CN106932442B - A kind of ZnO nano wall RGO heterojunction photovoltaic gas sensor and preparation method thereof - Google Patents
A kind of ZnO nano wall RGO heterojunction photovoltaic gas sensor and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to light-sensitive detector preparation method technical fields, and in particular to a kind of ZnO nano wall RGO heterojunction photovoltaic gas sensor and preparation method thereof.The present invention uses following steps: the 1) preparation of porous reduced graphene；2) ZnO seed layer is grown in RGO surface in situ；3) ZnO nano wall is grown in RGO surface in situ；4) aging finished product realizes its technical solution to overcome light sensitivity and NO under normal temperature condition in the prior art2The low problem of sensitivity.
Description
One, technical field
The present invention relates to light-sensitive detector preparation method technical fields, and in particular to a kind of ZnO nano wall RGO hetero-junctions light
Electrical dependent sensor and preparation method thereof.
Two, background technique:
Forbidden bandwidth is 3.37eV to metal oxide semiconductor material ZnO at normal temperature, is direct band-gap semicondictor, simultaneously
Its exciton bind energy is very big, about 60meV.After purple light excited, photo-generate electron-hole pair is generated, conductance increases；Meanwhile
Light induced electron or hole are induced to semiconductor surface and redox reaction occurs for the gas molecule of absorption, this process also can
The change of conductance occurs.Therefore, this has established good base in the application of light-sensitive detector and Photo-electric gas-sensitivity sensor for ZnO
Plinth！
But ZnO Photo-electric gas-sensitivity sensor prepared at present is unable to satisfy that adsorption capacity is strong, photosensitive property is good, external
The a series of properties such as boundary's gas sensitization, stability is good requirement, in order to solve this problem, there has been proposed metal ion mixing,
Surface modification noble metal (modification of such as Au, Ag, Pt), surface modification light sensitive material, composite material the methods of are constructed.Wherein
Composite material is constructed in addition to SnO2-ZnO、Fe2O3Other than the composite materials such as-ZnO, ZnO-CuO are constructed；Graphene and carbon nanotube
Equal substances have good charge transport properties, also be used to form composite material with ZnO.
S.Safa etc. is prepared for rGO-ZnO optical detector using dipping-pulling method and has studied its performance, is sent out by research
Existing pure ZnO, 0.0125wt.%, 0.025wt.%, 0.075wt.%, 0.225wt.% be respectively 2 to the sensitivity of purple light, 3,
3,4,2.5, thus, the luminous sensitivity of rGO-ZnO is better than pure ZnO；Wang Dejun etc. is passed through based on ZnO nano material
Doping method is prepared for Photo-electric gas-sensitivity sensor, and the zinc oxide film performance for obtaining 1% Copper-cladding Aluminum Bar after testing is best, ultraviolet
Light excitation is under room temperature 64,63 to 1120ppm ethyl alcohol and acetone response intensity, higher than the response intensity of pure ZnO, copper coin
The incorporation of element can promote the absorption of volatile organic matter；Bin Wu etc. is prepared using aqua-solution method and chemical vapour deposition technique
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；
Xie Tengfeng, Cui Jiabao etc. obtain research Ag by research and modify ZnO under room temperature, 370nm illumination condition to 40ppm HCHO's
Sensitivity is 119.8%, is 3 times of pure ZnO, in addition to this, they by research obtain Al ion doping zinc oxide room temperature,
It is 261.8% to the sensitivity of 50ppm HCHO under 370nm illumination condition, is 3 times of pure zinc oxide.
By reported above it can be concluded that the zno-based light-sensitive detector and photoelectricity gas constructed through overdoping, modification composite material
Compared with pure ZnO, performance increases dependent sensor, but light sensitivity and NO2Sensitivity is still lower.
Three, summary of the invention
The object of the present invention is to provide a kind of ZnO nano wall RGO heterojunction photovoltaic gas sensor 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, a kind of the technical solution adopted by the present invention are as follows: ZnO nano wall RGO heterojunction photovoltaic air-sensitive
The preparation method of sensor, comprising the following steps:
1) preparation of porous reduced graphene
The porous graphene powder for weighing 2-8mg respectively mixes it with the DMF of 10ml, and being configured to concentration is 0.2-
0.8mg/ml porous graphene-DMF suspension later seals above-mentioned suspension multilayer preservative film, at room temperature discontinuously
It is ultrasonically treated 72h, porous graphene dispersion liquid is obtained, is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, so
Supernatant liquid is drawn afterwards in clear glass bottle, obtains porous graphene dispersing solution；By Ag interdigital electrode respectively in acetone, anhydrous second
Alcohol is cleaned by ultrasonic in deionized water, and the pre-heat treatment 1h in the drying box that temperature is 110 DEG C is then placed in；Take 1ml configured
Good porous graphene dispersion liquid is passing through pretreated Ag interdigital electrode table using the spray gun spraying that nozzle diameter is 0.2mm
Then face is dried at 110 DEG C, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C of progress
It is heat-treated 0.5h；
2) ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O is mixed at room temperature with ethyl alcohol,
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 lifts the Ag interdigital electrode after step 1) heat treatment using SYDC-100 Best-Effort request machine, and pull rate is 6000 μ
Then m/s, dip time 30s dry 10min at 80 DEG C；It lifts 4 times repeatedly；Then in the atmosphere for being connected with Ar gas shielded
It is heat-treated in program-controlled high temperature furnace and is heat-treated 30min at 400 DEG C, obtain ZnO seed layer/RGO laminated film；
3) ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L, 70 DEG C of heating stirrings are configured to for 1:1 in molar ratio
1h stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after starting to occur muddy in solution, and
ZnO seed layer/RGO laminated film that step 2) obtains is inserted perpendicularly into wherein, 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water rinses and dries, and is finally heat-treated 1h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, pitches in Ag
Refer to that electrode surface obtains ZnO nano wall/RGO film.
4) aging finished product:
ZnO nano wall/RGO film that step 3) obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample
Area adjusts two probes, makes its two end in contact with electrode slice, when room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) aging, ageing time 1.5h are carried out under illumination condition.
ZnO nano wall RGO heterojunction photovoltaic gas sensor made from the preparation method.
Compared with prior art, the invention has the advantages that and effect: the present invention under provided low temperature have height
The light-sensitive detector and NO of sensitivity2Photo-electric gas-sensitivity sensor, ZnO are wide bandgap semiconductor materials, and forbidden bandwidth is
3.37eV is good to the photoresponse of ultraviolet light；In addition, porous reduced graphene has extraordinary electric conductivity, can quickly transmit
Carrier avoids photo-generate electron-hole from occurring compound.Therefore, porous ZnO nm wall/RGO photoelectric sensor has several below
The advantages of aspect: (1) light sensitive degree is high, is 13.107 to the photosensitive of 365nm light under 75 DEG C of operating temperatures, (2) are to NO2
High sensitivity, to the NO of 50ppm under the illumination condition that operating temperature is 75 DEG C, wavelength is 365nm2High sensitivity reaches
88.154, (3) stability is good, and (4) material is easily obtained, and (5) have the photosensitive coupled characteristic with air-sensitive；
Since the graphene of sheet is nano material, it is easy to produce agglomeration, so the actual specific surface of graphene
Product can not all be consistent with electric conductivity with theoretical value, seriously constrain the application of graphene.The present invention constructs three-dimensional communication
Network porous structure had not only constructed the channel that electronics, thermal energy and load are effectively transmitted, but also can effectively improve graphene-based porous
The specific surface area of material and active site abundant.
Four, Detailed description of the invention:
Fig. 1 (a) is the ZnO nano wall/RGO for preparing of embodiment 1 operating temperature is 75 DEG C, irradiation power is 100%
365nm photosensitive response figure；
Fig. 1 (b) is the ZnO nano wall/RGO for preparing of embodiment 1 operating temperature is 75 DEG C, irradiation power is 100%
To 50ppm NO under the conditions of the irradiation of 365nm light2The photosensitive coupling response figure of air-sensitive-；
Fig. 1 (c) be example 1 prepare ZnO nano wall/RGO operating temperature be 75 DEG C when to 365nm difference irradiation power light
According to photosensitive response figure；
Fig. 1 (d) be embodiment 1 prepare ZnO nano wall/RGO operating temperature be 75 DEG C, 365nm difference irradiation power
Illumination is to 50ppm NO2The photosensitive coupling response figure of air-sensitive-；
Fig. 1 (e) be embodiment 1 prepare ZnO nano wall/RGO operating temperature be 75 DEG C, irradiation power is 100%
To 5ppm-50ppm NO under the conditions of the irradiation of 365nm light2The photosensitive coupling response figure of air-sensitive-；
Fig. 1 (f) is that ZnO nano wall/RGO prepared by example 1 is 100% in different operating temperature to 365nm, irradiation power
Under photosensitive response figure, to 50ppm NO2The photosensitive coupling response figure of air-sensitive-；
Fig. 2 (a) is the ZnO nano wall/RGO for preparing of embodiment 2 operating temperature is 75 DEG C, irradiation power is 100%
365nm photosensitive response figure；
Fig. 2 (b) is the ZnO nano wall/RGO for preparing of embodiment 2 operating temperature is 75 DEG C, irradiation power is 100%
To 50ppm NO under the conditions of the irradiation of 365nm light2The photosensitive coupling response figure of air-sensitive-；
Fig. 3 (a) is the ZnO nano wall/RGO for preparing of embodiment 3 operating temperature is 75 DEG C, irradiation power is 100%
365nm photosensitive response figure；
Fig. 3 (b) is the ZnO nano wall/RGO for preparing of embodiment 3 operating temperature is 75 DEG C, irradiation power is 100%
To 50ppm NO under the conditions of the irradiation of 365nm light2The photosensitive coupling response figure of air-sensitive-；
Fig. 4 (a) is the ZnO nano wall/RGO for preparing of embodiment 4 operating temperature is 75 DEG C, irradiation power is 100%
365nm photosensitive response figure；
Fig. 4 (b) is the ZnO nano wall/RGO for preparing of embodiment 4 operating temperature is 75 DEG C, irradiation power is 100%
To 50ppm NO under the conditions of the irradiation of 365nm light2The photosensitive coupling response figure of air-sensitive-；
Fig. 5 is ZnO nano wall/RGO XRD diagram prepared by embodiment 1；
Fig. 6 (a) is ZnO nano wall/RGO SEM figure prepared by embodiment 1；
Fig. 6 (b) is ZnO nano wall/RGO EDS figure prepared by embodiment 1；
Fig. 7 (a) is ZnO nano wall/RGO TEM figure prepared by embodiment 1；
Fig. 7 (b) is ZnO nano wall/RGO high power TEM figure prepared by embodiment 1；
Fig. 8 is ZnO nano wall/RGO UV figure prepared by embodiment 1；
Fig. 9 is the surface ZnO nano wall/RGO photoelectricity flow graph prepared by embodiment 1.
Five, specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
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 sensor includes the following steps:
One, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) for weighing 2mg respectively, by the DMF of itself and 10ml
(n,N-Dimethylformamide) mixing, compound concentration are 0.2mg/ml porous graphene-DMF (n,N-Dimethylformamide) suspension
Liquid later seals above-mentioned suspension multilayer preservative film, is discontinuously ultrasonically treated 72h at room temperature, obtains porous graphene
Dispersion liquid is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, is then drawn supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；；By Ag interdigital electrode respectively in acetone, it is clear to carry out ultrasound in deionized water for dehydrated alcohol
It washes, is put into the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；The configured good porous graphene dispersion liquid of 1ml is taken, with spray
Outspoken diameter is that 0.2mm spray gun (Japanese Lumina Science and Technology Ltd.) is sprayed on by pretreated Ag interdigital electrode surface, so
It is dried at 110 DEG C afterwards, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C carry out hot place
Manage 0.5h；
Two, ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethyl alcohol mixes at room 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.G interdigital electrode after step 1) heat treatment is carried out using SYDC-100 Best-Effort request machine
Lifting, pull rate are 6000 μm/s, dip time 30s, and 10min is then dried at 80 DEG C；It lifts 4 times repeatedly；Then
It is heat-treated 30min at 400 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, it is multiple to obtain ZnO seed layer/RGO
Close film；
Three, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L, 70 DEG C of heating stirrings are configured to for 1:1 in molar ratio
1h stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after starting to occur muddy in solution, and
ZnO seed layer/RGO laminated film that step 2) obtains is inserted perpendicularly into wherein, 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water rinses and dries, and is finally heat-treated 1h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, pitches in Ag
Refer to that electrode surface obtains ZnO nano wall/RGO film；
Four, aging finished product:
ZnO nano wall/RGO film that step 3 obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample
Area adjusts two probes, makes its two end in contact with electrode slice.When room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) aging, ageing time 1.5h are carried out under illumination condition.
Performance detection:
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtain to the present embodiment carries out the detection of photosensitive property, by old
The resistance of the sample of change floats up and down in a certain range, cuts off light source at this time, and resistance rises, and reopens light after 50s
Source, resistance are replied, sensitivity S is defined as: S=Rg/Ra(RaIndicate resistance of the element under illumination condition, RgIndicate element cutting
Resistance when power supply).ZnO nano wall/RGO is to shown in 365nm, photosensitive response figure such as Fig. 1 (a) that irradiation power is 100%.
The light-sensitive detector and its Photo-electric gas-sensitivities sensor that obtain to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
It surveys, the resistance of the sample by aging floats up and down in a certain range, injects NO at this time2, while light source is cut off, resistance
Rise, open gas tank after 50s, open simultaneously light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaIndicate element in sky
There are the resistance of illumination, R in gasgIndicate the resistance of element no light in tested gas).ZnO nano wall/RGO of preparation exists
To 50ppm NO under the conditions of 365nm, the light that irradiation power is 100% irradiation2The photosensitive coupling response figure such as Fig. 1 of the air-sensitive-of room temperature
(b) shown in.
Embodiment 2:
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensor, includes the following steps:
One, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) for weighing 4mg respectively, by the DMF of itself and 10ml
(n,N-Dimethylformamide) mixing, compound concentration are 0.4mg/ml porous graphene-DMF (n,N-Dimethylformamide) suspension
Liquid later seals above-mentioned suspension multilayer preservative film, is discontinuously ultrasonically treated 72h at room temperature, obtains porous graphene
Dispersion liquid is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, is then drawn supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrode respectively in acetone, dehydrated 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 liquid of 1ml is taken, nozzle is used
Diameter is by pretreated Ag interdigital electrode surface, then 0.2mm spray gun (Japanese Lumina Science and Technology Ltd.) is sprayed on
It is dried at 110 DEG C, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C are heat-treated
0.5h；
Two, ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethyl alcohol mixes at room 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.G interdigital electrode after step 1) heat treatment is carried out using SYDC-100 Best-Effort request machine
Lifting, pull rate are 6000 μm/s, dip time 30s, and 10min is then dried at 80 DEG C；It lifts 4 times repeatedly；Then
It is heat-treated 30min at 400 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, it is multiple to obtain ZnO seed layer/RGO
Close film；
Three, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L, 70 DEG C of heating stirrings are configured to for 1:1 in molar ratio
1h stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after starting to occur muddy in solution, and
ZnO seed layer/RGO laminated film that step 2) obtains is inserted perpendicularly into wherein, 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water rinses and dries, and is finally heat-treated 1h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, pitches in Ag
Refer to that electrode surface obtains ZnO nano wall/RGO film；
Four, aging finished product:
ZnO nano wall/RGO film that step 3 obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample
Area adjusts two probes, makes its two end in contact with electrode slice.When room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) aging, ageing time 1.5h are carried out under illumination condition.
Performance detection:
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtain to the present embodiment carries out the detection of photosensitive property, by old
The resistance of the sample of change floats up and down in a certain range, cuts off light source at this time, and resistance rises, and reopens light after 50s
Source, resistance are replied, sensitivity S is defined as: S=Rg/Ra(RaIndicate resistance of the element under illumination condition, RgIndicate element cutting
Resistance when power supply).ZnO nano wall/RGO is to shown in 365nm, photosensitive response figure such as Fig. 2 (a) that irradiation power is 100%.
The light-sensitive detector and its Photo-electric gas-sensitivities sensor that obtain to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
It surveys, the resistance of the sample by aging floats up and down in a certain range, injects NO at this time2, while light source is cut off, resistance
Rise, open gas tank after 50s, open simultaneously light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaIndicate element in sky
There are the resistance of illumination, R in gasgIndicate the resistance of element no light in tested gas).ZnO nano wall/RGO of preparation exists
To 50ppm NO under the conditions of 365nm, the light that irradiation power is 100% irradiation2The photosensitive coupling response figure such as Fig. 2 of the air-sensitive-of room temperature
(b) shown in.
Embodiment 3:
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensor, includes the following steps:
One, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) for weighing 6mg respectively, by the DMF of itself and 10ml
(n,N-Dimethylformamide) mixing, compound concentration are 0.6mg/ml porous graphene-DMF (n,N-Dimethylformamide) suspension
Liquid later seals above-mentioned suspension multilayer preservative film, is discontinuously ultrasonically treated 72h at room temperature, obtains porous graphene
Dispersion liquid is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, is then drawn supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrode respectively in acetone, dehydrated 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 liquid of 1ml is taken, nozzle is used
Diameter is by pretreated Ag interdigital electrode surface, then 0.2mm spray gun (Japanese Lumina Science and Technology Ltd.) is sprayed on
It is dried at 110 DEG C, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C are heat-treated
0.5h；
Two, ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethyl alcohol mixes at room 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.G interdigital electrode after step 1) heat treatment is carried out using SYDC-100 Best-Effort request machine
Lifting, pull rate are 6000 μm/s, dip time 30s, and 10min is then dried at 80 DEG C；It lifts 4 times repeatedly；Then
It is heat-treated 30min at 400 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, it is multiple to obtain ZnO seed layer/RGO
Close film；
Three, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L, 70 DEG C of heating stirrings are configured to for 1:1 in molar ratio
1h stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after starting to occur muddy in solution, and
ZnO seed layer/RGO laminated film that step 2) obtains is inserted perpendicularly into wherein, 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water rinses and dries, and is finally heat-treated 1h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, pitches in Ag
Refer to that electrode surface obtains ZnO nano wall/RGO film；
Four, aging finished product:
ZnO nano wall/RGO film that step 3 obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample
Area adjusts two probes, makes its two end in contact with electrode slice.When room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) aging, ageing time 1.5h are carried out under illumination condition.
Performance detection:
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtain to the present embodiment carries out the detection of photosensitive property, by old
The resistance of the sample of change floats up and down in a certain range, cuts off light source at this time, and resistance rises, and reopens light after 50s
Source, resistance are replied, sensitivity S is defined as: S=Rg/Ra(RaIndicate resistance of the element under illumination condition, RgIndicate element cutting
Resistance when power supply).ZnO nano wall/RGO is to shown in 365nm, photosensitive response figure such as Fig. 3 (a) that irradiation power is 100%.
The light-sensitive detector and its Photo-electric gas-sensitivities sensor that obtain to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
It surveys, the resistance of the sample by aging floats up and down in a certain range, injects NO at this time2, while light source is cut off, resistance
Rise, open gas tank after 50s, open simultaneously light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaIndicate element in sky
There are the resistance of illumination, R in gasgIndicate the resistance of element no light in tested gas).ZnO nano wall/RGO of preparation exists
To 50ppm NO under the conditions of 365nm, the light that irradiation power is 100% irradiation2The photosensitive coupling response figure such as Fig. 3 of the air-sensitive-of room temperature
(b) shown in.
Embodiment 4:
A kind of preparation method of ZnO nano wall RGO heterojunction photovoltaic gas sensor, includes the following steps:
One, the preparation of porous reduced graphene
The porous graphene powder (Nanjing Ji Cang nanosecond science and technology Co., Ltd) for weighing 8mg respectively, by the DMF of itself and 10ml
(n,N-Dimethylformamide) mixing, compound concentration are 0.8mg/ml porous graphene-DMF (n,N-Dimethylformamide) suspension
Liquid later seals above-mentioned suspension multilayer preservative film, is discontinuously ultrasonically treated 72h at room temperature, obtains porous graphene
Dispersion liquid is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, is then drawn supernatant liquid in clear glass bottle
In, obtain porous graphene dispersing solution；By Ag interdigital electrode respectively in acetone, dehydrated 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 liquid of 1ml is taken, nozzle is used
Diameter is by pretreated Ag interdigital electrode surface, then 0.2mm spray gun (Japanese Lumina Science and Technology Ltd.) is sprayed on
It is dried at 110 DEG C, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C are heat-treated
0.5h；
Two, ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O (Zinc diacetate dihydrate, analyze pure) with
Ethyl alcohol mixes at room 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.G interdigital electrode after step 1) heat treatment is carried out using SYDC-100 Best-Effort request machine
Lifting, pull rate are 6000 μm/s, dip time 30s, and 10min is then dried at 80 DEG C；It lifts 4 times repeatedly；Then
It is heat-treated 30min at 400 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, it is multiple to obtain ZnO seed layer/RGO
Close film；
Three, ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L, 70 DEG C of heating stirrings are configured to for 1:1 in molar ratio
1h stops stirring, solution is poured into the polytetrafluoroethylliner liner of hydrothermal reaction kettle after starting to occur muddy in solution, and
ZnO seed layer/RGO laminated film that step 2) obtains is inserted perpendicularly into wherein, 80 DEG C of constant temperature grow 5h；Deionization is used after taking-up
Water rinses and dries, and is finally heat-treated 1h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, pitches in Ag
Refer to that electrode surface obtains ZnO nano wall/RGO film,
Four, aging finished product:
ZnO nano wall/RGO film that step 3 obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample
Area adjusts two probes, makes its two end in contact with electrode slice.When room temperature, in the 365nm band of light (LED of irradiation power 100%
Light source) aging, ageing time 1.5h are carried out under illumination condition.
Performance detection:
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtain to the present embodiment carries out the detection of photosensitive property, by old
The resistance of the sample of change floats up and down in a certain range, cuts off light source at this time, and resistance rises, and reopens light after 50s
Source, resistance are replied, sensitivity S is defined as: S=Rg/Ra(RaIndicate resistance of the element under illumination condition, RgIndicate element cutting
Resistance when power supply).ZnO nano wall/RGO is to shown in 365nm, photosensitive response figure such as Fig. 4 (a) that irradiation power is 100%.
The light-sensitive detector and its Photo-electric gas-sensitivities sensor that obtain to the present embodiment carry out the inspection of photosensitive-air-sensitive coupling effect
It surveys, the resistance of the sample by aging floats up and down in a certain range, injects NO at this time2, while light source is cut off, resistance
Rise, open gas tank after 50s, open simultaneously light source, resistance is replied, and sensitivity S is defined as S=Rg/Ra(RaIndicate element in sky
There are the resistance of illumination, R in gasgIndicate the resistance of element no light in tested gas).ZnO nano wall/RGO of preparation exists
To 50ppm NO under the conditions of 365nm, the light that irradiation power is 100% irradiation2The photosensitive coupling response figure such as Fig. 4 of the air-sensitive-of room temperature
(b) shown in.
The light-sensitive detector and its Photo-electric gas-sensitivity sensor obtained with embodiment 1 carries out related experiment, as a result as follows:
(a) ZnO nano wall/RGO XRD diagram
Referring to Fig. 5, the ZnO nano wall/edge RGO [002] direction preferential growth, and crystalline quality with higher.
(b) ZnO nano wall/RGO SEM, EDS scheme
Referring to Fig. 6, it is known that ZnO nano wall/RGO with porous structure orients the period along Ag interdigital electrode vertical direction
Property aligned growth, Zn can be seen that there are by EDS figure, O, C, five kinds of elements such as Al, Ag, wherein Zn, O derive from ZnO, the source C
In the Al (NO that RGO, Al are used in raw material3)3, Ag is from Ag interdigital electrode.
(c) ZnO nano wall/RGO TEM, high power TEM scheme
Referring to Fig. 7, for ZnO nano joist anchor on the surface of RGO, this further proves that ZnO nano wall/RGO hetero-junctions is prepared into
Function.
(d) the photosensitive coupling effect figure of the photosensitive and air-sensitive-of ZnO nano wall/RGO
Referring to Fig. 1 it is found that sensor prepared by embodiment 1 under the conditions of operating temperature is 75 DEG C under be to wavelength
The sensitivity of 365nm light is 13.107, to the NO of 50ppm2Sensitivity is 88.154, and significantly larger than other are reported in the literature sensitive
Degree.In addition to this, pass through the research to operating temperature, it can be deduced that first to the sensitivity of light with the raising of operating temperature
It is reduced after increasing, the sensitivity of detection gas is also changed correspondingly, obtain optimum value at 75 DEG C.By being ground to illumination power
Study carefully, obtain the reduction with power, the sensitivity of light is reduced, the sensitivity of detection gas is also reduced therewith.
(e) ZnO nano wall/RGO UV schemes
Referring to Fig. 8, ZnO nano wall/RGO has very strong absorption peak in 360nm.
(f) surface ZnO nano wall/RGO photoelectricity flow graph
Referring to Fig. 9 it is found that excitation wavelength is from 370nm to 300nm, photoelectric current is gradually reduced, when excitation wavelength is 370nm,
Surface photoelectric current reaches maximum value, is 19 × 10-12A, when wavelength is in 370nm to 394nm, photoelectric current with wavelength increase and
It reduces；When wavelength is located at 394nm to 500nm, there is faint photoelectric current to generate.
The above is only the preferred embodiment of the present invention, is 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 sensor, it is characterised in that: the preparation side
Method the following steps are included:
1) preparation of porous reduced graphene
The porous graphene powder for weighing 2-8mg mixes it with the DMF of 10ml, and being configured to concentration is that 0.2-0.8mg/ml is more
Hole graphene-DMF suspension later seals above-mentioned suspension multilayer preservative film, at room temperature discontinuous ultrasonic treatment
72h obtains porous graphene dispersion liquid, is stood for 24 hours, is that 4000r/min carries out centrifugal treating by revolving speed, then draws
Layer liquid obtains porous graphene dispersing solution in clear glass bottle；By Ag interdigital electrode respectively in acetone, dehydrated alcohol, go from
It is cleaned by ultrasonic in sub- water, is then placed in the pre-heat treatment 1h in the drying box that temperature is 110 DEG C；Take 1ml configured good more
Hole graphene dispersing solution is passing through pretreated Ag interdigital electrode surface using the spray gun spraying that nozzle diameter is 0.2mm, then
It is dried at 110 DEG C, by dried Ag interdigital electrode under conditions of being passed through Ar protection gas, 450 DEG C are heat-treated
0.5h；
2) ZnO seed layer is grown in RGO surface in situ
Zn (the CH for being 1:1 by molar ratio3COO)2·2H2O and Al (NO3)3.9H2O is mixed at room temperature with ethyl alcohol, 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
Ag interdigital electrode after step 1) heat treatment is lifted using SYDC-100 Best-Effort request machine, and pull rate is 6000 μm/s,
Dip time is 30s, then the dry 10min at 80 DEG C；It lifts 4 times repeatedly；Then at the atmosphere heat for being connected with Ar gas shielded
It manages in program-controlled high temperature furnace and is heat-treated 30min at 400 DEG C, obtain ZnO seed layer/RGO laminated film；
3) ZnO nano wall is grown in RGO surface in situ
By Zn (NO3)26H2O and (CH3)6N4The solution of 0.05mol/L is configured in molar ratio for 1:1,70 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
The rapid ZnO seed layer/RGO laminated film 2) obtained is inserted perpendicularly into wherein, and 80 DEG C of constant temperature grow 5h；It is rushed after taking-up with deionized water
It washes and dries, be finally heat-treated 1 h at 450 DEG C in the program-controlled high temperature furnace of atmosphere heat treatment for being connected with Ar gas shielded, it is interdigital in Ag
Electrode surface obtains ZnO nano wall/RGO film；
4) aging finished product:
ZnO nano wall/RGO film that step 3) obtains is placed on CGS-1TP intelligence air-sensitive analysis system thermal station sample area, is adjusted
Two probes are saved, make its two end in contact with electrode slice, when room temperature, under the 365nm band of light illumination condition of irradiation power 100%
Carry out aging, ageing time 1.5h.
2. ZnO nano wall RGO heterojunction photovoltaic gas sensor made from preparation method as described in claim 1.
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