CN106601857A - Photoconductive detector based on boron-doped silicon quantum dot/graphene/silicon dioxide and preparation method thereof - Google Patents

Photoconductive detector based on boron-doped silicon quantum dot/graphene/silicon dioxide and preparation method thereof Download PDF

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CN106601857A
CN106601857A CN201611045911.1A CN201611045911A CN106601857A CN 106601857 A CN106601857 A CN 106601857A CN 201611045911 A CN201611045911 A CN 201611045911A CN 106601857 A CN106601857 A CN 106601857A
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boron
quantum dot
graphene
electrode
film
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CN106601857B (en
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徐杨
马玲玲
刘雪梅
倪朕伊
杜思超
皮孝东
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浙江大学
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    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/08Semiconductor devices sensitive to infra-red 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
    • H01L31/09Devices sensitive to infra-red, visible or ultraviolet radiation
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    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
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    • H01L31/0224Electrodes
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/0248Semiconductor devices sensitive to infra-red 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
    • H01L31/0352Semiconductor devices sensitive to infra-red 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
    • H01L31/035209Semiconductor devices sensitive to infra-red 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 comprising a quantum structures
    • H01L31/035218Semiconductor devices sensitive to infra-red 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 comprising a quantum structures the quantum structure being quantum dots
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    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L31/00Semiconductor devices sensitive to infra-red 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
    • H01L31/18Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H01L31/1804Processes 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 System
    • YGENERAL 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
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Abstract

The invention discloses a photoconductive detector based on boron-doped silicon quantum dot/graphene/silicon dioxide and a preparation method thereof. The photoconductive detector includes a p-type silicon substrate, a silicon dioxide isolation layer, a top electrode, a graphene film, a boron-doped silicon quantum dot film and a bottom electrode. The photoconductive detector is capable of carrying out wide-spectrum detection, so that a problem of low response to infrared detection by the traditional silicon-based PIN structure can be solved. Because the graphene is used to form an active layer and a transparent electrode, a dead layer is eliminated and incident light absorption is enhanced. With the silicon dioxide isolation layer, the silicon surface state can be reduced. The detector can work normally at a low bias voltage; the absorbed light of the boron-doped silicon quantum dot layer is converted into photon-generated carriers and the generated photon-generated carriers being hole electron pairs are separated under the effect of the built-in electric field, so that the high gain can be obtained. In addition, the preparation method is simple; the cost is low; the response degree is high; the response speed is fast; the internal gain is high; the switch ratio is low; and integration is easy to realize.

Description

Photoconductive detector and preparation based on boron-doping silicon quantum dot/graphene/silicon dioxide Method
Technical field
The invention belongs to technical field of photoelectric detection, is related to photoelectric detector structure, more particularly to it is a kind of based on boron-doping The photoconductive detector (FET) of silicon quantum dot/graphene/silicon dioxide and preparation method.
Background technology
Optical detector has a wide range of applications at aspects such as chemical material analysis, health care, space technologies.Light electrical resistivity survey The advantages of survey utensil has high sensitivity, high optic response, fast response time, there is weight in terms of High Speed Modulation and small-signal monitoring Apply.Traditional silicon substrate PIN junction type sensitive detection parts need thermal diffusion or ion implantation technology, and infrared light is hardly inhaled Receive, therefore infrared band response reduces rapidly even zero with the increase of lambda1-wavelength.Accordingly, it would be desirable to improve silicon optical detection Response of the device to long-wavelength infrared light.
Graphene is by individual layer sp2Hydbridized carbon atoms constitute cellular two dimensional surface crystal film, with excellent power, The performances such as heat, light, electricity.Different from common metal, Graphene is a kind of with transparent and flexible New Two Dimensional conductive material.It is single Layer graphene only absorbs 2.3% light, can be used as transparent conductive film.Boron-doping silicon quantum dot is by cold plasma legal system Standby.Boron doped silicon quantum dot just can be prepared by adding the presoma of boron atom in the plasma.Boron-doping silicon quantum Point has absorption in visible ray near-infrared or even mid-infrared, and especially mid-infrared has stronger absworption peak, there is local plasma Excimer effect (LSPR), preparation process is simple is widely used in photodetection field.Due to boron-doping silicon quantum dot film and stone Black alkene contact, while being also a layer anti-reflection film, can reduce surface recombination to Graphene transfer charge, can solve the problems, such as dead layer, carry High IR optic response.
The content of the invention
Present invention aims to the deficiencies in the prior art, there is provided one kind is based on boron-doping silicon quantum dot/Graphene/bis- The photoconductive detector and preparation method of silica.
The purpose of the present invention is achieved through the following technical solutions:One kind is based on boron-doping silicon quantum dot/Graphene/bis- The photoconductive detector of silica, including:P-type silicon substrate, silica separation layer, top electrode, graphene film, boron-doped silicon amount Son point film and hearth electrode;Wherein, the upper surface of the p-type silicon substrate covers silica separation layer, in silica isolation The upper surface of layer covers two pieces of top electrodes, on the silica separation layer between two pieces of top electrode upper surfaces and two pieces of top electrodes Surface covers graphene film, and in graphene film upper surface boron-doping silicon quantum dot film is covered, and sets in p-type silicon substrate lower surface Bottom set electrode.
Further, described silica separation layer thickness is 100nm.
Further, described top electrode is metal film electrode, and material is aluminium, gold or golden evanohm.
Further, described hearth electrode is metal film electrode, and material is gallium-indium alloy, titanium alloy or aluminium.
Further, described boron-doping silicon quantum dot is prepared by cold plasma method, by the plasma The presoma for adding boron atom prepares boron doped silicon quantum dot;The presoma of boron atom is diborane (B2H6).Boron-doping silicon quantum Point has absorption in visible ray near-infrared or even mid-infrared, and especially mid-infrared has stronger absworption peak, there is local plasma Excimer effect (LSPR).
A kind of preparation method based on boron-doping silicon quantum dot/graphene/silicon dioxide photoconductive detector, including following step Suddenly:
(1) in the upper surface oxidation growth silica separation layer of p-type silicon substrate, the resistivity of p-type silicon substrate used is< 0.01Ω·cm;The thickness of silica separation layer is 100nm, and growth temperature is 900~1200 DEG C;
(2) two pieces of top electrode figures are made by lithography in silica insulation surface, it is first then using electron beam evaporation technique First growth thickness is about the chromium adhesion layer of 5nm, and then growth thickness is the top electrode of 60nm;
(3) preparation of graphene film:Graphene film is prepared in Copper Foil substrate using chemical gaseous phase depositing process;
(4) the silica separation layer upper surface between two pieces of top electrode upper surfaces and two pieces of top electrodes covers Graphene Film;Wherein, the transfer method of Graphene is:By graphene film surface, uniformly one strata methyl methacrylate of coating is thin Film, is then placed in 4h erosion removals Copper Foil in etching solution, leaves the graphene film supported by polymethyl methacrylate;Will Silica separation layer and top electrode are transferred to after the graphene film deionized water cleaning that polymethyl methacrylate is supported Upper surface;Finally remove polymethyl methacrylate with acetone and isopropanol;Wherein, the etching solution is by CuSO4、HCl With water composition, CuSO4:HCl:H2O=10g:50ml:50ml;
(5) in one layer of boron-doping silicon quantum dot film of patterned device surface spin coating, boron-doping silicon quantum dot is outstanding in visible ray Its infrared band has very strong absworption peak, particle size 6nm, rotating speed 2000rpm, 30s.Thickness is about 105nm.
(6) gallium indium slurry is coated in p-type silicon substrate bottom, prepares gallium indium hearth electrode, formed ohm with p-type silicon substrate and connect Touch.
The invention has the advantages that:
1. incident illumination is mapped to photodetector surfaces of the present invention, is inhaled by Graphene and boron-doping silicon quantum dot and substrate Receive.Plus little bias is added to device two ends, the photo-generated carrier (hole-electron pair) of generation is separated under built in field effect, empty Cave is captured in boron-doping silicon quantum dot by defect state, and electric charge is quickly detached under electric field action, before minority carrier is released, Repeatedly circulated in the loop equivalent to electric charge, so as to form very big optical signal current, with very high gain.
2. boron-doping silicon quantum dot has very strong absworption peak in visible ray especially infrared band, there is local plasma excimer effect Should.Incident light is easily inhaled, and the electron hole of generation is separated quickly by internal electric field, reduces surface recombination, eliminates dead layer.Red Outer smooth region, quantum efficiency is very high.
3. Graphene strengthens absorbing incident light as transparency electrode, photogenerated current is improved, with very high optic response. The carrier mobility of Graphene is very big, can improve the time response of device.
4. photodetector material therefor of the present invention is with silicon as stock, and preparation process is simple, low cost, easily with it is existing Semiconductor standard processes are compatible.
Description of the drawings
Fig. 1 is structural representation of the present invention based on the photoconductive detector of boron-doping silicon quantum dot/graphene/silicon dioxide Figure;
Fig. 2 is that the photodetector in the present invention prepared by embodiment is operated under -1-1V voltages, and 532nm, light energy are 0.2μW/cm2Infrared light light open with light close under device optical response plot figure.
Specific embodiment
With reference to the accompanying drawings and examples the present invention is further illustrated.
As shown in figure 1, a kind of photoconduction based on boron-doping silicon quantum dot/graphene/silicon dioxide that the present invention is provided is visited Device is surveyed, including:P-type silicon substrate 1, silica separation layer 2, top electrode 3, graphene film 4, the and of boron-doping silicon quantum dot film 5 Hearth electrode 6;Wherein, the upper surface of the p-type silicon substrate 1 covers silica separation layer 2, in the upper of silica separation layer 2 Surface covers two pieces of top electrodes 3, the upper table of silica separation layer 2 between two pieces of upper surfaces of top electrode 3 and two pieces of top electrodes 3 Face covers graphene film 4, boron-doping silicon quantum dot film 5 is covered in the upper surface of graphene film 4, in the lower surface of p-type silicon substrate 1 Hearth electrode 6 is set.
Further, the described thickness of silica separation layer 2 is 100nm.
Further, described top electrode 3 is metal film electrode, and material is aluminium, gold or golden evanohm.
Further, described hearth electrode 6 is metal film electrode, and material is gallium-indium alloy, titanium alloy or aluminium.
Further, described boron-doping silicon quantum dot 5 is prepared by cold plasma method, by the plasma The presoma for adding boron atom prepares boron doped silicon quantum dot;The presoma of boron atom is diborane (B2H6).Boron-doping silicon quantum Point has absorption in visible ray near-infrared or even mid-infrared, and especially mid-infrared has stronger absworption peak, there is local plasma Excimer effect (LSPR).
Operation principle of the present invention based on the photoconductive detector of boron-doping silicon quantum dot/graphene/silicon dioxide is as follows:
Incident illumination is mapped to photodetector surfaces of the present invention, is absorbed by Graphene and boron-doping silicon quantum dot and substrate. Plus little bias is added to device two ends, the photo-generated carrier (hole-electron pair) of generation is separated under built in field effect, hole Captured by defect state in boron-doping silicon quantum dot, electric charge is quickly detached under electric field action, before minority carrier is released, phase When repeatedly being circulated in the loop in electric charge, so as to form very big optical signal current, with very high gain.
Boron-doping silicon quantum dot has very strong absworption peak in visible ray especially infrared band, and incident light is easily inhaled, generation Electron hole is separated quickly by internal electric field, reduces surface recombination, eliminates dead layer.In infrared light region, quantum efficiency is very high.
The method for preparing the above-mentioned photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide, including it is following Step:
(1) in upper surface oxidation growth silica separation layer (2) of p-type silicon substrate (1), p-type silicon substrate (1) used Resistivity is<0.01Ω·cm;The thickness of silica separation layer (2) is 100nm, and growth temperature is 900~1200 DEG C;
(2) two pieces of top electrode (3) figures are gone out in silica separation layer (2) photomask surface, then using electron beam evaporation Technology, first growth thickness are about the chromium adhesion layer of 5nm, and then growth thickness is the gold electrode of 60nm;
(3) preparation of graphene film (4):Graphene film is prepared in Copper Foil substrate using chemical gaseous phase depositing process (4);
(4) silica separation layer (2) upper surface between two pieces of top electrode (3) upper surfaces and two pieces of top electrodes (3) Cover graphene film (4);Wherein, the transfer method of Graphene is:Graphene film (4) surface is uniformly coated into a strata first Base methyl acrylate (PMMA) film, is then placed in 4h erosion removals Copper Foil in etching solution, stays by poly-methyl methacrylate The graphene film (4) that ester is supported;Turn after graphene film (4) the deionized water cleaning that polymethyl methacrylate is supported Move on to the upper surface of silica separation layer (2) and top electrode (3);Finally remove poly-methyl methacrylate with acetone and isopropanol Ester;Wherein, the etching solution is by CuSO4, HCl and water composition, CuSO4:HCl:H2O=10g:50ml:50ml;
(5) in one layer of boron-doping silicon quantum dot film (5) of patterned device surface spin coating, boron-doping silicon quantum dot is in visible ray Especially infrared band has very strong absworption peak, particle size 6nm, rotating speed 2000rpm, 30s.
(6) gallium indium slurry is coated in p-type silicon substrate (1) bottom, gallium indium hearth electrode (6) is prepared, with p-type silicon substrate (1) shape Into Ohmic contact.
Little bias is added to the above-mentioned photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide so as to normal Work, plus different illumination conditions realize gain.As shown in Figure 1.
Being operated in based on the photoconductive detector of boron-doping silicon quantum dot/graphene/silicon dioxide prepared by this example- Under 1V-1V voltages, the photoelectric current and gain under the light irradiation of different wave length and power is as shown in Figure 2 with wavelength change curve. Add little bias wherein on the top electrode 3 of device, -50V-50V voltages are added on the hearth electrode 6 of device, to modulate Graphene Energy band, as shown in Figure 1.Figure it is seen that prepared device is under no light condition, the light of non-spin coating boron-doping silicon quantum dot Electric current and response very little;And produce obvious photoelectricity when the laser that incident wavelength 532nm, light energy are 0.2 μ W/cm2 irradiates Stream.When device is operated in 1V, in full spectral region (300~1900nm), optic response is 10^9, and gain is 10^12, it was demonstrated that Device has very superior photodetection characteristic especially infrared band.

Claims (6)

1. a kind of photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide, it is characterised in that include:P-type Silicon substrate (1), silica separation layer (2), top electrode (3), graphene film (4), boron-doping silicon quantum dot film (5) and bottom electricity Pole (6);Wherein, the upper surface of the p-type silicon substrate (1) covers silica separation layer (2), in silica separation layer (2) Upper surface cover two pieces of top electrodes (3), the silica between two pieces of top electrode (3) upper surfaces and two pieces of top electrodes (3) Separation layer (2) upper surface covers graphene film (4), and in graphene film (4) upper surface boron-doping silicon quantum dot film is covered (5), hearth electrode (6) is set in p-type silicon substrate (1) lower surface.
2. the photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide according to claim 1, it is special Levy and be, described silica separation layer (2) thickness is 100nm.
3. the photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide according to claim 1, it is special Levy and be, described top electrode (3) is metal film electrode, material is aluminium, gold or golden evanohm.
4. the photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide according to claim 1, it is special Levy and be, described hearth electrode (6) is metal film electrode, material is gallium-indium alloy, titanium alloy or aluminium.
5. the photoconductive detector based on boron-doping silicon quantum dot/graphene/silicon dioxide according to claim 1, it is special Levy and be, described boron-doping silicon quantum dot (5) is prepared by cold plasma method, by adding boron former in the plasma The presoma of son prepares boron doped silicon quantum dot;The presoma of boron atom is diborane (B2H6).Boron-doping silicon quantum dot is visible Light near-infrared or even mid-infrared have absorption, and especially mid-infrared has stronger absworption peak, there is local plasma excimer effect (LSPR)。
6. it is a kind of to prepare as claimed in claim 1 based on boron-doping silicon quantum dot/graphene/silicon dioxide photoconductive detector Method, it is characterised in that comprise the following steps:
(1) in upper surface oxidation growth silica separation layer (2) of p-type silicon substrate (1), the resistance of p-type silicon substrate (1) used Rate is<0.01Ω·cm;The thickness of silica separation layer (2) is 100nm, and growth temperature is 900~1200 DEG C;
(2) two pieces of top electrode (3) figures are gone out in silica separation layer (2) photomask surface, then using electron beam evaporation technique, First growth thickness is about the chromium adhesion layer of 5nm, and then growth thickness is the top electrode (3) of 60nm;
(3) preparation of graphene film (4):Graphene film (4) is prepared in Copper Foil substrate using chemical gaseous phase depositing process;
(4) silica separation layer (2) upper surface between two pieces of top electrode (3) upper surfaces and two pieces of top electrodes (3) covers Graphene film (4);Wherein, the transfer method of Graphene is:Graphene film (4) surface is uniformly coated into a strata methyl-prop E pioic acid methyl ester film, is then placed in 4h erosion removals Copper Foil in etching solution, leaves the stone supported by polymethyl methacrylate Black alkene film (4);Titanium dioxide is transferred to after graphene film (4) the deionized water cleaning that polymethyl methacrylate is supported The upper surface of silicon separation layer (2) and top electrode (3);Finally remove polymethyl methacrylate with acetone and isopropanol;Wherein, institute Etching solution is stated by CuSO4, HCl and water composition, CuSO4:HCl:H2O=10g:50ml:50ml;
(5) in one layer of boron-doping silicon quantum dot film (5) of patterned device surface spin coating, boron-doping silicon quantum dot in visible ray especially Infrared band has very strong absworption peak, particle size 6nm, rotating speed 2000rpm, 30s.Thickness is about 105nm.
(6) gallium indium slurry is coated in p-type silicon substrate (1) bottom, prepares gallium indium hearth electrode (6), with p-type silicon substrate (1) Europe is formed Nurse is contacted.
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