductive polymers to sensors | |
| Cuong et al. | Solution-processed ZnO-chemically converted graphene gas sensor | |
| CN110108375B (en) | MXene material-based electronic skin and preparation method thereof | |
| Song et al. | Characterization of electrospun ZnO–SnO2 nanofibers for ethanol sensor | |
| Lim et al. | A facile approach towards ZnO nanorods conductive textile for room temperature multifunctional sensors | |
| CN103871548B (en) | A kind of flexible transparent film electrode and preparation method thereof | |
| Song et al. | A highly sensitive ethanol sensor based on mesoporous ZnO–SnO2 nanofibers | |
| Hong et al. | Controllable growth of oriented ZnO nanorods using Ga-doped seed layers and surface acoustic wave humidity sensor | |
| Quan et al. | A flexible sensor based on polyaniline hybrid using ZnO as template and sensing properties to triethylamine at room temperature | |
| Shukla et al. | Fabrication of electro-chemical humidity sensor based on zinc oxide/polyaniline nanocomposites | |
| CN103675034A (en) | Semiconductor resistance-type gas sensor and preparation method thereof | |
| WO2015179320A1 (en) | Flexible sensor apparatus | |
| Zhang et al. | Fully embedded CuNWs/PDMS conductor with high oxidation resistance and high conductivity for stretchable electronics | |
| KR20130000786A (en) | Stable graphene film and preparing method of the same | |
| CN110396006B (en) | ZIF-8 film coated SnO2Composite gas-sensitive material and preparation method and application thereof | |
| Eom et al. | Single fiber UV detector based on hydrothermally synthesized ZnO nanorods for wearable computing devices | |
| Foo et al. | Au decorated ZnO thin film: application to DNA sensing | |
| Zhao et al. | Development of solution processible organic-inorganic hybrid materials with core-shell framework for humidity monitoring | |
| CN103469202A (en) | Method for manufacturing gas-sensitive composite nanometer film | |
| Ko et al. | High durability conductive textile using MWCNT for motion sensing | |
| KR101651108B1 (en) | Fabrication method for electrode using sensor and the sensor thereby | |
| Hsueh et al. | A flexible ZnO nanowire-based humidity sensor | |
| Mahmoodian et al. | Effect of anionic dopants on thickness, morphology and electrical properties of polypyrrole ultra-thin films prepared by in situ chemical polymerization | |
| Pawar et al. | 2D nanomaterials for realization of flexible and wearable gas sensors: A review |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |