CN107293602B - Based on zinc oxide/graphene/zinc oxide sandwich structure photodetector - Google Patents
Based on zinc oxide/graphene/zinc oxide sandwich structure photodetector Download PDFInfo
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- CN107293602B CN107293602B CN201710547609.4A CN201710547609A CN107293602B CN 107293602 B CN107293602 B CN 107293602B CN 201710547609 A CN201710547609 A CN 201710547609A CN 107293602 B CN107293602 B CN 107293602B
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 298
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 149
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 99
- 229960001296 zinc oxide Drugs 0.000 claims abstract description 147
- 238000000034 method Methods 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 25
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 239000011701 zinc Substances 0.000 claims abstract description 20
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 238000005245 sintering Methods 0.000 claims abstract description 13
- 238000013404 process transfer Methods 0.000 claims abstract description 10
- 239000013077 target material Substances 0.000 claims abstract description 10
- 238000005516 engineering process Methods 0.000 claims abstract description 9
- 238000002955 isolation Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000004544 sputter deposition Methods 0.000 claims description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 23
- 239000011889 copper foil Substances 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 14
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000005477 sputtering target Methods 0.000 claims description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- KRQUFUKTQHISJB-YYADALCUSA-N 2-[(E)-N-[2-(4-chlorophenoxy)propoxy]-C-propylcarbonimidoyl]-3-hydroxy-5-(thian-3-yl)cyclohex-2-en-1-one Chemical compound CCC\C(=N/OCC(C)OC1=CC=C(Cl)C=C1)C1=C(O)CC(CC1=O)C1CCCSC1 KRQUFUKTQHISJB-YYADALCUSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000010292 electrical insulation Methods 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- -1 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000010980 sapphire Substances 0.000 claims description 3
- 229910052594 sapphire Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 3
- 238000002207 thermal evaporation Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 5
- 238000010790 dilution Methods 0.000 claims 2
- 239000012895 dilution Substances 0.000 claims 2
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract description 6
- 239000010408 film Substances 0.000 description 47
- 239000010410 layer Substances 0.000 description 45
- 229910052799 carbon Inorganic materials 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 230000005622 photoelectricity Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
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- 239000002253 acid Substances 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/02002—Arrangements for conducting electric current to or from the device in operations
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
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- H—ELECTRICITY
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1828—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe
- H01L31/1836—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof the active layers comprising only AIIBVI compounds, e.g. CdS, ZnS, CdTe comprising a growth substrate not being an AIIBVI compound
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The present invention relates to a kind of based on zinc oxide/graphene/zinc oxide sandwich structure photodetector, belongs to material applied technical field.The technology of the present invention uses sintering oxidation zinc ceramics to do target material first, and in rf magnetron sputtering equipment, growth obtains one layer of zinc-oxide film on the substrate of electrical isolation；Then, one layer of graphene is shifted on zinc-oxide film with wet process transfer techniques；Again on graphene layer, one layer of zinc oxide is grown with radiofrequency magnetron sputtering technology, to obtain a kind of zinc oxide/graphene/zinc oxide sandwich structure；Finally, it is described based on zinc oxide/graphene/zinc oxide sandwich structure photodetector to get arriving to be coated with upper metal electrode on upper layer and lower layer zinc-oxide film.This structure can utilize the feature that zinc-oxide film is strong to light absorpting ability and graphene light transmittance is high, electron mobility is big, conductive capability is strong simultaneously；Photo detector signal based on this sandwich is strong, response is fast, detectivity is high.
Description
Technical field
The present invention relates to a kind of based on zinc oxide/graphene/zinc oxide sandwich structure photodetector, belongs to material
Applied technical field.
Background technique
Since 2004 are found, graphene nano material is in solid state physics, material science and microelectronics of receiving
Equal ambits cause the great interest of people.Graphene is arranged in a combination by single layer of carbon atom, hexagonal netted
Structure；It is known most thin two-dimensional material in the world because only that the thickness of a carbon atom.The unique network knot of graphene
Structure, make its electricity, mechanics and in terms of show unique property, in supercapacitor, fuel cell, phototube
The fields such as part and Flied emission are with a wide range of applications.Graphene has high electron mobility (200000cm2/Vs)、
High current density (> 108A/cm2), and due to its zero bandgap structure characteristic, a small amount of electronics can cause its conductance
Significant changes occur.In addition, although the light transmittance of graphene is high, its lower photonic absorption ability seriously constrain it
The application of field of photodetectors.
On the other hand, zinc oxide is a kind of semiconductor of direct band gap, band gap 3.37eV, very to uv absorption rate
It is high；If it is the zinc oxide of non-stoichiometric, then band gap is smaller, will also have very strong absorption to visible light.Meanwhile it aoxidizing
Zinc has very high exciton binding energy 60meV, and loss is lower, therefore has application prospect in optical detection field.With other broadbands
Gap semiconductor is compared, and since growth adaptability is strong on different substrates for zinc oxide, this is conducive to make the biggish photonics of area
Device, such as p-n junction, p-i-n junction, Schottky photo diode；It is with high quantum efficiency, and high response efficiency, low is dark
Electric current and high luminous sensitivity.But because zinc oxide is semiconductor material, conductive capability is poor.
In view of this, the present invention proposes to carry out graphene and zinc-oxide film compound, allow zinc oxide as photoinduction layer,
Graphene is fabricated to photodetector as carrier blocking layers, using the synergistic effect of the two, improves photodetection performance.This
What invention proposed is a kind of based on zinc oxide/graphene/zinc oxide sandwich structure photodetector.Proposed by the present invention
In technology, target material is done using sintering oxidation zinc ceramics first, it is raw on the substrate of electrical isolation in rf magnetron sputtering equipment
Length obtains one layer of zinc-oxide film；Then, one layer of graphene is shifted on zinc-oxide film with wet process transfer techniques；Again in graphite
On alkene layer, one layer of zinc oxide is grown with radiofrequency magnetron sputtering technology, to obtain a kind of zinc oxide/graphene/zinc oxide three
Mingzhi's structure；Zinc oxide/graphite is based on finally, being coated with upper metal electrode on upper layer and lower layer zinc-oxide film to get to described
Alkene/zinc oxide sandwich structure photodetector.
In technical solution proposed by the invention, radiofrequency magnetron sputtering technology is high, at low cost with film quality, prepares
Process is simple, technological parameter controllable precise, the features such as industrial mass production can be achieved；Used graphene wet process transfer
Technically simple easy to operate, product light transmittance is high, electron mobility is big, and raw material are nontoxic；Used zinc oxide light is inhaled
It is high to receive material efficiency, nontoxic, raw material is easy to get.Therefore, zinc oxide/graphite is based on method proposed by the present invention preparation is described
Alkene/zinc oxide sandwich structure photodetector, has excellent performance, low in cost, and makes and uses process economy, environmental protection.
Summary of the invention
It is a kind of based on zinc oxide/graphene/zinc oxide sandwich structure photoelectricity it is an object of the present invention to proposing
Detector, the core of this photodetector are the sandwich structures being made of zinc-oxide film/graphene/zinc-oxide film.
When this sandwich is used for photodetection, zinc oxide semi-conductor band gap can be made full use of adjustable, to ultraviolet light and can
Light-exposed absorbability is strong, while having very high exciton binding energy 60meV, and lower feature is lost, moreover it is possible in conjunction with graphene
The characteristic that light transmittance is high, electron mobility is big, makes upper layer and lower layer zinc oxide that can fully absorb signal light, efficiently separates generation
Light induced electron and hole, increase photogenerated current.Therefore, the photo detector signal based on this sandwich is strong, loud
Fast, detectivity height is answered, detector performance can be significantly improved, expand the application range of detector.
The second object of the present invention is to provide this based on zinc oxide/graphene/Zinc-oxide-based sandwich structure light
The corresponding preparation method of electric explorer.Zinc oxide/the graphene prepared in this way/Zinc-oxide-based sandwich structure is thin
Film uniformity is good, pattern thickness is controllable, without post-processing；And this method is simple with material preparation process, growth conditions is tight
Lattice are controllable, low in cost, product is nontoxic, make and use the advantages that process economy is environmentally friendly.
It is proposed by the present invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure light in order to reach above-mentioned target
Electric explorer, which is characterized in that the sandwich structure be grown on it is on the substrate of electrical isolation, from bottom to top, by aoxidizing
What zinc film/graphene/zinc-oxide film was constituted.In this zinc oxide/graphene/Zinc-oxide-based sandwich structure, zinc oxide
Film is the zinc oxide or oxygen-starved zinc-oxide film of stoichiometric ratio, and thickness 150-500nm has ultraviolet light and visible light
There is strong absorbability；Graphene is carbon monoatomic layer, and light transmittance is high, electron mobility is big, conductive capability is strong；This structure is same
When realize zinc oxide and graphene synergistic effect, have complementary advantages, the photo detector signal based on this sandwich
By force, response is fast, detectivity is high.
Preparation side provided by the invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Method, which is characterized in that the method uses sintering oxidation zinc ceramics to do target material first, in rf magnetron sputtering equipment,
Growth obtains one layer of zinc-oxide film on the substrate of electrical isolation；Then, one is shifted on zinc-oxide film with wet process transfer techniques
Layer graphene；Again on graphene layer, one layer of zinc oxide is grown with radiofrequency magnetron sputtering technology, to obtain a kind of oxidation
Zinc/graphene/zinc oxide sandwich structure；Finally, upper metal electrode is coated on upper layer and lower layer zinc-oxide film to get to institute
It states based on zinc oxide/graphene/zinc oxide sandwich structure photodetector.
Preparation side proposed by the present invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Method, includes the following steps and content:
(1) one layer of zinc-oxide film is deposited on an insulating substrate with radio-frequency magnetron sputter method；
(2) upper one layer of graphene is shifted on zinc-oxide film with wet process transfer techniques；
(3) one layer of zinc-oxide film is deposited on graphene with radio-frequency magnetron sputter method；
(4) it is coated with top electrode respectively on upper layer and lower layer zinc-oxide film, it is spare.
In the above preparation method, in the step (1) zinc-oxide film deposition method are as follows: set in rf magnetron sputtering
In standby, sintering oxidation zinc ceramics are installed on target position, cleaning substrate is fixed on sample stage；Unlatching mechanical pump is evacuated to low true
Sky, system vacuum open molecular pump when reaching 0.1Pa, until the vacuum degree of system reaches 2 × 10-4Pa or more；It then passes to
Argon working gas, first progress pre-sputtering 3-10min, the pollutant of target material surface is removed with this；After aura settles out,
It is passed through argon working gas and oxygen into system, starts the sputtering sedimentation of zinc-oxide film.
In the above preparation method, sputtering target material used in the step (1) is sintering oxidation zinc ceramics.
In the above preparation method, substrate used in the step (1) is the electrical insulation substrate of any surface finish, including band
There are silicon wafer, the sapphire sheet, one kind of strontium titanates chip of silicon dioxide insulating layer.
In the above preparation method, the depositing operation of the zinc-oxide film in the step (1) are as follows: phase is passed through into system
With the working gas oxygen and argon gas of throughput, sputtering pressure 0.3-2Pa, sputtering target power output is 60-240W, and sputtering time is
20-100min。
In the above preparation method, the graphene being grown in the step (2) on copper foil is commercial chemicals.
In the above preparation method, the technique of the graphene wet process transfer techniques in the step (2) are as follows: firstly, in life
It is longer than the graphene surface on copper foil and gets rid of a strata methyl methacrylate (PMMA), stands 1-2 days naturally dries；Then, will
FeCl3Powder is dissolved in hydrochloric acid solution (wherein, concentrated hydrochloric acid and H2O volume ratio is 1:1), it is configured to 300mL 0.1mol/L's
FeCl3Solution；The graphene being grown on copper foil is floated on into FeCl by the downward method of copper foil again3In solution, copper foil after 3-5h
Corroded completely, the graphene with PMMA is picked up with polyethylene terephthalate (PET), is put into deionized water and cleans
5-7 times；There is graphene of the substrate of zinc-oxide film by drift in deionized water surface to pick up with step (1) growth again, then will
It is put into baking oven, saves 30-60min at a temperature of 60 DEG C；Finally, sample is cleaned 5-7 times with acetone, graphene table is removed
The PMMA in face completes the transfer of graphene layer.
In the above preparation method, PMMA, PET, the FeCl used when graphene shifts in the step (2)3It is powder, dense
Hydrochloric acid is commercially available analysis pure chemistry reagent.
In the above preparation method, zinc oxide films in the deposition method of zinc-oxide film and step (1) in the step (3)
The deposition method of film is identical, and under identical process conditions, the regrowth zinc-oxide film on graphene layer, but without pre-
Sputtering.
In the above preparation method, the electrode metal used in the step (4) has one kind of gold, silver, platinum, copper, titanium.
In the above preparation method, the plating method of electrode is magnetron sputtering, thermal evaporation, electron beam in the step (4)
One kind of method of evaporating.
It is described based on zinc oxide/graphene/Zinc-oxide-based sandwich structure light using technology proposed by the present invention preparation
Electric explorer, with material preparation process, simple, growth conditions is strictly controllable, low in cost, product is nontoxic, prepares and makes
The advantages that economic and environment-friendly with process, and its zinc oxide/graphene/Zinc-oxide-based Sandwich film uniformity is good, pattern
Thickness is controllable, without post-processing；Photo detector signal based on this sandwich is strong, response is fast, detectivity
Height, excellent combination property have been widely used in field of photoelectric devices.
Detailed description of the invention
Fig. 1 is obtained by the embodiment of the present invention 1 based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photoelectricity
The schematic cross-section of detector；
Fig. 2 is obtained by the embodiment of the present invention 1 based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photoelectricity
The top view in kind of detector.
Fig. 3 is obtained by the embodiment of the present invention 1 based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photoelectricity
The photoresponse curve of detector.
Specific embodiment
Below with reference to embodiment, technical scheme is described further.
It is proposed by the present invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector, feature exists
In, the sandwich structure be grown on it is on the substrate of electrical isolation, from bottom to top, by zinc-oxide film/graphene/oxidation
What zinc film was constituted.In this zinc oxide/graphene/Zinc-oxide-based sandwich structure, zinc-oxide film is stoichiometric ratio
Zinc oxide or oxygen-starved zinc-oxide film, thickness 150-500nm have strong absorbability to ultraviolet light and visible light；Stone
Black alkene is carbon monoatomic layer, and light transmittance is high, electron mobility is big, conductive capability is strong；This structure realize simultaneously zinc oxide and
Graphene synergistic effect has complementary advantages, and the photo detector signal based on this sandwich is strong, response is fast, detection spirit
Sensitivity is high.
Preparation side provided by the invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Method, which is characterized in that the method uses sintering oxidation zinc ceramics to do target material first, in rf magnetron sputtering equipment,
Growth obtains one layer of zinc-oxide film on the substrate of electrical isolation；Then, one is shifted on zinc-oxide film with wet process transfer techniques
Layer graphene；Again on graphene layer, one layer of zinc oxide is grown with radiofrequency magnetron sputtering technology, to obtain a kind of oxidation
Zinc/graphene/zinc oxide sandwich structure；Finally, upper metal electrode is coated on upper layer and lower layer zinc-oxide film to get to institute
It states based on zinc oxide/graphene/zinc oxide sandwich structure photodetector.
Preparation side proposed by the present invention based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Method, includes the following steps and content:
(1) in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, cleaning substrate is fixed on sample
In sample platform；It opens mechanical pump and is evacuated to low vacuum, system vacuum opens molecular pump when reaching 0.1Pa, until the vacuum degree of system
Reach 2 × 10-4Pa or more；Argon working gas is then passed to, first progress pre-sputtering 3-10min, target material surface is removed with this
Pollutant；After aura settles out, it is passed through the working gas oxygen and argon gas of same airflow amount into system, adjusts sputtering
Air pressure is 0.3-2Pa, and sputtering target power output is 60-240W, starts the sputtering sedimentation of zinc-oxide film, sputtering time 20-100min.
(2) one layer of graphene is shifted on zinc-oxide film with wet process transfer techniques.Firstly, in the stone being grown on copper foil
One layer of PMMA is got rid of on black alkene surface, stands 1-2 days naturally dries；Then, by FeCl3Powder is dissolved in hydrochloric acid solution (wherein, dense salt
Acid and H2O volume ratio is 1:1), it is configured to the FeCl of 300mL0.1mol/L3Solution；Again by the graphene being grown on copper foil by
The downward method of copper foil floats on FeCl3In solution, copper foil is corroded completely after 3-5h, and the graphene of PMMA will be had with PET
It picks up, is put into deionized water and cleans 5-7 times；There is the substrate of zinc-oxide film that will float in deionized water with step (1) growth again
The graphene on surface picks up, and then places it into baking oven, saves 30-60min at a temperature of 60 DEG C；Finally, by sample with third
Ketone cleans 5-7 times, removes the PMMA of graphene surface, completes the transfer of graphene layer.
(3) in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, transfer in step (2) is had
The zinc oxide films membrane sample of graphene is fixed on sample stage；It opens mechanical pump and is evacuated to low vacuum, system vacuum reaches 0.1Pa
Shi Kaiqi molecular pump, until the vacuum degree of system reaches 2 × 10-4Pa or more；Then the work of same airflow amount is passed through into system
Make gas oxygen and argon gas, adjusting sputtering pressure is 0.3-2Pa, and sputtering target power output is 60-240W, starts splashing for zinc-oxide film
Penetrate deposition, sputtering time 20-100min.
(4) it is coated with respectively on upper layer and lower layer zinc-oxide film with magnetron sputtering, thermal evaporation or electron beam evaporation method
Electrode, it is spare.
(5) substrate used in the step (1) is the electrical insulation substrate of any surface finish, including has silicon dioxide insulator
The silicon wafer of layer, sapphire sheet, one kind of strontium titanates chip.
(6) in the above preparation method, the electrode metal used in the step (4) has one of gold, silver, platinum, copper, titanium
Kind.
Obtained zinc oxide/graphene/Zinc-oxide-based sandwich structure in appearance to be light yellow to light green color film,
It is surfacing, bright and clean, there is obvious line of demarcation between different layers.With composite electrode, that is, constitute proposed by the present invention based on zinc oxide/stone
Black alkene/Zinc-oxide-based sandwich structure photodetector.
Embodiment 1: in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, by what is cleaned up
Silicon chip substrate with silicon dioxide layer is fixed on sample stage；It opens mechanical pump and is evacuated to low vacuum, system vacuum reaches
Molecular pump is opened when 0.1Pa, until the vacuum degree of system reaches 2 × 10-4Pa or more；Argon working gas is then passed to, first
Pre-sputtering 5min is carried out, the pollutant of target material surface is removed with this；After aura settles out, same airflow is passed through into system
The working gas oxygen and argon gas of amount, adjusting sputtering pressure are 1Pa, and sputtering target power output is 120W, start splashing for zinc-oxide film
Penetrate deposition, sputtering time 30min.
Then one layer of graphene is shifted on zinc-oxide film with wet process transfer techniques.Firstly, on being grown on copper foil
Graphene surface gets rid of one layer of PMMA, stands 1 day naturally dry；Then, by FeCl3Powder is dissolved in concentrated hydrochloric acid and H2O volume ratio is 1:
In 1 hydrochloric acid solution, it is configured to the FeCl of 300mL 0.1mol/L3Solution；Again by the graphene being grown on copper foil by copper foil
Downward method floats on FeCl3In solution, copper foil is corroded completely after 3h, is picked up the graphene with PMMA with PET, is put
Enter in deionized water and cleans 5 times；There is the substrate of zinc-oxide film that will float in the graphite on deionized water surface with step (1) growth again
Alkene picks up, and then places it into baking oven, saves 60min at a temperature of 60 DEG C；Finally, sample is cleaned 5 times with acetone, remove
The PMMA of graphene surface completes the transfer of graphene layer.
Again in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, transfer is had to the oxygen of graphene
Change zinc film sample to be fixed on sample stage；It opens mechanical pump and is evacuated to low vacuum, system vacuum opens molecule when reaching 0.1Pa
Pump, until the vacuum degree of system reaches 2 × 10-4Pa or more；Then the working gas oxygen of same airflow amount is passed through into system
And argon gas, adjusting sputtering pressure are 1Pa, sputtering target power output is 120W, starts the sputtering sedimentation of zinc-oxide film, sputtering time
20-100min。
Finally upper gold electrode is coated with respectively on upper layer and lower layer zinc-oxide film with magnetron sputtering method, it is spare.
The obtained schematic cross-section based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Such as Fig. 1, top view in kind such as Fig. 2；After tested, when with irradiation level be 270 μ W/cm2, wavelength be 365nm light be irradiated,
Generating photoelectric current is about 10 μ A, and Photoresponse is about 37mA/W；Switching effect is significant, excellent combination property.
Claims (4)
1. a kind of based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector, which is characterized in that described three
Mingzhi's structure be grown on it is on the substrate of electrical isolation, from bottom to top, by zinc-oxide film/graphene/zinc-oxide film structure
At；In the zinc oxide/graphene/Zinc-oxide-based sandwich structure, zinc-oxide film be stoichiometric ratio zinc oxide or
Person's oxygen-starved zinc-oxide film.
2. the system described in accordance with the claim 1 based on zinc oxide/graphene/Zinc-oxide-based sandwich structure photodetector
Preparation Method, which is characterized in that the method uses sintering oxidation zinc ceramics to do target material first, in rf magnetron sputtering equipment
In, growth obtains one layer of zinc-oxide film on the substrate of electrical isolation；Then, turned on zinc-oxide film with wet process transfer techniques
Move one layer of graphene；Again on graphene layer, one layer of zinc oxide is grown with radiofrequency magnetron sputtering technology, to obtain a kind of oxygen
Change zinc/graphene/zinc oxide sandwich structure；Finally, upper metal electrode is coated on upper layer and lower layer zinc-oxide film to get arriving
It is described based on zinc oxide/graphene/zinc oxide sandwich structure photodetector；The following steps are included:
(1) in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, cleaning substrate is fixed on sample stage
On；It opens mechanical pump and is evacuated to low vacuum, system vacuum opens molecular pump when reaching 0.1Pa, until the vacuum degree of system reaches 2
×10-4Pa or more；Argon working gas is then passed to, first progress pre-sputtering 3-10min, the pollution of target material surface is removed with this
Object；After aura settles out, the working gas oxygen and argon gas of same airflow amount are passed through into system, adjusting sputtering pressure is
0.3-2Pa, sputtering target power output are 60-240W, start the sputtering sedimentation of zinc-oxide film, sputtering time 20-100min；
(2) a strata methyl methacrylate is got rid of in the graphene surface being grown on copper foil, stands 1-2 days naturally dries；So
Afterwards, by FeCl3Powder is dissolved in concentrated hydrochloric acid and H2In dilute hydrochloric acid solution made of O volume ratio 1:1 dilution, it is configured to 300mL
The FeCl of 0.1mol/L3Solution；The graphene being grown on copper foil is floated on into FeCl by the downward method of copper foil again3In solution,
Copper foil is corroded completely after 3-5h, is picked up the graphene with polymethyl methacrylate with polyethylene terephthalate,
It is put into deionized water and cleans 5-7 times；There is the substrate of zinc-oxide film that will float in deionized water surface with step (1) growth again
Graphene picks up, and then places it into baking oven, saves 30-60min at a temperature of 60 DEG C；Finally, sample is cleaned with acetone
5-7 times, the polymethyl methacrylate of graphene surface is removed, completes the transfer of graphene layer；
(3) in rf magnetron sputtering equipment, sintering oxidation zinc ceramics are installed on target position, transfer in step (2) is had into graphite
The zinc oxide films membrane sample of alkene is fixed on sample stage；It opens mechanical pump and is evacuated to low vacuum, system vacuum is opened when reaching 0.1Pa
Molecular pump is opened, until the vacuum degree of system reaches 2 × 10-4Pa or more；Then the work gas of same airflow amount is passed through into system
Body oxygen and argon gas, adjusting sputtering pressure are 0.3-2Pa, and sputtering target power output is 60-240W, and the sputtering for starting zinc-oxide film is heavy
Product, sputtering time 20-100min；
(4) it is coated with top electrode respectively on upper layer and lower layer zinc-oxide film with magnetron sputtering, thermal evaporation or electron beam evaporation method,
It is spare.
3. preparation method according to claim 2, which is characterized in that substrate used in the step (1) is surface light
Clean electrical insulation substrate, including the silicon wafer with silicon dioxide insulating layer, sapphire sheet, one kind of strontium titanates chip；The step
Suddenly the depositing operation of (1) and the zinc-oxide film in (3) are as follows: the working gas oxygen and argon of same airflow amount are passed through into system
Gas, sputtering pressure 0.3-2Pa, sputtering target power output are 60-240W, sputtering time 20-100min；It is adopted in the step (4)
Electrode metal has one kind of gold, silver, platinum, copper, titanium.
4. preparation method according to claim 2, which is characterized in that the graphene wet process in the step (2) shifts skill
The technique of art are as follows: firstly, getting rid of a strata methyl methacrylate in the graphene surface being grown on copper foil, stand 1-2 days certainly
So dry；Then, by FeCl3Powder is dissolved in concentrated hydrochloric acid and H2In dilute hydrochloric acid solution made of O volume ratio 1:1 dilution, it is configured to
The FeCl of 300mL0.1mol/L3Solution；The graphene being grown on copper foil is floated on into FeCl by the downward method of copper foil again3It is molten
In liquid, copper foil is corroded completely after 3-5h, and the graphene of polymethyl methacrylate will be had with polyethylene terephthalate
It picks up, is put into deionized water and cleans 5-7 times；There is the substrate of zinc-oxide film that will float in deionized water with step (1) growth again
The graphene on surface picks up, and then places it into baking oven, saves 30-60min at a temperature of 60 DEG C；Finally, by sample with third
Ketone cleans 5-7 times, removes the polymethyl methacrylate of graphene surface, completes the transfer of graphene layer.
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