CN112820787A - Photoelectric detector based on vertical two-dimensional thin film material and preparation method thereof - Google Patents
Photoelectric detector based on vertical two-dimensional thin film 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
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Abstract
The invention discloses a photoelectric detector made of a vertical two-dimensional thin film material and a preparation method thereof. The preparation method comprises the following steps: manufacturing and forming a first electrode layer on a substrate; manufacturing a nanosheet array on the first electrode layer, wherein the nanosheet array is formed by a vertical two-dimensional semiconductor material, a certain gap is formed between the nanosheets, glue is uniformly distributed on the nanosheet array so as to form an insulating glue layer in the gap of the nanosheet array, and the insulating glue layer is arranged on the first electrode layer exposed from the gap; and manufacturing and forming a second electrode layer on the nanosheet array and the insulating glue layer. The nanosheet array is manufactured to form a vertical type, the 3D vertical type nanosheet array has a good light sinking effect, the external quantum efficiency and the light responsivity of the detector are greatly improved, the insulating glue layer is arranged in the gap of the nanosheet array, the upper electrode layer and the lower electrode layer are prevented from being directly conducted through the gap, and therefore the stability and the feasibility of the photoelectric detector are guaranteed.
Description
Technical Field
The invention belongs to the technical field of photoelectric detectors, and particularly relates to a photoelectric detector based on a vertical two-dimensional thin film material and a preparation method thereof.
Background
In the field of mobile electronics such as smart phones, great challenges are faced on how to realize high-quality imaging under the condition of weak light, and strong demands are made on ultrahigh-sensitivity photoelectric detection materials and imaging chips. At present, core photosensitive materials of commercial photodetectors mainly comprise semiconductors such as Si, Ge, InGaAs, HgCdTe and the like, but the external quantum efficiency of photodetectors based on the traditional semiconductor materials is low, and the external quantum efficiency of mature Si devices is only about 50-80%, so that the detection capability of the detectors for weak light signals is insufficient, and the imaging quality of the detectors under the weak light conditions such as night, indoor without illumination light and the like is limited. Therefore, the search for new photoelectric conversion materials and the development of ultra-high sensitivity photodetectors remain the hot research directions in the material field and the photoelectric field.
Compared with the traditional semiconductor material, the charge separation process of the two-dimensional layered material is more efficient due to the benefit of the specific quantum confinement effect and the surface effect (larger specific surface area) of the nanoscale, and the photo-generated carriers with high density and longer service life are easily obtained, so that the external quantum efficiency and the photoresponse rate of the detector are improved.
Although single photodetection prototype devices based on two-dimensional materials have shown their excellent photoelectric conversion performance, their distance practicalization still requires a series of challenges to be solved. One reason for this is that the thickness of the semiconductor layer formed by two-dimensional materials is very thin, and the semiconductor layer generally has a gap, and at this time, the electrode pads on both sides of the semiconductor layer are easily and directly conducted, which may affect the normal operation of the photodetector. Another reason is the low light utilization efficiency of existing photodetectors based on two-dimensional materials.
Disclosure of Invention
(I) technical problems to be solved by the invention
The technical problem solved by the invention is as follows: how to improve the light utilization efficiency of the photoelectric detector and avoid the electrode plates at the two ends of the semiconductor layer from being directly conducted.
(II) the technical scheme adopted by the invention
A vertical two-dimensional thin film material-based photodetector, comprising:
a first electrode layer;
a nanosheet array disposed on the first electrode layer, the nanosheet array being formed of an upright two-dimensional semiconductor material, the nanosheet array having a gap that exposes a portion of the first electrode layer;
the insulating glue layer is positioned in the gap of the nanosheet array and is arranged on the first electrode layer exposed from the gap;
and the second electrode layer is arranged on the nanosheet array and the insulating glue layer.
Preferably, the photodetector further includes a passivation layer disposed on the nanosheet array and the insulating glue layer, and the passivation layer is located below the second electrode layer.
Preferably, the material of the passivation layer is aluminum oxide, and the thickness of the passivation layer ranges from 5nm to 10 nm.
Preferably, the material of the nanosheet array is a tin diselenide nanosheet.
The application also discloses a preparation method of the photoelectric detector based on the vertical two-dimensional thin film material, which comprises the following steps:
manufacturing and forming a first electrode layer on a substrate;
fabricating a nanosheet array on the first electrode layer, the nanosheet array being formed of an upstanding two-dimensional semiconductor material, the nanosheet array having a gap exposing a portion of the first electrode layer;
gluing the nanosheet array to form an insulating glue layer in the gap of the nanosheet array, wherein the insulating glue layer is arranged on the first electrode layer exposed from the gap;
and manufacturing and forming a second electrode layer on the nanosheet array and the insulating glue layer.
Preferably, a molecular beam epitaxy process is adopted to fabricate and form a nanosheet array on the first electrode layer.
Preferably, after the nanosheet array is fabricated and formed on the first electrode layer, the preparation method further comprises:
and carrying out thermal annealing treatment on the nanosheet array.
Preferably, before forming the second electrode layer, the preparation method further comprises:
and manufacturing and forming a passivation layer on the nanosheet array and the insulating glue layer, wherein the passivation layer is positioned below the second electrode layer.
Preferably, the second electrode layer is formed by an electron beam evaporation process.
Preferably, the material of the nanosheet array is a tin diselenide nanosheet.
(III) advantageous effects
The invention discloses a photoelectric detector made of vertical two-dimensional thin film material and a preparation method thereof, and compared with the traditional photoelectric detector, the photoelectric detector has the following technical effects:
the vertical nanosheet array is manufactured and formed firstly, the 3D vertical nanosheet array has a light trapping effect, the external quantum efficiency and the light responsivity are greatly improved, an insulating glue layer is further arranged in a gap of the nanosheet array, and the upper electrode layer and the lower electrode layer are directly conducted through the gap, so that the normal use of the photoelectric detector is ensured.
In addition, the nano-sheet array can be prepared uniformly in a large area by adopting a molecular beam epitaxy process.
Drawings
Fig. 1 is a flowchart of a method for manufacturing a vertical two-dimensional thin-film photodetector according to a first embodiment of the present invention;
fig. 2 is a schematic view of a vertical two-dimensional thin-film photodetector according to a second embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Before describing in detail the various embodiments of the present application, the inventive concepts of the present application are first briefly described: the utility model discloses a photoelectric detector based on two-dimensional semiconductor material's among the prior art light utilization ratio is lower, the thickness of semiconductor layer is thinner and have the clearance in addition, can lead to the electrode slice direct conduction of both sides, this application adopts vertical type two-dimensional semiconductor material to constitute the nanometer piece array at first, 3D vertical type nanometer piece array has the light trapping effect, the external quantum efficiency and the light responsivity of detector have greatly been improved, and further set up the insulating glue film in the clearance of nanometer piece array, upper and lower two electrode layers directly take place to switch on through the clearance, make between the upper and lower two electrodes switch on through the photogenerated carrier that nanometer piece array produced, thereby guarantee photoelectric detector's normal use.
Example one
Specifically, as shown in fig. 1, the method for manufacturing a vertical two-dimensional thin film material-based photodetector disclosed in this embodiment includes the following steps:
step S10: forming a first electrode layer 20 on the substrate 10;
step S20: fabricating a nanosheet array 30 on the first electrode layer 20, the nanosheet array 30 being formed of an upstanding two-dimensional semiconductor material, the nanosheet array 30 having a gap 31, the gap 31 exposing a portion of the first electrode layer 20;
step S30: gluing the nanosheet array 30 to form an insulating glue layer 40 in the gaps 31 of the nanosheet array 30, wherein the insulating glue layer 40 is disposed on the first electrode layer 20 exposed from the gaps 31;
step S40: and manufacturing and forming a second electrode layer 50 on the nanosheet array 30 and the insulating glue layer 40.
In step S10, the substrate 10 is a glass substrate, and the material of the first electrode layer 20 is a molybdenum electrode.
In step S20, a molecular beam epitaxy process is performed on the first electrode layer 20 to form a nano-chip array 30.
Illustratively, a high-purity selenium material source and a high-purity tin material source, which are preferably 99.99% pure, are respectively added to a molecular beam epitaxy apparatus (MBE) by which the selenium material source and the tin material source are respectively heated and sprayed onto a substrate in the form of a molecular beam or an atomic beam, wherein the temperatures of the Se, Sn source and substrate are 245 ℃, 1100 ℃ and 245 ℃, respectively, and the degree of vacuum is 2 × 105Pa, formation of SnSex(x is 1.6-2.2) nanosheet array structure. The growth time is 1-40 min, the width of the nano-sheet in the nano-sheet array 30 is 20-30 nm, and the height is 1-2 μm. It should be noted that when the growth temperature is lower (C)<250 c) and the molecular migration energy is insufficient to cross the potential barrier and thus evolve into a longitudinal growth mode.
In another embodiment, after the nanosheet array 30 is formed on the first electrode layer 20, the method of preparing further comprises: the nanosheet array 30 is subjected to a thermal annealing process.
Specifically, SnSe is regulated and controlled by adjusting substrate temperature2The crystal quality of the nanosheets and the late thermal annealing treatment regulate and control the surface defect state, including the adsorption (electron trap) of the internal defects (Vsn, Vse and SnSe) of the material and the surface defects (SnSe 2) of the material to O in the air. The temperature of the substrate is controlled to be (150 ℃ -250 ℃), and the thermal annealing treatment mainly comprises the utilization of 2% H2Se and 98% of N2The internal defects are regulated and controlled by controlling the temperature rise and the heat preservation temperature and time under the atmosphere, so that the temperature is controlled to be (200℃)The temperature rise and the heat preservation time of minus 280 ℃ are 30min to 60 min. Of course in other embodiments, at 3% H2S and 97% N2The internal defects are regulated and controlled by controlling the temperature rise and the heat preservation temperature and time under the atmosphere, so that the temperature rise and the heat preservation time are controlled to be 30-60 min at 200-280 ℃.
SnSe prepared in step S202The nanosheet array has extremely high light trapping effect, the absorption of 500-600nm band light is more than 96%, the external quantum efficiency and the light responsivity of the detector can be greatly improved, and the primarily prepared SnSe based on the 3D vertical structure2The external quantum efficiency of the nano-sheet photoelectric detector is as high as 6.43 multiplied by 105% and response time is less than 20 ms.
In step S30, the obtained SnSe2And (3) homogenizing the nanosheet two-dimensional thin film material, regulating and controlling the thickness of the homogenized glue by controlling the rotating speed, and then testing the thickness of the insulating glue layer by using a film thickness meter. The rotating speed range is 1000-4000 rpm, and the thickness is controlled to be about 1-2 um. The type of the insulating adhesive layer 40 is selected from PMMA, electron beam resist positive (RZJ-304), and epoxy negative (SN-100), and then the light transmittance of the adhesive is characterized, and the best light transmittance is selected.
In step S40, after the glue is homogenized, the second electrode layer 50 is formed by evaporation by an electron beam evaporation method, the second electrode layer 50 is an electrode in a Ni-Al-Ni form, which has good stability and can be uniformly prepared in a large area, the preparation method is simple and easy to operate, and the thickness can be controlled to be about 8000-10000 nm.
In another embodiment, before forming the second electrode layer 50, the preparation method further includes: a passivation layer 60 is formed on the nanosheet array 30 and the insulating glue layer 40, and the passivation layer 60 is located below the second electrode layer 50. Illustratively, the passivation layer 60 is formed using an atomic deposition process. The passivation layer 60 can regulate and control the surface defect state of the material, and the photon-generated electron-hole recombination rate is reduced by forming a Schottky barrier structure, namely, the dark current is reduced, and the photoresponse performance of the detector is improved.
The preparation method of the vertical two-dimensional thin-film-material-based photoelectric detector provided by the embodiment includes the steps of firstly manufacturing and forming a vertical nanosheet array, enabling the 3D vertical nanosheet array to have a light trapping effect, greatly improving the external quantum efficiency and the light responsivity of the detector, further arranging an insulating glue layer in a gap of the nanosheet array, and enabling an upper electrode layer and a lower electrode layer to be directly conducted through the gap, so that the normal use of the photoelectric detector is guaranteed. Meanwhile, the nano-sheet array can be prepared uniformly in a large area by adopting a molecular beam epitaxy process.
Example two
As shown in the figure, the photodetector based on the vertical two-dimensional thin film material disclosed in the second embodiment includes a first electrode layer 20, a nanosheet array 30, an insulating glue layer 40, and a second electrode layer 50. Wherein a nanoplatelet array 30 is disposed on the first electrode layer 20, the nanoplatelet array 30 is formed of an upstanding two-dimensional semiconductor material, the nanoplatelet array 30 has a gap 31, and the gap 31 exposes a portion of the first electrode layer 20. The insulating glue layer 40 is located in the gap 31 of the nanosheet array 30, and is disposed on the first electrode layer 20 exposed from the gap 31. The second electrode layer 50 is disposed on the nanosheet array 30 and the insulating glue layer 40.
In another embodiment, the photodetector further includes a passivation layer 60, the passivation layer 60 is disposed on the nanosheet array 30 and the insulating glue layer 40, and the passivation layer 60 is located below the second electrode layer 50.
Illustratively, the passivation layer 60 is made of aluminum oxide, the thickness of the passivation layer 60 is in a range of 5nm to 10nm, and the nanosheet array 30 is made of tin diselenide nanosheets.
The photoelectric detector of the second embodiment utilizes a vertical two-dimensional thin film material to form a vertical nanosheet array, the 3D vertical nanosheet array has a light trapping effect, the external quantum efficiency and the light responsivity of the detector are greatly improved, an insulating glue layer is further arranged in a gap of the nanosheet array, and an upper electrode layer and a lower electrode layer are directly conducted through the gap, so that the normal use of the photoelectric detector is ensured.
Although a few embodiments of the present invention have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the claims and their equivalents.
Claims (10)
1. A photodetector based on a vertical two-dimensional thin film material, comprising:
a first electrode layer;
a nanosheet array disposed on the first electrode layer, the nanosheet array being formed of an upright two-dimensional semiconductor material, the nanosheet array having a gap that exposes a portion of the first electrode layer;
the insulating glue layer is positioned in the gap of the nanosheet array and is arranged on the first electrode layer exposed from the gap;
and the second electrode layer is arranged on the nanosheet array and the insulating glue layer.
2. The upright two-dimensional thin-film material photodetector of claim 1, further comprising a passivation layer disposed on said nanosheet array and said layer of insulating glue, said passivation layer underlying said second electrode layer.
3. The vertical two-dimensional thin-film photodetector of claim 1, wherein the passivation layer is made of alumina and has a thickness ranging from 5nm to 10 nm.
4. The upright two-dimensional thin-film material photodetector of claim 2, wherein the material of the nanosheet array is a tin diselenide nanosheet.
5. A preparation method of a photoelectric detector based on a vertical two-dimensional thin film material is characterized by comprising the following steps:
manufacturing and forming a first electrode layer on a substrate;
fabricating a nanosheet array on the first electrode layer, the nanosheet array being formed of an upstanding two-dimensional semiconductor material, the nanosheet array having a gap exposing a portion of the first electrode layer;
gluing the nanosheet array to form an insulating glue layer in the gap of the nanosheet array, wherein the insulating glue layer is arranged on the first electrode layer exposed from the gap;
and manufacturing and forming a second electrode layer on the nanosheet array and the insulating glue layer.
6. The preparation method according to claim 5, characterized in that a molecular beam epitaxy process is adopted to fabricate and form a nanosheet array on the first electrode layer.
7. The preparation method according to claim 5, wherein after the nanosheet array is fabricated and formed on the first electrode layer, the preparation method further comprises:
and carrying out thermal annealing treatment on the nanosheet array.
8. The method according to claim 7, wherein before forming the second electrode layer, the method further comprises:
and manufacturing and forming a passivation layer on the nanosheet array and the insulating glue layer, wherein the passivation layer is positioned below the second electrode layer.
9. The method according to claim 7, wherein the second electrode layer is formed by an electron beam evaporation process.
10. The preparation method according to claim 6, wherein the material of the nanosheet array is a tin diselenide nanosheet.
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CN114122192A (en) * | 2021-11-04 | 2022-03-01 | 中国科学院深圳先进技术研究院 | Film preparation method and photoelectric detector |
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