CN107817271B - Preparation method of humidity sensitive device - Google Patents
Preparation method of humidity sensitive device Download PDFInfo
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- CN107817271B CN107817271B CN201711043470.6A CN201711043470A CN107817271B CN 107817271 B CN107817271 B CN 107817271B CN 201711043470 A CN201711043470 A CN 201711043470A CN 107817271 B CN107817271 B CN 107817271B
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Abstract
The invention provides a preparation method of a humidity sensitive device, and belongs to the field of preparation of sensing functional devices. The invention relates to a method for preparing a humidity sensitive device, which comprises the following steps: the method comprises the following steps: dropwise adding graphene oxide with the concentration of 3-5mg/mL prepared by a 30-microliter Hummer method between channels of metal electrodes; step two: naturally airing the metal electrode at room temperature; step three: under high humidity, the graphene oxide between metal electrode channels is asymmetrically reduced by applying voltage to the aired metal electrodes, and the device with the gradient distribution of the concentration of oxygen-containing functional groups of the graphene oxide is obtained. The invention relates to a preparation method of a non-contact man-machine interaction humidity sensitive functional device which has high sensitivity and can work independently without depending on external voltage, and is mainly used for detecting humidity signals.
Description
Technical Field
The invention relates to a preparation method of a humidity sensitive device, belonging to the field of preparation of sensing functional devices.
Background
Graphene Oxide (GO) contains abundant oxygen-containing functional groups such as hydroxyl, carboxyl, epoxy groups and the like on the surface and the edge, and has potential application in the fields of electricity, energy-related equipment and intelligent systems. The graphene oxide has high sensitivity to moisture, the oxygen-containing functional group of the graphene oxide can be subjected to hydration protonation under high humidity, and the epoxy group on the surface can form a hydrated proton transmission network, so that excellent proton conductivity is embodied.
The graphene oxide film assembled on the gas-liquid interface by people including Suzhou nanotechnology of Chinese academy of sciences and nephelometric institute Zhang can sense the three-dimensional distribution condition of a humidity source on the surface of a device array, but the device must work under certain external operating voltage, the sensitivity of the device is about 35%, and the lower sensitivity is caused by higher background current. Recent research shows that a humidity stimulus response system which can work without external voltage can be constructed by changing the gradient distribution of the concentration of the oxygen-containing functional groups of the graphene oxide.
Researches by the Quliang body of Beijing university of Physician and the like find that the moisture nano-generator prepared by taking the graphene oxide as the material can induce the change of external humidity without applying bias voltage and output an electrical signal. According to the change of the external humidity, the strength of the output electrical signal is changed accordingly. However, the reported graphene oxide-based humidity power generation research utilizes a sandwich type device structure, and the hydrated protons encounter great hindrance when crossing the graphene stacked sheets, so that the generated power and humidity response performance of the device are limited.
Research of the subject group of Ajayan, P.M. in the United states shows that the proton conductivity of the graphene oxide has anisotropy, and the in-plane conductivity is about 250 times larger than that of the cross-plane mode.
Disclosure of Invention
The invention aims to solve the problems in the prior art, and further provides a method for preparing a humidity sensitive device, which is a method for preparing a non-contact man-machine interaction humidity sensitive functional device which is high in sensitivity and can work independently of external voltage.
The purpose of the invention is realized by the following technical scheme:
a method for preparing a humidity sensitive device comprises the following steps:
the method comprises the following steps: dropwise adding graphene oxide with the concentration of 3-5mg/mL prepared by a 30-microliter Hummer method between channels of metal electrodes;
step two: naturally airing the metal electrode at room temperature;
step three: under high humidity, the graphene oxide between metal electrode channels is asymmetrically reduced by applying voltage to the aired metal electrodes, and the device with the gradient distribution of the concentration of oxygen-containing functional groups of the graphene oxide is obtained.
According to the preparation method of the humidity sensitive device, the micron width range of the metal electrode is 100-400 microns.
The invention relates to a preparation method of a humidity sensitive device, which responds to the humidity of the surface of a finger within a distance of 2 millimeters under the voltage of 0 volt.
The invention relates to a preparation method of a humidity sensitive device, which detects humidity signals by sensing voltage and current change values of a humidity source in the horizontal and vertical directions of the surface of a device array.
The invention relates to a method for preparing a humidity sensitive device, which is of a planar structure.
The method has the obvious advantages that the preparation steps are simple, the environment is protected, the used raw materials are all cheap and environment-friendly substances, the repeatability of the obtained humidity sensor is high, the humidity sensor is not required to be driven by external voltage, and the humidity sensor has excellent and stable output voltage and current and high sensitivity.
Drawings
FIG. 1 is a schematic diagram of a method for manufacturing a humidity sensitive device 5 × 5 array electrode according to the present invention;
FIG. 2 is a current-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 3 is a voltage-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 4 is a current-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 5 is a voltage-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 6 is a current-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 7 is a voltage-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 8 is a current-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 9 is a voltage-time diagram of a humidity sensitive device according to the second embodiment;
FIG. 10 is a graph of induced current versus time for different humidity source distances for the humidity sensitive device of the fourth embodiment;
FIG. 11 is a graph of voltage versus time induced by the humidity sensitive device for different humidity source distances in accordance with the fourth embodiment;
FIG. 12 is a three-dimensional response graph of a finger with 5 × 5 array electrodes on the surface of a device in the fifth embodiment;
FIG. 13 is a Raman diagram of a humidity sensitive device according to a seventh embodiment;
FIG. 14 is an enlarged view of the Raman spectrum peak position of the humidity sensitive device in the seventh embodiment;
FIG. 15 shows examples of the asymmetric reduction of the humidity sensitive device before and after ID/IGComparing the variation trends;
Detailed Description
The invention will be described in further detail below with reference to the accompanying drawings: the present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation is given, but the scope of the present invention is not limited to the following embodiments.
The first embodiment is as follows: as shown in fig. 1, the method for manufacturing a humidity sensitive device according to this embodiment includes the following steps:
the method comprises the following steps: dropwise adding graphene oxide with the concentration of 3-5mg/mL prepared by a 30-microliter Hummer method between channels of metal electrodes;
step two: naturally airing the metal electrode at room temperature;
step three: under high humidity, the graphene oxide between metal electrode channels is asymmetrically reduced by applying voltage to the aired metal electrodes, and the device with the gradient distribution of the concentration of oxygen-containing functional groups of the graphene oxide is obtained.
Example two: as shown in fig. 2 to fig. 9, in the method for manufacturing a humidity sensitive device according to the present embodiment, the micrometer width of the metal electrode is in a range of 100 to 400 μm.
In this example, when the width of the selected electrode channel is 100 μm, the specific preparation steps are as follows:
and dropwise adding the graphene oxide prepared by the 30-microliter Hummer method between copper electrode channels with the width of 100 microns, naturally airing, and applying voltage under high humidity to asymmetrically reduce the graphene oxide to obtain the device with the oxygen-containing functional group in gradient distribution. Applying 0V voltage and testing the humidity response current; a current of 0A was applied and the humidity response voltage was tested.
As shown in FIG. 2, the humidity response average current density of 3.802 μ A/cm for the device prepared in this example2。
As shown in FIG. 3, the humidity response of the device prepared in this example was 10.25 mV.
In this example, when the width of the selected electrode channel is 200 μm, the specific preparation steps are as follows:
and dropwise adding the graphene oxide prepared by the 30-microliter Hummer method between copper electrode channels with the width of 200 microns, naturally airing, and applying voltage under high humidity to asymmetrically reduce the graphene oxide to obtain the device with the oxygen-containing functional group in gradient distribution. Applying 0V voltage and testing the humidity response current; a current of 0A was applied and the humidity response voltage was tested.
As shown in FIG. 4, the humidity response average current density of the device prepared in this example was 1.097 μ A/cm2。
As shown in FIG. 5, the devices prepared in this example responded with an average humidity response voltage of 10.479 mV.
In this example, when the width of the selected electrode channel is 300 μm, the specific preparation steps are as follows:
and dropwise adding the graphene oxide prepared by the 30-microliter Hummer method between copper electrode channels with the width of 300 microns, naturally airing, and applying voltage under high humidity to asymmetrically reduce the graphene oxide to obtain the device with the oxygen-containing functional group in gradient distribution. Applying 0V voltage and testing the humidity response current; a current of 0A was applied and the humidity response voltage was tested.
As shown in FIG. 6, the devices prepared in this example had an average humidity responseThe current density is 2.93 mu A/cm2。
As shown in FIG. 7, the devices prepared in this example responded with an average humidity response voltage of 30.399 mV.
In this example, when the width of the selected electrode channel is 400 μm, the specific preparation steps are as follows:
and dropwise adding the graphene oxide prepared by the 30-microliter Hummer method between copper electrode channels with the width of 400 microns, naturally airing, and applying voltage under high humidity to asymmetrically reduce the graphene oxide to obtain the device with the oxygen-containing functional group in gradient distribution. Applying 0V voltage and testing the humidity response current; a current of 0A was applied and the humidity response voltage was tested.
As shown in FIG. 8, the humidity responsive average current density of the device prepared in this example was 0.949 μ A/cm2。
As shown in fig. 9, the devices prepared in this example responded with an average humidity response voltage of 10.447 mV.
Example three: as shown in fig. 1, the present embodiment relates to a method for manufacturing a humidity sensitive device, which responds to the humidity on the surface of a finger within a distance of 2 mm at a voltage of 0 volt. The humidity sensitive device can sense the humidity of the finger surface 2 mm away from the graphene oxide surface under the condition of applying 0 volt voltage, and a humidity signal is measured in a non-contact mode.
Example four: as shown in fig. 10 and 11, in the method for manufacturing a humidity sensitive device according to this embodiment, a sample used for analyzing the sensing capability test of the humidity sensitive device for humidity sources at different distances is a device with an electrode channel width of 300 μm.
As can be seen from fig. 10, the current value gradually increases as the humidity source distance decreases.
As can be seen from fig. 11, as the humidity source distance decreases, the voltage value gradually increases.
Fifth embodiment as shown in fig. 1 and 12, the present embodiment relates to a method for manufacturing a humidity sensitive device, which detects humidity signals by sensing voltage and current variation values of a humidity source in horizontal and vertical directions of a device array surface, and the 5 × 5 array electrode is specifically manufactured by the following steps:
and (3) using PET as a substrate, constructing a bottom copper electrode by adopting a thermal evaporation method, pasting a PDMS strip to prevent short circuit, constructing a top electrode by adopting the thermal evaporation method again to obtain a 5 × 5 array electrode, wherein the width of a channel of each pixel site is 300 mu m, dripping 2 mu L of graphene oxide aqueous solution into each site, and naturally drying.
Obtaining a three-dimensional response graph according to voltage values and current change values (namely response signals) in the metal electrodes in the horizontal (X-axis) direction and the vertical (Y-axis) direction; according to the fact that graphene oxide in a channel has high sensitivity to moisture, oxygen-containing functional groups in the graphene oxide are subjected to hydration protonation under high humidity, epoxy groups on the surface of the graphene oxide can form a hydrated proton transmission network, so that hydrated protons can carry out current transmission, and the positions of humidity sources are determined according to different distances between the humidity sources and pixel sites and different magnitudes of output electric signals.
Example six: as shown in fig. 1, the present embodiment relates to a method for manufacturing a humidity sensitive device, wherein the device has a planar structure. A transmission channel is established through a planar structure, and the traditional high-barrier cross-surface transmission mode is replaced, so that pulse voltage and current can be generated in the humidity change process.
Example seven: as shown in fig. 10, 11, 13, 14 and 15, in the method for manufacturing a humidity sensitive device according to this embodiment, a LabRAMXploRA raman spectrometer of HORIBA is used, the laser wavelength is 532nm, the power is 1Mw, and the reduction degree of graphene oxide is analyzed; the devices were subjected to electrical property analysis test using a semiconductor tester model 4200-SCS from KEITHLEY.
And analyzing the reduction degree of the graphene oxide, and obtaining a drawing of the humidity sensitive device by a Raman spectrometer. In FIGS. 13 and 14, 1-5 are 5 points from 1 to 5 points I in a straight line from the cathode to the anode of the deviceD/IGThe intensity ratio of the D peak near 1375 wavenumber to the G peak near 1590 wavenumber is gradually increased, which shows that the reduction degree is gradually increased, the asymmetric reduction effect is better, and the gradient change of the oxygen-containing functional group is constructed. FIG. 14 is an enlarged view of the peak position of the Raman spectrum for easy observation of ID/IGA trend of the value change.
FIG. 15 is I in Raman diagram before and after asymmetric reduction of humidity sensitive deviceD/IGComparative value diagram of original graphene oxide film ID/IGValue is basically unchanged, I after asymmetric reductionD/IGThe values gradually increased, demonstrating the successful construction of a gradient of oxygen-containing functional groups.
The above description is only a preferred embodiment of the present invention, and these embodiments are based on different implementations of the present invention, and the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (4)
1. A method for preparing a humidity sensitive device is characterized by comprising the following steps:
the method comprises the following steps: dropwise adding graphene oxide (3) with the concentration of 3-5mg/mL, which is prepared by a 30-microliter Hummer method, between channels (2) of metal electrodes (1);
step two: naturally airing the metal electrode (1) at room temperature;
step three: under high humidity, applying voltage to an air-dried metal electrode (1) to asymmetrically reduce graphene oxide (3) between metal electrode channels (2) to obtain a device with gradient distribution of oxygen-containing functional groups of the graphene oxide (3);
the device is of a planar structure and does not need to be driven by external voltage.
2. The method for preparing a humidity sensitive device according to claim 1, wherein the micrometer width of the metal electrode (1) is in the range of 100-400 μm.
3. The method of making a humidity sensitive device according to claim 1 wherein the device responds to humidity on the surface of a finger within a distance of 2 mm at 0 volts.
4. The method of claim 1, wherein the device detects the humidity signal by sensing voltage and current variation values of the humidity source in horizontal and vertical directions of the device array surface.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104749232A (en) * | 2015-03-09 | 2015-07-01 | 中南大学 | Manufacture method of detection electrode of micro-fluidic chip and preparation of electrophoresis non-contact type conductivity detection system |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104749232A (en) * | 2015-03-09 | 2015-07-01 | 中南大学 | Manufacture method of detection electrode of micro-fluidic chip and preparation of electrophoresis non-contact type conductivity detection system |
Non-Patent Citations (4)
| Title |
|---|
| "Direct Power Generation from a Graphene Oxide Film under Moisture";Fei Zhao等;《Advanced Materials》;20150805;第27卷(第29期);第4351页 * |
| "Exfoliation at the Liquid/Air Interface to Assemble Reduced Graphene Oxide Ultrathin Film for a Flexible Noncontact Sensing Device";Xuewen Wang等;《Advanced Materials》;20150225;第27卷(第8期);第1370-1374页、图3 * |
| "Highly efficient moisture-enabled electricity generation from graphene oxide frameworks";Fei Zhao等;《Energy Environmental Science》;20160930;第912-916页 * |
| "氧化石墨烯组装结构的湿气发电";赵飞等;《中国化学会第30届学术年会-第四十一分会：纳米材料与器件》;20160701;全文 * |
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