CN111430483A - Photoelectric detector, manufacturing method thereof and photoelectric detection system - Google Patents
Photoelectric detector, manufacturing method thereof and photoelectric detection system Download PDFInfo
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Abstract
The invention discloses a photoelectric detector, comprising: a substrate; a bottom electrode disposed on the substrate; an absorption layer disposed on the bottom electrode; the absorption layer is based on Cu2‑II‑IV‑VI4Group photoelectric film absorbing material Cu2CdaZn1‑aSnSe4A is more than or equal to 0 and less than or equal to 1; a buffer layer disposed on the absorber layer; a window layer disposed on the buffer layer; and an oxide barrier layer is also arranged between the buffer layer and the window layer. The invention also discloses a manufacturing method of the photoelectric detector.The invention also discloses a photoelectric detection system comprising the photoelectric detector or the photoelectric detector manufactured by the manufacturing method. The invention adopts Cu-based2‑II‑IV‑VI4Group photoelectric film absorbing material Cu2CdaZn1‑aSnSe4The oxide barrier layer is arranged between the buffer layer and the window layer and can block current carriers caused by a leakage channel, so that the dark current of the detector is reduced, and the photoelectric detection rate of the detector is improved.
Description
Technical Field
The invention relates to the field of photoelectric detectors, in particular to a photoelectric detector, a manufacturing method thereof and a photoelectric detection system.
Background
The near-infrared band photoelectric detector has higher definition and detail resolution, and has low-light night vision and stronger water mist penetrating capability, so that the photoelectric detector has a wide market in the fields of mobile phones, unmanned aerial vehicles, security protection, medical treatment and the like. The currently adopted indium gallium arsenic photoelectric detector needs to work at low temperature, and the cost is high due to the irreplaceability of the preparation process.
In addition, important parameters for measuring the photodetector include a photodetection rate D. Dark current is easily caused by carrier recombination and material defects in the working process of the photoelectric detector, the dark current can generate noise, the signal to noise ratio is reduced, and the photoelectric detection rate of the photoelectric detector is seriously influenced.
Therefore, how to reduce the expensive cost of the photodetector and reduce the dark current of the photodetector, and improve the photodetection rate of the photodetector is a technical problem to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a photoelectric detector, a method thereof and a photoelectric detection system, which can reduce dark current and improve photoelectric detection rate.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
according to an aspect of the present invention, there is provided a photodetector including:
a substrate;
a bottom electrode disposed on the substrate;
an absorption layer disposed on the bottom electrode; the absorption layer is based on Cu2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4A is more than or equal to 0 and less than or equal to 1;
a buffer layer disposed on the absorber layer;
a window layer disposed on the buffer layer;
and an oxide barrier layer is also arranged between the buffer layer and the window layer.
Further, the thickness of the absorption layer is 0.5 to 1.5 μm.
Further, the oxide barrier layer can adopt Al2O3Or Ga2O3Or ZnO or SnO or ZnbSn1-bOcWherein b is more than or equal to 0.3 and less than or equal to 1, and c is more than or equal to 1 and less than or equal to 3.
Further, the thickness of the oxide barrier layer is 1-10 nm.
Further, the thickness of the window layer is 300-400 nm.
Further, the window layer comprises a first window layer arranged on the buffer layer, and the first window layer is used for forming an N region with the buffer layer; the window layer further comprises a second window layer arranged on the first window layer, and the second window layer is used for transmitting light rays to be detected.
Further, the first window layer is made of intrinsic zinc oxide; and/or the second window layer is made of a doped zinc oxide or transparent conductive polymer film.
According to another aspect of the present invention, there is also provided a method for manufacturing the above-mentioned photodetector, the method comprising:
providing a substrate;
forming a bottom electrode on the substrate;
forming an absorption layer on the bottom electrode;
forming a buffer layer on the absorption layer;
forming an oxide barrier layer on the buffer layer;
forming a window layer on the oxide barrier layer.
Further, an oxide barrier layer is formed on the buffer layer by adopting an atomic layer deposition method or a magnetron sputtering method.
According to another aspect of the present invention, there is also provided a photodetection system, which includes the above-mentioned photodetector or the photodetector manufactured by the above-mentioned manufacturing method.
The invention has the beneficial effects that: the invention adopts Cu-based2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4The oxide barrier layer is arranged between the buffer layer and the window layer and can block current carriers caused by a leakage channel, so that the dark current of the detector is reduced, and the photoelectric detection rate of the detector is improved.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a photodetector structure according to an embodiment of the present invention;
fig. 2 is a flow chart illustrating a method of fabricating a photodetector according to an embodiment of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. In the drawings, the shapes and sizes of elements may be exaggerated for clarity, and the same reference numerals will be used throughout to designate the same or similar elements.
It will be understood that, although the terms first, second, etc. may be used herein to describe various elements, these elements should not be limited by these terms. These terms are only used to distinguish one element from another.
Example one
Fig. 1 is a schematic structural diagram of a photodetector according to an embodiment of the present invention.
With particular reference to fig. 1, a photodetector according to an embodiment of the invention comprises: a substrate 10, a bottom electrode 20, an absorber layer 30, a buffer layer 40, a window layer 60, and an oxide barrier layer 50. It will be appreciated that the invention is not so limited and that photodetectors according to embodiments of the invention may also include other components necessary to form a photodetector, such as a top electrode disposed on the window layer 60.
The choice of substrate 10 and the choice of material on which to fabricate bottom electrode 20 will be within the skill of the art. For example, the substrate 10 may be a clean soda-lime glass substrate 10 or a silicon wafer, and other structures of the photodetector are sequentially formed on the substrate 10. For example, the bottom electrode 20 may be made of Mo; preferably, the thickness of the bottom electrode 20 is preferably controlled to 400-600 nm.
The absorption layer 30 is disposed on the bottom electrode 20. The work of the indium gallium arsenic photoelectric detector in the prior art needs to be carried out at a low temperature (-80-20 ℃), and the cost of the photoelectric detector is high due to the non-substitutability of the preparation process. The photoelectric detector of the embodiment of the invention aims at overcoming the technical problem of high cost and low temperature workThe structure and material of photoelectric detection are improved. Specifically, in the embodiment of the present invention, the absorption layer 30 is based on Cu2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4(CCZTSE for short), wherein a is more than or equal to 0 and less than or equal to 1. The absorption layer 30 made of CCZTSe material can realize the response of visible light and near infrared band. Preferably, the thickness of the absorption layer 30 is preferably controlled to be 0.5 to 1.5 μm.
The buffer layer 40 is disposed on the absorption layer 30, and preferably, the buffer layer 40 is made of CdS material.
The material of the absorption layer 30 of the embodiment of the present invention is selected based on Cu2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4The (CCZTSE for short) has the defects that multiple uncontrollable factors of growth of a multi-component compound exist, multiple phases coexist, the grain size is not uniform, potential fluctuation in the working process of a device is easily caused by excessive grain boundaries, carriers are captured and compounded by the defects to cause excessive dark current, so that large energy consumption is generated, and the efficiency of a photoelectric detector is seriously influenced. In the prior art, a method of performing wet etching after the absorber layer 30 is prepared is adopted in the technical art to appropriately reduce the dark current of the device, but the mechanism of action of the wet etching is yet to be explored, and whether the device is negatively affected is still left to be studied.
In the embodiment of the invention, in order to reduce the dark current of the photodetector, the oxide blocking layer 50 is disposed on the buffer layer 40, and the oxide blocking layer 50 has a modifying effect on a leakage channel of a crystal interface and simultaneously blocks a leakage current caused by a hole existing in the material of the absorption layer 30.
Preferably, the oxide barrier layer 50 may be Al, and the oxide barrier layer 50 may be Al2O3Or Ga2O3Or ZnO or SnO or ZnbSn1-bOcThe preparation is that b is more than or equal to 0.3 and less than or equal to 1, and c is more than or equal to 1 and less than or equal to 3.
If the thickness of the oxide blocking layer 50 is thick, light can be blocked from entering the absorption layer 30, so that the light detectivity is reduced, and if the thickness of the oxide blocking layer 50 is too thin, the effect of blocking dark current is not obvious, so that the effect cannot be achieved. Generally, the thickness of the oxide barrier layer 50 may be selected in the range of 1-10nm depending on the material or area of the photodetector, and preferably, the thickness of the oxide barrier layer 50 is controlled to be 1-2 nm.
By increasing the oxide barrier layer 50 and controlling the thickness of the oxide barrier layer 50, the dark current of the photodetector can be reduced, and since the thickness of the oxide barrier layer 50 is controlled within a suitable range, the thickness of the oxide barrier layer 50 is small relative to the thickness of the photodetector, and the influence on the detection of the photocurrent is not large even at a large photocurrent.
Further, a window layer 60 is provided on the oxide barrier layer 50. Specifically, the window layer 60 includes a first window layer 60 disposed on the buffer layer 40 and a second window layer 60 disposed on the first window layer 60. The first window layer 60 and the second window layer 60 each perform different functions.
The first window layer 60 is an important component of the photodetector, and the first window layer 60 is used to form an N region with the buffer layer 40. Preferably, intrinsic zinc oxide is used for the first window layer 60. The high resistance intrinsic zinc oxide can form a good N region with the CdS buffer layer 40.
The second window layer 60 is for transmitting light to be detected. Preferably, the second window layer 60 is made of a doped zinc oxide or a transparent conductive polymer film. As the doping element for doping zinc oxide, Al, In, Ga, Sn, or the like can be used. The low resistance second window layer 60 has a high transmittance.
The window layer 60 of the embodiment of the present invention not only has a good lattice match with the buffer layer 40, but also has a high transmittance with the top electrode disposed thereon. Preferably, the window layer 60 of embodiments of the present invention has a thickness in the range of 300-400 nm.
The photoelectric detector of the embodiment adopts the Cu-based2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4As a material for the absorber layer 30 of the photodetector, and the oxide barrier layer 50 disposed between the buffer layer 40 and the window layer 60, it is possible to realize a chamber-in-chamber structureThe photoelectric detector can normally work at the temperature of 20-25 ℃, can have larger photocurrent under weaker illumination, reduces the application cost of the photoelectric detector, can block carriers caused by a leakage channel, reduces the dark current of the detector, and improves the photoelectric detection rate of the detector.
Example two
Fig. 2 is a flow chart of a method of fabricating a photodetector according to an embodiment of the present invention.
Referring specifically to fig. 2, the method for fabricating a photodetector according to the present embodiment includes the following steps:
in step S100, a substrate 10 is provided, and the substrate 10 is selected by one skilled in the art according to the prior art. For example, the substrate 10 may be a clean soda lime glass substrate 10 or a silicon wafer.
In step S200, a bottom electrode 20 is formed on the substrate 10. Selection of the material for the bottom electrode 20 will be within the skill of the art. For example, the bottom electrode 20 may be made of Mo.
In step S300, the absorption layer 30 is formed on the bottom electrode 20. In the embodiment of the present invention, the absorption layer 30 is based on Cu2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4(CCZTSE for short), wherein a is more than or equal to 0 and less than or equal to 1. Preferably, the thickness of the absorption layer 30 is preferably controlled to be 0.5 to 1.5 μm.
In step S400, the buffer layer 40 is formed on the absorber layer 30. Preferably, the buffer layer 40 is made of CdS material.
In step S500, an oxide barrier layer 50 is formed on the buffer layer 40. Preferably, the oxide barrier layer 50 may be Al, and the oxide barrier layer 50 may be Al2O3Or Ga2O3Or ZnO or SnO or ZnbSn1-bOcThe preparation is that b is more than or equal to 0.3 and less than or equal to 1, and c is more than or equal to 1 and less than or equal to 3. Preferably, the thickness of the oxide barrier layer 50 is controlled to be 1-2 nm. Preferably, the thickness of the oxide barrier layer 50 can be precisely controlled by forming the oxide barrier layer 50 by atomic layer deposition. In other embodiments, magnetron sputtering may be used inAn oxide barrier layer 50 is formed on the buffer layer 40.
In step S600, a window layer 60 is formed on the oxide barrier layer 50. Specifically, first window layer 60 is formed on oxide barrier layer 50, and then second window layer 60 is formed on first window layer 60. Preferably, intrinsic zinc oxide is used for the first window layer 60. Preferably, the second window layer 60 is made of a doped zinc oxide or a transparent conductive polymer film. As the doping element for doping zinc oxide, Al, In, Ga, Sn, or the like can be used. Preferably, the window layer 60 of embodiments of the present invention has a thickness in the range of 300-400 nm.
The method for manufacturing the photoelectric detector of the embodiment adopts the Cu-based2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4As the material of the absorption layer 30 of the photoelectric detector, and the oxide barrier layer 50 is arranged between the buffer layer 40 and the window layer 60, normal operation at room temperature (20-25 ℃) can be realized, a large photocurrent can be obtained under weak illumination, the application cost of the photoelectric detector is reduced, the photoelectric detector of the embodiment can block carriers caused by a leakage channel, the dark current of the detector is reduced, and the photoelectric detection rate of the detector is improved.
EXAMPLE III
A third embodiment of the present invention provides a specific implementation manner of a manufacturing method of a photodetector, and the manufacturing method of the photodetector includes the following steps:
in step S100, a substrate 10 is provided. In this embodiment, a soda-lime glass substrate 10 or a silicon wafer is used,
Step S200, forming a bottom electrode 20 on the substrate 10. Specifically, the substrate 10 in step S100 is cleaned and placed in a vacuum molybdenum chamber, Ar gas is introduced, the gas pressure in the chamber is controlled at 2.0Pa, dc sputtering is performed for 8 cycles with 350W power, sputtering is performed for 4 cycles with 1000W power under 0.3Pa, Ar gas is turned off, and the sample is taken out after cooling for 5-10 min. A Mo substrate having a thickness of about 500nm is formed on the base 10 as the bottom electrode 20. This embodiment only shows one embodiment of fabricating the bottom electrode 20, and other fabrication methods can be adopted to fabricate the bottom electrode 20 in other embodiments.
Step S300, forming an absorption layer 30 on the bottom electrode 20. The sample prepared in the step S200 is sent into an MBE vacuum coating cavity, and the vacuum degree is controlled to be 2X10-5Pa. And a five-source evaporation method is adopted, Cu, Zn, Cd, Sn and Se are used as target materials, and a precursor is grown by a one-step method. Firstly, heating the sample prepared in the step S200 to 430 ℃ and stabilizing, respectively preheating five source targets for 20min, then opening a baffle, and simultaneously closing a Cu target baffle after evaporation for 45 min. And closing the Zn and Cd target baffle after 9 min. After another 2min, the Sn target baffle is closed. And finally stopping heating after 1min, closing the main baffle and the Se target baffle when the temperature is reduced to 300 ℃, cooling to room temperature, and taking out to obtain the absorption layer 30 with the thickness of 1 micron.
Step S400, forming a buffer layer 40 on the absorption layer 30. Specifically, a mixed solution of cadmium sulfate and ammonia water is prepared, and the thiourea solution is poured into a reactor, the sample prepared in the step S400 is placed in the center of the reactor, the reactor is placed into a water bath kettle with the constant temperature of 69 ℃, a stirrer is opened, and the CdS buffer layer 40 material uniformly grows by a chemical water bath method. After 9min of reaction, the instrument was closed, the sample was removed, the sample was quickly rinsed with deionized water, and N was used2Blow-drying, annealing in a 160 ℃ oven for 2min, and finally forming the buffer layer 40 on the absorption layer 30.
S500, forming an oxide barrier layer 50 on the buffer layer 40, and producing a 1nm alumina barrier layer on the surface of the buffer layer 40 by using an Atomic layer Deposition method (Atomic L a layer Deposition, A L D). concretely, the sample prepared in the step S400 is placed into an A L D reaction chamber, the vacuum pressure is 5Pa, the temperature of the sample is adjusted to be 250 ℃, an aluminum source is introduced for 300ms, the aluminum atoms are deposited on the buffer layer 40, the vacuum pressure is 8S, excessive aluminum sources are removed, N2500ms is introduced, the aluminum source in the chamber is washed off, the aluminum source in the chamber is pumped and washed out as far as possible, then, water vapor is introduced for 30ms, an oxygen source is provided, the air is pumped for 8S, and N500 ms is continuously introduced2And pumping for 15s, washing off excessive oxygen source, repeating the cycle for 10 times, and depositing an aluminum oxide barrier layer with the thickness of 1nm on the buffer layer 40.
Step (ii) ofAnd S600, forming a window layer 60 on the oxide barrier layer 50. The window layer 60 is comprised of two parts, a first window layer 60 on the oxide barrier layer 50 and a second window layer 60 on the first window layer 60. The first window layer 60 is made of intrinsic zinc oxide and the second window layer 60 is made of aluminum-doped zinc oxide. The sample prepared in the step S500 is sent into a cavity of intrinsic zinc oxide and aluminum-doped zinc oxide, Ar and O are introduced2The intrinsic zinc oxide is ignited under the power of 120W, then sputtering is carried out for 40 circles under the power of 220W, and then Ar and H are introduced2After the aluminum-doped zinc oxide target is ignited at 500W, sputtering is carried out for 20 circles at 750W, and a window layer 60 with the thickness of 300-400nm is obtained.
Example four
The fourth embodiment of the invention discloses a photoelectric detection system, which comprises the photoelectric detector or performs photoelectric detection by adopting the photoelectric detection manufactured by the manufacturing method, can be applied to the fields of mobile phones, unmanned aerial vehicles, security, medical treatment and the like, and is not limited in the aspects.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (10)
1. A photodetector, comprising:
a substrate;
a bottom electrode disposed on the substrate;
an absorption layer disposed on the bottom electrode; the absorption layer is based on Cu2-II-IV-VI4Group photoelectric film absorbing material Cu2CdaZn1-aSnSe4A is more than or equal to 0 and less than or equal to 1;
a buffer layer disposed on the absorber layer;
a window layer disposed on the buffer layer;
and an oxide barrier layer is also arranged between the buffer layer and the window layer.
2. The photodetector of claim 1, wherein the absorbing layer has a thickness of 0.5 to 1.5 μm.
3. The photodetector of claim 1, wherein the oxide barrier layer is made of Al2O3Or Ga2O3Or ZnO or SnO or ZnbSn1-bOcWherein b is more than or equal to 0.3 and less than or equal to 1, and c is more than or equal to 1 and less than or equal to 3.
4. The photodetector of claim 1 or 3, wherein the oxide barrier layer has a thickness of 1-10 nm.
5. The photodetector of claim 1, wherein the thickness of the window layer is 300-400 nm.
6. The photodetector of claim 1, wherein the window layer comprises a first window layer disposed on the buffer layer, the native oxide layer for forming an N-region with the buffer layer; the window layer further comprises a second window layer arranged on the first window layer, and the second window layer is used for transmitting light rays to be detected.
7. The photodetector of claim 6, wherein the first window layer is made of intrinsic zinc oxide; and/or the second window layer is made of a doped zinc oxide or transparent conductive polymer film.
8. A method of fabricating a photodetector as claimed in any one of claims 1 to 7, characterized in that the method of fabricating comprises:
providing a substrate;
forming a bottom electrode on the substrate;
forming an absorption layer on the bottom electrode;
forming a buffer layer on the absorption layer;
forming an oxide barrier layer on the buffer layer;
forming a window layer on the oxide barrier layer.
9. The method of manufacturing according to claim 8, wherein an oxide barrier layer is formed on the buffer layer by using an atomic layer deposition method or a magnetron sputtering method.
10. A photodetection system, characterized in that the photodetection system comprises the photodetector according to any one of claims 1 to 7 or the photodetector manufactured by the manufacturing method according to claim 8 or 9.
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