CN106932442A - A kind of ZnO nano wall RGO heterojunction photovoltaic gas sensors and preparation method thereof - Google Patents
A kind of ZnO nano wall RGO heterojunction photovoltaic gas sensors and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to light-sensitive detector preparation method technical field, and in particular to a kind of ZnO nano wall RGO heterojunction photovoltaic gas sensors and preparation method thereof.The present invention uses following steps：1）The preparation of porous reduced graphene；2）ZnO Seed Layers are grown in RGO surface in situ；3）ZnO nano wall is grown in RGO surface in situ；4）Aging finished product realizes its technical scheme to overcome light sensitivity and NO under normal temperature condition in the prior art2The low problem of sensitivity.
Description
First, technical field
The present invention relates to light-sensitive detector preparation method technical field, and in particular to a kind of ZnO nano wall RGO hetero-junctions light
Electric dependent sensor and preparation method thereof.
2nd, background technology：
Energy gap is 3.37eV to metal oxide semiconductor material ZnO at normal temperatures, is direct band-gap semicondictor, while
Its exciton bind energy is very big, about 60meV.After purple light excited, photo-generate electron-hole pair is produced, conductance increases；Meanwhile,
Light induced electron or hole are induced to semiconductor surface and redox reaction occur with the gas molecule of absorption, and this process also can
There is the change of conductance.Therefore, this has established good base for ZnO in the application of light-sensitive detector and Photo-electric gas-sensitivity sensor
Plinth[1,3]！
But, it is good, external that current prepared ZnO Photo-electric gas-sensitivities sensor cannot meet high adsorption capacity, photosensitive property
The a series of properties such as boundary's gas sensitization, good stability requirement, in order to solve this problem, there has been proposed metal ion mixing,
Surface modification noble metal (such as modification of Au, Ag, Pt), surface modification light sensitive material, composite such as construct at the method.Wherein
Composite is constructed except SnO2-ZnO、Fe2O3Beyond the composites such as-ZnO, ZnO-CuO are constructed；Graphene and CNT
There are good charge transport properties Deng material, also be used to form composite with ZnO[2,4,5]。
S.Safa etc. is prepared for rGO-ZnO photo-detectors and have studied its performance using dipping-pulling method, is sent out by studying
The existing sensitivity of pure ZnO, 0.0125wt.%, 0.025wt.%, 0.075wt.%, 0.225wt.% to purple light is respectively 2,3,
3rd, 4,2.5, it can thus be concluded that, the luminous sensitivity of rGO-ZnO is better than pure ZnO[6]；Wang Dejun etc. is led to based on ZnO nano material
Overdoping method is prepared for Photo-electric gas-sensitivity sensor, and the zinc oxide film performance for obtaining 1% Copper-cladding Aluminum Bar by detection is best, in purple
Outer light is excited, under room temperature condition to 1120ppm ethanol and acetone response intensity be 64,63, higher than the response intensity of pure ZnO, copper
The incorporation of element can promote the absorption of volatile organic matter[2]；Bin Wu etc. utilize aqua-solution method and chemical vapour deposition technique system
Standby ZnO-CdSe hetero-junctions, under the conditions of 160 DEG C of optimum working temperature, radiation of visible light, the sensitivity to 50ppm alcohol is
7.5[7]；Xie Tengfeng, Cui Jiabao etc. obtain research Ag and modify ZnO under room temperature, 370nm illumination conditions to 40ppm by research
The sensitivity of HCHO is 119.8%, is 3 times of pure ZnO, and in addition, they obtain Al ion doping zinc oxide by research
Sensitivity to 50ppm HCHO under room temperature, 370nm illumination conditions is 261.8%, is 3 times of pure zinc oxide[5]。
By it is reported above can draw it is electric through overdoping, the zno-based light-sensitive detector constructed of modification composite and light
Compared with pure ZnO, performance increases dependent sensor, but light sensitivity and NO2Sensitivity is still relatively low.
3rd, the content of the invention
It is an object of the invention to provide a kind of ZnO nano wall RGO heterojunction photovoltaic gas sensors and preparation method thereof, with
Overcome light sensitivity and NO under normal temperature condition in the prior art2The low problem of sensitivity.
To achieve the above object, the technical solution adopted by the present invention is：A kind of ZnO nano wall RGO heterojunction photovoltaic air-sensitives
The preparation method of sensor, comprises the following steps：
1) preparation of porous reduced graphene
The porous graphene powder of 2-8mg is weighed respectively, it is mixed with the DMF of 10ml, be configured to concentration for 0.2-
0.8mg/ml porous graphene-DMF suspension, seals above-mentioned suspension with multilayer preservative film, at room temperature discontinuously afterwards
Ultrasonically treated 72h, obtains porous graphene dispersion liquid, is stood through 24h, by rotating speed for 4000r/min carries out centrifugal treating, so
Supernatant liquid is drawn afterwards in clear glass bottle, obtains porous graphene dispersing solution；By Ag interdigital electrodes respectively in acetone, anhydrous second
Alcohol, is cleaned by ultrasonic in deionized water, is then placed in the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；Take 1ml configured
Good porous graphene dispersion liquid, using nozzle diameter for the spray gun spraying of 0.2mm is passing through the Ag interdigital electrode tables of pretreatment
Face, then the dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas, and 450 DEG C are carried out
Heat treatment 0.5h；
2) ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O mixes at ambient temperature with ethanol,
Make Zn2+Concentration is 0.2mol/L, is placed in water-bath, with magnetic stirring apparatus at 70 DEG C heating stirring 1h, obtain uniform molten
Liquid, by step 1) heat treatment after Ag interdigital electrodes lifted using SYDC-100 Best-Effort request machines, pull rate be 6000 μ
M/s, dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then it is being connected with the atmosphere of Ar gas shieldeds
It is heat-treated in program control high temperature furnace and is heat-treated 30min at 400 DEG C, obtains ZnO Seed Layers/RGO laminated films；
3) ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirrings
1h, after starting to occur muddy in solution, stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and
By step 2) ZnO Seed Layers/RGO laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water is rinsed and dried, and is finally heat-treated 1h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, in Ag forks
Refer to that electrode surface obtains ZnO nano wall/RGO films.
4) aging finished product：
By step 3) ZnO nano wall/RGO films for obtaining are placed on CGS-1TP intelligence air-sensitive analysis system thermal station samples
Area, adjusts two probes, makes its two end in contact with electrode slice, during room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) carry out under illumination condition aging, ageing time is 1.5h.
ZnO nano wall RGO heterojunction photovoltaic gas sensors obtained in described preparation method.
Compared with prior art, the invention has the advantages that and effect：The present invention has height in a low temperature of providing
The light-sensitive detector and NO of sensitivity2Photo-electric gas-sensitivity sensor, ZnO is wide bandgap semiconductor materials, and its energy gap is
3.37eV, the photoresponse to ultraviolet light is good；Additionally, porous reduced graphene has extraordinary electric conductivity, can quickly transmit
Carrier, it is to avoid photo-generate electron-hole occurs compound.Therefore, porous ZnO nm wall/RGO photoelectric sensors possess several below
The advantage of aspect：(1) it is high to photaesthesia degree, to the photosensitive of 365nm light it is 13.107 under 75 DEG C of operating temperatures, (2) are to NO2
High sensitivity, operating temperature be 75 DEG C, wavelength for the illumination condition of 365nm under to the NO of 50ppm2Sensitivity is up to
88.154, (3) good stability, (4) material is easily obtained, and (5) are with photosensitive and air-sensitive coupled characteristic；
Because the Graphene of sheet is nano material, agglomeration is easily produced, so the actual specific surface of Graphene
Product cannot all be consistent with electric conductivity with theoretical value, seriously constrain the application of Graphene.The present invention builds three-dimensional communication
Network loose structure, had both constructed the passage of electronics, heat energy and load effectively transmission, can effectively improve again graphene-based porous
The specific surface area of material and abundant avtive spot.
4th, illustrate：
Fig. 1 (a) be the ZnO nano wall/RGO for preparing of embodiment 1 operating temperature be 75 DEG C, irradiation power be 100%
365nm photosensitive response figures；
(b) be the ZnO nano wall/RGO for preparing of embodiment 1 operating temperature be 75 DEG C, irradiation power be 100%
To 50ppm NO under the conditions of 365nm light irradiations2Air-sensitive-photosensitive coupling response figure；
C () is to 365nm difference irradiation power illumination when ZnO nano wall/RGO operating temperatures prepared by example 1 are 75 DEG C
Photosensitive response figure；
D () is that ZnO nano wall/RGO prepared by embodiment 1 is 75 DEG C, 365nm difference irradiation power illumination in operating temperature
To 50ppm NO2Air-sensitive-photosensitive coupling response figure；
(e) be embodiment 1 prepare ZnO nano wall/RGO operating temperatures be 75 DEG C, the 365nm that irradiation power is 100%
To 5ppm-50ppm NO under the conditions of light irradiation2Air-sensitive-photosensitive coupling response figure；
F () is that ZnO nano wall/RGO prepared by example 1 is 100% at a temperature of different operating to 365nm, irradiation power
Photosensitive response figure, to 50ppm NO2Air-sensitive-photosensitive coupling response figure；
Fig. 2 (a) be the ZnO nano wall/RGO for preparing of embodiment 2 operating temperature be 75 DEG C, irradiation power be 100%
365nm photosensitive response figures；
(b) be the ZnO nano wall/RGO for preparing of embodiment 2 operating temperature be 75 DEG C, irradiation power be 100%
To 50ppm NO under the conditions of 365nm light irradiations2Air-sensitive-photosensitive coupling response figure；
Fig. 3 (a) be the ZnO nano wall/RGO for preparing of embodiment 3 operating temperature be 75 DEG C, irradiation power be 100%
365nm photosensitive response figures；
(b) be the ZnO nano wall/RGO for preparing of embodiment 3 operating temperature be 75 DEG C, irradiation power be 100%
To 50ppm NO under the conditions of 365nm light irradiations2Air-sensitive-photosensitive coupling response figure；
Fig. 4 (a) be the ZnO nano wall/RGO for preparing of embodiment 4 operating temperature be 75 DEG C, irradiation power be 100%
365nm photosensitive response figures；
(b) be the ZnO nano wall/RGO for preparing of embodiment 4 operating temperature be 75 DEG C, irradiation power be 100%
To 50ppm NO under the conditions of 365nm light irradiations2Air-sensitive-photosensitive coupling response figure；
Fig. 5 is the XRD of ZnO nano wall/RGO prepared by embodiment 1；
Fig. 6 (a) is the SEM figures of ZnO nano wall/RGO prepared by embodiment 1；
B () is the EDS figures of ZnO nano wall/RGO prepared by embodiment 1；
Fig. 7 (a) is the TEM figures of ZnO nano wall/RGO prepared by embodiment 1；
B () is the high power TEM figures of ZnO nano wall/RGO prepared by embodiment 1；
Fig. 8 is the UV figures of ZnO nano wall/RGO prepared by embodiment 1；
Fig. 9 is the surface photoelectricity flow graph of ZnO nano wall/RGO prepared by embodiment 1.
5th, specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
Embodiment one：A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensors, comprises the steps：
First, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) of 2mg is weighed respectively, by its DMF with 10ml
(DMF) mixes, and compound concentration suspends for 0.2mg/ml porous graphenes-DMF (DMF)
Liquid, seals above-mentioned suspension with multilayer preservative film afterwards, and discontinuous ultrasonically treated 72h, obtains porous graphene at room temperature
Dispersion liquid, stands through 24h, by rotating speed for 4000r/min carries out centrifugal treating, then draws supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；；By Ag interdigital electrodes respectively in acetone, absolute ethyl alcohol is carried out ultrasonic clear in deionized water
Wash, be put into the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；The configured good porous graphene dispersion liquids of 1ml are taken, with spray
The a diameter of 0.2mm spray guns of mouth (Japanese Lumina Science and Technology Ltd.) are sprayed on the Ag interdigital electrodes surface by pre-processing, so
The dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas afterwards, and 450 DEG C carry out hot place
Reason 0.5h；
2nd, ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethanol mixes at ambient temperature, makes Zn2+Concentration is 0.2mol/L, is placed in water-bath, is added at 70 DEG C with magnetic stirring apparatus
Thermal agitation 1h, obtains uniform solution.By step 1) heat treatment after g interdigital electrodes carried out using SYDC-100 Best-Effort requests machine
Lifting, pull rate is 6000 μm/s, and dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then
30min is heat-treated at 400 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, obtain ZnO Seed Layers/RGO multiple
Close film；
3rd, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirrings
1h, after starting to occur muddy in solution, stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and
By step 2) ZnO Seed Layers/RGO laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water is rinsed and dried, and is finally heat-treated 1h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, in Ag forks
Refer to that electrode surface obtains ZnO nano wall/RGO films；
4th, aging finished product：
ZnO nano wall/RGO films that step 3 is obtained are placed on CGS-1TP intelligence air-sensitive analysis system thermal station samples
Area, adjusts two probes, makes its two end in contact with electrode slice.During room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) carry out under illumination condition aging, ageing time is 1.5h.
Performance detection：
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the detection of photosensitive property, by old
The resistance of the sample of change fluctuates within the specific limits, now cuts off light source, and resistance rises, and light is reopened after 50s
Source, resistance is replied, and sensitivity S is defined as：S=Rg/Ra(RaRepresent resistance of the element under illumination condition, RgRepresent element cut-out
Resistance during power supply).ZnO nano wall/RGO is shown to photosensitive response figure such as Fig. 1 (a) that 365nm, irradiation power are 100%.
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
Survey, fluctuated within the specific limits by the resistance of aging sample, now inject NO2, while cutting off light source, resistance
Rise, gas tank is opened after 50s, while opening light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaRepresent element in sky
There are the resistance of illumination, R in gasgRepresent the resistance of element no light in tested gas).ZnO nano wall/the RGO of preparation exists
365nm, irradiation power be 100% light irradiation under the conditions of to 50ppm NO2The air-sensitive of room temperature-photosensitive coupling response figure such as Fig. 1
Shown in (b).
Embodiment 2：
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensors, comprises the steps：
First, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) of 4mg is weighed respectively, by its DMF with 10ml
(DMF) mixes, and compound concentration suspends for 0.4mg/ml porous graphenes-DMF (DMF)
Liquid, seals above-mentioned suspension with multilayer preservative film afterwards, and discontinuous ultrasonically treated 72h, obtains porous graphene at room temperature
Dispersion liquid, stands through 24h, by rotating speed for 4000r/min carries out centrifugal treating, then draws supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrodes respectively in acetone, absolute ethyl alcohol is cleaned by ultrasonic in deionized water,
It is put into the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；The configured good porous graphene dispersion liquids of 1ml are taken, nozzle is used
A diameter of 0.2mm spray guns (Japanese Lumina Science and Technology Ltd.) are sprayed on the Ag interdigital electrodes surface by pre-processing, then
The dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas, and 450 DEG C are heat-treated
0.5h；
2nd, ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethanol mixes at ambient temperature, makes Zn2+Concentration is 0.2mol/L, is placed in water-bath, is added at 70 DEG C with magnetic stirring apparatus
Thermal agitation 1h, obtains uniform solution.By step 1) heat treatment after g interdigital electrodes carried out using SYDC-100 Best-Effort requests machine
Lifting, pull rate is 6000 μm/s, and dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then
30min is heat-treated at 400 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, obtain ZnO Seed Layers/RGO multiple
Close film；
3rd, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirrings
1h, after starting to occur muddy in solution, stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and
By step 2) ZnO Seed Layers/RGO laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water is rinsed and dried, and is finally heat-treated 1h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, in Ag forks
Refer to that electrode surface obtains ZnO nano wall/RGO films；
4th, aging finished product：
ZnO nano wall/RGO films that step 3 is obtained are placed on CGS-1TP intelligence air-sensitive analysis system thermal station samples
Area, adjusts two probes, makes its two end in contact with electrode slice.During room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) carry out under illumination condition aging, ageing time is 1.5h.
Performance detection：
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the detection of photosensitive property, by old
The resistance of the sample of change fluctuates within the specific limits, now cuts off light source, and resistance rises, and light is reopened after 50s
Source, resistance is replied, and sensitivity S is defined as：S=Rg/Ra(RaRepresent resistance of the element under illumination condition, RgRepresent element cut-out
Resistance during power supply).ZnO nano wall/RGO is shown to photosensitive response figure such as Fig. 2 (a) that 365nm, irradiation power are 100%.
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
Survey, fluctuated within the specific limits by the resistance of aging sample, now inject NO2, while cutting off light source, resistance
Rise, gas tank is opened after 50s, while opening light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaRepresent element in sky
There are the resistance of illumination, R in gasgRepresent the resistance of element no light in tested gas).ZnO nano wall/the RGO of preparation exists
365nm, irradiation power be 100% light irradiation under the conditions of to 50ppm NO2The air-sensitive of room temperature-photosensitive coupling response figure such as Fig. 2
Shown in (b).
Embodiment 3：
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensors, comprises the steps：
First, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) of 6mg is weighed respectively, by its DMF with 10ml
(DMF) mixes, and compound concentration suspends for 0.6mg/ml porous graphenes-DMF (DMF)
Liquid, seals above-mentioned suspension with multilayer preservative film afterwards, and discontinuous ultrasonically treated 72h, obtains porous graphene at room temperature
Dispersion liquid, stands through 24h, by rotating speed for 4000r/min carries out centrifugal treating, then draws supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrodes respectively in acetone, absolute ethyl alcohol is cleaned by ultrasonic in deionized water,
It is put into the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；The configured good porous graphene dispersion liquids of 1ml are taken, nozzle is used
A diameter of 0.2mm spray guns (Japanese Lumina Science and Technology Ltd.) are sprayed on the Ag interdigital electrodes surface by pre-processing, then
The dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas, and 450 DEG C are heat-treated
0.5h；
2nd, ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethanol mixes at ambient temperature, makes Zn2+Concentration is 0.2mol/L, is placed in water-bath, is added at 70 DEG C with magnetic stirring apparatus
Thermal agitation 1h, obtains uniform solution.By step 1) heat treatment after g interdigital electrodes carried out using SYDC-100 Best-Effort requests machine
Lifting, pull rate is 6000 μm/s, and dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then
30min is heat-treated at 400 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, obtain ZnO Seed Layers/RGO multiple
Close film；
3rd, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirrings
1h, after starting to occur muddy in solution, stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and
By step 2) ZnO Seed Layers/RGO laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water is rinsed and dried, and is finally heat-treated 1h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, in Ag forks
Refer to that electrode surface obtains ZnO nano wall/RGO films；
4th, aging finished product：
ZnO nano wall/RGO films that step 3 is obtained are placed on CGS-1TP intelligence air-sensitive analysis system thermal station samples
Area, adjusts two probes, makes its two end in contact with electrode slice.During room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) carry out under illumination condition aging, ageing time is 1.5h.
Performance detection：
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the detection of photosensitive property, by old
The resistance of the sample of change fluctuates within the specific limits, now cuts off light source, and resistance rises, and light is reopened after 50s
Source, resistance is replied, and sensitivity S is defined as：S=Rg/Ra(RaRepresent resistance of the element under illumination condition, RgRepresent element cut-out
Resistance during power supply).ZnO nano wall/RGO is shown to photosensitive response figure such as Fig. 3 (a) that 365nm, irradiation power are 100%.
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
Survey, fluctuated within the specific limits by the resistance of aging sample, now inject NO2, while cutting off light source, resistance
Rise, gas tank is opened after 50s, while opening light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaRepresent element in sky
There are the resistance of illumination, R in gasgRepresent the resistance of element no light in tested gas).ZnO nano wall/the RGO of preparation exists
365nm, irradiation power be 100% light irradiation under the conditions of to 50ppm NO2The air-sensitive of room temperature-photosensitive coupling response figure such as Fig. 3
Shown in (b).
Embodiment 4：
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensors, comprises the steps：
First, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) of 8mg is weighed respectively, by its DMF with 10ml
(DMF) mixes, and compound concentration suspends for 0.8mg/ml porous graphenes-DMF (DMF)
Liquid, seals above-mentioned suspension with multilayer preservative film afterwards, and discontinuous ultrasonically treated 72h, obtains porous graphene at room temperature
Dispersion liquid, stands through 24h, by rotating speed for 4000r/min carries out centrifugal treating, then draws supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrodes respectively in acetone, absolute ethyl alcohol is cleaned by ultrasonic in deionized water,
It is put into the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；The configured good porous graphene dispersion liquids of 1ml are taken, nozzle is used
A diameter of 0.2mm spray guns (Japanese Lumina Science and Technology Ltd.) are sprayed on the Ag interdigital electrodes surface by pre-processing, then
The dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas, and 450 DEG C are heat-treated
0.5h；
2nd, ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethanol mixes at ambient temperature, makes Zn2+Concentration is 0.2mol/L, is placed in water-bath, is added at 70 DEG C with magnetic stirring apparatus
Thermal agitation 1h, obtains uniform solution.By step 1) heat treatment after g interdigital electrodes carried out using SYDC-100 Best-Effort requests machine
Lifting, pull rate is 6000 μm/s, and dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then
30min is heat-treated at 400 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, obtain ZnO Seed Layers/RGO multiple
Close film；
3rd, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirrings
1h, after starting to occur muddy in solution, stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and
By step 2) ZnO Seed Layers/RGO laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water is rinsed and dried, and is finally heat-treated 1h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, in Ag forks
Refer to that electrode surface obtains ZnO nano wall/RGO films,
4th, aging finished product：
ZnO nano wall/RGO films that step 3 is obtained are placed on CGS-1TP intelligence air-sensitive analysis system thermal station samples
Area, adjusts two probes, makes its two end in contact with electrode slice.During room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) carry out under illumination condition aging, ageing time is 1.5h.
Performance detection：
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the detection of photosensitive property, by old
The resistance of the sample of change fluctuates within the specific limits, now cuts off light source, and resistance rises, and light is reopened after 50s
Source, resistance is replied, and sensitivity S is defined as：S=Rg/Ra(RaRepresent resistance of the element under illumination condition, RgRepresent element cut-out
Resistance during power supply).ZnO nano wall/RGO is shown to photosensitive response figure such as Fig. 4 (a) that 365nm, irradiation power are 100%.
The light-sensitive detector and its Photo-electric gas-sensitivity sensor that are obtained to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
Survey, fluctuated within the specific limits by the resistance of aging sample, now inject NO2, while cutting off light source, resistance
Rise, gas tank is opened after 50s, while opening light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaRepresent element in sky
There are the resistance of illumination, R in gasgRepresent the resistance of element no light in tested gas).ZnO nano wall/the RGO of preparation exists
365nm, irradiation power be 100% light irradiation under the conditions of to 50ppm NO2The air-sensitive of room temperature-photosensitive coupling response figure such as Fig. 4
Shown in (b).
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtained with embodiment 1, carry out related experiment, as a result as follows：
The XRD of (a) ZnO nano wall/RGO
Referring to Fig. 5, ZnO nano wall/RGO along [002] direction preferential growth, and with crystalline quality higher.
SEM, EDS figure of (b) ZnO nano wall/RGO
Referring to Fig. 6, it is known that the ZnO nano wall/RGO with loose structure, the cycle is oriented along Ag interdigital electrodes vertical direction
Property aligned growth, schemed it can be seen that there is Zn by EDS, five kinds of elements such as O, C, Al, Ag, wherein Zn, O derives from ZnO, C sources
In the Al (NO that RGO, Al are used in raw material3)3, Ag is from Ag interdigital electrodes.
TEM, high power the TEM figure of (c) ZnO nano wall/RGO
Referring to Fig. 7, on the surface of RGO, this further proves that ZnO nano wall/RGO hetero-junctions is prepared into ZnO nano joist anchor
Work(.
The photosensitive and air-sensitive of (d) ZnO nano wall/RGO-photosensitive coupling effect figure
It can be seen from Fig. 1, the sensor prepared by embodiment 1 is to wavelength under under the conditions of operating temperature is for 75 DEG C
The sensitivity of 365nm light is 13.107, to the NO of 50ppm2Sensitivity is 88.154, and significantly larger than other document reports is sensitive
Degree.In addition, by the research to operating temperature, it can be deduced that with the rising of operating temperature, its sensitivity elder generation to light
Reduced after increasing, the sensitivity to detecting gas also changes therewith, and optimum value is obtained at 75 DEG C.Ground by illumination power
Study carefully, draw with the reduction of power, its sensitivity to light reduces, and the sensitivity to detecting gas also reduces therewith.
The UV figures of (e) ZnO nano wall/RGO
Referring to Fig. 8, ZnO nano wall/RGO has very strong absworption peak in 360nm.
The surface photoelectricity flow graph of (f) ZnO nano wall/RGO
It can be seen from Fig. 9, from 370nm to 300nm, photoelectric current is gradually reduced excitation wavelength, when excitation wavelength is 370nm,
Surface photoelectric current reaches maximum, is 19 × 10-12A, when wavelength is in 370nm to 394nm, photoelectric current is with wavelength increase
Reduce；When wavelength is located at 394nm to 500nm, there is faint photoelectric current to produce.
The above, only present pre-ferred embodiments are not intended to limit the scope of the present invention.
Claims (2)
1. a kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensors, it is characterised in that：Described preparation side
Method is comprised the following steps：
1）The preparation of porous reduced graphene
The porous graphene powder of 2-8mg is weighed respectively, it is mixed with the DMF of 10ml, be configured to concentration for 0.2-0.8mg/
Ml porous graphene-DMF suspension, seals above-mentioned suspension with multilayer preservative film afterwards, at room temperature at discontinuous ultrasound
Reason 72h, obtains porous graphene dispersion liquid, is stood through 24h, by rotating speed for 4000r/min carries out centrifugal treating, then draws
Supernatant liquid obtains porous graphene dispersing solution in clear glass bottle；By Ag interdigital electrodes respectively in acetone, absolute ethyl alcohol goes
It is cleaned by ultrasonic in ionized water, is then placed in the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；Take 1ml configured good
Porous graphene dispersion liquid, using nozzle diameter for the spray gun spraying of 0.2mm is passing through the Ag interdigital electrodes surface of pretreatment, so
The dried process at 110 DEG C, dried Ag interdigital electrodes are being passed through under conditions of Ar protection gas afterwards, and 450 DEG C carry out hot place
Reason 0.5h；
2）ZnO Seed Layers are grown in RGO surface in situ
It is 1 by mol ratio:1 Zn (CH3COO)2·2H2O and Al (NO3)3.9H2O mixes at ambient temperature with ethanol, makes Zn2 +Concentration is 0.2mol/L, is placed in water-bath, with magnetic stirring apparatus at 70 DEG C heating stirring 1h, obtain uniform solution, will
Step 1）Ag interdigital electrodes after heat treatment are lifted using SYDC-100 Best-Effort request machines, and pull rate is 6000 μm/s,
Dip time is 30s, then dries 10min at 80 DEG C；Lift 4 times repeatedly；Then it is being connected with the atmosphere heat of Ar gas shieldeds
Manage in program control high temperature furnace and be heat-treated 30min at 400 DEG C, obtain ZnO Seed Layers/RGO laminated films；
3）ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4It is in molar ratio 1:1 solution for being configured to 0.05mol/L, 70 DEG C of heating stirring 1h,
After starting to occur muddy in solution, stop stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle, and will step
Rapid 2）ZnO Seed Layers/RGO the laminated films for obtaining are inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；Rushed with deionized water after taking-up
Wash and dry, be finally heat-treated 1 h at 450 DEG C in the program control high temperature furnace of atmosphere heat treatment for being connected with Ar gas shieldeds, it is interdigital in Ag
Electrode surface obtains ZnO nano wall/RGO films；
4）Aging finished product：
By step 3）ZnO nano wall/RGO the films for obtaining are placed on CGS-1TP intelligence air-sensitive analysis system thermal stations sample area, adjust
Two probes are saved, makes its two end in contact with electrode slice, during room temperature, in the 365nm band of light of irradiation power 100%（LED light source）Light
Carried out according under the conditions of aging, ageing time is 1.5h.
2. ZnO nano wall RGO heterojunction photovoltaic gas sensors obtained in preparation method as claimed in claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030578A (en) * | 2018-07-30 | 2018-12-18 | 清华大学 | A kind of NO based on the nano heterogeneous junction structure of CdTe/ZnO2The preparation method of gas sensor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103496734A (en) * | 2013-10-15 | 2014-01-08 | 哈尔滨理工大学 | Manufacturing method and application for zinc oxide nano-plate spherical/foamy graphene composite |
| CN104076073A (en) * | 2014-07-10 | 2014-10-01 | 南京理工大学 | Short-bar-shaped nano-zinc oxide/graphene compound 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 |
| CN105021655A (en) * | 2015-07-03 | 2015-11-04 | 西安工业大学 | ZnO nano wall/RGO heterojunction gas-sensitive sensor and preparation method thereof |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN105259218A (en) * | 2015-10-28 | 2016-01-20 | 上海交通大学 | Zinc oxide nanowire-graphene gas sensor and preparation method thereof |
| CN105699433A (en) * | 2016-01-21 | 2016-06-22 | 安徽工业大学 | Graphene quantum dot-ZnO composite gas-sensitive material with high sensitivity to acetic acid gas |
| CN106442642A (en) * | 2016-08-30 | 2017-02-22 | 安徽师范大学 | Preparation method of zinc oxide/graphene composite material and resistance type gas sensor |
-
2017
- 2017-03-20 CN CN201710164282.2A patent/CN106932442B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103496734A (en) * | 2013-10-15 | 2014-01-08 | 哈尔滨理工大学 | Manufacturing method and application for zinc oxide nano-plate spherical/foamy graphene composite |
| CN104076073A (en) * | 2014-07-10 | 2014-10-01 | 南京理工大学 | Short-bar-shaped nano-zinc oxide/graphene compound 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 |
| CN105021655A (en) * | 2015-07-03 | 2015-11-04 | 西安工业大学 | ZnO nano wall/RGO heterojunction gas-sensitive sensor and preparation method thereof |
| CN105092646A (en) * | 2015-08-19 | 2015-11-25 | 电子科技大学 | Graphene/metal oxide composite film gas sensor and preparation method |
| CN105259218A (en) * | 2015-10-28 | 2016-01-20 | 上海交通大学 | Zinc oxide nanowire-graphene gas sensor and preparation method thereof |
| CN105699433A (en) * | 2016-01-21 | 2016-06-22 | 安徽工业大学 | Graphene quantum dot-ZnO composite gas-sensitive material with high sensitivity to acetic acid gas |
| CN106442642A (en) * | 2016-08-30 | 2017-02-22 | 安徽师范大学 | Preparation method of zinc oxide/graphene composite material and resistance type gas sensor |
Non-Patent Citations (1)
| Title |
|---|
| 张利锋 等.: "《水热法制备ZnO/石墨烯复合材料及其电化学性能研究》", 《人工晶体学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030578A (en) * | 2018-07-30 | 2018-12-18 | 清华大学 | A kind of NO based on the nano heterogeneous junction structure of CdTe/ZnO2The preparation method of gas sensor |
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