CN106346016A - Preparation method of silver/graphene composite films and application of preparation method in ultraviolet detectors - Google Patents
Preparation method of silver/graphene composite films and application of preparation method in ultraviolet detectors Download PDFInfo
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- CN106346016A CN106346016A CN201610763647.9A CN201610763647A CN106346016A CN 106346016 A CN106346016 A CN 106346016A CN 201610763647 A CN201610763647 A CN 201610763647A CN 106346016 A CN106346016 A CN 106346016A
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 94
- 239000004332 silver Substances 0.000 title claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 34
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 17
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- 238000011065 in-situ storage Methods 0.000 claims abstract description 11
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000010931 gold Substances 0.000 claims abstract description 6
- 229910052737 gold Inorganic materials 0.000 claims abstract description 6
- 238000004544 sputter deposition Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 85
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 11
- 239000010409 thin film Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- 238000010894 electron beam technology Methods 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 7
- 230000004044 response Effects 0.000 abstract description 7
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- 239000010703 silicon Substances 0.000 abstract description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 6
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- -1 graphite alkene Chemical class 0.000 description 5
- 238000001237 Raman spectrum Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- 238000000825 ultraviolet detection Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/42—Photometry, e.g. photographic exposure meter using electric radiation detectors
- G01J1/429—Photometry, e.g. photographic exposure meter using electric radiation detectors applied to measurement of ultraviolet light
Abstract
The invention discloses a preparation method of silver/graphene composite films and an application of the preparation method in ultraviolet detectors and belongs to the technical field of functional materials. The graphene/silver nanoparticle composite films are prepared through two-step in-site reduction on graphene oxide and silver salt through hydrazine hydrate and sodium citrate, silver ion takes a graphene sheet as nuclear crystallization as compared with a single-step reduction method and is more evenly modified on the graphene, and the problem about agglomeration of silever nanoparticles is effectively improved. A graphene/silver nanoparticle composite solution is prepared through two-step in-situ reduction on the graphene oxide and silver nitrate through the hydrazine hydrate and the sodium citrate and is coated on a silicon substrate to be dried to form the films, and finally a sputtering gold electrode serves as a top electrode to complete the ultraviolet detectors; the ultraviolet detectors based on the graphene/silver nanoparticle composite films are high in light current and short in response and recovery time.
Description
Technical field
The invention belongs to technical field of function materials is and in particular to a kind of modified by silver nanoparticles Graphene prepares THIN COMPOSITE
The method of film, and application in ultraviolet detector for this laminated film.
Background technology
Graphene is a kind of sp with honeycomb texture2Hydridization two-dimensional material, has excellent mechanics, optics, electricity, heat
Etc. property.At present, method predominantly organic tool stripping method, vapour deposition process and the redox graphene method of Graphene are prepared.
The unique nanostructured of Graphene is that the derivant that it is carried out with modification formation Graphene is provided convenience, in recent years, by spy
Fixed functional material performance that is grapheme modified and then improving device causes the extensive concern of researcher.Oxygen reduction fossil
Black alkene method can effectively be realized the modification to functional material and be easy to large-scale production, thus the laminated film obtaining specific function comes
Improve the performance of device.However, when laminated film is prepared using redox graphene method, the official on graphene oxide can be removed
Can roll into a ball, increase the probability of Graphene reunion while reducing graphene layer spacing, limit the extensive application of the method.
Scientific experimentss proof modified by silver nanoparticles Graphene can suppress Graphene to reunite effectively, and this phenomenon can attribution
Can be used as interlayer partition in silver nano-grain.In addition, silver nano-grain is due to its special electronic structure and larger ratio table
It is important that area makes it have at aspects such as chemical reaction catalysis, the scattering of medical science antibacterial, surface Raman enhancement and enhancing light absorbs
Application.At present, modified by silver nanoparticles Graphene generally adopt hydrazine hydrate one step redox graphene and silver compound molten
Liquid completes, but in reduction process, silver ion can centered on itself nucleation and crystallization, lead to silver nano-grain to be reunited, and then
The performance of impact laminated film.
Content of the invention
The present invention is directed to the defect that background technology exists it is proposed that a kind of hydrazine hydrate and sodium citrate two step in-situ reducing oxygen
Graphite alkene and silver nitrate are preparing the method for Graphene-silver nano-grain laminated film and this laminated film in ultraviolet detection
Application in device.The inventive method is simple to operate, low cost, and the thin film obtaining compared to hydrazine hydrate single step reducing process is hence it is evident that press down
Make the reunion in graphenic surface for the silver nano-grain, and then the ultraviolet detector of high-quality and high stability can have been prepared；
The laminated film that the present invention obtains is used in ultraviolet detector, and the ultraviolet detector that obtains has larger photoelectric current, shorter
Response and turnaround time.
Technical scheme is as follows:
A kind of preparation method of Graphene-silver nano-grain laminated film, comprises the following steps:
Step 1: graphene oxide, hydrazine hydrate are added in deionized water, ultrasonic mixing, obtain uniform graphene oxide
Dispersion liquid；Wherein, graphene oxide and the mass concentration ratio of hydrazine hydrate are 1:(10～40), the mass concentration of graphene oxide is
0.3～0.6g/l；
Step 2: the graphene oxide dispersion that step 1 is obtained stirring reaction 24～48h under 100 DEG C of oil baths, complete
First time in-situ reducing；
Step 3: soluble silver salt, sodium citrate are added in deionized water, ultrasonic mixing, obtain mixed liquor；Wherein, may be used
The amount of soluble silver salt and the material of sodium citrate is than being (50～100): 1, the substance withdrawl syndrome of soluble silver salt is 0.02～
0.05mol/l；
Step 4: the solution after the completion of the mixed liquor that step 3 is obtained is reacted with step 2 mixes, ultrasonic uniformly after, 100
Stirring reaction 1～2h under DEG C oil bath, after completing second in-situ reducing, you can obtain Graphene-silver nano-grain composite solution；
Step 5: the Graphene that step 4 is obtained-silver nano-grain composite solution is through ultrasonic, centrifugation, deionized water cleaning
Process, to remove unnecessary reducing agent and free silver nano-grain, be coated on substrate, then dry and can get graphite
Alkene-silver nano-grain laminated film.
Further, soluble silver salt described in step 3 is silver nitrate, silver chloride etc..
Further, the rotating speed of the centrifugation described in step 5 is 8000r/min, and the temperature of drying is 60～100 DEG C.
The Graphene that said method obtains-silver nano-grain laminated film is as p-type material in pn-junction ultraviolet detector
Application.
A kind of preparation side of the ultraviolet detector of the Graphene-silver nano-grain laminated film being obtained based on said method
Method, comprises the following steps:
Step 1: the Graphene that above-mentioned steps 4 are obtained-silver nano-grain composite solution through repeated ultrasonic, be centrifuged, go from
Sub- water cleaning treatment, to remove unnecessary reducing agent and free silver nano-grain, obtains Graphene-silver nano-grain and is combined rotation
Masking liquid；
Step 2: Graphene-silver nano-grain that step 1 is obtained is combined the base that spin coating liquid is evenly applied to tape insulation layer
On plate, dry, you can Graphene-silver nano-grain laminated film is obtained on substrate, then on laminated film, preparation is pushed up again
Electrode, you can obtain ultraviolet detector.
Further, substrate described in step 2 is n-type silicon substrate.
Further, the method preparing top electrode described in step 2 is sputtering method, electron-beam vapor deposition method etc..
Further, top electrode described in step 2 is gold electrode, platinum electrode etc..
Further, the temperature of the drying described in step 2 is 60～100 DEG C.
Further, the thickness of Graphene described in step 2-silver nano-grain laminated film is 1～5 μm.
The invention has the benefit that
1st, the present invention prepares Graphene-silver by hydrazine hydrate and sodium citrate two step in-situ reducing graphene oxide and silver salt
Nanoparticle composite film, compared with single step reducing process, silver ion more uniformly can be modified with flake graphite alkene as crystalline nucleation
On Graphene, effectively improve the problem of silver nano-grain reunion.
2nd, the present invention first passes through hydrazine hydrate and sodium citrate two step in-situ reducing graphene oxide and silver nitrate is obtained stone
Black alkene-silver nano-grain composite solution, is coated on silicon substrate and is dried film forming, and finally sputtering gold electrode is as top electrode
Complete the preparation of ultraviolet detector；Prepare is had based on the ultraviolet detector of Graphene-silver nano-grain laminated film
Larger photoelectric current, shorter response and turnaround time.
3rd, the present invention prepare Graphene-silver nano-grain laminated film and prepare ultraviolet detector method simple, become
This is cheap, has good process controllability and repeatability, is advantageously implemented large-scale batch production.
Brief description
Fig. 1 is the preparation flow schematic diagram of ultraviolet detector of the present invention；
Fig. 2 be comparative example 1 be obtained graphene film and comparative example 2, embodiment be obtained Graphene-silver nano-grain multiple
Close the sem figure of thin film；Wherein, the graphene film that (a) corresponding comparative example 1 is obtained, the Graphene that (b) corresponding embodiment is obtained-
Silver nano-grain laminated film, Graphene-silver nano-grain laminated film that (c) corresponding comparative example 2 is prepared into；
Fig. 3 is that Graphene-silver nano-grain that the graphene film (gns) that comparative example 1 is obtained is obtained with embodiment is combined
The tem figure of thin film (ag/gns)；
Fig. 4 is Graphene-silver nano-grain laminated film that the graphene film that comparative example 1 is obtained is obtained with embodiment
X-ray diffraction spectrum and Raman spectrum；Wherein, (a) is the stone that the graphene film (gns) that comparative example 1 is obtained is obtained with embodiment
The x-ray diffraction spectrum of black alkene-silver nano-grain laminated film (ag/gns), (b) is the graphene film that comparative example 1 is obtained
(gns) Raman spectrum of the Graphene-silver nano-grain laminated film (ag/gns) being obtained with embodiment；
Fig. 5 is the Graphene-silver nano-grain laminated film preparation of the graphene film based on comparative example 1 and embodiment
The performance test results of ultraviolet detector；Wherein, (a) is the graphite of the graphene film (gns) based on comparative example 1 and embodiment
Ultraviolet detector prepared by alkene-silver nano-grain laminated film (ag/gns) i-v under dark surrounds and ultra-vioket radiation environment
Relation contrast curve chart；B () is the photoresponse time of ultraviolet detector prepared by the graphene film (gns) based on comparative example 1
And turnaround time；C () is ultraviolet detector prepared by the Graphene-silver nano-grain laminated film (ag/gns) based on embodiment
The photoresponse time and turnaround time；D () is Graphene-silver nano-grain laminated film (ag/gns) preparation based on embodiment
Ultraviolet detector reperformance test result.
Specific embodiment
With reference to the accompanying drawings and examples, technical scheme is described in detail in detail.
Embodiment
In embodiment, each raw material sources are: graphene oxide (> 99wt%) and hydrazine hydrate (> 98wt%) it is purchased from Nanjing pioneer
Scientific ＆ technical corporation, silver nitrate and sodium citrate powder are purchased from Aladdin biochemical technology company.
A kind of preparation method of Graphene-silver nano-grain laminated film, comprises the following steps:
Step 1: under room temperature, weigh 30mg graphene oxide (> 99wt%) pulverize and 1ml hydrazine hydrate (> 98wt%)
100ml deionized water is added, ultrasonic 1h, to no obvious granule, obtains uniform graphene oxide dispersion after mixing；
Step 2: the graphene oxide dispersion that step 1 is obtained stirring reaction 24h under 100 DEG C of oil baths, complete first
Secondary in-situ reducing；
Step 3: under room temperature, weigh 45mg silver nitrate powder and 1mg sodium citrate, add in 20ml deionized water, ultrasonic
Mix homogeneous to solution, obtain mixed liquor；
Step 4: the solution after the completion of the mixed liquor that step 3 is obtained is reacted with step 2 mixes, ultrasonic uniformly after, 100
Stirring reaction 1h under DEG C oil bath, after completing second in-situ reducing, you can obtain Graphene-silver nano-grain composite solution；
Step 5: the Graphene that step 4 is obtained-silver nano-grain composite solution through repeated ultrasonic, 8000r/min be centrifuged,
Deionized water cleaning treatment, to remove unnecessary reducing agent and free silver nano-grain, is coated on substrate, then 60 DEG C of bakings
Dry, you can to obtain Graphene-silver nano-grain laminated film.
A kind of preparation side of the ultraviolet detector of the Graphene-silver nano-grain laminated film being obtained based on said method
Method, comprises the following steps:
Step 1: the Graphene that above-mentioned steps 4 are obtained-silver nano-grain composite solution is through repeated ultrasonic, 8000r/min
Centrifugation, deionized water cleaning treatment, to remove unnecessary reducing agent and free silver nano-grain, obtain Graphene-silver nanoparticle
Particles dispersed spin coating liquid；
Step 2: by smooth n-type silicon chip with, after mask plate covering, preparing the zirconium oxide of one layer of 100nm using magnetron sputtering method
Thin film, as insulating barrier；
Step 3: Graphene-silver nano-grain that step 1 is obtained is combined the N-shaped that spin coating liquid is evenly applied to tape insulation layer
On silicon substrate, dry at 60 DEG C, you can obtain Graphene-silver nano-grain laminated film that thickness is 2 μm, then again multiple
Close, on thin film, gold electrode is prepared as top electrode using magnetron sputtering method, obtain ultraviolet detector.
Comparative example 1
A kind of preparation method of graphene film and its application as ultraviolet detector, wherein, prepare graphene film
Detailed process be:
Step 1: under room temperature, weigh 30mg graphene oxide (> 99wt%) pulverize and 1ml hydrazine hydrate (> 98wt%)
100ml deionized water is added, ultrasonic 1h, to no obvious granule, obtains uniform graphene oxide dispersion after mixing；
Step 2: the graphene oxide dispersion that step 1 is obtained stirring reaction 24h under 100 DEG C of oil baths；
Step 3: the solution obtaining after step 2 is reacted is centrifuged through repeated ultrasonic, 8000r/min, at deionized water cleaning
Reason, to remove unnecessary reducing agent, is coated on substrate, then dries at 60 DEG C, you can obtain graphene film.
A kind of preparation method of the ultraviolet detector of the graphene film being obtained based on said method, is comprised the following steps:
Step 1: the solution obtaining after above-mentioned steps 2 are reacted is centrifuged through repeated ultrasonic, 8000r/min, deionized water is clear
Wash process, to remove unnecessary reducing agent, obtain Graphene spin coating liquid；
Step 2: by smooth n-type silicon chip with, after mask plate covering, preparing the zirconium oxide of one layer of 100nm using magnetron sputtering method
Thin film, as insulating barrier；
Step 3: the Graphene spin coating liquid that step 1 is obtained is evenly applied on the n-type silicon substrate of tape insulation layer, at 60 DEG C
Lower drying, you can obtain the graphene film that thickness is 2 μm, then thereon gold electrode conduct is prepared using magnetron sputtering method again
Top electrode, obtains ultraviolet detector.
Comparative example 2
A kind of preparation method of Graphene-silver nano-grain laminated film, comprises the following steps:
Under step 1, room temperature, weigh 30mg graphene oxide (> 99wt%) pulverize and 1ml hydrazine hydrate (> 98wt%)
100ml deionized water is added, ultrasonic 1h, to no obvious granule, obtains uniform graphene oxide dispersion after mixing；
Under step 2, room temperature, weigh 45mg silver nitrate powder and 1mg sodium citrate, add in 20ml deionized water, ultrasonic
Mix homogeneous to solution, obtain mixed liquor；
Step 3: the mixed liquor that step 2 is obtained uniformly is mixed with the graphene oxide dispersion of step 1, in 100 DEG C of oil
Lower stirring reaction 24h of bath, after completing in-situ reducing, you can obtain Graphene-silver nano-grain composite solution；
Step 4: the Graphene that step 3 is obtained-silver nano-grain composite solution through repeated ultrasonic, 8000r/min be centrifuged,
Deionized water cleaning treatment, to remove unnecessary reducing agent and free silver nano-grain, is coated on substrate, then 60 DEG C of bakings
Dry, you can to obtain Graphene-silver nano-grain laminated film.
Graphene-the silver nano-grain below prepared graphene film of comparative example 1 and comparative example 2, embodiment being obtained
Laminated film and its performance as ultraviolet detector are analyzed:
Using sem, morphology analysis are carried out to embodiment and comparative example gained thin film, result is as shown in Figure 2.Fig. 2 is comparative example
1 be obtained graphene film and comparative example 2, embodiment be obtained Graphene-silver nano-grain laminated film sem figure；Wherein,
A graphene film that () corresponding comparative example 1 is obtained, Graphene-silver nano-grain laminated film that (b) corresponding embodiment is obtained,
C Graphene-silver nano-grain laminated film that () corresponding comparative example 2 is prepared into.As shown in Figure 2, it is obtained compared to comparative example 1
Graphene film, passes through silver nanoparticle in hydrazine hydrate and the laminated film of sodium citrate two step local reduction way preparation in embodiment
Grain is more uniformly modified in graphenic surface, and directly use in comparative example 2 in the laminated film of hydrazine hydrate reduction silver-colored in graphite
Agglomeration in alkene surface.
Fig. 3 is that Graphene-silver nano-grain that the graphene film (gns) that comparative example 1 is obtained is obtained with embodiment is combined
The tem figure of thin film (ag/gns)；From the figure 3, it may be seen that in the laminated film that obtains of embodiment a diameter of 2-10nm silver nano-grain
Uniformly modify on flake graphite alkene.
Fig. 4 is Graphene-silver nano-grain laminated film that the graphene film that comparative example 1 is obtained is obtained with embodiment
X-ray diffraction spectrum and Raman spectrum；Wherein, (a) composes for x-ray diffraction, and (b) is Raman spectrum.From Fig. 4 (a), pass through
θ -2 θ the scanning of xrd is analyzed to the structure and composition of thin film, and collection of illustrative plates shows does not have it in addition to the diffraction maximum of Graphene and silver
Its miscellaneous peak, shows successfully to prepare Graphene-silver nano-grain laminated film.From Fig. 4 (b), due to silver nano-grain tool
There is Raman surface scattering enhancement effect, d, g and 2d peak intensity of the Graphene after modified by silver strengthens, and it strengthens coefficient (180%-
250%) show to define good contact between silver nano-grain and Graphene.
By agilent 2902b analyser and functional generator to the graphene film based on comparative example 1 and embodiment
The performance under dark surrounds and ultra-vioket radiation environment for the ultraviolet detector of Graphene-silver nano-grain laminated film preparation,
Response time, repeatability are tested, and result is as shown in Figure 5.Fig. 5 (a) be graphene film (gns) based on comparative example 1 with
Ultraviolet detector prepared by the Graphene of embodiment-silver nano-grain laminated film (ag/gns) is in dark surrounds and ultra-vioket radiation
I-v relation contrast curve chart under environment；From Fig. 5 (a), compared to unmodified Graphene, based on the stone after modified by silver
The ultraviolet detector of black alkene film preparation substantially has larger photoelectric current.Fig. 5 (b) is the graphene film based on comparative example 1
(gns) the photoresponse time of the ultraviolet detector prepared and turnaround time, Fig. 5 (c) is the Graphene-silver nanoparticle based on embodiment
The photoresponse time of ultraviolet detector prepared by Particles dispersed thin film (ag/gns) and turnaround time；From Fig. 5 (b) and (c),
The photoresponse time of ultraviolet detector prepared by the graphene film (gns) based on comparative example 1 and turnaround time are less than 20ms, base
The photoresponse time of the ultraviolet detector prepared in the Graphene-silver nano-grain laminated film (ag/gns) of embodiment and reply
Time is less than 2ms, and the embodiment of the present invention substantially has faster response and turnaround time.Graphenic surface can adsorb oxygen molecule and
Electronically form negative oxygen ion (o2(g)+e-→o2 -), and there is the Graphene-silver nano-grain laminated film of 3d open structure then
Surface depletion layer can be formed by the more oxygen molecule of absorption, contribute to the separation in electronics and hole during ultraviolet lighting, thus have relatively
Big photoelectric current and faster response and turnaround time；Meanwhile, silver nano-grain has surface plasmon resonance effect, purple
Silver nano-grain surface electronic cloud quick oscillation during external exposure, has speeded the rate travel of electronics, thus increasing photoelectricity further
Stream.
Fig. 5 (d) is ultraviolet detector prepared by the Graphene-silver nano-grain laminated film (ag/gns) based on embodiment
Reperformance test result；In order to test the reliability of device further, carry out the test of multiple cycle periods, result shows
Ultraviolet detector prepared by the Graphene based on embodiment-silver nano-grain laminated film (ag/gns) has stable well
Property.
The invention provides the preparation method of a kind of Graphene-silver nano-grain laminated film and its as ultraviolet detector
Application, method is simple to operate, low cost, and in prepared laminated film, silver nano-grain is uniformly modified and formed in graphenic surface
3d open structure；And larger photoelectric current and shorter response and reply are had based on the Ultraviolet sensor of this laminated film preparation
Time.
Claims (7)
1. the preparation method of a kind of Graphene-silver nano-grain laminated film, comprises the following steps:
Step 1: graphene oxide, hydrazine hydrate are added in deionized water, ultrasonic mixing, obtain uniform graphene oxide dispersion
Liquid；Wherein, graphene oxide and the mass concentration ratio of hydrazine hydrate are 1:(10～40), the mass concentration of graphene oxide is 0.3
～0.6g/l；
Step 2: the graphene oxide dispersion that step 1 is obtained stirring reaction 24～48h under 100 DEG C of oil baths, complete first
Secondary in-situ reducing；
Step 3: soluble silver salt, sodium citrate are added in deionized water, ultrasonic mixing, obtain mixed liquor；Wherein, solubility
The amount of silver salt and the material of sodium citrate is than being (50～100): 1, the substance withdrawl syndrome of soluble silver salt is 0.02～
0.05mol/l；
Step 4: the solution after the completion of the mixed liquor that step 3 is obtained is reacted with step 2 mixes, ultrasonic uniformly after, in 100 DEG C of oil
The lower stirring reaction 1～2h of bath, after completing second in-situ reducing, you can obtain Graphene-silver nano-grain composite solution；
Step 5: the Graphene that step 4 is obtained-silver nano-grain composite solution through ultrasonic, centrifugation, deionized water cleaning treatment,
To remove unnecessary reducing agent and free silver nano-grain, it is coated on substrate, then dries and can get Graphene-Yin Na
Rice grain laminated film.
2. the preparation method of Graphene according to claim 1-silver nano-grain laminated film is it is characterised in that step 3
Described soluble silver salt is silver nitrate or silver chloride.
3. Graphene-silver nano-grain laminated film that method any one of claim 1 to 2 obtains is as pn-junction ultraviolet
The application of p-type material in detector.
4. a kind of ultraviolet detector of the Graphene-silver nano-grain laminated film being obtained based on claim 1 methods described
Preparation method, comprises the following steps:
Step 1: by the Graphene obtaining-silver nano-grain composite solution through repeated ultrasonic, centrifugation, deionized water cleaning treatment,
To remove unnecessary reducing agent and free silver nano-grain, obtain Graphene-silver nano-grain and be combined spin coating liquid；
Step 2: Graphene-silver nano-grain that step 1 is obtained is combined spin coating liquid and is evenly applied on the substrate of tape insulation layer,
Dry, you can Graphene-silver nano-grain laminated film is obtained on substrate, then prepares top electrode on laminated film again,
Can get ultraviolet detector.
5. according to claim 4 the preparation method of ultraviolet detector it is characterised in that preparing top electrode described in step 2
Method be sputtering method or electron-beam vapor deposition method.
6. according to claim 4 ultraviolet detector preparation method it is characterised in that top electrode described in step 2 be gold electricity
Pole or platinum electrode.
7. according to claim 4 the preparation method of ultraviolet detector it is characterised in that Graphene-silver nanoparticle described in step 2
The thickness of Particles dispersed thin film is 1～5 μm.
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