CN116799093A - Photodiode based on two-dimensional semiconductor material and preparation method thereof - Google Patents
Photodiode based on two-dimensional semiconductor material and preparation method thereof Download PDFInfo
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- 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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Abstract
The invention belongs to the technical field of semiconductor devices, and particularly relates to a photodiode based on a two-dimensional semiconductor material and a preparation method thereof. The invention is a vertical structure device, which is formed by taking an N-type semiconductor material as a substrate and combining a plurality of layers of P-type two-dimensional semiconductor materials as photosensitive units, and has a fast photoelectric response; the P-type two-dimensional semiconductor material with short-wave near-infrared photoelectric response is selected, the asymmetric contact electrodes respectively contacting the P-type semiconductor material and the N-type semiconductor material are selected, and the structural design of the annular metal contact electrode is combined, so that the photoelectric detection performance of the semiconductor material is greatly improved. The preparation method comprises the following steps: n-type semiconductor substrate treatment; preparing a multi-layer P-type two-dimensional semiconductor material; preparing N-type and p-type asymmetric contact electrodes by maskless lithography; and preparing an insulating layer for isolating each part. The photodiode designed and prepared by the invention has the advantages of high response speed, high quantum efficiency, wide detection range and the like in a room temperature environment.
Description
Technical Field
The invention belongs to the technical field of semiconductor devices, and particularly relates to a photodiode and a preparation method thereof.
Background
Short-Wave near Infrared (SWIR) photodetectors are widely used in the fields of military, industry, medical treatment, communication, etc. Currently, commercial photodetectors based on HgCdTe, inGaAs, inAs/GaSb II superlattice materials are complex in device manufacturing process, high in cost, poor in process compatibility and even in the low-temperature environment when the detectors are used. The development of new short wave infrared absorbing materials and device design has become an important direction of current development in this field.
The two-dimensional material has the advantages of unique photoelectric performance, adjustable band gap, high carrier mobility and the like, and has great application potential in the field of room temperature short wave infrared detectors. The two-dimensional short wave infrared absorption materials which are widely researched at present mainly comprise PtSe 2 、MoTe 2 ，WSe 2 ，WS 2 ，MoSe 2 Black phosphorus, doped black phosphorus, and the like. Compared with other materials, the two-dimensional semiconductor material has a plurality of advantages at room temperature, such as an adjustable energy band structure and photoelectric property, so that the two-dimensional semiconductor material can realize high-efficiency photoelectric conversion in a short wave to near infrared range; the atomic layer ultrathin structure has good ductility and plasticity, and is suitable for flexible electronic devices and micro-nano electronic systems; the high carrier mobility makes the photoelectric detector show high sensitivity, and can detect very weak optical signals; excellent environmental stability, and the large-area film-forming CVD technology which is mature at present, and the like can be well compatible with the traditional silicon. However, the photodetector with broad spectrum, high sensitivity, high speed and stability needs to further optimize the preparation process of the two-dimensional semiconductor material and design the structure of the two-dimensional photodetector with more perfect design.
The infrared reflection imaging principle of the near infrared detector is passive detection, and compared with visible light, radar and laser, the infrared reflection imaging principle has the advantages of good concealment, high sensitivity, high resolution, fog, smoke, dust and the like. The infrared technology which originates from the military field and is continuously advancing has the application prospect in multiple fields to embody the extremely high commercial value of the near infrared detector. Because the existing infrared devices have the defects of complex preparation process, high cost, poor process compatibility and the like, development of new high-photoelectric-performance and low-cost short-wave infrared absorption photoelectric detectors is needed to be used as commercial substitutes.
Disclosure of Invention
The invention aims to provide a novel photodiode device based on a two-dimensional semiconductor material and a preparation method thereof. The device has the advantages of near infrared band enhancement response in room temperature environment, high sensitivity, high resolution and the like, and can further promote the application of two-dimensional materials in the technical field of infrared photoelectric.
The photodiode device based on the two-dimensional semiconductor material is of a vertical structure type; the structure of which is shown in fig. 1, comprises: an N-type semiconductor substrate, a p-type two-dimensional semiconductor material layer on the substrate, an insulating layer and an N-type metal contact electrode beside the p-type two-dimensional semiconductor material layer, and a p-type metal contact electrode on the p-type two-dimensional semiconductor material layer; the p-type two-dimensional semiconductor material is of a multilayer film structure and is used as a short-wave near infrared light absorption layer; the N-type metal contact electrode and the p-type metal contact electrode are of asymmetric structures.
The invention provides a photodiode preparation method based on a two-dimensional semiconductor material, which comprises the following specific steps.
(1) Preparing an N-type semiconductor substrate, including selecting materials of the N-type semiconductor, cleaning and preprocessing;
the N-type semiconductor substrate material is selected from Si, inP, gaAs, geAs, geSn and the like, and the material selection can be selected according to the compatibility of the existing film making process of the P-type two-dimensional semiconductor material to be prepared;
the substrate cleaning refers to removing impurities and dust on the surface of the substrate, such as metal ions, organic pollutants, oxides and the like, and the substrate cleaning adopts methods of organic solvent, dilute acid alkali liquor, water leaching, ultrasonic cleaning and the like;
the pretreatment of the substrate is to treat the substrate in a vacuum constant-temperature heating oven or a heating table for heating, plasma treatment and other modes, and aims to remove water molecules adsorbed on the surface of the substrate, reduce the roughness of the surface of the substrate and enhance the adhesion between the two-dimensional material and the substrate.
(2) Preparing a plurality of layers of P-type two-dimensional semiconductor materials serving as short-wave near-infrared light absorption layers on an N-type semiconductor substrate;
the prepared P-type two-dimensional semiconductor material can be directly grown on a substrate by adopting a chemical vapor deposition method and a physical vapor deposition method to prepare a two-dimensional atomic crystal film material with a larger area, and the P-type two-dimensional semiconductor film can be transferred onto an N-type semiconductor substrate by adopting a dry method and a wet method according to a substrate and a film through a hand tearing and transferring process, so that the quantum efficiency of a device can be improved to a certain extent while the growth or the transfer process of the material is uniform and reliable;
here, the P-type two-dimensional semiconductor material is selected from MoTe 2 , WSe 2 , WS 2 , MoSe 2 , PtSe 2 p-BN, etc., 10 nm-500 nm thick.
(3) Preparing a P-type contact electrode with an annular structure at the side of the P-type two-dimensional semiconductor material layer;
selecting a P-type contact electrode material, and preparing a P-type contact electrode with an annular structure by adopting technologies such as maskless lithography, film deposition and the like on the basis of a P-type two-dimensional semiconductor film;
the P-type two-dimensional semiconductor film is a film which is prepared in the step (2) and fully covers the N-type substrate, so that only P-type contact exists;
the maskless lithography uses electron beam lithography, laser direct writing and other equipment for patterning and defining the structure of the device; the thin film deposition adopts methods such as Electron Beam Evaporation (EBE), thermal Evaporation (TE), magnetron sputtering, physical Vapor Deposition (PVD) and the like, and is used for depositing a thin film to prepare a metal electrode of a bottom layer transistor;
the P-type metal contact electrode can be combined with the process research of the existing literature according to the comparison table of metal function, and one or more metals with larger work functions such as Pt, pd, cr, au and the like are selected to be of a laminated structure;
the design of the contact electrode with the annular structure greatly reduces the running distance of the photo-generated carriers in the thin-layer two-dimensional semiconductor, thereby increasing the photoelectric conversion efficiency of the photodiode.
(4) Etching the photosensitive unit based on the P-type two-dimensional semiconductor material;
the etching is mainly used for etching the redundant part of the P-type two-dimensional semiconductor material, and the etching can be dry etching or wet etching by using Reactive Ion (RIE) containing F+ gas, plasma Etching (PE) or inductively coupled plasma etching (ICP) equipment and the like.
(5) Preparing an isolation insulating layer of a P-type contact electrode and an N-type semiconductor substrate material;
the isolation insulating layer is made of hafnium oxide (HfO) prepared by adopting thin film growth equipment such as electron beam evaporation, magnetron sputtering, thermal evaporation and the like 2 ) Alumina (Al) 2 O 3 ) Silicon oxide (SiO) 2 ) Zirconium oxide (ZrO) 2 ) An insulator film such as rare earth element oxide, or a film such as uniform metal oxide and organic insulating material prepared by spin coating technique. Its thickness is between 1 nm and 500 nm.
(6) Preparation of Metal electrode in contact with N-type semiconductor Material and P-type contact electrode (PAD)
The N-type metal contact electrode can select one or more metals with smaller work functions such as Ti, Y, yb, zn, al and the like according to a metal work function table, is of a laminated structure, is matched with the metal contact electrode after the work functions, and can be used for forming a contact potential barrier of a junction region, so that the reverse bias cut-off performance of the diode is more obvious, and the dark current of the photodiode under the negative bias is further reduced.
The photodiode designed and prepared by the invention adopts a ring electrode structure, and adopts asymmetric electrodes with different work functions, and has the advantages of high response speed, high quantum efficiency, wide detection range and the like in a room temperature environment; the preparation process is simple, the cost is low, the device process compatibility is good, the device can be integrated into a multifunctional circuit or a readout circuit, and specific short-wave near-infrared detection signal reading and imaging products are realized.
Drawings
Fig. 1 is a top view and a side view of a single photodiode structure of the present invention. The substrate is an N-type semiconductor, the photosensitive unit is a P-type two-dimensional semiconductor material, and the N-type contact electrode is directly contacted with the N-type semiconductor material at the lower layer.
FIG. 2 is a flow chart of the photodiode manufacturing process according to the present invention. The substrate is an N-type semiconductor, the photosensitive unit is made of a P-type two-dimensional semiconductor material, the P-type two-dimensional semiconductor material contact electrode is of an annular structure, and the N-type contact electrode is directly contacted with the N-type semiconductor material to form a complete photodiode device.
Fig. 3 is a graph of the photo-electric performance test of the photodiode of the present invention. Wherein (a) is a photodiodeI-VCharacteristic curve (b) isI-VA curve of the characteristic curve in a log coordinate system; graphs (c) and (d) are the time photoresponse of photodiode dynamics.
Description of the embodiments
The invention is further illustrated by the following examples in connection with the accompanying drawings.
Fig. 2 is a process flow chart of the preparation of the photodiode according to the present invention, which comprises the following specific steps:
(1) The N-Si substrate (1) is selected in the embodiment:
preparing a substrate, and sequentially and respectively ultrasonically cleaning the substrate by using acetone, isopropanol, ammonia water and hydrogen peroxide mixed solvent and deionized water to remove impurities, dust and oxides on the surface of the substrate; vacuum annealing treatment, namely removing moisture adsorbed on the surface of the substrate and enhancing the adhesion between the two-dimensional material and the substrate;
(2) Preparing a multilayer P-type two-dimensional semiconductor material (2):
this example shows the growth of large area multilayer MoTe for CVD 2 A thickness of about 14 a nm a;
(3) Preparing a P-type two-dimensional semiconductor material contact metal electrode (3):
this example is a 40 nmAu/10 nmPd laminated metal electrode: exposing the pattern at the position (3) by laser direct writing, preparing 40 nmAu/10 nmPd by Electron Beam Evaporation (EBE), taking out after completely cooling, and preparing a metal electrode with an annular pattern after lift-off;
(4) EngravingEtching the excess P-type two-dimensional semiconductor material leaves the photosensitive cells: laser direct writing exposure (2) pattern, plasma etching (ICP) in SF 6 Etching off redundant P-type MoTe under the atmosphere of (2) 2 Left MoTe after left-off 2 A photosensitive cell array;
(5) Preparing an isolation insulating layer (4) of a P-type contact electrode and an N-type semiconductor substrate material:
the pattern at the laser direct writing exposure (4) is evaporated by adopting Electron Beam Evaporation (EBE) to form an alumina insulating layer of 40 nm, and an insulating layer for isolating a P-type contact electrode from an N-type semiconductor substrate material and an insulating layer between the two electrodes are left around the photosensitive unit after lift-off;
(6) Depositing a metal electrode (5) of the N-type semiconductor contact;
and filling a P-type contact electrode PAD (3), wherein (5) is selected as a 40 nmAu/10 nmTi laminated metal electrode: exposing (5) patterns by direct writing of laser, evaporating 40 nmAu/10 nmTi laminated metal electrodes by adopting Electron Beam Evaporation (EBE), and preparing an N-type contact electrode after lift-off; again laser direct write exposure of the 3 pattern was performed and Electron Beam Evaporation (EBE) was used to prepare PAD for testing or P-type contact electrodes integrated onto the circuit, here 40 nmau, after lift-off to prepare a complete photodiode array.
Fig. 3 is a graph for testing the photoelectric performance of the photodiode according to the present invention, specifically:
figure (a) is a photodiodeI-VCharacteristic curve, device test conditions were 900 nm (324.6. Mu.W/cm 2 ) And 1000 nm (190.8. Mu.W/cm) 2 ) Under the condition of light wavelength, it can be seen that p-MoTe in this example 2 The n-Si photodiode has a characteristic of reverse cut-off under a distinct dark state condition. The device has the advantages that larger and stable photocurrent is generated under the illumination condition, so that the device has good photovoltaic characteristics;
FIG. (b) isI-VA curve of the characteristic curve in a log coordinate system;
graphs (c) and (d) are dynamic time photoresponse of the photodiode, and the almost vertical rise and fall delays when the light source is turned on and off indicate that the device responds very rapidly in the near infrared bands 900 nm and 1000 nm.
The dark current of the stable nanoampere level of the device in the embodiment is a great advantage of realizing photoelectric application by matching a read-out circuit, and the rapid near infrared response enhancement characteristic enables the device to have great application potential in the near infrared detection field.
Claims (8)
1. A photodiode based on two-dimensional semiconductor material, characterized by a vertical structure; comprising the following steps: an N-type semiconductor substrate, a p-type two-dimensional semiconductor material layer on the substrate, an insulating layer and an N-type metal contact electrode beside the p-type two-dimensional semiconductor material layer, and a p-type metal contact electrode on the p-type two-dimensional semiconductor material layer; the p-type two-dimensional semiconductor material is of a multilayer film structure and is used as a short-wave near infrared light absorption layer; the N-type metal contact electrode and the p-type metal contact electrode are of asymmetric structures.
2. A method for fabricating a two-dimensional semiconductor material-based photodiode as claimed in claim 1, comprising the steps of:
(1) Preparing an N-type semiconductor substrate, including selecting materials of the N-type semiconductor, cleaning and preprocessing;
(2) Preparing a plurality of layers of P-type two-dimensional semiconductor materials serving as short-wave near-infrared light absorption layers on an N-type semiconductor substrate;
(3) Preparing a P-type contact electrode with an annular structure at the side of the P-type two-dimensional semiconductor material layer;
(4) Etching the short-wave near-infrared light absorption layer based on the P-type two-dimensional semiconductor material;
(5) Preparing an isolation insulating layer of a P-type contact electrode and an N-type semiconductor substrate material;
(6) And preparing a metal electrode contacted with the N-type semiconductor material and a P-type contact electrode.
3. The method according to claim 2, wherein in step (1):
the N-type semiconductor substrate material is selected from Si, inP, gaAs, geAs, geSn;
the substrate cleaning is to remove impurities and dust on the surface of the substrate, and comprises the steps of removing metal ions, organic pollutants and oxides, wherein the substrate cleaning adopts an organic solvent, dilute acid alkali liquor, water leaching and ultrasonic cleaning method;
the pretreatment of the substrate is to treat the substrate by adopting a vacuum constant-temperature heating oven or a heating table for heating and a plasma treatment mode, remove water molecules adsorbed on the surface of the substrate, reduce the roughness of the surface of the substrate and strengthen the adhesion between the two-dimensional material and the substrate.
4. The method according to claim 2, wherein in step (2):
the preparation of the P-type two-dimensional semiconductor material is to directly grow on a substrate by adopting a chemical vapor deposition method or a physical vapor deposition method to obtain a two-dimensional atomic crystal film material, or to transfer the P-type two-dimensional semiconductor film prepared by adopting a dry method and a wet method to an N-type semiconductor substrate by adopting a manual tearing and transferring process;
the P-type two-dimensional semiconductor material is selected from MoTe 2 , WSe 2 , WS 2 , MoSe 2 , PtSe 2 p-BN, 10 nm-500 nm.
5. The method according to claim 2, wherein in step (3):
the P-type contact electrode is prepared by adopting maskless photoetching and thin film deposition technologies;
the maskless lithography, using electron beam lithography or laser direct writing equipment, is used for patterning and defining the structure of the device; the film deposition adopts electron beam evaporation, thermal evaporation, magnetron sputtering and physical vapor deposition methods, and is used for depositing the film to prepare the metal electrode of the bottom layer transistor;
the P-type metal contact electrode material is one or more than one of Pt, pd, cr, au metals with larger work functions.
6. The method according to claim 2, wherein in step (4):
the etching is used for etching the redundant part of the P-type two-dimensional semiconductor material;
the etching equipment adopts reactive ion body containing F+ gas, plasma etching or inductively coupled plasma etching equipment;
the etching mode is dry etching or wet etching.
7. The method according to claim 2, wherein in step (5):
the isolation insulating layer is made of hafnium oxide, aluminum oxide, silicon oxide or zirconium oxide rare earth element oxide insulator films prepared by adopting thin film growth equipment such as electron beam evaporation, magnetron sputtering, thermal evaporation and the like, or is made of uniform metal oxide or organic insulating material films prepared by adopting a spin coating technology;
the isolation insulating layer has a thickness of 1 nm to 500 nm.
8. The method of claim 2, wherein the N-type metal contact electrode in step (6) is made of one or more metals selected from the group consisting of Ti, Y, yb, zn, al metals having a low work function.
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