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Ti3C2Tx作为新型二维过渡金属碳化物/氮化物(MXene)中的一类, 具有丰富的表面官能团(—OH, —F和—O等), 并能够通过进一步的表面功能化调控表现出半导体特性. 目前将Ti3C2Tx半导体性质应用在红外光电探测器中的研究还很少. 本文研制了一种基于C14H31O3P-Ti3C2/Au肖特基结的自驱动近红外光电探测器. 通过膦酸基团与Ti3C2Tx表面羟基的缩合反应, 制备了改性的C14H31O3P-Ti3C2二维纳米半导体; 并采用滴涂法构建了C14H31O3P-Ti3C2/Au肖特基结光电探测器. 该器件在近红外波段(808—1342 nm)显示出良好的检测性能和循环稳定性, 1064 nm近红外光照射下最高响应度为0.28 A/W, 比探测率为4.3×107 Jones, 经10次I-t循环后器件性能保持稳定. 由于C14H31O3P-Ti3C2/Au肖特基结光电探测器具备自驱动特性和简单的制备工艺, 因此在弱光信号检测方面表现出良好的应用潜力, 例如在天文学和生物医学领域. 这为基于MXene的近红外探测器的设计和研制提供了新思路.Ti3C2Tx, as one of new two-dimensional materials MXene, has abundant surface functional groups (—OH, —F, and —O, etc.) and can exhibit semiconductor properties through further surface functionalization. In addition, it has excellent absorption capabilities for both infrared and visible light. Currently, there is limited research on applying the semiconductor properties of Ti3C2Tx to infrared photodetectors. In this study, a self-driven near-infrared photodetector based on a C14H31O3P-Ti3C2/Au Schottky junction is developed. The modified C14H31O3P-Ti3C2 two-dimensional semiconductor is prepared by a simple solution method, in which the phosphonic acid group reacts with the hydroxyl group on the Ti3C2Tx surface. The C14H31O3P-Ti3C2/Au photodetector is constructed by using a drop-coating method at room temperature. The observation of an S-shaped curve in the I-V characteristics indicates the formation of a Schottky junction between C14H31O3P-Ti3C2 nanosheets and the Au electrode. The device exhibits good detection performance in the near-infrared band (808–1342 nm), with a maximum responsivity of 0.28 A/W, a detectivity of 4.3×107 Jones and an external quantum efficiency (EQE) of 32.75% under 1064 nm infrared light illumination. The Ion/Ioff ratio is 10.4, which is about 7.3 times higher than that under 1342 nm light. The response time and the recovery time of the device are 0.9 s and 0.5 s, respectively. After 10 cycles of I-t, the photocurrent does not show any significant decay, indicating excellent repeatability and cycle stability of the device. Owing to the built-in electric field formed by the Schottky junction, photo-generated electrons and holes can quickly separate and produce photocurrent in the external circuit without the need for external voltage driving. In addition, the C14H31O3P-Ti3C2 film obtained by drop-casting on Au is composed of several layers of nanosheets that are randomly stacked, which can effectively relax the plasma momentum limitation, promote the generation of hot electrons, and contribute to the photocurrent. As the C14H31O3P-Ti3C2/Au Schottky junction photodetector possesses self-driven characteristics and simple fabrication process, it exhibits great potential applications in detecting weak light signals, such as in the fields of astronomy and biomedical science. The successful fabrication of this photodetector provides a new approach for designing and developing MXene-based near-infrared detectors, thus promoting further advancements in this field.
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Keywords:
- near infrared photoelectric detectors /
- Schottky junction /
- MXene /
- self-drive
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图 1 (a) C14H31O3P改性Ti3C2Tx的过程示意图; Ti3AlC2 MAX, Ti3C2Tx, C14H31O3P-Ti3C2的XRD衍射图谱(b)及红外光谱(c)
Fig. 1. (a) C14H31O3P modification Ti3C2Tx process schematic diagram; XRD diffraction diagram (b) and infrared spectrum (c) of Ti3AlC2 MAX, Ti3C2Tx, C14H31O3P-Ti3C2.
图 2 Ti3C2Tx, C14H31O3P-Ti3C2的AFM表征(a), (b)和SEM表征(c), (d). C14H31O3P-Ti3C2的XPS谱 (e)宽扫描; (f) Ti 2p的高分辨率; (g) O 1s区的高分辨率; (h) P 2p区的高分辨率
Fig. 2. AFM characteristic (a), (b) and SEM characteristics (c), (d) of Ti3C2Tx and C14H31O3P-Ti3C2. XPS spectra of C14H31O3P-Ti3C2 nanosheets: (e) Wide scan; (f) high-resolution of Ti 2p region; (g) high-resolution of O 1s region; (h) high-resolution of P 2p region.
图 3 C14H31O3P-Ti3C2/Au肖特基结器件 (a) I-V 特性曲线; (b)在808—1342 nm波长下的开关比Ion/Ioff; (c)不同光功率密度下的光电流; (d)光响应度和比探测率; (e) I-t曲线; (f)响应时间和恢复时间
Fig. 3. Schottky junction device of C14H31O3P-Ti3C2/Au: (a) I-V characteristic curve; (b) switching ratio Ion/Ioff at 808–1342 nm wavelength; (c) plots of photocurrent changes with different optical power densities; (d) light response and ratio detection rate; (e) I-t characteristic curve; (f) response time and recovery time.
图 4 (a) C14H31O3P-Ti3C2/Au光电探测器示意图; (b) 肖特基结的能带示意图
Fig. 4. (a) Schematic diagram of C14H31O3P-Ti3C2/Au photodetector; (b) schematic energy band diagram of the Schottky.
表 1 不同光功率下的响应度、比探测率以及外量子效率
Table 1. Responsivity, specific detection rate, and external quantum efficiency at different light power.
${P/({\rm{m} }{\rm{W} }{\cdot}{\rm{c} }{\rm{m} } }^{-2})$ $ R/( $10–1${\rm{A} }{\cdot}{ {\rm{W} } }^{-1}$) $ {D}^{*}/( $107$ {\rm{J}}{\rm{o}}{\rm{n}}{\rm{e}}{\rm{s}}) $ $ {\rm{E}}{\rm{Q}}{\rm{E}}/{\text{%}} $ 9.2 2.8 4.3 32.75 25.2 2.0 3.1 23.62 44.9 1.8 2.6 20.44 111.5 1.0 1.3 11.80 178.3 0.86 1.4 10.00 
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[1] Tantum S L, Yu Y L, Collins L M 2008 IEEE Geosci. Remote Sens. Lett. 5 103
Google Scholar
[2] Xu H H, Liu J, Zhang J, Zhou G D, Luo N Q, Zhao N 2017 Adv. Mater. 29 1700975
Google Scholar
[3] Millan M S, Escofet J 2004 Opt. Lett. 29 1440
Google Scholar
[4] Jonsson P, Casselgren J, Thornberg B 2015 IEEE Sens. J. 15 1641
Google Scholar
[5] Homan K A, Souza M, Truby R, Luke G P, Green C, Vreeland E, Emelianov S 2012 ACS Nano 6 641
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[6] Zeng L H, Lin S H, Li Z J, Zhang Z X, Zhang T F, Xie C, Mak C H, Chai Y, Lau S P, Luo L B, Tsang Y H 2018 Adv. Funct. Mater. 28 1705970
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Google Scholar
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Google Scholar
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Google Scholar
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