CN115440838A - A photodetector based on bismuth selenide oxide/indium selenide heterojunction and its preparation method and application - Google Patents
A photodetector based on bismuth selenide oxide/indium selenide heterojunction and its preparation method and application 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 75
- SYYDNLBOFQOSGT-UHFFFAOYSA-N [Bi]=O.[Se] Chemical compound [Bi]=O.[Se] SYYDNLBOFQOSGT-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000002135 nanosheet Substances 0.000 claims abstract description 65
- 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 11
- 239000000843 powder Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000010445 mica Substances 0.000 claims description 15
- 229910052618 mica group Inorganic materials 0.000 claims description 15
- GIWPWWQKBCCJTP-UHFFFAOYSA-N [Bi].[Se]=O Chemical compound [Bi].[Se]=O GIWPWWQKBCCJTP-UHFFFAOYSA-N 0.000 claims description 14
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 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
- 239000013078 crystal Substances 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 4
- 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
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 claims description 3
- ZNKMCMOJCDFGFT-UHFFFAOYSA-N gold titanium Chemical compound [Ti].[Au] ZNKMCMOJCDFGFT-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910001258 titanium gold Inorganic materials 0.000 claims description 3
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 claims 17
- 238000001816 cooling Methods 0.000 claims 1
- 238000001259 photo etching Methods 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 7
- 229910052738 indium Inorganic materials 0.000 abstract description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 abstract description 3
- 150000003346 selenoethers Chemical class 0.000 abstract description 2
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 13
- 239000004205 dimethyl polysiloxane Substances 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
- 230000003287 optical effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 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
- 238000005516 engineering process Methods 0.000 description 2
- 238000004299 exfoliation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000000879 optical micrograph Methods 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
本发明属于红外‑可见光探测技术领域，公开了一种基于硒氧化铋/硒化铟异质结的光电探测器及其制备方法和应用。所述光电探测器包括硒氧化铋/硒化铟异质结和金属电极，该硒氧化铋/硒化铟异质结位于两侧金属电极之间；所述光电探测器是将二维硒化铟纳米片转移至二维硒氧化铋纳米片上，形成二维硒氧化铋/硒化铟异质结，在不重合的二维硒化铟纳米片和二维硒氧化铋纳米片上制作金属电极得到。本发明的基于硒氧化铋/硒化铟异质结的光电探测器具有高开关比、宽光谱探测、自驱动等特点，在高性能自驱动光电探测器应用中显示出良好的潜力。
The invention belongs to the technical field of infrared-visible light detection, and discloses a photodetector based on a bismuth selenide oxide/indium selenide heterojunction, a preparation method and an application thereof. The photodetector includes a bismuth selenide oxide/indium selenide heterojunction and a metal electrode, and the bismuth selenide oxide/indium selenide heterojunction is located between the metal electrodes on both sides; the photodetector is a two-dimensional selenide Indium nanosheets are transferred to two-dimensional bismuth selenide oxide nanosheets to form a two-dimensional bismuth oxide selenide/indium selenide heterojunction, and metal electrodes are fabricated on non-overlapping two-dimensional indium selenide nanosheets and two-dimensional bismuth selenide oxide nanosheets to obtain . The photodetector based on the bismuth selenide oxide/indium selenide heterojunction of the present invention has the characteristics of high switching ratio, wide spectrum detection, self-driving, etc., and shows good potential in the application of high-performance self-driving photodetectors.
Description
技术领域technical field
本发明属于红外-可见光探测技术领域，更具体地，涉及一种基于硒氧化铋/硒化铟异质结的光电探测器及其制备方法和应用。The invention belongs to the technical field of infrared-visible light detection, and more specifically relates to a photodetector based on bismuth selenide oxide/indium selenide heterojunction and its preparation method and application.
背景技术Background technique
光电探测技术是影响人类现代生活的众多技术之一，具有高灵敏度、低噪声、快速响应以及宽谱探测的光电器件是丰富和方便人们日常生活的迫切要求；受益于优越的电子迁移率和良好的空气稳定性，新兴的层状三元素硒氧化铋纳米片受到了广泛的关注，具有良好的电子和光电子应用前景。然而，硒氧化铋的高电荷载流子浓度和辐射热效应导致其具有高暗电流，这阻碍了硒氧化铋基光电探测器性能的进一步提高。硒氧化铋/硒化铟异质结构，具有宽带光响应能力、自驱动和高光开关比等优点，在高性能自驱动光电探测器应用中显示出良好的潜力。Photoelectric detection technology is one of the many technologies that affect modern human life. Photoelectric devices with high sensitivity, low noise, fast response and wide-spectrum detection are urgent requirements for enriching and facilitating people's daily life; benefiting from superior electron mobility and good The air-stable, emerging layered three-element bismuth selenide nanosheets have received extensive attention for their promising electronic and optoelectronic applications. However, the high charge-carrier concentration and radiant heating effect of BiSe-based photodetectors hinder the further improvement of the performance of BiSe-based photodetectors due to its high dark current. The bismuth oxyselenide/indium selenide heterostructure, which has the advantages of broadband photoresponse capability, self-driving, and high optical switching ratio, shows good potential for high-performance self-driving photodetector applications.
发明内容Contents of the invention
为了解决上述现有技术存在的不足和缺点，本发明目的在于提供一种基于硒氧化铋/硒化铟异质结的光电探测器。该光电探测器具有宽谱(405～1064nm)自驱动光探测性能，同时，具有较低的暗电流亚皮安量级、超高的光开关值(>105)和快速光响应(响应时间约5.8ms)。其中，二维硒氧化铋纳米片具有大尺寸(30～150μm)制备的优点，制备的异质结光电探测器性能优异。In order to solve the deficiencies and shortcomings of the above-mentioned prior art, the object of the present invention is to provide a photodetector based on bismuth oxide selenide/indium selenide heterojunction. The photodetector has wide-spectrum (405-1064nm) self-driven photodetection performance, and at the same time, has low dark current sub-picoampere level, ultra-high optical switching value (>10 5 ) and fast photoresponse (response time about 5.8ms). Among them, the two-dimensional bismuth selenium oxide nanosheet has the advantage of being prepared in a large size (30-150 μm), and the prepared heterojunction photodetector has excellent performance.
本发明的另一目的在于提供上述光电探测器的制备方法。Another object of the present invention is to provide a method for preparing the above-mentioned photodetector.
本发明的再一目的在于提供上述光电探测器的应用。Another object of the present invention is to provide the application of the above-mentioned photodetector.
本发明的目的通过下述技术方案来实现：The purpose of the present invention is achieved through the following technical solutions:
一种基于硒氧化铋/硒化铟异质结的光电探测器，所述光电探测器包括硒氧化铋/硒化铟异质结和金属电极，该硒氧化铋/硒化铟异质结位于两侧金属电极之间；所述光电探测器是将二维硒化铟纳米片转移至二维硒氧化铋纳米片上，形成硒氧化铋/硒化铟异质结，在不重合的二维硒化铟纳米片和二维硒氧化铋纳米片上制作金属电极得到。A photodetector based on a bismuth selenide oxide/indium selenide heterojunction, the photodetector includes a bismuth selenide oxide/indium selenide heterojunction and a metal electrode, and the bismuth selenide oxide/indium selenide heterojunction is located at Between the metal electrodes on both sides; the photodetector is to transfer the two-dimensional indium selenide nanosheet to the two-dimensional bismuth selenide oxide nanosheet to form a bismuth selenide oxide/indium selenide heterojunction. Metal electrodes were prepared on indium nanosheets and two-dimensional bismuth selenide oxide nanosheets.
优选地，所述二维硒化铟纳米片的尺寸为30～120μm，所述二维硒氧化铋纳米片的尺寸为30～150μm；所述金属电极为金、钛金或镍金。Preferably, the size of the two-dimensional indium selenide nanosheet is 30-120 μm, the size of the two-dimensional bismuth selenide nanosheet is 30-150 μm; the metal electrode is gold, titanium gold or nickel gold.
优选地，所述的二维硒氧化铋纳米片是以硒化铋和氧化铋粉末为原料，通过化学气相沉积法进行生长得到；所述的二维硒化铟纳米片是以硒化铟单晶为原料，通过机械剥离法制备。Preferably, the two-dimensional bismuth selenide oxide nanosheets are obtained by growing bismuth selenide and bismuth oxide powder by chemical vapor deposition; the two-dimensional indium selenide nanosheets are obtained from indium selenide single crystals as raw materials, prepared by mechanical exfoliation.
所述的基于硒氧化铋/硒化铟异质结的光电探测器的制备方法，包括以下步骤：The preparation method of the photodetector based on bismuth selenide oxide/indium selenide heterojunction comprises the following steps:
S1.将硒化铋粉末和氧化铋化粉末进行配比，分别放置在石英管一侧和中心，将云母片阵列放置在石英管另一侧；将石英管置于设定温区中，起始温度为20～30℃，以速率为10～12℃/min升温至690～700℃，保温120～150min，随后自然降至室温，通过化学气相沉积法生长3～4h后，得到二维硒氧化铋纳米片；所述二维硒氧化铋纳米片的分子式为Bi2O2Se，空间群为I4/mmm。S1. Proportionate the bismuth selenide powder and the bismuth oxide powder, place them on one side and the center of the quartz tube respectively, and place the array of mica sheets on the other side of the quartz tube; place the quartz tube in a set temperature zone to start The initial temperature is 20-30°C, and the temperature is raised to 690-700°C at a rate of 10-12°C/min, kept for 120-150min, and then naturally lowered to room temperature. After growing for 3-4 hours by chemical vapor deposition, two-dimensional selenium is obtained. Bismuth oxide nanosheets; the molecular formula of the two-dimensional bismuth selenium oxide nanosheets is Bi 2 O 2 Se, and the space group is I4/mmm.
S2.通过机械剥离法将硒化铟单晶剥离，制得二维硒化铟纳米片；S2. The indium selenide single crystal is peeled off by a mechanical peeling method to prepare two-dimensional indium selenide nanosheets;
S3.将二维硒化铟纳米片转移至二维半导体硒氧化铋纳米片上，得到硒氧化铋/硒化铟异质结；S3. Transferring the two-dimensional indium selenide nanosheets to the two-dimensional semiconductor bismuth selenide oxide nanosheets to obtain a bismuth selenide oxide/indium selenide heterojunction;
S4.采用光刻法在不重合的二维硒化铟纳米片和二维硒氧化铋纳米片上，对硒氧化铋/硒化铟异质结制作两侧金属电极，得到基于硒氧化铋/硒化铟异质结的光电探测器。S4. On non-overlapping two-dimensional indium selenide nanosheets and two-dimensional bismuth selenide nanosheets using photolithography, metal electrodes on both sides of the bismuth selenide oxide/indium selenide heterojunction are fabricated to obtain a bismuth selenide oxide-based/selenium-based Indium oxide heterojunction photodetectors.
优选地，步骤S1中硒化铋粉末和氧化铋化粉末的摩尔为1:2。Preferably, the molar ratio of bismuth selenide powder and bismuth oxide powder in step S1 is 1:2.
所述的基于硒氧化铋/硒化铟异质结的光电探测器在宽谱自驱动光电探测领域中的应用，所述宽谱的波长为405～1064nm。The application of the photodetector based on bismuth selenide oxide/indium selenide heterojunction in the field of wide-spectrum self-driven photodetection, the wavelength of the wide-spectrum is 405-1064nm.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1.本发明的基于二维硒氧化铋/硒化铟异质结的光电探测器具有高开关比(>105)，宽光谱自驱动探测(405～1064nm)等特点，同时，具有较低的暗电流亚皮安量级、超高的光开关值(>105)和快速光响应(响应时间约5.8ms，可对405～1064nm波长的光进行吸收，可作为红外-可见光电探测器，在高性能自驱动光电探测器应用中显示出良好的潜力。1. The photodetector based on the two-dimensional bismuth selenide oxide/indium selenide heterojunction of the present invention has the characteristics of high switching ratio (>10 5 ), wide-spectrum self-driven detection (405-1064nm), and at the same time, has a low Dark current of sub-picoampere level, ultra-high optical switching value (>10 5 ) and fast photoresponse (response time is about 5.8ms, can absorb light with a wavelength of 405-1064nm, and can be used as an infrared-visible photodetector , showing good potential in high-performance self-driven photodetector applications.
2.本发明的二维硒氧化铋纳米片属于空间群为I4/mmm的正方晶系结构，其在室温下极为稳定，带隙为0.11～1.27eV左右；2. The two-dimensional bismuth selenium oxide nanosheets of the present invention belong to a tetragonal crystal structure with a space group of I4/mmm, which is extremely stable at room temperature and has a band gap of about 0.11-1.27eV;
3.本发明采用高温管式炉烧结，可简单直接得到晶体结晶质量高的硒氧化铋纳米片。该方法成本低，性能优异，能够大规模可重复地生产，对环境无污染。3. The present invention uses a high-temperature tube furnace for sintering, and can simply and directly obtain bismuth selenium oxide nanosheets with high crystal quality. The method is low in cost, excellent in performance, capable of large-scale and repeatable production, and has no pollution to the environment.
附图说明Description of drawings
图1为本发明制备的硒氧化铋纳米片的实验装置示意图；Fig. 1 is the experimental setup schematic diagram of the bismuth selenium oxide nanosheet that the present invention prepares;
图2为本发明制备硒氧化铋/硒化铟异质结的流程示意图；Fig. 2 is the schematic flow chart of preparing bismuth selenide oxide/indium selenide heterojunction in the present invention;
图3为生长的硒氧化铋纳米片和实施例1中的基于硒氧化铋/硒化铟异质结的光电探测器的光学显微图片以及硒氧化铋纳米片和硒化铟纳米片的厚度数据。Fig. 3 is the optical micrograph of the photodetector based on bismuth selenide oxide/indium selenide heterojunction in the growing bismuth oxide nanosheet and
图4为实施例1中，在自驱动模式下，基于硒氧化铋/硒化铟异质结的光电探测器的宽谱和在405nm的光响应特性。FIG. 4 shows the wide spectrum and photoresponse characteristics at 405 nm of the photodetector based on bismuth oxide selenide/indium selenide heterojunction in the self-driving mode in
具体实施方式detailed description
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。The content of the present invention will be further described below in conjunction with specific examples, but it should not be construed as a limitation of the present invention. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the technical field.
本发明的二维硒氧化铋纳米片(分子结构式为Bi2O2Se)，空间群为I4/mmm的正方晶系结构，层与层之间通过离子键[Bi2O2]n 2n+和[Se]n 2n-连接，通过高温管式炉烧结即可直接获得，所获材料制作的光电探测器性能优异，开关比高，可以用于高集成度的光电探测器件中。The two-dimensional bismuth selenium oxide nanosheets of the present invention (molecular structural formula is Bi 2 O 2 Se), the space group is a tetragonal crystal structure of I4/mmm, and the layers are separated by ionic bonds [Bi 2 O 2 ] n 2n+ and [Se] n 2n -connection can be directly obtained by sintering in a high-temperature tube furnace. The photodetector made of the obtained material has excellent performance and high on-off ratio, and can be used in highly integrated photodetection devices.
实施例1Example 1
如图1所示，本发明二维硒氧化铋纳米片的制备方法，包括如下具体步骤：As shown in Figure 1, the preparation method of the two-dimensional bismuth selenium oxide nanosheet of the present invention comprises the following specific steps:
1.按照Bi2O2Se化学计量比进行称重配比，将摩尔比为1:2的硒化铋粉末和氧化铋粉末进行配比；1. According to the stoichiometric ratio of Bi 2 O 2 Se, the weighing ratio is carried out, and the molar ratio of bismuth selenide powder and bismuth oxide powder is 1:2;
2.将硒化铋和氧化铋粉末分别放置在石英管一侧(气体的入口处，即气流方向的上游)和石英管中心，将新鲜剥离的云母片阵列放置在石英管另一侧(即为气流方向的下游)；2. Place bismuth selenide and bismuth oxide powder on one side of the quartz tube (at the inlet of the gas, i.e. the upstream of the gas flow direction) and the center of the quartz tube, respectively, and place the freshly stripped mica sheet array on the other side of the quartz tube (i.e. is the downstream of the airflow direction);
其中，热源在石英管的中心区域，氧化铋(Bi2O3)粉末放置于热源正上方位置，距离石英管的管口约9～11cm，硒化铋(Bi2Se3)粉末放置于气流(氩气)的进气口附近2～3cm处，Bi2Se3粉末距离Bi2O3粉末约为6～9cm。云母片阵列包含4个新鲜剥离的云母片(单个云母片尺寸为：10mm×10mm×0.2mm)，呈2×2平面分布，放置于气流输运方向下游带有氧化层的硅片(长宽约为4cm×2.2cm)上。此外，云母片阵列的中心位置放置在距离上游初始位置为22cm处。本发明首次采用云母片阵列作为生长基底，该方法可以显著提高硒氧化铋纳米片的产率。Among them, the heat source is in the central area of the quartz tube, the bismuth oxide (Bi 2 O 3 ) powder is placed directly above the heat source, about 9 to 11 cm away from the nozzle of the quartz tube, and the bismuth selenide (Bi 2 Se 3 ) powder is placed in the air flow (Argon) In the vicinity of the gas inlet 2-3cm, the Bi 2 Se 3 powder is about 6-9cm away from the Bi 2 O 3 powder. The mica sheet array consists of 4 freshly peeled mica sheets (the size of a single mica sheet is: 10mm×10mm×0.2mm), distributed in a 2×2 plane, and placed on a silicon chip with an oxide layer downstream of the airflow direction (length, width About 4cm×2.2cm). In addition, the center position of the mica sheet array was placed at a distance of 22 cm upstream from the initial position. The invention adopts the mica sheet array as the growth substrate for the first time, and the method can significantly improve the yield of bismuth selenium oxide nanosheets.
3.将封口的石英管置于设定温区，先通入流量为200sccm的氩气约10min，排出石英管中的空气。之后，保持氩气的流量不变，设定管式炉的起始温度为20～30℃，以速率为10～12℃/min升温至690～700℃，保持时间在120～150min，随后自然降温至室温，通过化学气相沉积法生长3～4h后，在云母片阵列上生长得到二维硒氧化铋纳米片。从云母片阵列中选择生长出具有高质量的硒氧化铋纳米片的云母片备用。3. Place the sealed quartz tube in the set temperature zone, first pass in argon gas with a flow rate of 200 sccm for about 10 minutes, and discharge the air in the quartz tube. Afterwards, keep the flow rate of argon constant, set the initial temperature of the tube furnace at 20-30°C, raise the temperature to 690-700°C at a rate of 10-12°C/min, keep the time at 120-150min, and then naturally The temperature is lowered to room temperature, and the two-dimensional bismuth selenium oxide nanosheets are grown on the mica sheet array after growing for 3-4 hours by chemical vapor deposition. Select and grow mica sheets with high-quality bismuth selenium oxide nanosheets from the mica sheet array for future use.
4.通过机械剥离法采用介质为聚二甲硅氧烷(PDMS)薄膜作为介质，将硒化铟单晶剥离，制备二维硒化铟纳米片。4. Using the medium of polydimethylsiloxane (PDMS) film as the medium by the mechanical exfoliation method, the indium selenide single crystal is exfoliated to prepare two-dimensional indium selenide nanosheets.
5.将二维硒化铟纳米片转移至二维硒氧化铋纳米片上，得到二维硒氧化铋/硒化铟异质结。图2为本发明制备硒氧化铋/硒化铟异质结的流程示意图。首先将硒化铟单晶粘在思高胶带上，来回对折多次。之后，用PDMS薄膜轻轻压在带有硒化铟的胶带上。用镊子揭开PDMS薄膜，就得到了机械解离的硒化铟纳米片(尺寸为30～120μm)。5. Transferring the two-dimensional indium selenide nanosheets to the two-dimensional bismuth selenide oxide nanosheets to obtain a two-dimensional bismuth selenide oxide/indium selenide heterojunction. Fig. 2 is a schematic flow chart for preparing bismuth selenide oxide/indium selenide heterojunction according to the present invention. First, stick the indium selenide single crystal on Scotch tape, and fold it back and forth in half several times. Afterwards, lightly press the PDMS film on the tape with indium selenide. The PDMS film was uncovered with tweezers, and mechanically dissociated indium selenide nanosheets (30-120 μm in size) were obtained.
6.通过二维材料转移平台，将带有硒化铟纳米片的PDMS薄膜精确堆叠到生长在云母片上二维硒氧化铋纳米片上，去除PDMS薄膜后，得到了硒氧化铋/硒化铟异质结，其具体步骤为：6. Through the two-dimensional material transfer platform, the PDMS film with indium selenide nanosheets was accurately stacked on the two-dimensional bismuth selenide oxide nanosheets grown on the mica sheet. After removing the PDMS film, a bismuth selenide oxide/indium selenide iso Quality knot, its specific steps are:
(1)将生长有高质量的二维半导体硒氧化铋纳米片的云母片置于加热台100℃/10min，去除表面水分子。(1) Place the mica sheet grown with high-quality two-dimensional semiconductor bismuth selenide oxide nanosheets on a heating stage at 100°C/10min to remove surface water molecules.
(2)将云母片放置于转移平台上，设置平台温度为60℃，将PDMS上的二维硒化铟纳米片转移至二维半导体硒氧化铋纳米片上，得到二维硒氧化铋/硒化铟异质结。(2) Place the mica sheet on the transfer platform, set the platform temperature to 60°C, and transfer the two-dimensional indium selenide nanosheets on PDMS to the two-dimensional semiconductor bismuth selenide oxide nanosheets to obtain a two-dimensional bismuth selenide oxide/selenide nanosheet Indium heterojunction.
(3)转移完成后，将承载有二维硒氧化铋/硒化铟异质结的云母片置于氮气氛围中退火，加热150℃/30min，以去除水分子和残留的有机小分子。(3) After the transfer is completed, the mica sheet carrying the two-dimensional bismuth selenide oxide/indium selenide heterojunction is annealed in a nitrogen atmosphere and heated at 150°C/30min to remove water molecules and residual small organic molecules.
7.采用光刻法在不重合的二维硒化铟纳米片和二维硒氧化铋纳米片上，对硒氧化铋/硒化铟异质结制作两侧金属电极(金、钛金或镍金)，得到基于硒氧化铋/硒化铟异质结的光电探测器。7. On non-overlapping two-dimensional indium selenide nanosheets and two-dimensional bismuth selenide nanosheets, use photolithography to make metal electrodes (gold, titanium gold or nickel gold) on both sides of the bismuth selenide oxide/indium selenide heterojunction ), to obtain a photodetector based on bismuth selenide oxide/indium selenide heterojunction.
图3为本实施例中的硒氧化铋/硒化铟异质结的光电探测器的光学显微图片以及硒氧化铋纳米片和硒化铟纳米片的厚度数据。其中，(a)为硒氧化铋纳米片，(b)为硒氧化铋/硒化铟异质结的光探测器；(c)和(d)分别为硒化铟纳米片和硒氧化铋纳米片的原子力显微镜图片和厚度数据。从图3中可知，硒化铟纳米片和硒氧化铋纳米片的厚度分别约为332nm和7nm。3 is an optical micrograph of the photodetector of the bismuth oxide selenide/indium selenide heterojunction in this embodiment and the thickness data of the bismuth oxide selenide nanosheets and the indium selenide nanosheets. Among them, (a) is a bismuth selenide nanosheet, (b) is a photodetector of a bismuth selenide/indium selenide heterojunction; (c) and (d) are an indium selenide nanosheet and a bismuth selenide nanosheet, respectively. AFM images and thickness data of the flakes. It can be seen from FIG. 3 that the thicknesses of the indium selenide nanosheets and the bismuth selenide oxide nanosheets are about 332nm and 7nm, respectively.
图4为实施例1中，自驱动模式下，基于硒氧化铋/硒化铟异质结的光电探测器的宽谱和在405nm的光响应特性。其中，(a)和(b)分别为硒氧化铋/硒化铟异质结的光探测器的自驱动宽谱光响应和不同波长光照射下的源漏电流-时间曲线图。(c)为自驱动模式下，光电探测在波长为405nm光照时的光响应时间、光照和黑暗条件下的源漏电流的比值。(d)为在0V偏压下，多次循环后，光电探测器的光开关曲线。从图4(a)和4(b)可知，基于硒氧化铋/硒化铟异质结的光电探测器对405～1064nm的光均有响应，且具有自驱动特性。图4(c)和4(d)可以得到光电探测器的光响应时间约为5.8ms，光开关比超过105，说明该光电探测器具有快速的光响应性能和较高的光灵敏度。此外，稳定的光开关曲线也说明了该光电探测器具有较高的工作稳定性。FIG. 4 shows the broad spectrum and photoresponse characteristics at 405 nm of the photodetector based on the bismuth oxide selenide/indium selenide heterojunction in the self-driving mode in
本发明的基于硒氧化铋/硒化铟异质结的光电探测器，具有405～1064nm的可见-红外宽带检测能力、自驱动、105的高光开/关比和高稳定性等优点，在高性能自驱动光电探测器应用中显示出良好的潜力。The photodetector based on bismuth selenide oxide/indium selenide heterojunction of the present invention has the advantages of visible-infrared broadband detection capability of 405-1064 nm, self-driving, high light on/off ratio of 10 5 and high stability, etc. High-performance self-driven photodetector applications show good potential.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations and modifications made without departing from the spirit and principles of the present invention Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.
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