CN107146830B - A method for preparing flexible and transparent graphene/silicon metal-semiconductor-metal photodetectors - Google Patents
A method for preparing flexible and transparent graphene/silicon metal-semiconductor-metal photodetectors Download PDFInfo
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- CN107146830B CN107146830B CN201710423821.XA CN201710423821A CN107146830B CN 107146830 B CN107146830 B CN 107146830B CN 201710423821 A CN201710423821 A CN 201710423821A CN 107146830 B CN107146830 B CN 107146830B
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- H10F30/00—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors
- H10F30/20—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors
- H10F30/21—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation
- H10F30/22—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes
- H10F30/227—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a Schottky barrier
- H10F30/2275—Individual radiation-sensitive semiconductor devices in which radiation controls the flow of current through the devices, e.g. photodetectors the devices having potential barriers, e.g. phototransistors the devices being sensitive to infrared, visible or ultraviolet radiation the devices having only one potential barrier, e.g. photodiodes the potential barrier being a Schottky barrier being a metal-semiconductor-metal [MSM] Schottky barrier
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Abstract
The invention discloses a kind of methods of graphene/silicon MSM-PD with low for preparing flexible and transparent, comprising: the silicon thin film of SOI silicon substrate is etched into silicon strip；Gold electrode figure, gold-plated electrode are made by lithography in the silica upper surface of the barrier of SOI silicon substrate；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 film is covered in patterned device upper surface, edge PC film is scraped off, puts into BOE etching liquid and etch away silicon substrate；Photodetector of the present invention can carry out wide spectrum detection, and it is low to solve the problems, such as that traditional silicon substrate PIN junction responds ultraviolet detector, and photo-generated carrier and silicon crystal lattice generate electron impact ionization, obtain very high gain；Preparation process of the present invention is simple, low in cost, has responsiveness high, fast response time, internal gain is big, and on-off ratio is small, the characteristics of being easily integrated.
Description
Technical field
The invention belongs to technical field of photoelectric detection, it is related to photoelectric detector structure more particularly to a kind of prepares flexibility
The method of transparent graphene/silicon MSM-PD with low
Background technique
Good electric conductivity, higher optical clarity and good mechanical flexibility make graphene become next-generation soft
Property electronic device has relatively good application prospect.Wherein graphene forms schottky junction in conjunction with semiconductor, can be applied to electricity
Son and optoelectronic areas.Although organic semiconductor is substantially flexibly, graphene-semiconductor Schottky knot is flexible electronic
The ideal chose of device.However, such as stability is poor, the main problems such as not reproducible response and device performance difference, especially with
Silicon-based devices are compared, and are limited it and are widely applied.In addition, organic semiconductor has lower migration compared with monocrystalline silicon
Rate.
Silicon pushes always electronics, photoelectron and solar-electricity as one of most important semiconductor material of twentieth century
The immense success of pond industry, wherein being used mostly in the form of monocrystalline, polycrystalline silicon wafer and amorphous and nanocrystalline thin film.By
In the bandgap structure that silicon is suitable for, mature CMOS fabrication technology, high reliability, the surface state well controlled can with low cost
Extension production and high speed optoelectronic detection, make silicon become the ideal semiconductor material for photoelectric detector.However body silicon crystal
Rigidity limit it in the application in flexible optoelectronic detector field, in terms of especially flexible detection electronic device.But work as Si
It is preferable using flexibility when film is thinned to less than 50 microns, be easily bent, and common scissor cut can be used, make its
There is certain application value in flexible electronic application.
Summary 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 preparing flexible and transparent
Category-semiconductor-metal photodetector method, comprising the following steps:
(1) silicon thin film of SOI silicon substrate is etched into 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) the gold electrode figure of silicon strip is made positioned at silicon strip two sides and is parallel to by lithography in silica upper surface of the barrier,
Then electron beam evaporation technique gold-plated electrode is used；
(3) single crystal graphene film is prepared in copper foil substrate using chemical vapor deposition method；
(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, is gone followed by plasma etching
Except extra graphene, it is graphical after single crystal graphene film coverage area in the range of gold electrode surrounds；
(6) PC film is covered in the patterned device upper surface that step obtains, scrapes off edge PC film, and put BOE quarter into
Silicon substrate is etched away in erosion liquid, prepares the ultra-thin graphene/silicon MSM-PD with low of flexible and transparent.
Further, in the step, the silicon film thickness is 200nm, silicon strip with a thickness of 200nm, silica every
Absciss layer is with a thickness of 100nm.
Further, in the step, growth thickness is the chromium adhesion layer of 5nm first on silica separation layer, so
The gold electrode of 60nm is grown afterwards.
Further, in the step, the transfer method of graphene are as follows: single crystal graphene film surface is uniformly coated one
Layer polymethyl methacrylate film, is then placed in 4h erosion removal 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 supports 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 methylene chloride and isopropanol
E pioic acid methyl ester；Wherein, the etching solution is made of CuSO4, HCl and water, CuSO4:HCl:H2O=10g:50ml:50ml.
The invention has the following advantages: the detector using graphene as active layer and transparent electrode, eliminates dead layer,
Enhance the absorption of incident light；Silica separation layer reduces the influence of silicon face state, while inhibiting reverse saturation current；?
Smaller bias can work normally, and patterned silicon strip thickness used in the present invention is about 200nm, 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, improve the performance of photodetector；
The ultra-thin graphene MSM photoelectric detector flexibility prepared is good and transparent, can theoretically be transferred on any carrier, 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 directed toward by silicon.Electric field is stronger under reverse biased, and photohole is mobile 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
For electric explorer material therefor using silicon as basic material, preparation process is simple, at low cost, easily simultaneous with existing semiconductor standard processes
Hold.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of the graphene/silicon MSM-PD with low of flexible and transparent of the present invention；
Fig. 2 be in the present invention work of photodetector prepared by embodiment at -2-2V, under different incident optical powers
Light opens the optical response plot figure that lower device is closed with light；
(a) is equipment used in ultraviolet imagery in the present invention in Fig. 3；(b) it is labeled as the original image of ZJU；It (c) is ultraviolet lighting
Penetrate the lower figure that ZJU is presented；(d) it is labeled as the original image of ISEE；(e) figure for ISEE is presented under ultraviolet light.
Specific embodiment
A kind of work of the graphene/silicon MSM-PD with low of flexible and transparent provided by the invention is former
It manages 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 is directed toward graphene by silicon.Electric field is more under reverse biased
By force, photohole is mobile to graphene, and light induced electron then flows to silicon substrate, forms photogenerated current.Patterned silicon strip thickness is about
Brightness electricity can be effectively distinguished much smaller than the separation that the diffusion length (μm) of body silicon is conducive to photo-generated carrier for 200nm
Stream, improves the performance of photodetector.Graphene MSM detector of the invention can be transferred on PC film.
The present invention is further illustrated with reference to the accompanying drawings and examples.
A kind of graphene/silicon MSM-PD with low preparing above-mentioned flexible and transparent provided by the invention
Method, comprising the following steps:
(1) silicon thin film of SOI silicon substrate (1) is etched into rectangular silicon strip (3) using deep energy level reactive ion etching machine ICP,
The SOI silicon substrate (1) includes silicon thin film, silica separation layer (2) and silicon substrate (1) from top to bottom；
(2) it makes by lithography in silica separation layer (2) upper surface positioned at silicon strip (3) two sides and is parallel to the gold of silicon strip (3)
Then electrode pattern uses electron beam evaporation technique gold-plated electrode (4)；
(3) single crystal graphene film (5) are prepared in copper foil substrate using chemical vapor deposition method；
(4) single crystal graphene film (5) are covered in silica separation layer (2), silicon strip (3) and gold electrode (4) upper surface；
(5) single crystal graphene film (5) are patterned into interdigitation using photoetching technique, followed by plasma etching
Remove extra graphene, it is graphical after single crystal graphene film (5) the range surrounded in gold electrode (4) of coverage area
It is interior；
(6) PC film is covered in the patterned device upper surface that step (5) obtains, scrapes off edge PC film, and put BOE into
Silicon substrate (1) is etched away in etching liquid, prepares the ultra-thin graphene/silicon metal-semiconductor-metal photodetection of flexible and transparent
Device.
The graphene/silicon MSM-PD with low ultra-thin to above-mentioned flexible and transparent adds small bias, makes it
It works normally, adds different incident optical powers to realize gain, as shown in Figure 2.
Flexible and transparent prepared by the present embodiment graphene/silicon MSM-PD with low work-
Under 2-2V, the brightness current curve variation under the light irradiation of the different incident optical powers of 405nm 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 generate apparent photoelectric current when being gradually increased to 0.4mW from 0.2 smooth function.As shown in Figure 2
When device works in -2-2V, curve is in smooth S type curve, i.e., back-to-back schottky junction characteristic curve.Discovery is tested simultaneously
Device all has 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, and is had excellent performance.
Claims (3)
1. a kind of method for the graphene/silicon MSM-PD with low for preparing flexible and transparent, which is characterized in that
The following steps are included:
(1) silicon thin film of SOI silicon substrate (1) is etched rectangular silicon strip (3) using deep energy level reactive ion etching machine ICP, it is described
SOI silicon substrate (1) includes silicon thin film, silica separation layer (2) and silicon substrate (1) from top to bottom；
The silicon film thickness is 200 nm, and silicon strip (3) is with a thickness of 200 nm, and silica separation layer (2) is with a thickness of 100 nm；
(2) it makes by lithography in silica separation layer (2) upper surface positioned at silicon strip (3) two sides and is parallel to the gold electrode of silicon strip (3)
Then figure uses electron beam evaporation technique gold-plated electrode (4)；
(3) single crystal graphene film (5) are prepared in copper foil substrate using chemical vapor deposition method；
(4) single crystal graphene film (5) are covered in silica separation layer (2), silicon strip (3) and gold electrode (4) upper surface；
(5) single crystal graphene film (5) are patterned into interdigitation using photoetching technique, are removed followed by plasma etching
Extra graphene, it is graphical after single crystal graphene film (5) coverage area in the range of gold electrode (4) surround；
(6) PC film is covered in the patterned device upper surface that step (5) obtains, scrapes off edge PC film, and put BOE etching into
Silicon substrate (1) is etched away in liquid, prepares the ultra-thin graphene/silicon MSM-PD with low of flexible and transparent.
2. a kind of graphene/silicon metal-semiconductor-metal photodetection for preparing flexible and transparent according to claim 1
The method of device, which is characterized in that in the step (2), growth thickness is the chromium of 5 nm first on silica separation layer (2)
Then adhesion layer grows the gold electrode (4) of 60 nm.
3. a kind of graphene/silicon metal-semiconductor-metal photodetection for preparing flexible and transparent according to claim 1
The method of device, which is characterized in that in the step (4), the transfer method of graphene are as follows: by single crystal graphene film (5) surface
Uniformly one layer of polymethyl methacrylate film of coating, is then placed in 4h erosion removal 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 of CuSO4, HCl and water, CuSO4:
HCl:H2O=10g:50ml:50ml.
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| CN108257946B (en) * | 2017-11-30 | 2020-05-12 | 中国科学院微电子研究所 | Photodetector and method of making the same |
| 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 |
| CN108281443B (en) * | 2018-01-29 | 2021-05-11 | 杭州紫元科技有限公司 | Graphene/silicon heterojunction CCD pixel array based on SOI substrate and preparation method thereof |
| 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 |
| CN111952402B (en) * | 2020-08-26 | 2023-04-25 | 合肥工业大学 | A color detector based on graphene/ultra-thin silicon/graphene heterojunction and its preparation method |
| CN113782640B (en) * | 2021-09-10 | 2023-02-21 | 中国科学院半导体研究所 | Preparation method and system of detector chip based on graphene-CMOS monolithic integration |
| 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 |
| CN114583003B (en) * | 2022-04-29 | 2022-10-11 | 浙江大学 | Vertical photoelectric detector based on silicon/graphene nano-film/germanium and preparation method |
| CN119836113B (en) * | 2025-01-02 | 2025-12-05 | 浙江大学 | A self-driven transparent ultraviolet flexible photodetector and image sensing array |
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| CN104810411B (en) * | 2014-01-24 | 2018-07-06 | 中国科学院上海微系统与信息技术研究所 | A kind of photoconductive UV detector and preparation method thereof |
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