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1. The influence of crystal thickness and interlayer interactions on the properties of heavy ion irradiated MoS 2

   https://doi.org/10.1088/2053-1583/ab817b  

   Isherwood, Liam H. ; Hennighausen, Zachariah ; Son, Seok-Kyun ; Spencer, Ben F. ; Wady, Paul T. ; Shubeita, Samir M. ; Kar, Swastik ; Casiraghi, Cinzia ; Baidak, Aliaksandr ( May 2020 , 2D Materials)

   Ion irradiation is a versatile tool to introduce controlled defects into two-dimensional (2D) MoS₂on account of its unique spatial resolution and plethora of ion types and energies available. In order to fully realise the potential of this technique, a holistic understanding of ion-induced defect production in 2D MoS₂crystals of different thicknesses is mandatory. X-ray photoelectron spectroscopy, electron diffraction and Raman spectroscopy show that thinner MoS₂crystals are more susceptible to radiation damage caused by 225 keV Xe⁺ions. However, the rate of defect production in quadrilayer and bulk crystals is not significantly different under our experimental conditions. The rate at which S atoms are sputtered as a function of radiation exposure is considerably higher for monolayer MoS₂, compared to bulk crystals, leading to MoO₃formation. P-doping of MoS₂is observed and attributed to the acceptor states introduced by vacancies and charge transfer interactions with adsorbed species. Moreover, the out-of-plane vibrational properties of irradiated MoS₂crystals are shown to be strongly thickness-dependent: in mono- and bilayer MoS₂, the confinement of phonons by defects results in a blueshift of the$A_{1g}$mode. Whereas, a redshift is observed in bulk crystals due to attenuation of the effective restoring forces acting on S atoms caused by vacancies in adjacent MoS₂layers. Consequently, the$A_{1g}$frequency of tri- and quadrilayer crystals is statistically invariant on account oft competition between phonon confinement effects and interlayer interactions. The$A_{1g}$linewidth is observed to decrease in bi- and trilayer crystals after low dose irradiation and is attributed to layer decoupling. This work shows that there is a complex interplay between defect production, crystal thickness and interlayer interactions in MoS₂. Our results demonstrate that ion irradiation is an effective tool to modulate the electronic, vibrational and structural properties of MoS₂, which may prove beneficial for practical applications.

    

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2. Glass‐Like Through‐Plane Thermal Conductivity Induced by Oxygen Vacancies in Nanoscale Epitaxial La 0.5 Sr 0.5 CoO 3− δ

   https://doi.org/10.1002/adfm.201704233  

   Wu, Xuewang ; Walter, Jeff ; Feng, Tianli ; Zhu, Jie ; Zheng, Hong ; Mitchell, John F. ; Biškup, Neven ; Varela, Maria ; Ruan, Xiulin ; Leighton, Chris ; et al ( November 2017 , Advanced Functional Materials)

   Ultrafast time‐domain thermoreflectance (TDTR) is utilized to extract the through‐plane thermal conductivity (Λ_LSCO) of epitaxial La_0.5Sr_0.5CoO_3−δ(LSCO) of varying thickness (<20 nm) on LaAlO₃and SrTiO₃substrates. These LSCO films possess ordered oxygen vacancies as the primary means of lattice mismatch accommodation with the substrate, which induces compressive/tensile strain and thus controls the orientation of the oxygen vacancy ordering (OVO). TDTR results demonstrate that the room‐temperatureΛ_LSCOof LSCO on both substrates (1.7 W m⁻¹K⁻¹) are nearly a factor of four lower than that of bulk single‐crystal LSCO (6.2 W m⁻¹K⁻¹). Remarkably, this approaches the lower limit of amorphous oxides (e.g., 1.3 W m⁻¹K⁻¹for glass), with no dependence on the OVO orientation. Through theoretical simulations, origins of the glass‐like thermal conductivity of LSCO are revealed as a combined effect resulting from oxygen vacancies (the dominant factor), Sr substitution, size effects, and the weak electron/phonon coupling within the LSCO film. The absence of OVO dependence in the measuredΛ_LSCOis rationalized by two main effects: (1) the nearly isotropic phononic thermal conductivity resulting from the imperfect OVO planes when δ is small; (2) the missing electronic contribution toΛ_LSCOalong the through‐plane direction for these ultrathin LSCO films on insulating substrates.

    

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3. The in-plane structure domain size of nm-thick MoSe 2 uncovered by low-momentum phonon scattering

   https://doi.org/10.1039/d0nr09099a  

   Lin, Huan ; Wang, Ridong ; Zobeiri, Hamidreza ; Wang, Tianyu ; Xu, Shen ; Wang, Xinwei ( April 2021 , Nanoscale)

   null (Ed.)

   Although 2D materials have been widely studied for more than a decade, very few studies have been reported on the in-plane structure domain (STD) size even though such a physical property is critical in determining the charge carrier and energy carrier transport. Grazing incidence X-ray diffraction (XRD) can be used for studying the in-plane structure of very thin samples, but it becomes more challenging to study few-layer 2D materials. In this work the nanosecond energy transport state-resolved Raman (nET-Raman) technique is applied to resolve this key problem by directly measuring the thermal reffusivity of 2D materials and determining the residual value at the 0 K-limit. Such a residual value is determined by low-momentum phonon scattering and can be directly used to characterize the in-plane STD size of 2D materials. Three suspended MoSe 2 (15, 50 and 62 nm thick) samples are measured using nET-Raman from room temperature down to 77 K. Based on low-momentum phonon scattering, the STD size is determined to be 58.7 nm and 84.5 nm for 50 nm and 62 nm thick samples, respectively. For comparison, the in-plane structure of bulk MoSe 2 that is used to prepare the measured nm-thick samples is characterized using XRD. It uncovers crystallite sizes of 64.8 nm in the (100) direction and 121 nm in the (010) direction. The STD size determined by our low momentum phonon scattering is close to the crystallite size determined by XRD, but still shows differences. The STD size by low-momentum phonon scattering is more affected by the crystallite sizes in all in-plane directions rather than that by XRD that is for a specific crystallographic orientation. Their close values demonstrate that during nanosheet preparation (peeling and transfer), the in-plane structure experiences very little damage. 

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4. Stacking‐Order‐Driven Optical Properties and Carrier Dynamics in ReS 2

   https://doi.org/10.1002/adma.201908311  

   Zhou, Yongjian ; Maity, Nikhilesh ; Rai, Amritesh ; Juneja, Rinkle ; Meng, Xianghai ; Roy, Anupam ; Zhang, Yanyao ; Xu, Xiaochuan ; Lin, Jung‐Fu ; Banerjee, Sanjay K. ; et al ( April 2020 , Advanced Materials)

   Two distinct stacking orders in ReS₂are identified without ambiguity and their influence on vibrational, optical properties and carrier dynamics are investigated. With atomic resolution scanning transmission electron microscopy (STEM), two stacking orders are determined as AA stacking with negligible displacement across layers, and AB stacking with about a one‐unit cell displacement along theaaxis. First‐principles calculations confirm that these two stacking orders correspond to two local energy minima. Raman spectra inform a consistent difference of modes I & III, about 13 cm⁻¹for AA stacking, and 20 cm⁻¹for AB stacking, making a simple tool for determining the stacking orders in ReS₂. Polarized photoluminescence (PL) reveals that AB stacking possesses blueshifted PL peak positions, and broader peak widths, compared with AA stacking, indicating stronger interlayer interaction. Transient transmission measured with femtosecond pump–probe spectroscopy suggests exciton dynamics being more anisotropic in AB stacking, where excited state absorption related to Exc. III mode disappears when probe polarization aligns perpendicular tobaxis. The findings underscore the stacking‐order driven optical properties and carrier dynamics of ReS₂, mediate many seemingly contradictory results in the literature, and open up an opportunity to engineer electronic devices with new functionalities by manipulating the stacking order.

    

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5. Near-infrared optical transitions in PdSe 2 phototransistors

   https://doi.org/10.1039/c9nr03505b  

   Walmsley, Thayer S. ; Andrews, Kraig ; Wang, Tianjiao ; Haglund, Amanda ; Rijal, Upendra ; Bowman, Arthur ; Mandrus, David ; Zhou, Zhixian ; Xu, Ya-Qiong ( August 2019 , Nanoscale)

   We investigate electronic and optoelectronic properties of few-layer palladium diselenide (PdSe 2 ) phototransistors through spatially-resolved photocurrent measurements. A strong photocurrent resonance peak is observed at 1060 nm (1.17 eV), likely attributed to indirect optical transitions in few-layer PdSe 2 . More interestingly, when the thickness of PdSe 2 flakes increases, more and more photocurrent resonance peaks appear in the near-infrared region, suggesting strong interlayer interactions in few-layer PdSe 2 help open up more optical transitions between the conduction and valence bands of PdSe 2 . Moreover, gate-dependent measurements indicate that remarkable photocurrent responses at the junctions between PdSe 2 and metal electrodes primarily result from the photovoltaic effect when a PdSe 2 phototransistor is in the off-state and are partially attributed to the photothermoelectric effect when the device turns on. We also demonstrate PdSe 2 devices with a Seebeck coefficient as high as 74 μV K −1 at room temperature, which is comparable with recent theoretical predications. Additionally, we find that the rise and decay time constants of PdSe 2 phototransistors are ∼156 μs and ∼163 μs, respectively, which are more than three orders of magnitude faster than previous PdSe 2 work and two orders of magnitude over other noble metal dichalcogenide phototransistors, offering new avenues for engineering future optoelectronics. 

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