CN107146830A - A kind of method for the graphene/silicon metal-semiconductor-metal photo detector for preparing flexible and transparent - Google Patents
A kind of method for the graphene/silicon metal-semiconductor-metal photo detector for preparing flexible and transparent Download PDFInfo
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- CN107146830A CN107146830A CN201710423821.XA CN201710423821A CN107146830A CN 107146830 A CN107146830 A CN 107146830A CN 201710423821 A CN201710423821 A CN 201710423821A CN 107146830 A CN107146830 A CN 107146830A
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- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 79
- 239000010703 silicon Substances 0.000 title claims abstract description 79
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 9
- 239000002184 metal Substances 0.000 title claims abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000010408 film Substances 0.000 claims abstract description 35
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 238000005530 etching Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000001459 lithography Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001020 plasma etching Methods 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 239000011889 copper foil Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims description 3
- 238000005566 electron beam evaporation Methods 0.000 claims description 3
- 230000003628 erosive effect Effects 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 238000001514 detection method Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000004043 responsiveness Effects 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 7
- 230000005684 electric field Effects 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 230000005693 optoelectronics Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Classifications
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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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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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
- H01L31/10—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 characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
- H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type
- H01L31/1085—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type the devices being of the Metal-Semiconductor-Metal [MSM] Schottky barrier type
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a kind of method for the graphene/silicon metal-semiconductor-metal photo detector for preparing flexible and transparent, including：The silicon thin film of SOI silicon substrates is etched into silicon strip；Gold electrode figure, gold-plated electrode are made by lithography in the silica separation layer upper surface of SOI silicon substrates；Prepare single crystal graphene film；Single crystal graphene film is covered in silica separation layer, silicon strip and gold electrode upper surface；Single crystal graphene film pattern is melted into interdigitation；PC films are covered in patterned device upper surface, edge PC films is scraped off, puts into BOE etching liquids and etch away silicon substrate；Photodetector of the present invention can carry out wide spectrum detection, solve the problem of traditional silicon substrate PIN junction is low to ultraviolet detector response, photo-generated carrier produces electron impact ionization with silicon crystal lattice, obtains very high gain；Preparation technology of the present invention is simple, with low cost, high with responsiveness, and fast response time, internal gain is big, and on-off ratio is small, it is easy to the characteristics of integrated.
Description
Technical field
The invention belongs to technical field of photoelectric detection, it is related to photoelectric detector structure, more particularly to one kind prepares flexibility
The method of transparent graphene/silicon MSM-PD with low
Background technology
Good electric conductivity, higher optical clarity and good mechanical flexibility cause graphene to turn into of future generation soft
Property electronic device has relatively good application prospect.Wherein graphene combines to form schottky junction with semiconductor, can be applied to electricity
Son and optoelectronic areas.Although organic semiconductor is substantially flexible, graphene-semiconductor Schottky knot is flexible electronic
The ideal chose of device.However, such as stability is poor, the subject matter such as not reproducible response and device performance difference, particularly with
Silicon-based devices are compared, and are limited it and are widely applied.In addition, compared with monocrystalline silicon, organic semiconductor has relatively low migration
Rate.
Silicon promotes electronics, photoelectron and solar-electricity always as one of most important semi-conducting material of twentieth century
The immense success of pond industry, wherein many used in the form of monocrystalline, polycrystalline silicon wafer and amorphous and nanocrystalline thin film.By
In the suitable bandgap structure of silicon, ripe CMOS fabrication technology, high reliability, the surface state well controlled can with low cost
Extension production and high speed optoelectronic detection, make silicon turn into the ideal semiconductor material for photoelectric detector.But body silicon crystal
Rigidity limit its application in flexible optoelectronic detector field, in terms of particularly flexible detection electronic device.But, work as Si
When film is thinned to less than 50 microns, using pliability preferably, be easily bent, and common scissor cut can be used, make its
There is certain application value in flexible electronic application.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of graphene/silicon gold for preparing flexible and transparent
The method of category-SEMICONDUCTOR-METAL (MSM) photodetector.
The purpose of the present invention is achieved through the following technical solutions：A kind of graphene/silicon gold for preparing flexible and transparent
The method of category-SEMICONDUCTOR-METAL photodetector, comprises the following steps：
(1) silicon thin film of SOI silicon substrates is etched to rectangular silicon strip, the SOI using deep energy level reactive ion etching machine ICP
Silicon substrate includes silicon thin film, silica separation layer and silicon substrate from top to bottom；
(2) made by lithography in silica separation layer upper surface positioned at silicon strip both sides and parallel to the gold electrode figure of silicon strip,
Then electron beam evaporation technique gold-plated electrode is used；
(3) single crystal graphene film is prepared in copper foil substrate using chemical gaseous phase depositing process；
(4) single crystal graphene film is covered in silica separation layer, silicon strip and gold electrode upper surface；
(5) single crystal graphene film is patterned into interdigitation using photoetching technique, gone followed by plasma etching
Except unnecessary graphene, it is graphical after single crystal graphene film coverage in the range of gold electrode encirclement；
(6) the patterned device upper surface obtained in step covers PC films, scrapes off edge PC films, and put BOE quarters into
Silicon substrate is etched away in erosion liquid, the ultra-thin graphene/silicon MSM-PD with low of flexible and transparent is prepared.
Further, in the step, the silicon film thickness be 200nm, silicon strip thickness be 200nm, silica every
Absciss layer thickness is 100nm.
Further, in the step, growth thickness is 5nm chromium adhesion layer first on silica separation layer, so
60nm gold electrode is grown afterwards.
Further, in the step, the transfer method of graphene is：By the uniformly coating one of single crystal graphene film surface
Layer polymethyl methacrylate film, is then placed in 4h erosion removals copper foil in etching solution, leaves by poly-methyl methacrylate
The single crystal graphene film of ester support；After the single crystal graphene film that polymethyl methacrylate is supported is cleaned with deionized water
It is transferred to the upper surface of silica separation layer, silicon strip and gold electrode；Finally poly- methyl-prop is removed with dichloromethane and isopropanol
E pioic acid methyl ester；Wherein, the etching solution is made up of CuSO4, HCl and water, CuSO4：HCl：H2O=10g:50ml:50ml.
The invention has the advantages that：The detector eliminates dead layer using graphene as active layer and transparency electrode,
Strengthen the absorption of incident light；Silica separation layer reduces the influence of silicon face state, while inhibiting reverse saturation current；
Smaller bias can normal work, the patterned silicon strip thickness about 200nm that uses in the present invention, much smaller than the diffusion of body silicon
Length (μm), is conducive to the separation of photo-generated carrier, can effectively distinguish brightness electric current, improves the performance of photodetector；
The ultra-thin graphene MSM photoelectric detector pliability prepared is good and transparent, can be transferred on any carrier in theory, and have
There is good performance.Ultraviolet imagery can be carried out to its array simultaneously.Incident light is irradiated to photodetector surfaces of the present invention, by stone
Black alkene and silicon substrate absorb.The photo-generated carrier (hole-electron pair) of generation is separated under built-in electric field action, direction of an electric field
Graphene is pointed to by silicon.Electric field is stronger under reverse biased, and photohole is moved to graphene, and light induced electron then flows to silicon substrate,
Form photogenerated current.MSM photoelectric detector is interdigital structure in the present invention, can carry out ultraviolet imagery to its array.Light of the present invention
Electric explorer material therefor is using silicon as stock, and preparation process is simple, and cost is low, easily simultaneous with existing semiconductor standard processes
Hold.
Brief description of the drawings
Fig. 1 is the structural representation of the graphene/silicon MSM-PD with low of flexible and transparent of the present invention；
Fig. 2 is operated under -2-2V for the photodetector in the present invention prepared by embodiment, under different incident optical powers
Light opens the optical response plot figure that lower device is closed with light；
(a) is the equipment used in ultraviolet imagery in the present invention in Fig. 3；(b) it is labeled as ZJU artwork；(c) it is ultraviolet lighting
Penetrate lower presentation ZJU figure；(d) it is labeled as ISEE artwork；(e) it is the figure of presentation ISEE under ultraviolet light.
Embodiment
A kind of work of the graphene/silicon MSM-PD with low for flexible and transparent that the present invention is provided is former
Reason is as follows：
Incident light is irradiated to photodetector surfaces of the present invention, is absorbed by graphene and silicon substrate.The photoproduction current-carrying of generation
Sub (hole-electron pair) is separated under built-in electric field action, and direction of an electric field points to graphene by silicon.Electric field is more under reverse biased
By force, photohole is moved to graphene, and light induced electron then flows to silicon substrate, forms photogenerated current.Patterned silicon strip thickness is about
For 200nm, the diffusion length (μm) much smaller than body silicon is conducive to the separation of photo-generated carrier, can effectively distinguish brightness electricity
Stream, improves the performance of photodetector.The graphene MSM detectors of the present invention can be transferred on PC films.
The present invention is further illustrated with reference to the accompanying drawings and examples.
A kind of graphene/silicon MSM-PD with low for preparing above-mentioned flexible and transparent that the present invention is provided
Method, comprise the following steps：
(1) silicon thin film of SOI silicon substrates (1) is etched to rectangular silicon strip (3) using deep energy level reactive ion etching machine ICP,
The SOI silicon substrates (1) include silicon thin film, silica separation layer (2) and silicon substrate (1) from top to bottom；
(2) made by lithography in silica separation layer (2) upper surface positioned at silicon strip (3) both sides and parallel to the gold of silicon strip (3)
Electrode pattern, then using electron beam evaporation technique gold-plated electrode (4)；
(3) single crystal graphene film (5) is prepared in copper foil substrate using chemical gaseous phase depositing process；
(4) in silica separation layer (2), silicon strip (3) and gold electrode (4) upper surface covering single crystal graphene film (5)；
(5) single crystal graphene film (5) is patterned into interdigitation using photoetching technique, followed by plasma etching
Remove unnecessary graphene, it is graphical after single crystal graphene film (5) the scope surrounded in gold electrode (4) of coverage
It is interior；
(6) the patterned device upper surface obtained in step (5) covers PC films, scrapes off edge PC films, and put BOE into
Silicon substrate (1) is etched away in etching liquid, the ultra-thin graphene/silicon metal-semiconductor-metal photodetection of flexible and transparent is prepared
Device.
The graphene/silicon MSM-PD with low ultra-thin to above-mentioned flexible and transparent adds small bias, makes it
Normal work, plus different incident optical powers realize gain, as shown in Figure 2.
The graphene/silicon MSM-PD with low of flexible and transparent prepared by the present embodiment is operated in-
Under 2-2V, the brightness current curve change under the light irradiation of 405nm different incident optical powers is as shown in Figure 2.Wherein in device
Add small bias on the gold electrode 4 of part.Figure it is seen that prepared device is under no light condition, dark current very little；And work as
Incident wavelength 405nm, incident optical power produce obvious photoelectric current when being gradually increased to 0.4mW from 0.2 smooth work(.As shown in Figure 2
When device is operated in -2-2V, curve is in smooth S type curves, i.e., back-to-back schottky junction characteristic curve.Test and find simultaneously
Device is respectively provided with very superior photodetection characteristic to near-infrared ultraviolet.
Fig. 3 is array type device in ultraviolet imagery figure, it can be seen that figure is apparent from, excellent performance.
Claims (4)
1. a kind of method for the graphene/silicon MSM-PD with low for preparing flexible and transparent, it is characterised in that
Comprise the following steps：
(1) silicon thin film of SOI silicon substrates (1) is etched to rectangular silicon strip (3) using deep energy level reactive ion etching machine ICP, it is described
SOI silicon substrates (1) include silicon thin film, silica separation layer (2) and silicon substrate (1) from top to bottom；
(2) made by lithography in silica separation layer (2) upper surface positioned at silicon strip (3) both sides and parallel to the gold electrode of silicon strip (3)
Figure, then using electron beam evaporation technique gold-plated electrode (4)；
(3) single crystal graphene film (5) is prepared in copper foil substrate using chemical gaseous phase depositing process；
(4) in silica separation layer (2), silicon strip (3) and gold electrode (4) upper surface covering single crystal graphene film (5)；
(5) single crystal graphene film (5) is patterned into interdigitation using photoetching technique, removed followed by plasma etching
Unnecessary graphene, it is graphical after single crystal graphene film (5) coverage in the range of gold electrode (4) encirclement；
(6) the patterned device upper surface obtained in step (5) covers PC films, scrapes off edge PC films, and put BOE etchings into
Silicon substrate (1) is etched away in liquid, the ultra-thin graphene/silicon MSM-PD with low of flexible and transparent is prepared.
2. a kind of graphene/silicon metal-semiconductor-metal photodetection for preparing flexible and transparent according to claim 1
The method of device, it is characterised in that in the step (1), the silicon film thickness is 200nm, and silicon strip (3) thickness is 200nm, two
Silica separation layer (2) thickness is 100nm.
3. a kind of graphene/silicon metal-semiconductor-metal photodetection for preparing flexible and transparent according to claim 1
The method of device, it is characterised in that in the step (2), growth thickness is 5nm chromium first on silica separation layer (2)
Adhesion layer, then grows 60nm gold electrode (4).
4. a kind of graphene/silicon metal-semiconductor-metal photodetection for preparing flexible and transparent according to claim 1
The method of device, it is characterised in that in the step (4), the transfer method of graphene is：By single crystal graphene film (5) surface
Uniformly one layer of polymethyl methacrylate film of coating, is then placed in 4h erosion removals copper foil in etching solution, leaves by poly- first
The single crystal graphene film (5) of base methyl acrylate support；The single crystal graphene film (5) that polymethyl methacrylate is supported
The upper surface of silica separation layer (2), silicon strip (3) and gold electrode (4) is transferred to after being cleaned with deionized water；Finally use dichloro
Methane and isopropanol remove polymethyl methacrylate；Wherein, the etching solution is made up of CuSO4, HCl and water, CuSO4：
HCl：H2O=10g:50ml:50ml.
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Cited By (8)
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| CN108054180A (en) * | 2018-01-29 | 2018-05-18 | 杭州紫元科技有限公司 | A kind of charge coupling device based on graphene/insulating layer/semiconductor structure |
| CN108257946A (en) * | 2017-11-30 | 2018-07-06 | 中国科学院微电子研究所 | Photodetector and its production method |
| CN108281453A (en) * | 2018-01-29 | 2018-07-13 | 杭州紫元科技有限公司 | A kind of flexibility charge coupling device and preparation method thereof |
| CN108281443A (en) * | 2018-01-29 | 2018-07-13 | 杭州紫元科技有限公司 | A kind of graphene/silicon hetero-junctions CCD pixel array and preparation method thereof based on SOI substrate |
| CN111952402A (en) * | 2020-08-26 | 2020-11-17 | 合肥工业大学 | Color detector based on graphene/ultrathin silicon/graphene heterojunction and preparation method thereof |
| CN113782640A (en) * | 2021-09-10 | 2021-12-10 | 中国科学院半导体研究所 | Preparation method and system of detector chip based on graphene-CMOS monolithic integration |
| CN114583003A (en) * | 2022-04-29 | 2022-06-03 | 浙江大学 | Vertical photoelectric detector based on silicon/graphene nano-film/germanium and preparation method |
| CN114864736A (en) * | 2022-02-24 | 2022-08-05 | 电子科技大学 | Novel exciton regulating device based on two-dimensional transition metal sulfide semiconductor and preparation method and regulating method thereof |
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