CN111446333B - Construction method of near-infrared self-driven photoelectric detector based on semiconductor nanowire/graphene - Google Patents
Construction method of near-infrared self-driven photoelectric detector based on semiconductor nanowire/graphene Download PDFInfo
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Abstract
The invention relates to a construction method of a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene, wherein the interface optimization is carried out by designing a geometrically asymmetric semiconductor nanowire/graphene composite structure, utilizing the doping effect of substrate Ge on graphene and controlling the annealing temperature and time of a device, and the device has remarkably enhanced self-driving characteristics and photoresponse sensitivity. The method successfully constructs the self-driven photoelectric detector which is ideal in response to near infrared light and based on the semiconductor nanowire/graphene.
Description
Technical Field
The invention belongs to the field of optoelectronic devices, and particularly relates to a construction method of a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene.
Background
In the field of substance analysis detection, due to the abundance of molecular signature spectra in the Near Infrared (NIR) region, near infrared photodetectors are required to collect and "interpret" these signature spectral signals in the near infrared band. The current commercial near infrared photodetectors still have limitations: silicon-based and InGaAs-based photodetectors work normally at room temperature but have limited response sensitivity to near-infrared light, and cannot meet the detection requirements of people. Photoelectric detectors based on HgCdTe, InSb and GaSb/InAs have excellent response performance to near infrared light, but can normally work at the liquid nitrogen temperature (77K), and arsenic with ideal response performance to near infrared light
The operating temperature of doped silicon-based electrical detectors is even as low as liquid helium (4.2K), which undoubtedly increases the cost of analytical detection.
For the above reasons, heterojunctions composed of two-dimensional materials and conventional narrow bandgap semiconductor materials are of great interest because of their promising optoelectronic properties. Graphene is one of representatives of two-dimensional materials, and has abundant electronic properties, for example, graphene has the characteristics of intrinsic zero band gap metalloid property, bipolar electrical property and capability of opening and regulating band gap after doping; in addition, under light excitation, a large number of hot electrons are generated in graphene, i.e., the graphene shows a significant photoelectric and thermal effect. These unique electronic properties make graphene particularly important in optoelectronic device applications. Among them, the combination of graphene and semiconductor materials to develop a new near infrared photodetector is being widely studied.
2011 Echtermeyer et al general SiO 2 Nanoparticle arrays incorporating graphene, benefiting from SiO 2 A strong local electric field is generated between the nano particles after light absorption and the graphene, and the nano particles are based on graphene/SiO 2 The photoresponse rate of the photoelectric detector is improved by 20 times compared with that of a graphene-based device (Echtermayer T J. et al; stress plasma enhancement of photovoltage in graphene, nat. Commun., 2011, 2: 458).
In 2014, Zhang et al constructed a graphene/MoS based material 2 FET type photodetectors. Due to the vertical electric field formed by the built-in electric field and the applied electrostatic field in the junction, the optical gain of the device is as high as 10 8 (Zhang W et al； Ultrahigh-gain photodetectors based on atomically thin graphene-MoS2 heterostructures, Science Report, 2014, 4(7484): 3826-3835.)。
In 2016, Long et al designed MoS 2 (p-type) -graphene- (n-type) WSe 2 The sandwich heterostructure, the constructed photoelectric detector keeps 10 in the near infrared wave band 11 Detectivity of the order of Jones (Long M et al; Broadband photonic detectors based on a atomic thin resist, Nano Letters, 2016, 16(4): 2254-.
Graphene-based optoelectronic devices are being extensively researched and perfected, however, research and development on graphene-based near-infrared photodetectors with high responsivity, low power consumption, and even self-driven are still facing a great challenge.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for constructing a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene.
The invention is realized by the following scheme: a construction method of a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene is characterized in that interface optimization is carried out by designing a semiconductor nanowire/graphene composite structure with geometric asymmetry, utilizing the doping effect of substrate Ge on graphene and controlling the annealing temperature and time of a device, and comprises the following steps:
1) Transferring the graphene film prepared by the chemical vapor deposition method to a proper Ge substrate to obtain a graphene/Ge sample, and then coating a semiconductor nanowire turbid liquid with proper concentration on the graphene/Ge sample in a proper mode;
2) putting the semiconductor nanowire/graphene/Ge sample into a vacuum oven for annealing;
3) selecting a proper position on the sample processed in the step 2) to manufacture an electrode.
The coating mode of the semiconductor nanowire suspension in the step 1) is as follows: quantitatively dripping the semiconductor nanowire turbid liquid from a position fixed at one end of the graphene/Ge sample by using a liquid transfer gun, automatically spreading the semiconductor nanowire turbid liquid to the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying; repeating the method for several times to obtain a semiconductor nanowire film or a semiconductor nanowire network with a section of a wedge-like shape from thick to thin; and obtaining the semiconductor nanowire/graphene composite structure with geometric asymmetry.
On the basis of the scheme, in the step 1), the semiconductor type carbon nanotube or Si nanowire suspension with the concentration of 0.1mg/mL is dripped from a position fixed at one end of the graphene/Ge sample by using a liquid transfer gun with the single dripping amount of 200 muL, then the sample is placed on a hot plate to be dried, and the step is repeated for 3 to 7 times.
The annealing temperature range of the semiconductor nanowire/graphene/Ge sample in the step 2) is 40-100 ℃, and the annealing time range is 10-30 min.
The optimal annealing temperature of the semiconductor nanowire/graphene/Ge sample in the step 2) is 60 ℃, and the optimal annealing time is 20 min.
The electrode positions in the step 3) are positioned on the surface of the semiconductor nanowire, between the interfaces of the semiconductor nanowire and the graphene, between the interfaces of the graphene and the Ge substrate and on the back of the Ge substrate.
The optimal electrode position in step 3) is between the semiconductor nanowire/graphene interfaces.
By utilizing the geometric asymmetry of the semiconductor nanowire/graphene composite structure, the constructed photoelectric detector has a photoconductive performance under light excitation, and simultaneously generates a photovoltaic effect so as to have a self-driven characteristic. In addition, the semiconductor Ge is used as a substrate of the semiconductor nanowire/graphene heterojunction. Due to the doping effect of the substrate Ge on the graphene, the self-driving characteristic and the photoresponse sensitivity of the semiconductor nanowire/graphene composite system are remarkably enhanced. Meanwhile, in the device construction process, the annealing temperature and time of the device are accurately controlled to optimize the interface contact between the semiconductor nanowire-graphene-Ge substrate, the semiconductor nanowire/graphene near infrared self-driven photoelectric detector with Ge as the substrate is successfully prepared, the response sensitivity of the photoelectric detector can reach 100 times under the condition that the light with the wavelength of 1064nm is excited and no external bias is applied, and the response and recovery time can reach millisecond level; in addition, the device also shows good photoresponse cycle stability under self-driving. The device construction method is simple and controllable, has high repeatability, and has obvious application value.
The invention provides a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene, wherein a semiconductor nanowire/graphene composite structure with asymmetric geometry is designed, and the doping effect of a Ge substrate on graphene is utilized, so that the device has remarkably enhanced self-driven characteristics and photoresponse sensitivity. Meanwhile, the annealing condition of the device is accurately controlled, the contact of each interface in the device can be optimized, and the prepared semiconductor nanowire/graphene is used for constructing a near-infrared self-driven photoelectric detector. The flexible device has the advantages of simple and controllable construction method, high repeatability and important application potential.
Drawings
FIG. 1: photoresponsive sensitivity-time curve of the device of example 1;
FIG. 2: single cycle response curve of the example 1 device.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Transferring a graphene film prepared by a chemical vapor deposition method onto commercial intrinsic Ge to obtain a graphene/Ge sample, depositing an Au/Ti electrode on the graphene surface of the sample, dropwise adding a semiconductor type carbon nanotube turbid liquid with the concentration of 0.1mg/mL (the single dropwise adding amount is 200 mu L) from a position fixed at one end of the graphene/Ge sample by using a liquid-transferring gun, automatically spreading the semiconductor type carbon nanotube turbid liquid onto the whole surface of the graphene/Ge sample, and then placing the sample on a hot plate for drying. After the step is repeated for 5 times, the semiconductor type carbon nano tube/graphene/Ge sample is placed in a vacuum oven, and annealing is carried out for 20min at the temperature of 60 ℃, so that the semiconductor type carbon nano tube/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity can be obtained. FIG. 1 is a graph of photoresponsive sensitivity versus time for device 1 of the present example; fig. 2 is a single cycle response curve of the device 1 of the present embodiment.
Example 2
Transferring a graphene film prepared by a chemical vapor deposition method onto a commercial n-type Ge substrate to obtain a graphene/Ge sample, dropwise adding a semiconductor type carbon nanotube turbid liquid with the concentration of 0.1mg/mL (the single dropwise adding amount is 200 mu L) from a position fixed at one end of the graphene/Ge sample by using a liquid-transferring gun, automatically spreading the semiconductor type carbon nanotube turbid liquid to the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the steps for 5 times, putting the semiconductor type carbon nano tube/graphene/Ge sample into a vacuum oven, annealing at 80 ℃ for 20min, and evaporating an Al electrode on the carbon nano tube network to obtain the semiconductor type carbon nano tube/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity.
Example 3
Depositing Au on the front surface of a commercial p-type Ge substrate by adopting an electron beam deposition method, transferring a graphene film prepared by a chemical vapor deposition method onto the p-type Ge substrate to obtain a graphene/Ge sample, dropwise adding a semiconductor type carbon nanotube suspension with the concentration of 0.1mg/mL (the single dropwise adding amount is 200 mu L) from a position fixed at one end of the graphene/Ge sample by using a liquid-transferring gun, automatically spreading the semiconductor type carbon nanotube suspension liquid onto the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the step for 5 times, putting the semiconductor type carbon nano tube/graphene/Ge sample into a vacuum oven, and annealing at 70 ℃ for 30min to obtain the semiconductor type carbon nano tube/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity;
Example 4
Depositing Ag on the front surface of a commercial p-type Ge substrate by adopting an electron beam deposition method, transferring a graphene film prepared by a chemical vapor deposition method onto the p-type Ge substrate to obtain a graphene/Ge sample, quantitatively dripping a Si nanowire turbid liquid prepared by a solution method with proper concentration from a position fixed at one end of the graphene/Ge sample by using a liquid transfer gun, automatically spreading a semiconductor type carbon nanotube turbid liquid onto the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the step for proper times, putting the Si nanowire/graphene/Ge sample into a vacuum oven, and annealing at 80 ℃ for 30min to obtain the Si nanowire/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity;
example 5
Depositing Ge on any substrate by using an atomic deposition method, transferring a graphene film prepared by using a chemical vapor deposition method onto the Ge film to obtain a graphene/Ge sample, depositing an Au/Ti electrode on the graphene surface of the sample, then dropwise adding a semiconductor type carbon nanotube suspension with the concentration of 0.1mg/mL (the single dropwise adding amount is 200 mu L) from a position fixed at one end of the graphene/Ge sample by using a liquid-transferring gun, automatically spreading the semiconductor type carbon nanotube suspension liquid onto the whole surface of the graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the step for 5 times, putting the semiconductor type carbon nanotube/graphene/Ge sample into a vacuum oven, and annealing at 60 ℃ for 20min to obtain the semiconductor type carbon nanotube/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity;
Example 6
Transferring a graphene film prepared by a chemical vapor deposition method onto commercial intrinsic Ge to obtain a graphene/Ge sample, then quantitatively dripping a Si nanowire turbid liquid prepared by a solution method with a proper concentration from a fixed position at one end of the graphene/Ge sample by using a liquid transfer gun, automatically spreading a semiconductor type carbon nanotube turbid liquid onto the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the steps for proper times, putting the Si nanowire/graphene/Ge sample into a vacuum oven, annealing at 80 ℃ for 30min, and pressing an indium electrode on the back surface of the substrate Ge by a cold welding method to obtain the Si nanowire/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity;
example 7
Transferring a graphene film prepared by a chemical vapor deposition method onto commercial intrinsic Ge to obtain a graphene/Ge sample, then quantitatively dripping a Ge nanowire turbid liquid prepared by a solution method with a proper concentration from a fixed position at one end of the graphene/Ge sample by using a liquid transfer gun, automatically spreading a semiconductor type carbon nanotube turbid liquid onto the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying. After repeating the steps for proper times, putting the Si nanowire/graphene/Ge sample into a vacuum oven, annealing at 90 ℃ for 30min, and pressing an indium electrode on the back of the substrate Ge by a cold welding method, so that the Ge nanowire/graphene-based near infrared photoelectric detector with ideal self-driving performance and sensitivity can be obtained.
Claims (6)
1. A construction method of a near-infrared self-driven photoelectric detector based on semiconductor nanowires/graphene is characterized in that interface optimization is carried out by designing a semiconductor nanowire/graphene composite structure with geometric asymmetry, utilizing the doping effect of substrate Ge on graphene and controlling the annealing temperature and time of a device, and comprises the following steps:
1) transferring the graphene film prepared by the chemical vapor deposition method onto a Ge substrate to obtain a graphene/Ge sample, and then coating the semiconductor nanowire suspension on the graphene/Ge sample to obtain a semiconductor nanowire/graphene/Ge sample;
2) putting the semiconductor nanowire/graphene/Ge sample into a vacuum oven for annealing treatment;
3) manufacturing an electrode on the sample processed in the step 2); wherein,
the coating mode of the semiconductor nanowire suspension in the step 1) is as follows: quantitatively dripping the semiconductor nanowire turbid liquid from a position fixed at one end of the graphene/Ge sample by using a liquid transfer gun, automatically spreading the semiconductor nanowire turbid liquid to the surface of the whole graphene/Ge sample, and then placing the sample on a hot plate for drying; repeating the method for several times to obtain a semiconductor nanowire film or a semiconductor nanowire network with a section of a wedge-like shape from thick to thin; and obtaining the semiconductor nanowire/graphene composite structure with the asymmetric geometry.
2. The method for constructing a semiconductor nanowire/graphene-based near-infrared self-driven photodetector as claimed in claim 1, wherein the method comprises the steps of: in the step 1), a Si nanowire suspension with the concentration of 0.1mg/mL is dripped from a position fixed at one end of a graphene/Ge sample by a liquid-transferring gun with the single dripping amount of 200 muL, then the sample is placed on a hot plate to be dried, and the step is repeated for 3 to 7 times.
3. The method for constructing a semiconductor nanowire/graphene-based near-infrared self-driven photodetector as claimed in claim 1, wherein the method comprises the steps of: the annealing conditions of the semiconductor nanowire/graphene/Ge sample in the step 2) are as follows: the annealing temperature is 40-100 ℃, and the annealing time is 10-30 min.
4. The method for constructing a semiconductor nanowire/graphene-based near-infrared self-driven photodetector as claimed in claim 2, wherein: the annealing temperature of the semiconductor nanowire/graphene/Ge sample in the step 2) is 60 ℃, and the annealing time is 20 min.
5. The method for constructing a semiconductor nanowire/graphene-based near-infrared self-driven photodetector as claimed in claim 1, wherein the method comprises the steps of: the electrode position in the step 3) is on the surface of the semiconductor nanowire, or between the interfaces of the semiconductor nanowire and the graphene, or between the interfaces of the graphene and the Ge substrate and on the back of the Ge substrate.
6. The method for constructing a semiconductor nanowire/graphene-based near-infrared self-driven photodetector as claimed in claim 5, wherein: the electrode position in the step 3) is between the semiconductor nanowire/graphene interface.
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| CN103280484A (en) * | 2013-05-28 | 2013-09-04 | 合肥工业大学 | p-type graphene film/n-type Ge schottky junction near-infrared photoelectric detector and preparation method thereof |
| CN104766902A (en) * | 2014-06-16 | 2015-07-08 | 南京大学 | Infrared light detecting transistor based on graphene carbon nano tube composite absorption layer |
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| CN109768114A (en) * | 2018-12-04 | 2019-05-17 | 东南大学 | It is a kind of based on graphene-heterojunction semiconductor position sensitive photodetector |
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| CN104810426A (en) * | 2014-01-26 | 2015-07-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Self-driven light detector and preparation method thereof |
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