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Mos2 Based Photodetectors: a Review sensors Review MoS2 Based Photodetectors: A Review Alberto Taffelli *, Sandra Dirè , Alberto Quaranta and Lucio Pancheri Department of Industrial Engineering, University of Trento, Via Sommarive 9, 38123 Trento, Italy; [email protected] (S.D.); [email protected] (A.Q.); [email protected] (L.P.) * Correspondence: [email protected] Abstract: Photodetectors based on transition metal dichalcogenides (TMDs) have been widely reported in the literature and molybdenum disulfide (MoS2) has been the most extensively explored for photodetection applications. The properties of MoS2, such as direct band gap transition in low dimensional structures, strong light–matter interaction and good carrier mobility, combined with the possibility of fabricating thin MoS2 films, have attracted interest for this material in the field of optoelectronics. In this work, MoS2-based photodetectors are reviewed in terms of their main performance metrics, namely responsivity, detectivity, response time and dark current. Although neat MoS2-based detectors already show remarkable characteristics in the visible spectral range, MoS2 can be advantageously coupled with other materials to further improve the detector performance Nanoparticles (NPs) and quantum dots (QDs) have been exploited in combination with MoS2 to boost the response of the devices in the near ultraviolet (NUV) and infrared (IR) spectral range. Moreover, heterostructures with different materials (e.g., other TMDs, Graphene) can speed up the response of the photodetectors through the creation of built-in electric fields and the faster transport of charge carriers. Finally, in order to enhance the stability of the devices, perovskites have been exploited both as passivation layers and as electron reservoirs. Keywords: MoS2; TMD; photodetector; heterostructure; thin film Citation: Taffelli, A.; Dirè, S.; Quaranta, A.; Pancheri, L. MoS2 Based Photodetectors: A Review. Sensors 2021, 21, 2758. https:// 1. Introduction doi.org/10.3390/s21082758 Recent improvements in optoelectronics have been partly focused on the use of two- dimensional materials to produce photodetectors. The possibility of fabricating very thin Academic Editor: optoelectronic devices, having high performance, low production costs and mechanical Guillermo Villanueva flexibility has been emerging in the last decade. Graphene was the first 2D material con- sidered for photodetection applications, thanks to its outstanding electrical properties, in Received: 9 March 2021 particular its impressive planar mobility, reaching 200,000 cm2/(V s), that allows to build Accepted: 8 April 2021 Published: 14 April 2021 photodetectors with bandwidth up to 40 GHz [1,2]. However, one of its mayor limitation for its use as photodetector active layer is the absence of an energy band gap, leading to high Publisher’s Note: MDPI stays neutral noise contribution to the signal, arising from dark currents. with regard to jurisdictional claims in Therefore, the investigation of 2D materials with finite bandgap has increased in published maps and institutional affil- recent years and transition metal dichalcogenides (TMDs) have aroused more and more iations. interest. Despite the modest mobility reported for these materials, which can reach about 200 cm2/(V s) [3], TMDs possess interesting electro-optical properties. A transition from indirect to direct bandgap has been observed in TMDs by reducing the dimensions from the bulk material to the monolayer limit [4]. Moreover, a strong light–matter interaction is observed for 2D-TMDs, due to the direct band gap and to the strong excitonic nature Copyright: © 2021 by the authors. Licensee MDPI, Basel, Switzerland. of their low dimensional structures. For TMDs, absorbance values that are one order of This article is an open access article magnitude higher than Si and GaAs are reported [5], thus providing strong light absorption distributed under the terms and with a very thin layer of the photoactive material. These features, combined with a higher conditions of the Creative Commons mechanical flexibility of 2D-TMDs compared to their bulk structures, allow us to fabricate Attribution (CC BY) license (https:// very thin photodetectors also based on flexible substrates, opening the possibility to realize creativecommons.org/licenses/by/ flexible and wearable devices. Applications for such devices can be related to medicine, 4.0/). biosensing, optical communications and security. Sensors 2021, 21, 2758. https://doi.org/10.3390/s21082758 https://www.mdpi.com/journal/sensors Sensors 2021, 21, x FOR PEER REVIEW 2 of 24 very thin photodetectors also based on flexible substrates, opening the possibility to real- ize flexible and wearable devices. Applications for such devices can be related to medi- Sensors 2021, 21, 2758 cine, biosensing, optical communications and security. 2 of 22 Among the TMDs, molybdenum disulfide (MoS2) attracted much interest in the last decade, also due to the relative abundance of molybdenite in nature. MoS2 belongs to the family of the groupAmong VI transition the TMDs, metal molybdenum dichalcogenides, disulfide where (MoS a 2layer) attracted of transition much interestmetal atoms in the (Mo, last decade, also due to the relative abundance of molybdenite in nature. MoS belongs to the W) is sandwiched between two layers of chalcogen atoms (S, Se, Te) as depicted2 in Figure family of the group VI transition metal dichalcogenides, where a layer of transition metal 1.atoms (Mo, W) is sandwiched between two layers of chalcogen atoms (S, Se, Te) as depicted in Figure1. Figure 1. Transformation of the hexagonal 2H polymorph of MoS2 into its 1T phase, through electron transfer. Reprinted with permission from ref. [6]. © 2017 AIP Publishing. Figure 1. Transformation of the hexagonal 2H polymorph of MoS2 into its 1T phase, through electron transfer. Reprinted with permission from ref. [6]. © 2017Each AIP MoS Publishing.2 layer is generally stacked onto each other via weak van der Waals forces in an ABA stacking sequence, building a hexagonal structure (2H-TMD), which possesses a semiconductingEach MoS2 layer behaviour. is generally Another stacked metastable onto each phase other of MoS via2 weakis known, van der with Waals a tetragonal forces insymmetry an ABA stacking (1T-MoS sequence,2) and ABC building stacking a hexagonal sequence (Figure structure1). The(2H-TMD), 1T phase which of MoS possesses2 is not astable semiconducting at room temperature behaviour. [7 ],An butother it can metastable be induced phase by several of MoS processes2 is known, such with as a chemical tetrag- onaltreatment symmetry [8], plasmonic (1T-MoS2) hot and electron ABC stacking transfer sequence [9], electron (Figure beam 1). irradiation The 1T phase [6,10 of], throughMoS2 is notcharge stable transfer at room in thetemperature TMD lattice. [7], Abut subsequent it can be induced annealing by processseveral isprocesses then required such as to chemicalrestore the treatment 2H-MoS [8],2 phase plasmonic [6]. hot electron transfer [9], electron beam irradiation [6], [10], throughBulk TMD charge electronic transfer properties in the TMD are dominatedlattice. A subsequent by indirect annealing transition process from the is maxi-then requiredmum of to the restore valence the band, 2H-MoS located2 phase at the [6]G. point of the Brillouin zone, and the minimum of theBulk conduction TMD electronic band [ 11properties–13]. For are MoS dominat2, the bulked by electronic indirect structuretransition isfrom characterized the maxi- mumby an of indirect the valence energy band, band located gap of at about the Γ 1.2point eV of [14 the]. AsBrillouin with other zone, group and the VI minimum TMDs, at ofthe the monolayer conduction limit band MoS [11–13].2 modifies For MoS its energy2, the bulk band electronic structure structure towards is a characterized direct electronic by antransition indirect fromenergy the band K and gap K’ pointsof about of 1.2 the eV Brillouin [14]. As zone, with reaching other group an energy VI TMDs, band gapat the of monolayer1.8 eV [14, 15limit]. This MoS behaviour2 modifies its can energy be explained band structure by an increase towards in a thedirect indirect electronic band tran- gap sitiondue to from a considerable the K and K’ quantum points of confinement the Brillouin effect zone, in reaching the out-of-plane an energy direction band gap when of 1.8 the eVdimensions [14,15]. This of thebehaviour material can are be reduced explained to few by an layers. increase On thein the other indirect hand, band the direct gap due transi- to ation considerable remains unaffected, quantum confinement becoming the effect minimum in the energeticout-of-plane band-to-band direction when transition the dimen- [11–13] sions(Figure of2 thea) . material Moreover, are TMDs reduced are reported to few layers. to have On strong the other spin-orbit hand, coupling the direct (SOC), transition associ- remainsated with unaffected, the d-orbitals becoming of transition the minimum metals [6,16 energetic,17]. The band-to-band SOC breaks the transition degeneracy [11–13] in the (Figurevalence 2a). band, Moreover, leading TMDs to two are energetic reported maxima to have located strongat spin-orbit the K and coupling K’ points, (SOC), separated asso- ciatedby an with energy the splittingd-orbitals of of 160 transition meV for metals a monolayer [6,16,17]. MoS The2 SOC[16] breaks (Figure the2b). degeneracy This broken in degeneracy opens for MoS2 the possibility for optoelectronic applications in the field of valleytronics [18,19]. Sensors 2021, 21, x FOR PEER REVIEW 3 of 24 Sensors 2021, 21, x FOR PEER REVIEW 3 of 24 the valence band, leading to two energetic maxima located at the K and K’ points, sepa- therated valence by an band, energy leading splitting to two of energetic160 meV formaxima a monolayer located MoSat the2 [16]K and (Figure K’ points, 2b). This sepa- broken Sensors 2021, 21, 2758 3 of 22 rateddegeneracy by an energy opens splitting for MoS of 1602 the meV possibility for a monolayer for optoelectronic MoS2 [16] (Figure applications 2b). This in broken the field of degeneracyvalleytronics opens [18,19]. for MoS 2 the possibility for optoelectronic applications in the field of valleytronics [18,19].
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