CN112687809B - Antimony telluride photoelectric detector and preparation method thereof - Google Patents
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Abstract
The invention discloses an antimony telluride photoelectric detector and a preparation method thereof, wherein the method comprises the following steps: vapor deposition of Sb on a substrate2Te3A catalytic layer for film growth; vapor deposition of Sb on a substrate having a catalyst layer2Te3A film; for Sb2Te3Annealing the film; sb after completion of annealing treatment2Te3Evaporating a first organic material on the film to form an enhanced absorption layer and form a substrate material/Sb2Te3A first organic material heterojunction; electrodes are prepared at two ends of the heterojunction to obtain the antimony telluride photoelectric detection device or line array, the absorption in a visible light-near infrared band is obviously improved, and the antimony telluride photoelectric detection device has high electron mobility. Compared with coating methods such as a chemical vapor deposition method (CVD), Molecular Beam Epitaxy (MBE), magnetron sputtering and the like, the method is short in preparation period, simple to operate and excellent in performance of the prepared detector, and provides reference and theoretical practical basis for research on novel low-dimensional materials and topological insulator photoelectric detectors.
Description
Technical Field
The invention relates to the technical field of preparation and application of topological insulator photoelectric materials, in particular to an antimony telluride photoelectric detector and a preparation method thereof.
Background
In recent years, with the third generation of topological insulator (Bi)2Te3、Bi2Se3、Sb2Te3) Theoretical experiment ofThe synthesis with the laboratory and the new physical effects (quantum Hall effect, quantum spin Hall effect, reversible phase change, etc.) caused by the synthesis with the laboratory have attracted the wide attention of scientists. It is particularly noteworthy that unlike the special band structure of semiconductors and insulators, the inside is an insulator with a band gap, while the surface is in a metallic state without a band gap. And the surface states are determined by the topology of their bulk electronic states and are symmetrically protected. The special structure enables the topological insulator to have high carrier mobility, and meanwhile, the narrow band gap of the topological insulator enables the topological insulator to be very suitable for application in the field of wide-spectrum photoelectric detection.
For Bi2Te3、Bi2Se3There have been many reports of photodetectors as an old material in the field of thermoelectric materials, phase change memory devices, Sb2Te3Has only recently been demonstrated as a topological insulator, and has had limited research in the field of photodetection. Sb2Te3The synthesis method comprises a molecular beam epitaxy method, a chemical vapor deposition method, a Metal Organic Chemical Vapor Deposition (MOCVD) method, a solution chemical synthesis method, an evaporation coating method, a Pulse Laser Deposition (PLD) method, magnetron sputtering and the like. For Sb2Te3The different morphological states (nano-sheet and film) of the film have been studied to a certain extent. Kun Zheng et al (K.Zheng, L. -B.Luo, T. -F.Zhang, Y. -H.Liu, Y. -Q.Yu, R.Lu, H. -L.Qiu, Z. -J.Li and J.C.Andrew. optoelectronic characteristics of a near-isolated light photodetector based on a polar inductor Sb2Te3 film[J]Journal of Materials Chemistry C.2015,3:9154-9160.) Sb grown by MBE method2Te3The film is sensitive to 980nm laser in a low-temperature state (8.5K), and the response rate and the on-off ratio respectively reach 21.7A/W and 2.36. 2019 Huawei Liu et al (H.Liu, D.Li, C.Ma, X.Zhang, X.Sun, C.Zhu, B.ZHEN, Z.Zou, Z.Luo, X.Zhu, X.Wang and A.Pan.Van der Waals epithelial growth of vertical stacked Sb2Te3/MoS2 p–n heterojunctions for high performance optoelectronics[J]Nano energy.2019,59:66-74.) preparation of Sb by chemical vapor deposition2Te3/MoS2The nano-sheet heterojunction structure has a nano-sheet heterojunction structure,with a current switching ratio of up to 106The quantum efficiency reaches 4.5%, and meanwhile, the response rate of the structure reaches 330A/W at a 520nm wave band. However, the antimony telluride photoelectric detection device prepared by the MBE method or the chemical vapor deposition method has the problems of complex preparation process, high cost, difficulty in mass production, insufficient response wave band and low response rate.
Disclosure of Invention
The invention aims to solve the problems that the response wave band of the existing antimony telluride photoelectric detection device is not wide enough and the response rate is not high enough, and provides an antimony telluride photoelectric detection device and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme: an antimony telluride photodetector and a method for manufacturing the same, the method comprising:
vapor deposition of Sb on a substrate2Te3A catalytic layer for film growth; vapor deposition of Sb on a substrate having a catalyst layer2Te3A film; for Sb2Te3Annealing the film; sb after completion of annealing treatment2Te3Evaporating a first organic material on the film to form an enhanced absorption layer and form a substrate material/Sb2Te3A first organic material heterojunction; and preparing electrodes at two ends of the heterojunction to obtain the antimony telluride photoelectric detection device or the line array.
As an option, the substrate is evaporated with Sb2Te3The catalyst layer for the film growth is specifically as follows: evaporating and plating metallic tin by an evaporation film plating machine with the air pressure of 3 multiplied by 10-4～8×10-4pa at a rotational speed of 10 DEG/s and an evaporation rate of
Obtaining the tin film catalyst layer with the film thickness of 5-10 nm.
As an option, the vapor deposition Sb2Te3The film is specifically as follows: sb is coated by an evaporation coating machine2Te3The material was evaporated at a pressure of 3X 10-4～8×10-4pa at a rotational speed of 10 DEG/s and an evaporation rate of
As an option, the pair Sb2Te3The annealing conditions of the film are as follows: heating at 200-500 deg.C for 30min at a temperature rise rate of 10 deg.C/s.
As an option, the Sb after the annealing treatment is completed2Te3Before the evaporation plating of the enhanced absorption layer on the film, the method also comprises the following steps: sb after completion of annealing treatment2Te3Evaporating a second organic material layer on the film, and evaporating a first organic material layer on the second organic material layer to form Sb2Te3A second organic material/first organic material heterojunction, with electrodes prepared at both ends of the heterojunction.
As an option, the first organic material is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine; the organic material of the second organic material layer is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine.
As an option, the substrate is evaporated with Sb2Te3The catalyzing layer step for film growth also comprises:
cleaning the substrate: and sequentially putting the substrate into acetone, alcohol and deionized water, respectively carrying out ultrasonic treatment for 30min, and then carrying out UV (ultraviolet) cleaning for 30 min.
As an option, the substrate is any one of silicon oxide wafer, silicon wafer, fluorine crystal mica and quartz.
It should be further noted that the technical features corresponding to the above-mentioned method options can be combined with each other or replaced to form a new technical solution.
The invention also comprises an antimony telluride photoelectric detection device which is prepared by adopting the preparation method of the antimony telluride photoelectric detection device, and the device sequentially comprises the following components from bottom to top: substrate, Sb2Te3Thin film layer, first organic material layer, substrate material/Sb2Te3First organic material heterojunction, electrodes are prepared at both ends of the heterojunction.
As an option, the device further comprises a second organic material layer, the second organic material layerEvaporating the layer on the first organic material layer to form Sb2Te3A second organic material/first organic material heterojunction, with electrodes prepared at both ends of the heterojunction.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, Sb is evaporated on a substrate with a catalyst layer2Te3Film of Sb2Te3The film grows in an island shape and is matched with Sb which is subjected to annealing treatment2Te3The film is coated with the first organic material by vaporization to form the enhanced absorption layer, so that the enhanced absorption layer has higher electron mobility, the response rate of the detection device is improved, and the response waveband of the detection device is widened. Compared with coating methods such as a chemical vapor deposition method (CVD), Molecular Beam Epitaxy (MBE), magnetron sputtering and the like, the method has the advantages of short preparation period, simplicity in operation and excellent performance of the prepared detector, and provides reference and theoretical practical basis for research on novel low-dimensional materials and topological insulator photoelectric detectors.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention.
FIG. 1 is a flowchart of a method of example 1 of the present invention;
FIG. 2 shows PbPc/Sb in example 1 of the present invention2Te3Sb of/n-Si heterojunction2Te3SEM images of the film before annealing and after annealing at 300 ℃ for 30 min;
FIG. 3 shows PbPc/Sb with different thicknesses in example 1 of the present invention2Te3An ultraviolet-visible light absorption spectrum diagram of the/n-Si heterojunction film;
FIG. 4 shows PbPc/Sb in example 1 of the present invention2Te3A curve graph of the response rate of the/n-Si heterojunction at 450nm along with the change of incident power density;
FIG. 5 shows an embodiment of the present inventionPbPc/Sb in example 32Te3The device structure schematic diagram of the/n-Si heterojunction thin-film photoelectric detector;
FIG. 6 shows Sb in example 4 of the present invention2Te3/C60The device structure of the/CuPc heterojunction thin-film photoelectric detector is shown schematically.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that directions or positional relationships indicated by "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like are directions or positional relationships based on the drawings, and are only for convenience of description and simplification of description, and do not indicate or imply that the device or element referred to must have a specific orientation, be configured and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly stated or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
In this embodiment, PbPc/Sb is used2Te3A preparation method of a/n-Si heterojunction linear thin-film photoelectric detector is explained, wherein Sb2Te3As a light absorbing material, n-Si as a substrate and Sb2Te3A heterojunction is formed in the vertical direction, and PbPc is used as a light-reinforced absorption material.
As shown in fig. 1, in embodiment 1, a method for manufacturing an antimony telluride photodetector specifically includes the following steps:
s01: vapor deposition of Sb on a substrate2Te3A catalytic layer for film growth; in this embodiment, 1.5cm × 1.5cm of n-Si is used as the substrate, the substrate is placed in acetone, alcohol, and deionized water, and subjected to ultrasonic treatment for 30min, so as to remove organic and inorganic impurities on the surface of the substrate, and then the substrate is treated in a UV cleaner for 30min, so that the surface of the substrate is hydrophilic.
S02: vapor deposition of Sb on a substrate having a catalyst layer2Te3A film;
s03: for Sb2Te3Annealing the film;
s04: sb after completion of annealing treatment2Te3Evaporating a first organic material on the film to form an enhanced absorption layer and form a substrate material/Sb2Te3A first organic material heterojunction; wherein the first organic material is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine.
S05: and preparing electrodes at two ends of the heterojunction to obtain the antimony telluride photoelectric detection device or the line array.
Further, in step S01, Sb is evaporated on the substrate2Te3The catalyst layer for the film growth is specifically as follows:
evaporating tin metal by using an evaporation coating machine, preferably using Sn particles, placing the Sn particles in an evaporation boat of the evaporation coating machine, arranging a substrate on a sample table, adjusting the vertical distance between the sample table and the evaporation boat to be 260mm, vacuumizing a cavity of the evaporation coating machine, and maintaining the air pressure of the cavity at 5 x 10-4pa, turning on the temperature control power supply to rotate the sample stage at 10 °/s, and maintaining the evaporation rate at
The Sn film thickness was 8 nm. It should be noted that, in this embodiment, the detection device is prepared by evaporation of an evaporation coater, which is only a preferred method, and those skilled in the art can prepare the detection device of the present invention by other methods such as sputtering and vapor deposition, and belongs to simple replacement of conventional technical means without creative work.
Further, in step S02, Sb is evaporated2Te3The film is specifically as follows: sb2Te3The powder is put into an evaporation boat of an evaporation coating machine, and the substrate dried by nitrogen is attached to the center of a sample table. Adjusting the vertical distance between the sample stage and the evaporation boat to 260mm, vacuumizing the cavity, and maintaining the air pressure of the cavity at 5 × 10-4pa, turning on the temperature control power supply, rotating the sample stage at 10 °/s, and maintaining the evaporation rate at the same value by the PID controller
Regulating and controlling the thickness of the film by controlling the evaporation time, calibrating the thickness by using a step profiler, and evaporating to obtain Sb with the thickness of 30nm2Te3A film.
Further, in step S03, Sb is treated2Te3The annealing treatment of the film comprises the following specific steps: sb vapor-deposited in step S022Te3Placing the film into an annealing furnace, heating at 300 deg.C for 30min at a heating rate of 10 deg.C/s, and adding Sb2Te3The film is converted to an amorphous state.
Further, in step S04, Sb after annealing2Te3On a film with
A 50nm PbPc film is deposited as an enhanced absorption layer.
Further, in step S05, a line mask (channel length 50 μm) is applied to the annealed PbPc film, and a plurality of 150nm gold electrodes are deposited on both ends of the heterojunction structure (n-Si substrate, PbPc film) to obtain a patterned probe cell device.
As shown in FIG. 2, PbPc/Sb2Te3Sb of/n-Si heterojunction2Te3SEM images of the film before annealing and after annealing at 300 deg.C for 30min, after annealing (b) forming polycrystals on the surface of the film, and Sb before annealing (a)2Te3The film forms a sharp contrast.
FIG. 3 shows different thicknesses of PbPc/Sb2Te3The ultraviolet-visible light absorption spectrogram of the/n-Si heterojunction film can see that the photoelectric detector has obvious absorption from 405nm to 980 nm.
Shown as PbPc/Sb in FIG. 42Te3The response rate of the/n-Si heterojunction at 450nm (different channel length L) is shown as a curve along with the incident power density. When the channel L of the photoelectric detection device is 150 mu m, the maximum response rate Ri108.37A/W, the detectivity D reached 1.11X 1012Jones, its good photoelectric properties, provides reference and theoretical practical basis for the research of novel low-dimensional materials, topological insulator photodetectors.
Example 2
In this example, Sb is used2Te3/C60The preparation of a/CuPc heterojunction thin film photodetector is illustrated, wherein Sb2Te3As light-absorbing material, C60And Sb2Te3As shown in fig. 1, in embodiment 2, a method for manufacturing an antimony telluride photodetector includes the following steps:
s11: vapor deposition of Sb on a substrate2Te3A catalytic layer for film growth; wherein the substrate is any one of silicon oxide wafer, silicon wafer, fluorine crystal mica and quartz, in this embodiment, a 1.5cm × 1.5cm silicon oxide wafer is used as the substrate, the substrate is placed into acetone, alcohol and deionized water, respectively and ultrasonically treated for 30min, organic and inorganic impurities on the surface of the substrate are removed, then the substrate is placed into a UV cleaning machine for treatment for 30min,rendering the substrate surface hydrophilic.
S12: vapor deposition of Sb on a substrate having a catalyst layer2Te3A film;
s13: for Sb2Te3Annealing the film;
s14: sb after completion of annealing treatment2Te3Evaporating a second organic material layer on the film; wherein the second organic material is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine.
S15: evaporating the first organic material layer on the second organic material layer to form Sb2Te3A second organic material/first organic material heterojunction; wherein the first organic material is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine.
S16: and preparing electrodes at two ends of the heterojunction to obtain the antimony telluride photoelectric detection device or the line array.
Further, in step S11, Sb is evaporated on the substrate2Te3The catalyst layer for the film growth is specifically as follows:
evaporating tin metal by using an evaporation coating machine, preferably using Sn particles, placing the Sn particles in an evaporation boat of the evaporation coating machine, arranging a substrate on a sample table, adjusting the vertical distance between the sample table and the evaporation boat to be 260mm, vacuumizing a cavity of the evaporation coating machine, and maintaining the air pressure of the cavity at 5 x 10-4pa, turning on the temperature control power supply to rotate the sample stage at 10 °/s, and maintaining the evaporation rate at
The Sn film thickness was 8 nm. It should be noted that, in this embodiment, the detection device is prepared by evaporation of an evaporation coater, which is only a preferred method, and those skilled in the art can prepare the detection device of the present invention by other methods such as sputtering and vapor deposition, and belongs to simple replacement of conventional technical means without creative work.
Further, in step S12, Sb is evaporated2Te3The film is specifically as follows: sb2Te3Putting the powder into evaporationIn an evaporation boat of a film plating machine, a substrate dried by nitrogen is attached to the center of a sample table. Adjusting the vertical distance between the sample stage and the evaporation boat to 260mm, vacuumizing the cavity, and maintaining the air pressure of the cavity at 5 × 10-4pa, turning on the temperature control power supply, rotating the sample stage at 10 °/s, and maintaining the evaporation rate at the same value by the PID controller
Regulating and controlling the thickness of the film by controlling the evaporation time, calibrating the thickness by using a step profiler, and evaporating to obtain Sb with the thickness of 30nm2Te3A film.
Further, in step S13, Sb is treated2Te3The annealing treatment of the film comprises the following specific steps: sb vapor-deposited in step S022Te3Placing the film into an annealing furnace, heating at 300 deg.C for 30min at a heating rate of 10 deg.C/s, and adding Sb2Te3The film is converted to an amorphous state.
Further, in step S14, Sb after annealing2Te3The film was covered with a mask (channel length 50 μm) to
C of 30nm thickness by rapid evaporation60And (5) forming a P-N heterojunction structure.
Further, in step S15, in C60On a film with
A 50nm CuPc film is evaporated at the speed of the second layer to be used as an enhanced absorption layer;
further, in step S16, Sb2Te3And (4) evaporating and plating 150nm gold electrodes on two ends of the CuPc to obtain the graphical detection unit device.
Example 3
The present embodiment has the same inventive concept as embodiment 1, and on the basis of embodiment 1, there is provided an antimony telluride photodetector, as shown in fig. 5, the photodetector sequentially includes, from bottom to top: substrate, Sb2Te3A thin film layer, a first organic material layer, and an electrode. Wherein the substrate is n-Si, the first organic material is PbPc, Sb2Te3The thin film and the first organic material form Sb2Te3a/PbPc heterojunction, and a plurality of Au electrodes are evaporated at two ends (an n-Si substrate and a PbPc film) of the heterojunction to obtain patterned PbPc/Sb2Te3the/n-Si heterojunction photoelectric detection unit device.
In FIG. 5, 1 is an n-Si substrate, and 2 is Sb2Te3And 3, an Au electrode.
Example 4
The present embodiment has the same inventive concept as embodiment 2, and on the basis of embodiment 2, there is provided an antimony telluride photodetector, as shown in fig. 6, the photodetector sequentially includes, from bottom to top: substrate, Sb2Te3The thin film layer, the second organic material layer, the first organic material layer and the electrode. Wherein the substrate is made of Si (SiO)2) The first organic material is CuPc and the second organic material is C60The second organic material layer and the first organic material layer form C60a/CuPc heterojunction with Sb at both ends of the heterojunction2Te3Preparing Au electrode by the film and the CuPc light-enhanced absorption layer to obtain patterned Sb2Te3/C60the/CuPc heterojunction photoelectric detection unit device.
In fig. 6, 3 denotes an Au electrode, and 4 denotes Si (SiO)2) Substrate, 5 is Sb2Te3Film, 6 is C60a/CuPc heterojunction.
The above detailed description is for the purpose of describing the invention in detail, and it should not be construed that the detailed description is limited to the description, and it will be apparent to those skilled in the art that various modifications and substitutions can be made without departing from the spirit of the invention.
Claims (8)
1. A preparation method of an antimony telluride photoelectric detector is characterized by comprising the following steps: the method comprises the following steps:
vapor deposition of Sb on a substrate2Te3A catalytic layer for film growth;
vapor deposition of Sb on a substrate having a catalyst layer2Te3A film;
for Sb2Te3Annealing the film;
sb after completion of annealing treatment2Te3Evaporating a second organic material layer on the film, and evaporating a first organic material layer on the second organic material layer to form Sb2Te3And preparing electrodes at two ends of the heterojunction to obtain the antimony telluride photoelectric detector or the line array.
2. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the Sb is evaporated on the substrate2Te3The catalyst layer for the film growth is specifically as follows:
evaporating and plating metallic tin by an evaporation film plating machine with the air pressure of 3 multiplied by 10-4～8×10-4pa at a rotational speed of 10 DEG/s and an evaporation rate of
Obtaining the tin film catalyst layer with the film thickness of 5-10 nm.
3. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the vapor deposition Sb2Te3The film is specifically as follows:
sb is coated by an evaporation coating machine2Te3The material was evaporated at a pressure of 3X 10-4～8×10-4pa at a rotational speed of 10 DEG/s and an evaporation rate of
4. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the pair of Sb2Te3Film feedingThe conditions for the line annealing treatment were: heating at 200-500 deg.C for 30min at a temperature rise rate of 10 deg.C/s.
5. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the first organic material is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine; the organic material of the second organic material layer is any one of fullerene, copper phthalocyanine, pentacene and lead phthalocyanine.
6. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the Sb is evaporated on the substrate2Te3The catalyzing layer step for film growth also comprises:
cleaning the substrate: and sequentially putting the substrate into acetone, alcohol and deionized water, respectively carrying out ultrasonic treatment for 30min, and then carrying out UV (ultraviolet) cleaning for 30 min.
7. The method for preparing an antimony telluride photodetector as claimed in claim 1, wherein: the substrate is any one of an oxygen silicon wafer, a silicon wafer, fluorine crystal mica and quartz.
8. An antimony telluride photoelectric detection device is characterized in that: the preparation method of the antimony telluride photoelectric detection device as claimed in any one of claims 1 to 7 is adopted for preparation, and the device sequentially comprises the following steps from bottom to top: substrate, Sb2Te3A thin film layer, a second organic material layer, a first organic material layer to form Sb2Te3A second organic material/first organic material heterojunction, with electrodes prepared at both ends of the heterojunction.
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