CN104810426A - Self-driven light detector and preparation method thereof - Google Patents
Self-driven light detector and preparation method thereof Download PDFInfo
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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
- H01L31/109—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the PN heterojunction type
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The invention discloses a self-driven light detector comprising a substrate, a photosensitive material layer arranged on the substrate, a first electrode connected with the substrate, and a second electrode connected with the photosensitive material layer, wherein a p-n heterojunction is formed between the photosensitive material layer and the substrate, and the photosensitive material layer is made of reduced graphene oxide. As the p-n heterojunction is formed between the photosensitive material layer and the substrate of the self-driven light detector provided by the invention, the self-driven light detector can absorb light within a wide spectrum range, can be used for detecting light within a wide range of wavelengths, and can detect the intensity of light of different wavelengths in real time without the need for an external power supply.
Description
Technical field
The present invention relates to electronic device manufacturing technology field, be specifically related to the preparation method of a kind of self-driven photo-detector and this photo-detector.
Background technology
Photo-detector is the various interactions utilizing light and material, is the various devices of other perceived amounts transform light energy.In traditional photo-detector, the photo-detector material used is mostly the inorganic semiconductor material of broad-band gap, as nitrogenize is sowed, zinc oxide nanowire, stannic oxide nano wire, stannic selenide etc., preparation method is comparatively complicated, as chemical vapour deposition (CVD), molecular beam epitaxy, ion sputtering etc., energy consumption is large, the large-scale instrument and equipment that needs some valuable, and this causes production cost higher.And another direction organic semiconductor photo-detector that Recent study is comparatively popular, although also for the development of photo-detector provides new approaches, because the shortcomings such as organic semi-conductor unsteadiness, electron mobility are low limit its application.
Graphene is a kind of Two-dimensional Carbon nano material with monolayer carbon atomic structure, since obtaining Graphene first, has just had received increasing attention immediately from 2004 by mechanical stripping method.It has excellent electric property; optical property; thermal property and mechanical property; at room temperature electron mobility at a high speed and lower thermal coefficient of expansion; to the spectrum of wide region, there is absorption; these character can make Graphene replace other materials in some application, and graphene optical detector is the part that current photonic device research field is enlivened very much.Traditional semiconductor photodetector can be limited to the detection range of spectrum, and can detect from ultraviolet to infrared wide region spectrum based on the photo-detector of Graphene, and its device volume is little, can prepare on any substrate, is expected to be prepared into flexible device.
At present with the composite material of Graphene and inorganic semiconductor nanometer material and carry out doping to Graphene and have relevant report to prepare photo-detector, some of them achieve good effect, but its material synthesis method and device preparation technology flow process comparatively complicated, production cost is high, photo-detector performance reproducibility is poor, need additional power source to provide electric field, observable index is higher.
Summary of the invention
For the above-mentioned the deficiencies in the prior art mentioned, the present invention proposes a kind of self-driven photo-detector and preparation method thereof, this photo-detector does not need additional power source can detect the intensity of different wavelengths of light in real time.
To achieve these goals, present invention employs following technical scheme:
A kind of self-driven photo-detector, comprising:
Substrate;
Be arranged at the photosensitive material layer on described substrate, between described photosensitive material layer and described substrate, form p-n heterojunction; Wherein, the material of described photosensitive material layer is redox graphene;
The first electrode be connected with described substrate and the second electrode be connected with described photosensitive material layer.
Preferably, the thickness of described photosensitive material layer is 1nm ~ 50 μm.
Preferably, the material of described substrate is silicon, GaAs or gallium nitride.
Preferably, the material of described first electrode is metal material or material with carbon element; The material of described second electrode is metal material or material with carbon element.
Another aspect of the present invention is to provide a kind of preparation method of self-driven photo-detector, comprises step:
S101, provide a substrate;
S102, over the substrate coating or printing redox graphene solution, dry described redox graphene solution and form photosensitive material layer;
S103, prepare the first electrode over the substrate, described photosensitive material layer is prepared the second electrode.
Preferably, the material of described substrate is silicon, GaAs or gallium nitride.
Preferably, the method also comprises the step preparing redox graphene solution, specifically comprises step:
A () is that raw material prepares graphene oxide by the Hummers method improved with graphite powder;
B the aqueous solution of graphene oxide under 30 ~ 120 DEG C of oil bath conditions, is carried out reduction treatment by hydrazine hydrate or hydroiodic acid or thermal reduction technique, prepares redox graphene by ();
C redox graphene is scattered in dispersant and obtains described redox graphene solution by ().
Preferably, described dispersant is that 1-Methyl-2-Pyrrolidone, dimethyl formamide, lauryl sodium sulfate aqueous solution, ethanol, ethylene glycol or song draw water flowing solution.
Preferably, the concentration of redox graphene solution is 0.001mg/mL ~ 50mg/mL.
Preferably, the thickness of described photosensitive material layer is 1nm ~ 50 μm.
Preferably, described first electrode and the second electrode are prepared by evaporation process, printing technique or sputtering technology; The material of described first electrode is metal material or material with carbon element; The material of described second electrode is metal material or material with carbon element.
Compared with prior art, photo-detector provided by the invention, forms p-n heterojunction between photosensitive material layer and substrate, has absorption to the light compared with wide spectral range, can be used for the light detecting wide wavelength range, do not need additional power source can detect the intensity of different wavelengths of light in real time; And this photo-detector novel structure, its preparation technology is simple, and cost is lower, is conducive to industrialization large-scale production.
Accompanying drawing explanation
Fig. 1 is the structural representation of the photo-detector that the embodiment of the present invention provides.
Fig. 2 is the process chart of the preparation method of the photo-detector that the embodiment of the present invention provides.
Fig. 3 is that the photo-detector that provides of the embodiment of the present invention is at the schematic diagram carrying out optical detection.
Fig. 4 is the current signal schematic diagram that photo-detector that the embodiment of the present invention provides carries out optical detection acquisition.
Fig. 5 is that the photo-detector that provides of the embodiment of the present invention 1 is to the response schematic diagram of light.
Fig. 6 is that the photo-detector that provides of the embodiment of the present invention 2 is to the response schematic diagram of light.
Fig. 7 is that the photo-detector that provides of the embodiment of the present invention 3 is to the response schematic diagram of light.
Fig. 8 is that the photo-detector that provides of the embodiment of the present invention 4 is to the response schematic diagram of light.
Fig. 9 is that the photo-detector that provides of the embodiment of the present invention 5 is to the response schematic diagram of light.
Figure 10 is that the photo-detector that provides of the embodiment of the present invention 6 is to the response schematic diagram of light.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
As previously mentioned, in view of the deficiency that prior art exists, the present invention proposes a kind of self-driven photo-detector, as shown in Figure 1, this detector comprises: substrate 1; Be arranged at the photosensitive material layer 2 on described substrate 1, between described photosensitive material layer 2 and described substrate 1, form p-n heterojunction; Wherein, the material of described photosensitive material layer 2 is redox graphene; The first electrode 3 be connected with described substrate 1 and the second electrode 4 be connected with described photosensitive material layer 2.
As shown in Figure 2, the preparation method of self-driven photo-detector as above comprises step:
S101, provide substrate 1;
S102, on substrate 1 coating or printing redox graphene solution, dry redox graphene solution and form photosensitive material layer 2;
S103, over the substrate 1 prepare the first electrode 3, and photosensitive material layer 2 is prepared the second electrode 4.
In some preferred embodiments, the material of described substrate is silicon, GaAs or gallium nitride.
In some preferred embodiments, the concentration of redox graphene solution is 0.001mg/mL ~ 50mg/mL.
In some preferred embodiments, the temperature range of drying described redox graphene solution is 1 ~ 300 DEG C, and time range is 1s ~ 36h; The thickness of described photosensitive material layer is 1nm ~ 50 μm.
In some preferred embodiments, described first electrode and the second electrode are prepared by evaporation process, printing technique or sputtering technology; The material of described first electrode is metal material or material with carbon element; The material of described second electrode is metal material or material with carbon element.
The photo-detector more than provided forms p-n heterojunction between photosensitive material layer and substrate, has absorption to the light compared with wide spectral range, can be used for the light detecting wide wavelength range, does not need additional power source can detect the intensity of different wavelengths of light in real time.
In the present embodiment, the method also comprises the step preparing redox graphene solution, specifically comprises step:
A () is that raw material prepares graphene oxide by the Hummers method improved with graphite powder.Specific as follows: former graphite powder to be joined 80 DEG C containing dense H
2sO
4, K
2s
2o
8and P
2o
5mixed solution in, then after room temperature reaction 6h, obtain pre-oxidation Graphene through filtering and washing.Then continuation Hummers method pair and pre-oxidation Graphene are oxidized further and obtain graphene oxide: joined by 20g pre-oxidation Graphene in the cold concentrated sulfuric acid of 460mL (0 DEG C), slowly add 60g potassium permanganate (KMnO when stirring
4), whole experimental procedure carries out guaranteeing that temperature is no more than 20 DEG C under the cooling of ice-water bath; React 2 hours at adding 920mL deionized water 35 DEG C.Then hydrogen peroxide (the H of 2.8L deionized water and 50mL30% is added
2o
2) solution with terminate reaction.Finally carry out suction filtration and wash with hydrochloric acid (HCl) solution (5L) of 1:10, and when ultrasonic, disperse graphene oxide with deionized water thus obtain final graphene oxide solution.
B the aqueous solution of graphene oxide under 30 ~ 120 DEG C of oil bath conditions, is carried out reduction treatment by hydrazine hydrate or hydroiodic acid or thermal reduction technique, prepares redox graphene by ().In the present embodiment, under 90 DEG C of oil bath conditions, adopt hydrazine hydrate to reduce to graphene oxide, hydrazine hydrate with the quality of graphene oxide than scope is: 0.001 ~ 10000:1, and the temperature range of reduction is 20 ~ 300 DEG C, and the recovery time is 1min ~ 60h.The reducing degree of controlled oxidization Graphene can be carried out by the mass ratio controlling hydrazine hydrate and graphene oxide.
C redox graphene is scattered in dispersant and obtains described redox graphene solution by ().Dispersant, for disperseing redox graphene, makes redox graphene be evenly distributed in dispersant, and after ensureing to dry substrate in subsequent operation, redox graphene is evenly distributed on substrate.Dispersant can adopt as drawn water flowing solution at 1-Methyl-2-Pyrrolidone (NMP) or dimethyl formamide (DMF) or lauryl sodium sulfate (SDS) aqueous solution or ethanol or ethylene glycol or song.
In aforesaid step S101, need to clean the surface of substrate; Such as, when adopting silicon substrate, with hydrofluoric acid, the silicon dioxide layer of silicon face is removed, silicon is in atmosphere exposed, and with deionized water and alcohol rinse, residual hydrofluoric acid is removed.
In aforesaid step S102, the temperature range of drying redox graphene solution controls at 1 ~ 300 DEG C, and time range is 1s ~ 36h.Temperature when drying thorough is corresponding with the time of baking needed, and along with the raising of temperature, corresponding required drying time shortens, and in the present embodiment, bake out temperature is preferably 80 DEG C.Dry redox graphene solution to carry out in any atmosphere, certainly preferably adopt the interference carrying out as far as possible avoiding external environment in vacuum environment.Here it should be noted that, the gas be full of in surrounding environment when " atmosphere " mentioned in the present invention refers to operation.
After preparing photo-detector above, as shown in Figure 3, the first electrode 3 and the second electrode 4 are connected to current sensing means 6 respectively by wire, form a closed circuit.When carrying out optical detection, light beam 5 is irradiated to photosensitive material layer 2, and the p-n heterojunction of light signal between photosensitive material layer 2 and substrate 1 is converted to the signal of telecommunication, this signal of telecommunication detected by current sensing means 6.As shown in Figure 4, the photo-detector adopting the present embodiment to provide is 600nm to wavelength, and power is 2 μ W/cm
2light source detect, what replace during detection controls light source switch, carries out the detection of repetitive cycling, and when not having illumination to be mapped to photosensitive material layer, the signal of telecommunication is 0, and when there being illumination to be mapped to photosensitive material layer, current sensing means 6 can detect current signal.
Embodiment 1
Get and be dispersed in the solution that dispersant 1-Methyl-2-Pyrrolidone (NMP) concentration is the redox graphene of 1mg/mL, be added drop-wise on the silicon substrate of 1 × 1.5cm, drying at the temperature of 80 DEG C and obtaining thickness is the oxidation graphene film of 1nm, forms photosensitive material layer.Then in photosensitive material layer and silicon substrate, electrode is being made respectively.Be connected with outer lead by electrode with silver slurry, the device baking 2h will made at 70 DEG C, dries silver slurry, is then prepared into self-driven photo-detector.The photo-detector adopting the present embodiment to provide is 365nm to wavelength, and power is 6.5mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 5.
Embodiment 2
As different from Example 1, in the self-driven photo-detector that the present embodiment prepares, the thickness of oxidation graphene film (photosensitive material layer) is 1 μm.The photo-detector adopting the present embodiment to provide is 365nm to wavelength, and power is 6.5mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 6.
Embodiment 3
As different from Example 1, in the self-driven photo-detector that the present embodiment prepares, the thickness of oxidation graphene film (photosensitive material layer) is 50 μm.The photo-detector adopting the present embodiment to provide is 365nm to wavelength, and power is 6.5mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 7.
Reference example 1-3, the curve in contrast accompanying drawing 5-7 is known, can realize the self-driven photo-detector preparing different sensitivity by regulating the thickness of redox graphene (photosensitive material layer); Further, along with the thickness of photosensitive material layer increases gradually, the sensitivity of self-driven photo-detector reduces (under identical illumination condition, the current density of the current signal of detection is less gradually) gradually.
Embodiment 4
Time in abovementioned steps (b) with hydrazine hydrate reduction graphene oxide, the mass ratio of hydrazine hydrate and graphene oxide is 10:1, reduces to graphene oxide; To redox graphene be obtained and be dispersed in dispersant dimethyl formamide (DMF).Get and be dispersed in the solution that dispersant dimethyl formamide (DMF) concentration is the redox graphene of 10mg/mL, be added drop-wise on the gallium nitride substrate of 1 × 1.5cm, drying at the temperature of 80 DEG C and obtaining thickness is the oxidation graphene film of 200nm, forms photosensitive material layer.Then in photosensitive material layer and silicon substrate, electrode is being made respectively.Be connected with outer lead by electrode with silver slurry, the device baking 2h will made at 70 DEG C, dries silver slurry, is then prepared into self-driven photo-detector.The photo-detector adopting the present embodiment to provide is 420nm to wavelength, and power is 4.9mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 8.
Embodiment 5
As different from Example 4, during with hydrazine hydrate reduction graphene oxide, the mass ratio of hydrazine hydrate and graphene oxide is 1:1, reduces to graphene oxide.The photo-detector adopting the present embodiment to provide is 420nm to wavelength, and power is 4.9mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 9.
Embodiment 6
As different from Example 4, when graphene oxide is reduced, do not add hydrazine hydrate; The mass ratio of hydrazine hydrate and graphene oxide is 0:1 in other words, directly adopts thermal reduction technique to reduce to graphene oxide.The photo-detector adopting the present embodiment to provide is 420nm to wavelength, and power is 4.9mW/cm
2light source detect, detect the current signal that obtains as shown in Figure 10.
Reference example 4-6, curve in contrast accompanying drawing 8-10 is known, by regulating the reducing degree of redox graphene, (above-mentioned three embodiments are reducing degrees that mass ratio by controlling hydrazine hydrate and graphene oxide carrys out controlled oxidization Graphene, the mass ratio of hydrazine hydrate and graphene oxide is less, reducing degree is lower), because the reducing degree of redox graphene is different, its energy gap and conductivity all can be variant, thus cause the sensitivity of the redox graphene of different reducing degree different, realize the self-driven photo-detector of preparation different sensitivity.Further, when the reducing degree of redox graphene is lower, the sensitivity of self-driven photo-detector is slighter (under identical illumination condition, the current density of the current signal of detection is less gradually).
It should be noted that, in this article, the such as relational terms of first and second grades and so on is only used for an entity or operation to separate with another entity or operating space, and not necessarily requires or imply the relation that there is any this reality between these entities or operation or sequentially.And, term " comprises ", " comprising " or its any other variant are intended to contain comprising of nonexcludability, thus make to comprise the process of a series of key element, method, article or equipment and not only comprise those key elements, but also comprise other key elements clearly do not listed, or also comprise by the intrinsic key element of this process, method, article or equipment.When not more restrictions, the key element limited by statement " comprising ... ", and be not precluded within process, method, article or the equipment comprising described key element and also there is other identical element.
The above is only the embodiment of the application; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the protection range of the application.
Claims (11)
1. a self-driven photo-detector, is characterized in that, comprising:
Substrate;
Be arranged at the photosensitive material layer on described substrate, between described photosensitive material layer and described substrate, form p-n heterojunction; Wherein, the material of described photosensitive material layer is redox graphene;
The first electrode be connected with described substrate and the second electrode be connected with described photosensitive material layer.
2. self-driven photo-detector according to claim 1, is characterized in that, the thickness of described photosensitive material layer is 1nm ~ 50 μm.
3. self-driven photo-detector according to claim 1, is characterized in that, the material of described substrate is silicon, GaAs or gallium nitride.
4., according to the arbitrary described self-driven photo-detector of claim 1-3, it is characterized in that, the material of described first electrode is metal material or material with carbon element; The material of described second electrode is metal material or material with carbon element.
5. a preparation method for self-driven photo-detector, is characterized in that, comprises step:
S101, provide a substrate;
S102, over the substrate coating or printing redox graphene solution, dry described redox graphene solution and form photosensitive material layer;
S103, prepare the first electrode over the substrate, described photosensitive material layer is prepared the second electrode.
6. the preparation method of self-driven photo-detector according to claim 5, is characterized in that, the material of described substrate is silicon, GaAs or gallium nitride.
7. the preparation method of self-driven photo-detector according to claim 5, is characterized in that, the method also comprises the step preparing redox graphene solution, specifically comprises step:
A () is that raw material prepares graphene oxide by the Hummers method improved with graphite powder;
B the aqueous solution of graphene oxide under 30 ~ 120 DEG C of oil bath conditions, is carried out reduction treatment by hydrazine hydrate or hydroiodic acid or thermal reduction technique, prepares redox graphene by ();
C redox graphene is scattered in dispersant and obtains described redox graphene solution by ().
8. the preparation method of self-driven photo-detector according to claim 7, is characterized in that, described dispersant is that 1-Methyl-2-Pyrrolidone, dimethyl formamide, lauryl sodium sulfate aqueous solution, ethanol, ethylene glycol or song draw water flowing solution.
9., according to the preparation method of the arbitrary described self-driven photo-detector of claim 5-8, it is characterized in that, the concentration of redox graphene solution is 0.001mg/mL ~ 50mg/mL.
10. the preparation method of self-driven photo-detector according to claim 9, is characterized in that, the thickness of described photosensitive material layer is 1nm ~ 50 μm.
The preparation method of 11. self-driven photo-detectors according to claim 9, is characterized in that, described first electrode and the second electrode are prepared by evaporation process, printing technique or sputtering technology; The material of described first electrode is metal material or material with carbon element; The material of described second electrode is metal material or material with carbon element.
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