CuPc/MoS<sub>2</sub>范德瓦耳斯异质结荧光特性

孔宇晗; 王蓉; 徐明生

doi:10.7498/aps.71.20220132

摘要

在众多二维材料中, 过渡金属硫族化合物由于其具有独特的光电特性深受广大研究者喜爱. 近年来, 由二维过渡金属硫族化合物材料与有机半导体结合构建的范德瓦耳斯异质结受到极大的关注. 这种异质结可以利用两者的优势对光电特性等性能进行调控, 为许多基础物理和功能器件的构建提供了研究思路. 本文构建了酞菁铜/二硫化钼(CuPc/MoS₂)范德瓦耳斯异质结, 并对其荧光特性进行了表征和分析. 与单层MoS₂相比较发现, 引入有机半导体CuPc后, 异质结当中发生了明显的荧光淬灭现象. 通过荧光分析, 该现象可以用引入CuPc后异质结中负三激子与中性激子之比增加来解释. 此外, 通过第一性原理计算分析发现, 引入CuPc会在MoS₂的禁带中引入中间带隙态, 使得CuPc与MoS₂之间产生非辐射复合, 这同样会导致荧光淬灭的发生. CuPc/MoS₂异质结的荧光淬灭现象可以为同类型范德瓦耳斯异质结的光电特性调控研究提供参考和思路.

关键词:

Abstract

Among two-dimensional (2D) materials, transition metal chalcogenides (TMDs) have attracted much attention due to their unique photoelectric properties. On the other hand, organic molecules have the characteristics of flexibility, wide source, easy fabrication and low cost. The van der Waals heterostructure constructed by the combination of 2D TMDs and organic semiconductors has attracted enormous attention in recent years. When organic semiconductors combine with TMDs to form van der Waals heterostructure, the hybridization of organic molecules could improve the photoelectric properties and other properties by taking the advantages of these two materials, Therefore, the combination of organic semiconductor molecules and TMDs can provide a research platform for designing many basic physics and functional devices and interesting optoelectronic applications. In this work, CuPc/MoS₂ van der Waals heterostructure is built, and its photoluminescence (PL) properties are investigated. It is observed that after introducing CuPc, a significant PL quenching phenomenon occurs in the heterostructure compared with the single layer MoS₂ and pure CuPc only. After fitting the PL of CuPc/MoS₂ heterostructure system and monolayer MoS₂ only, the ratio of trion to neutral exciton is clearly increased in the heterostructure. Furthermore, it is found that two mid-gap states D1 and D2 related to the CuPc are introduced into the band gap of MoS₂ by first principle calculation. Through the charge density analysis, we find that the D1 state originates from the sp² bonding state of the C-C bond while the D2 state comes from the anti-bonding state of the N-Cu bond. Meanwhile, the valence band maximum (VBM) and conduction band minimum (CBM) of CuPc/MoS₂ heterostructure are derived from the bonding and anti-bonding states of MoS₂, respectively. The charge transfer occurs between the mid-gap states of CuPc and MoS₂. However, owing to different positions of charge density distribution of CBM, D2, D1 and VBM, the charge pathway is dominated by non-radiation recombination, which cannot give new PL peak in heterostructure. However, this process reduces the number of carriers involved in the direct recombination of MoS₂, which leads PL to quench in the heterostructure. This work would be applied to the manipulation of photoelectric characteristics and the design of TMD/organic-based photovoltaic applications.

Keywords:

作者及机构信息

1.
浙江大学, 高分子科学与工程学系, 微纳电子学院, 硅材料国家重点实验室, 杭州　310027

2.
浙江大学杭州国际科创中心, 杭州　311215

通信作者: 王蓉, rong_wang@zju.edu.cn ; 徐明生, msxu@zju.edu.cn

基金项目: 国家自然科学基金(批准号: 62090030, 62090031, 51872257, 51672244)和浙江省自然科学基金(批准号: LZ20F040001)资助的课题

Authors and contacts

1.
State Key Laboratory of Silicon Materials, School of Micro-Nano Electronics, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China

2.
Hangzhou Global Scientific and Technological Innovation Center, Zhejiang University, Hangzhou 311215, China

Corresponding author: Wang Rong, rong_wang@zju.edu.cn ; Xu Ming-Sheng, msxu@zju.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 62090030, 62090031, 51872257, 51672244) and the Natural Science Foundation of Zhejiang Pvovince, China (Grant No. LZ20F040001).

文章全文 : translate this paragraph

参考文献

[1]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A 2004 Science 306 666 Google Scholar
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施引文献

图 1 制备MoS₂单晶的CVD装置图

Fig. 1. Schematic illustration of the growth of monolayer MoS₂ by CVD.

下载: 全尺寸图片幻灯片

图 2 CuPc/MoS₂异质结的形貌表征　(a)单层MoS₂的AFM图; (b) CuPc/MoS₂异质结的SEM图

Fig. 2. Morphology characterization of CuPc/MoS₂ heterostructure system: (a) AFM image of monolayer MoS₂; (b) SEM image of CuPc/MoS₂ heterostructure.

下载: 全尺寸图片幻灯片

图 3 CuPc与单层MoS₂复合前后的拉曼散射图谱

Fig. 3. Raman scattering spectra of CuPc and monolayer MoS₂ (ML-MoS₂) before and after recombination.

下载: 全尺寸图片幻灯片

图 4 CuPc/MoS₂异质结的荧光发光图谱　(a) CuPc与单层MoS₂复合前后的荧光发光图谱; (b) CuPc/MoS₂异质结的荧光面扫描图; (c)单层MoS₂的荧光面扫描图

Fig. 4. PL spectra of CuPc/MoS₂ heterostructure system: (a) PL spectra of CuPc and monolayer MoS₂ before and after recombination; (b) PL mapping image of CuPc/MoS₂ heterostructure; (c) PL mapping image of ML-MoS₂.

下载: 全尺寸图片幻灯片

图 5 (a) CuPc/MoS₂异质结和(b)单层MoS₂的荧光分峰拟合曲线, 其中负三激子A^–位置约为1.84 eV, 中性激子A位置约为1.88 eV, B激子位置约为2.01 eV

Fig. 5. PL fitting of (a) CuPc/MoS₂ heterostructure and (b) ML-MoS₂, where the negative trions A^– site is about 1.84 eV, the neutral exciton A site is about 1.88 eV, and the B exciton site is about 2.01 eV.

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图 6 (a) CuPc/MoS₂异质结的分波态密度图; (b)—(e)分别为VBM, D1, D2, CBM的电荷密度分布图

Fig. 6. (a) Partial density of states of CuPc/MoS₂ heterostructure; (b)–(e) charge density distribution of VBM, D1, D2, CBM, respectively.

下载: 全尺寸图片幻灯片

图 7 CuPc/MoS₂异质结体系的荧光淬灭示意图 (实心及空心圆分别代表电子及空穴)

Fig. 7. Schematic diagram of PL quenching of CuPc/MoS₂ heterostructure system (Solid and hollow circles represent electrons and holes respectively).

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map

[1]	Novoselov K S, Geim A K, Morozov S V, Jiang D, Zhang Y, Dubonos S V, Grigorieva I V, Firsov A A 2004 Science 306 666 Google Scholar
[2]	Mak K F, Lee C, Hone J, Shan J, Heinz T F 2010 Phys. Rev. Lett. 105 136805 Google Scholar
[3]	Fabbri F, Rotunno E, Cinquanta E, et al. 2016 Nat. Commun. 7 13044 Google Scholar
[4]	Li H, Zhang Q, Yap C C R, Tay B K, Edwin T H T, Olivier A, Baillargeat D 2012 Adv. Funct. Mater. 22 1385 Google Scholar
[5]	Amani M, Lien D H, Kiriya D, et al. 2015 Science 350 1065 Google Scholar
[6]	Xu M S, Liang T, Shi M M, Chen H Z 2013 Chem. Rev. 113 3766 Google Scholar
[7]	Song I, Park C, Choi H C 2015 Rsc. Adv. 5 7495 Google Scholar
[8]	Huang Y L, Zheng Y J, Song Z B, Chi D Z, Wee A T S, Quek S Y 2018 Chem. Soc. Rev. 47 3241 Google Scholar
[9]	Zhang X N, de Oteyza D G, Wakayama Y, Dosch H 2009 Surf. Sci. 603 3179 Google Scholar
[10]	Fan Q P, Li M, Yang P G, Liu Y, Xiao M J, Wang X D, Tan H, Wang Y F, Yang R Q, Zhu W G 2015 Dyes Pigments 116 13 Google Scholar
[11]	Li Q F, Liu S, Chen H Z, Li H Y 2016 Chin. Chem. Lett. 27 1421 Google Scholar
[12]	Gehring P, Thijssen J M, van der Zant H S J 2019 Nat. Rev. Phys. 1 381 Google Scholar
[13]	Aradhya S V, Venkataraman L 2013 Nat. Nanotechnol. 8 399 Google Scholar
[14]	Choi J, Zhang H Y, Choi J H 2016 Acs Nano 10 1671 Google Scholar
[15]	Zhao H J, Zhao Y B, Song Y X, et al. 2019 Nat. Commun. 10 5589 Google Scholar
[16]	Obaidulla S M, Habib M R, Khan Y, Kong Y H, Liang T, Xu M S 2020 Adv. Mater. Interfaces 7 1901197 Google Scholar
[17]	Wang S Y, Chen C S, Yu Z H, He Y L, Chen X Y, Wan Q, Shi Y, Zhang D W, Zhou H, Wang X R, Zhou P 2019 Adv. Mater. 31 1806227 Google Scholar
[18]	Huang Y, Zhuge F W, Hou J X, Lv L, Luo P, Zhou N, Gan L, Zhai T Y 2018 Acs Nano 12 4062 Google Scholar
[19]	Homan S B, Sangwan V K, Balla I, Bergeron H, Weiss E A, Hersam M C 2017 Nano Lett. 17 164 Google Scholar
[20]	Park C J, Park H J, Lee J Y, Kim J, Lee C H, Joo J 2018 Acs Appl. Mater. Inter. 10 29848 Google Scholar
[21]	Habib M R, Li H F, Kong Y H, Liang T, Obaidulla S M, Xie S, Wang S P, Ma X Y, Su H X, Xu M S 2018 Nanoscale 10 16107 Google Scholar
[22]	Khan Y, Obaidulla S M, Habib M R, Kong Y H, Xu M S 2020 Appl. Sur. Sci. 530 147213 Google Scholar
[23]	Mouri S, Miyauchi Y, Matsuda K 2013 Nano. Lett. 13 5944 Google Scholar
[24]	Kresse G, Furthmuller J 1996 Comp. Mater. Sci. 6 15 Google Scholar
[25]	Heyd J, Scuseria G E, Ernzerhof M 2003 J. Chem. Phys. 118 8207 Google Scholar
[26]	Choudhury P, Ravavarapu L, Dekle R, Chowdhury S 2017 J. Phys. Chem. C 121 2959 Google Scholar

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CuPc/MoS₂范德瓦耳斯异质结荧光特性