CN115440838A - Photoelectric detector based on bismuth selenide/indium selenide heterojunction and preparation method and application thereof - Google Patents
Photoelectric detector based on bismuth selenide/indium selenide heterojunction and preparation method and application thereof Download PDFInfo
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- AKUCEXGLFUSJCD-UHFFFAOYSA-N indium(3+);selenium(2-) Chemical compound [Se-2].[Se-2].[Se-2].[In+3].[In+3] AKUCEXGLFUSJCD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 64
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 238000001228 spectrum Methods 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- SYYDNLBOFQOSGT-UHFFFAOYSA-N [Bi]=O.[Se] Chemical compound [Bi]=O.[Se] SYYDNLBOFQOSGT-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 239000010445 mica Substances 0.000 claims description 15
- 229910052618 mica group Inorganic materials 0.000 claims description 15
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 14
- 239000010453 quartz Substances 0.000 claims description 13
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- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 12
- GIWPWWQKBCCJTP-UHFFFAOYSA-N [Bi].[Se]=O Chemical compound [Bi].[Se]=O GIWPWWQKBCCJTP-UHFFFAOYSA-N 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 8
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
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- ZNKMCMOJCDFGFT-UHFFFAOYSA-N gold titanium Chemical compound [Ti].[Au] ZNKMCMOJCDFGFT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001259 photo etching Methods 0.000 claims description 3
- 229910001258 titanium gold Inorganic materials 0.000 claims description 3
- 238000001514 detection method Methods 0.000 abstract description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 7
- 239000011669 selenium Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- -1 Polydimethylsiloxane Polymers 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
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- H01L31/0264—Inorganic materials
- H01L31/0328—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032
- H01L31/0336—Inorganic materials including, apart from doping materials or other impurities, semiconductor materials provided for in two or more of groups H01L31/0272 - H01L31/032 in different semiconductor regions, e.g. Cu2X/CdX hetero- junctions, X being an element of Group VI of the Periodic Table
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Abstract
The invention belongs to the technical field of infrared-visible light detection, and discloses a photoelectric detector based on a bismuth selenide/indium selenide heterojunction and a preparation method and application thereof. The photoelectric detector comprises a bismuth selenide/indium selenide heterojunction and metal electrodes, wherein the bismuth selenide/indium selenide heterojunction is positioned between the metal electrodes on two sides; the photoelectric detector is obtained by transferring a two-dimensional indium selenide nanosheet onto a two-dimensional bismuth selenide nanosheet to form a two-dimensional bismuth selenide/indium selenide heterojunction, and manufacturing metal electrodes on the two-dimensional indium selenide nanosheet and the two-dimensional bismuth selenide nanosheet which are not overlapped. The photoelectric detector based on the bismuth selenide/indium selenide heterojunction has the characteristics of high on-off ratio, wide spectrum detection, self-driving and the like, and has good potential in the application of high-performance self-driven photoelectric detectors.
Description
Technical Field
The invention belongs to the technical field of infrared-visible light detection, and particularly relates to a photoelectric detector based on a bismuth selenide/indium selenide heterojunction and a preparation method and application thereof.
Background
The photoelectric detection technology is one of numerous technologies which influence the modern life of human beings, and the photoelectric device with high sensitivity, low noise, quick response and wide-spectrum detection is an urgent requirement for enriching and facilitating the daily life of people; due to the benefit of excellent electron mobility and good air stability, the emerging layered ternary selenium bismuth oxide nanosheet is widely concerned, and has good electronic and optoelectronic application prospects. However, the high charge carrier concentration and the radiant heat effect of bismuth selenide result in high dark current, which hinders further improvement of the performance of bismuth selenide-based photodetectors. The bismuth selenide/indium selenide heterostructure has the advantages of broadband light response capability, self-driving, high optical on-off ratio and the like, and has good potential in application of a high-performance self-driving photoelectric detector.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a photoelectric detector based on a bismuth selenide/indium selenide heterojunction. The photoelectric detector has wide-spectrum (405-1064 nm) self-driven light detection performance, and simultaneously has a low dark current sub-picoampere magnitude and an ultrahigh optical switch value (>10 5 ) And a fast optical response (response time of about 5.8 ms). The two-dimensional selenium bismuth oxide nanosheet has the advantage of large-size (30-150 mu m) preparation, and the prepared heterojunction photoelectric detector is excellent in performance.
Another object of the present invention is to provide a method for manufacturing the above photodetector.
It is a further object of the present invention to provide a use of the above photodetector.
The purpose of the invention is realized by the following technical scheme:
a photoelectric detector based on a bismuth selenide/indium selenide heterojunction comprises a bismuth selenide/indium selenide heterojunction and metal electrodes, wherein the bismuth selenide/indium selenide heterojunction is positioned between the metal electrodes on two sides; the photoelectric detector is obtained by transferring two-dimensional indium selenide nanosheets to two-dimensional bismuth selenide nanosheets to form bismuth selenide/indium selenide heterojunctions and manufacturing metal electrodes on the two-dimensional indium selenide nanosheets and the two-dimensional bismuth selenide nanosheets which are not overlapped.
Preferably, the size of the two-dimensional indium selenide nanosheet is 30-120 μm, and the size of the two-dimensional bismuth selenide nanosheet is 30-150 μm; the metal electrode is gold, titanium gold or nickel gold.
Preferably, the two-dimensional selenium bismuth oxide nanosheet is obtained by growing bismuth selenide and bismuth oxide powder serving as raw materials through a chemical vapor deposition method; the two-dimensional indium selenide nanosheet is prepared from an indium selenide single crystal serving as a raw material by a mechanical stripping method.
The preparation method of the photoelectric detector based on the bismuth selenide oxide/indium selenide heterojunction comprises the following steps:
s1, proportioning bismuth selenide powder and bismuth oxide powder, respectively placing the bismuth selenide powder and the bismuth oxide powder at one side and the center of a quartz tube, and placing a mica sheet array at the other side of the quartz tube; placing a quartz tube in a set temperature zone, wherein the initial temperature is 20-30 ℃, heating to 690-700 ℃ at the speed of 10-12 ℃/min, preserving the temperature for 120-150 min, then naturally cooling to room temperature, and growing for 3-4 h by a chemical vapor deposition method to obtain a two-dimensional selenium bismuth oxide nanosheet; the molecular formula of the two-dimensional selenium bismuth oxide nanosheet is Bi 2 O 2 Se, space group is I4/mmm.
S2, stripping the indium selenide single crystal by a mechanical stripping method to prepare a two-dimensional indium selenide nanosheet;
s3, transferring the two-dimensional indium selenide nanosheets to a two-dimensional semiconductor bismuth selenide nanosheet to obtain a bismuth selenide/indium selenide heterojunction;
and S4, manufacturing metal electrodes on two sides of the selenium oxide bismuth/indium selenide heterojunction on the two-dimensional indium selenide nanosheets and the two-dimensional selenium oxide bismuth nanosheets which are not overlapped by adopting a photoetching method, and obtaining the photoelectric detector based on the selenium oxide bismuth/indium selenide heterojunction.
Preferably, the molar ratio of the bismuth selenide powder and the bismuth oxide powder in step S1 is 1:2.
The photoelectric detector based on the bismuth selenide/indium selenide heterojunction is applied to the field of wide-spectrum self-driven photoelectric detection, and the wavelength of the wide spectrum is 405-1064 nm.
Compared with the prior art, the invention has the following beneficial effects:
1. the photoelectric detector based on the two-dimensional selenium bismuth oxide/indium selenide heterojunction has high on-off ratio (>10 5 ) Wide spectrum self-driven detection (405-1064 nm), and has low dark current sub-picoampere level and ultrahigh optical switch value>10 5 ) And fast optical response (response time is about 5.8ms, light with wavelength of 405-1064 nm can be absorbed, and the light-absorbing material can be used as an infrared-visible photodetector and has good potential in high-performance self-driven photodetector application.
2. The two-dimensional selenium bismuth oxide nanosheet belongs to a tetragonal crystal system structure with a space group of I4/mmm, is extremely stable at room temperature, and has a band gap of about 0.11-1.27 eV;
3. the invention adopts a high-temperature tube furnace for sintering, and can simply and directly obtain the selenium bismuth oxide nanosheet with high crystal quality. The method has low cost and excellent performance, can be repeatedly produced in a large scale, and has no pollution to the environment.
Drawings
FIG. 1 is a schematic diagram of an experimental apparatus for preparing a selenium bismuth oxide nanosheet according to the present invention;
FIG. 2 is a schematic flow diagram of the preparation of a bismuth selenide/indium selenide heterojunction in accordance with the present invention;
fig. 3 is an optical micrograph of grown bismuth oxyselenide nanosheets and the bismuth oxyselenide/indium selenide heterojunction based photodetector of example 1, along with thickness data for the bismuth oxyselenide nanosheets and the indium selenide nanosheets.
Fig. 4 shows the broad spectrum and the photoresponse characteristics at 405nm of the photodetector based on the seleno-bi oxide/indium selenide heterojunction in the self-driven mode in example 1.
Detailed Description
The following examples are presented to further illustrate the invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. The reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
The two-dimensional selenium bismuth oxide nanosheet (with the molecular structural formula of Bi) provided by the invention 2 O 2 Se), with a tetragonal structure with space group of I4/mmm, and ionic bonds [ Bi ] are arranged between layers 2 O 2 ] n 2n+ And [ Se ]] n 2n- The material is connected and can be directly obtained by sintering in a high-temperature tube furnace, and the photoelectric detector made of the material has excellent performance and high on-off ratio and can be used in a photoelectric detector with high integration level.
Example 1
As shown in fig. 1, the preparation method of the two-dimensional selenium bismuth oxide nanosheet of the present invention comprises the following specific steps:
1. according to Bi 2 O 2 Weighing and proportioning Se according to a stoichiometric ratio, and proportioning bismuth selenide powder and bismuth oxide powder according to a molar ratio of 1:2;
2. respectively placing bismuth selenide and bismuth oxide powder at one side (gas inlet, namely upstream in the direction of gas flow) of a quartz tube and the center of the quartz tube, and placing a freshly peeled mica sheet array at the other side (namely downstream in the direction of gas flow) of the quartz tube;
wherein the heat source is in the central region of the quartz tube, and bismuth oxide (Bi) 2 O 3 ) The powder is placed right above the heat source and is about 9-11 cm away from the pipe orifice of the quartz tube, and bismuth selenide (Bi) 2 Se 3 ) The powder is placed at the position of 2-3 cm near the air inlet of the air flow (argon), and Bi 2 Se 3 Distance of powder Bi 2 O 3 The powder is about 6-9 cm. The mica sheet array comprises 4 freshly peeled mica sheets (the size of each mica sheet is 10mm multiplied by 0.2 mm), is distributed in a 2 multiplied by 2 plane and is placed on a silicon wafer (the length and the width are about 4cm multiplied by 2.2 cm) with an oxidation layer at the downstream in the air flow conveying direction. Further, the central position of the mica sheet array was placed 22cm from the upstream initial position. The invention adopts the mica sheet array as the growth substrate for the first time, and the method can obviously improveHigh yield of selenium-rich bismuth oxide nanosheets.
3. And (3) placing the sealed quartz tube in a set temperature zone, firstly introducing argon with the flow of 200sccm for about 10min, and discharging air in the quartz tube. Then keeping the flow of argon unchanged, setting the initial temperature of the tube furnace to be 20-30 ℃, heating to 690-700 ℃ at the speed of 10-12 ℃/min, keeping the time to be 120-150 min, then naturally cooling to room temperature, growing for 3-4 h by a chemical vapor deposition method, and then growing on a mica sheet array to obtain the two-dimensional selenium bismuth oxide nano sheet. And selecting the mica sheet with high-quality selenium bismuth oxide nano-sheets from the mica sheet array for later use.
4. The method comprises the steps of taking Polydimethylsiloxane (PDMS) film as a medium and stripping the indium selenide single crystal by a mechanical stripping method to prepare the two-dimensional indium selenide nanosheet.
5. And transferring the two-dimensional indium selenide nanosheets to two-dimensional bismuth selenide nanosheets to obtain two-dimensional bismuth selenide/indium selenide heterojunctions. FIG. 2 is a schematic flow diagram of the preparation of a bismuth selenide/indium selenide heterojunction in accordance with the present invention. Firstly, the indium selenide single crystal is stuck on the Sigao adhesive tape and is folded back and forth for a plurality of times. After that, the tape with indium selenide was lightly pressed with a PDMS film. And (3) uncovering the PDMS film by using tweezers to obtain the mechanically dissociated indium selenide nanosheet (with the size of 30-120 mu m).
6. Accurately stacking a PDMS film with indium selenide nanosheets on two-dimensional selenium bismuth oxide nanosheets growing on mica plates through a two-dimensional material transfer platform, and removing the PDMS film to obtain a bismuth oxide selenide/indium selenide heterojunction, wherein the method comprises the following specific steps:
(1) And (3) placing the mica sheet grown with the high-quality two-dimensional semiconductor selenium bismuth oxide nano-sheet in a heating table at the temperature of 100 ℃/10min, and removing surface water molecules.
(2) And (3) placing the mica sheet on a transfer platform, setting the temperature of the platform to be 60 ℃, and transferring the two-dimensional indium selenide nanosheet on the PDMS onto a two-dimensional semiconductor bismuth selenide nanosheet to obtain a two-dimensional bismuth selenide/indium selenide heterojunction.
(3) And after the transfer is finished, placing the mica sheet carrying the two-dimensional selenium bismuth oxide/indium selenide heterojunction in a nitrogen atmosphere for annealing, and heating at 150 ℃/30min to remove water molecules and residual organic micromolecules.
7. And (3) manufacturing metal electrodes (gold, titanium gold or nickel gold) on two sides of the bismuth selenide/indium selenide heterojunction by adopting a photoetching method on the two-dimensional indium selenide nanosheets and the two-dimensional bismuth selenide oxide nanosheets which are not overlapped, so as to obtain the photoelectric detector based on the bismuth selenide/indium selenide heterojunction.
Fig. 3 is an optical micrograph of a photodetector with a bismuth oxyselenide/indium selenide heterojunction in this example and thickness data for bismuth oxyselenide nanosheets and indium selenide nanosheets. Wherein, (a) is a bismuth oxide selenide nanosheet, and (b) is a photodetector of a bismuth oxide selenide/indium selenide heterojunction; (c) And (d) atomic force microscope pictures and thickness data of indium selenide nanosheets and bismuth selenide nanosheets, respectively. As can be seen from fig. 3, the thicknesses of the indium selenide nanosheets and the bismuth selenide nanosheets are about 332nm and 7nm, respectively.
Fig. 4 shows the broad spectrum and the photoresponse characteristic at 405nm of the photodetector based on the seleno-bi oxide/indium selenide heterojunction in the self-driven mode in example 1. Wherein, the (a) and the (b) are respectively self-driven wide-spectrum photoresponse of the photodetector of the bismuth selenide/indium selenide heterojunction and source-drain current-time curve graphs under the irradiation of light with different wavelengths. (c) In the self-driven mode, the ratio of the light response time of light with the wavelength of 405nm to the source-drain current under the light and dark conditions is detected by a photoelectric detector. (d) Is the light switch curve of the photoelectric detector after multiple cycles under the bias of 0V. As can be seen from fig. 4 (a) and 4 (b), the photodetector based on the seleno-bismuth oxide/indium selenide heterojunction responds to light of 405 to 1064nm and has a self-driving characteristic. FIGS. 4 (c) and 4 (d) can obtain the photo-response time of the photo-detector of about 5.8ms and the optical on-off ratio of more than 10 5 The photoelectric detector is proved to have rapid light response performance and higher light sensitivity. In addition, the stable optical switch curve also shows that the photoelectric detector has higher working stability.
The photoelectric detector based on the bismuth selenide/indium selenide heterojunction has the visible-infrared broadband detection capability of 405-1064 nm, self-driving and 10 5 Has the advantages of high light on/off ratio, high stability and the likeHigh performance self-driven photodetector applications show good potential.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (7)
1. A photoelectric detector based on a bismuth selenide/indium selenide heterojunction is characterized by comprising a bismuth selenide/indium selenide heterojunction and metal electrodes, wherein the bismuth selenide/indium selenide heterojunction is positioned between the metal electrodes on two sides; the photoelectric detector is obtained by transferring two-dimensional indium selenide nanosheets to two-dimensional bismuth selenide nanosheets to form bismuth selenide/indium selenide heterojunctions and manufacturing metal electrodes on the two-dimensional indium selenide nanosheets and the two-dimensional bismuth selenide nanosheets which are not overlapped.
2. The bismuth selenide/indium selenide heterojunction-based photodetector of claim 1, wherein the size of the two-dimensional indium selenide nanosheets is 30-120 μ ι η, and the size of the two-dimensional bismuth selenide nanosheets is 30-150 μ ι η; the metal electrode is gold, titanium gold or nickel gold.
3. The photodetector of claim 1, wherein the two-dimensional seleno-bismuth oxide nanosheets are obtained by growing bismuth selenide and bismuth oxide powder as raw materials by a chemical vapor deposition method; the two-dimensional indium selenide nanosheet is prepared from an indium selenide single crystal serving as a raw material by a mechanical stripping method.
4. The method of any one of claims 1-3 for fabricating a bismuth selenide/indium selenide heterojunction-based photodetector, comprising the steps of:
s1, proportioning bismuth selenide powder and bismuth oxide powder, respectively placing the bismuth selenide powder and the bismuth oxide powder at one side and the center of a quartz tube, and placing a mica sheet array at the other side of the quartz tube; placing a quartz tube in a set temperature zone, wherein the initial temperature is 20-30 ℃, heating to 690-700 ℃ at the speed of 10-12 ℃/min, preserving the temperature for 120-150 min, then naturally cooling to room temperature, and growing for 3-4 h by a chemical vapor deposition method to obtain a two-dimensional selenium bismuth oxide nanosheet;
s2, stripping the indium selenide single crystal by a mechanical stripping method to prepare a two-dimensional indium selenide nanosheet;
s3, transferring the two-dimensional indium selenide nanosheets to a two-dimensional semiconductor bismuth selenide nanosheet to obtain a bismuth selenide/indium selenide heterojunction;
and S4, manufacturing metal electrodes on two sides of the selenium oxide bismuth/indium selenide heterojunction on the two-dimensional indium selenide nanosheets and the two-dimensional selenium oxide bismuth nanosheets which are not overlapped by adopting a photoetching method, and obtaining the photoelectric detector based on the selenium oxide bismuth/indium selenide heterojunction.
5. The method of claim 4, wherein the molar ratio of the bismuth selenide powder to the bismuth oxide powder in step S1 is 1:2.
6. Use of a bismuth selenide/indium selenide heterojunction-based photodetector as claimed in any one of claims 1 to 3 in the field of high performance wide spectrum self-driven photodetection.
7. The use of a bismuth selenide/indium selenide heterojunction-based photodetector as claimed in claim 6 in the field of wide-spectrum self-driven photodetection, wherein the wavelength of the wide spectrum is 405-1064 nm.
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