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"Qiao Jingsi"
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High-mobility transport anisotropy and linear dichroism in few-layer black phosphorus
2014
Two-dimensional crystals are emerging materials for nanoelectronics. Development of the field requires candidate systems with both a high carrier mobility and, in contrast to graphene, a sufficiently large electronic bandgap. Here we present a detailed theoretical investigation of the atomic and electronic structure of few-layer black phosphorus (BP) to predict its electrical and optical properties. This system has a direct bandgap, tunable from 1.51 eV for a monolayer to 0.59 eV for a five-layer sample. We predict that the mobilities are hole-dominated, rather high and highly anisotropic. The monolayer is exceptional in having an extremely high hole mobility (of order 10,000 cm
2
V
−1
s
−1
) and anomalous elastic properties which reverse the anisotropy. Light absorption spectra indicate linear dichroism between perpendicular in-plane directions, which allows optical determination of the crystalline orientation and optical activation of the anisotropic transport properties. These results make few-layer BP a promising candidate for future electronics.
Two-dimensional (2D) materials with a large electronic bandgap in addition to high carrier mobility are required for future nanoelectronics. Here, the authors present a theoretical investigation of black phosphorous, a new category of 2D semiconductor with high potential for nanoelectronic applications.
Journal Article
Giant anisotropic photonics in the 1D van der Waals semiconductor fibrous red phosphorus
2021
A confined electronic system can host a wide variety of fascinating electronic, magnetic, valleytronic and photonic phenomena due to its reduced symmetry and quantum confinement effect. For the recently emerging one-dimensional van der Waals (1D vdW) materials with electrons confined in 1D sub-units, an enormous variety of intriguing physical properties and functionalities can be expected. Here, we demonstrate the coexistence of giant linear/nonlinear optical anisotropy and high emission yield in fibrous red phosphorus (FRP), an exotic 1D vdW semiconductor with quasi-flat bands and a sizeable bandgap in the visible spectral range. The degree of photoluminescence (third-order nonlinear) anisotropy can reach 90% (86%), comparable to the best performance achieved so far. Meanwhile, the photoluminescence (third-harmonic generation) intensity in 1D vdW FRP is strong, with quantum efficiency (third-order susceptibility) four (three) times larger than that in the most well-known 2D vdW materials (e.g., MoS
2
). The concurrent realization of large linear/nonlinear optical anisotropy and emission intensity in 1D vdW FRP paves the way towards transforming the landscape of technological innovations in photonics and optoelectronics.
One-dimensional van der Waals (1D vdW) materials derive interesting behaviour from dimensional confinement. Here the authors study a 1D vdW semiconductor, fibrous red phosphorous, and observe exceptional optical properties of large optical anisotropy and high photoluminescence.
Journal Article
Partitioning the interlayer space of covalent organic frameworks by embedding pseudorotaxanes in their backbones
2020
Mono- or few-layer sheets of covalent organic frameworks (COFs) represent an attractive platform of two-dimensional materials that hold promise for tailor-made functionality and pores, through judicious design of the COF building blocks. But although a wide variety of layered COFs have been synthesized, cleaving their interlayer stacking to obtain COF sheets of uniform thickness has remained challenging. Here, we have partitioned the interlayer space in COFs by incorporating pseudorotaxane units into their backbones. Macrocyclic hosts based on crown ethers were embedded into either a ditopic or a tetratopic acylhydrazide building block. Reaction with a tritopic aldehyde linker led to the formation of acylhydrazone-based layered COFs in which one basal plane is composed of either one layer, in the case of the ditopic macrocyclic component, or two adjacent layers covalently held together by its tetratopic counterpart. When a viologen threading unit is introduced, the formation of a host–guest complex facilitates the self-exfoliation of the COFs into crystalline monolayers or bilayers, respectively.Layered COFs are attractive precursors for two-dimensional materials but they are difficult to cleave into mono- or few-layer sheets. Pseudorotaxane moieties have now been embedded into layered COFs to facilitate their cleavage into sheets of uniform thickness. Crown-ether macrocycles within the COF backbone bind to ionic viologen guests, leading to electrostatic repulsion between layers.
Journal Article
Ultralow contact resistance in organic transistors via orbital hybridization
by
Li, Yating
,
Xie, Jiacheng
,
Wang, Peng
in
639/301/1005/1007
,
639/925/927/998
,
Contact resistance
2023
Organic field-effect transistors (OFETs) are of interest in unconventional form of electronics. However, high-performance OFETs are currently contact-limited, which represent a major challenge toward operation in the gigahertz regime. Here, we realize ultralow total contact resistance (
R
c
) down to 14.0 Ω ∙ cm in C
10
-DNTT OFETs by using transferred platinum (Pt) as contact. We observe evidence of Pt-catalyzed dehydrogenation of side alkyl chains which effectively reduces the metal-semiconductor van der Waals gap and promotes orbital hybridization. We report the ultrahigh performance OFETs, including hole mobility of 18 cm
2
V
−1
s
−1
, saturation current of 28.8 μA/μm, subthreshold swing of 60 mV/dec, and intrinsic cutoff frequency of 0.36 GHz. We further develop resist-free transfer and patterning strategies to fabricate large-area OFET arrays, showing 100% yield and excellent variability in the transistor metrics. As alkyl chains widely exist in conjugated molecules and polymers, our strategy can potentially enhance the performance of a broad range of organic optoelectronic devices.
The limitation in metal-semiconductor contact has been a major challenge for high-performance organic field-effect transistors. Here, the authors fabricate the contact by transferring platinum electrode on solution-processed organic films, realizing ultralow total contact resistance down to 14 Ω ∙ cm.
Journal Article
Discovery and construction of surface kagome electronic states induced by p-d electronic hybridization in Co3Sn2S2
2023
Kagome-lattice materials possess attractive properties for quantum computing applications, but their synthesis remains challenging. Herein, based on the compelling identification of the two cleavable surfaces of Co
3
Sn
2
S
2
, we show surface kagome electronic states (SKESs) on a Sn-terminated triangular Co
3
Sn
2
S
2
surface. Such SKESs are imprinted by vertical
p-d
electronic hybridization between the surface Sn (subsurface S) atoms and the buried Co kagome-lattice network in the Co
3
Sn layer under the surface. Owing to the subsequent lateral hybridization of the Sn and S atoms in a corner-sharing manner, the kagome symmetry and topological electronic properties of the Co
3
Sn layer is proximate to the Sn surface. The SKESs and both hybridizations were verified via qPlus non-contact atomic force microscopy (nc-AFM) and density functional theory calculations. The construction of SKESs with tunable properties can be achieved by the atomic substitution of surface Sn (subsurface S) with other group III-V elements (Se or Te), which was demonstrated theoretically. This work exhibits the powerful capacity of nc-AFM in characterizing localized topological states and reveals the strategy for synthesis of large-area transition-metal-based kagome-lattice materials using conventional surface deposition techniques.
Kagome materials host 2D planes which give rise to kagome physics, but these are typically embedded in the bulk. Huang et al. demonstrate a strategy for generating surface kagome electronic states by vertical
p-d
electronic hybridization between surface atoms and the buried Co kagome network in Co
3
Sn
2
S
2
.
Journal Article
Atomically engineering interlayer symmetry operations of two-dimensional crystals
2024
Crystal symmetry, which governs the local atomic coordination and bonding environment, is one of the paramount constituents that intrinsically dictate materials’ functionalities. However, engineering crystal symmetry is not straightforward due to the isotropically strong covalent/ionic bonds in crystals. Layered two-dimensional materials offer an ideal platform for crystal engineering because of the ease of interlayer symmetry operations. However, controlling the crystal symmetry remains challenging due to the ease of gliding perpendicular to the Z direction. Herein, we proposed a substrate-guided growth mechanism to atomically fabricate AB′-stacked SnSe
2
superlattices, containing alternating SnSe
2
slabs with periodic interlayer mirror and gliding symmetry operations, by chemical vapor deposition. Some higher-order phases such as 6 R, 12 R, and 18 C can be accessed, exhibiting modulated nonlinear optical responses suggested by first-principle calculations. Charge transfer from mica substrates stabilizes the high-order SnSe
2
phases. Our approach shows a promising strategy for realizing topological phases via stackingtronics.
van der Waals (vdW) materials offer unique opportunities to engineer their crystal symmetry, but usually require top-down fabrication approaches. Here, the authors report a mica substrate-guided bottom-up method to grow exotic phases of SnSe
2
and other vdW materials, showing tunable nonlinear optical properties.
Journal Article
Realizing nearly-free-electron like conduction band in a molecular film through mediating intermolecular van der Waals interactions
2019
Collective molecular physical properties can be enhanced from their intrinsic characteristics by templating at material interfaces. Here we report how a black phosphorous (BP) substrate concatenates a nearly-free-electron (NFE) like conduction band of a C
60
monolayer. Scanning tunneling microscopy reveals the C
60
lowest unoccupied molecular orbital (LUMO) band is strongly delocalized in two-dimensions, which is unprecedented for a molecular semiconductor. Experiment and theory show van der Waals forces between C
60
and BP reduce the inter-C
60
distance and cause mutual orientation, thereby optimizing the π-π wave function overlap and forming the NFE-like band. Electronic structure and carrier mobility calculations predict that the NFE band of C
60
acquires an effective mass of 0.53–0.70
m
e
(
m
e
is the mass of free electrons), and has carrier mobility of ~200 to 440 cm
2
V
−1
s
−1
. The substrate-mediated intermolecular van der Waals interactions provide a route to enhance charge delocalization in fullerenes and other organic semiconductors.
Fullerenes are promising organic semiconducting materials for electronic applications, but of low conductivity due to limited intermolecular hybridization. Cui et al. show a black phosphorous substrate organizes C
60
monolayers to form delocalized semiconducting band with tens times enhanced conductivity.
Journal Article
Shallowing interfacial carrier trap in transition metal dichalcogenide heterostructures with interlayer hybridization
by
Wang, Cong
,
Wang, Yeliang
,
Shao, Yan
in
Atomic/Molecular Structure and Spectra
,
Bilayers
,
Biomedicine
2021
With the unique properties, layered transition metal dichalcogenide (TMD) and its heterostructures exhibit great potential for applications in electronics. The electrical performance, e.g., contact barrier and resistance to electrodes, of TMD heterostructure devices can be significantly tailored by employing the functional layers, called interlayer engineering. At the interface between different TMD layers, the dangling-bond states normally exist and act as traps against charge carrier flow. In this study, we propose a technique to suppress such carrier trap that uses enhanced interlayer hybridization to saturate dangling-bond states, as demonstrated in a strongly interlayer-coupled monolayer-bilayer PtSe
2
heterostructure. The hybridization between the unsaturated states and the interlayer electronic states of PtSe
2
significantly reduces the depth of carrier traps at the interface, as corroborated by our scanning tunnelling spectroscopic measurements and density functional theory calculations. The suppressed interfacial trap demonstrates that interlayer saturation may offer an efficient way to relay the charge flow at the interface of TMD heterostructures. Thus, this technique provides an effective way for optimizing the interface contact, the crucial issue exists in two-dimensional electronic community.
Journal Article
Deriving phosphorus atomic chains from few-layer black phosphorus
by
Zhangru Xiao Jingsi Qiao Wanglin Lu Guojun Ye Xianhui Chen Ze Zhang Wei Ji Jixue Li Chuanhong Jin
in
Atomic/Molecular Structure and Spectra
,
Biomedicine
,
Biotechnology
2017
Phosphorus atomic chains, the narrowest nanostructures of black phosphorus (BP), are highly relevant to the in-depth development of BP-based one-dimensional (1D) nano-electronics components. In this study, we report a top-down route for the preparation of phosphorus atomic chains via electron beam sculpturing inside a transmission electron microscope (TEM). The growth and dynamics (i.e., rupture and edge migration) of 1D phosphorus chains are experimentally captured for the first time. Furthermore, the dynamic behavior and associated energetics of the as-formed phosphorus chains are further investigated by density functional theory (DFT) calculations. It is hoped that these 1D BP structures will serve as a novel platform and inspire further exploration of the versatile properties of BP.
Journal Article
Tuning the Crystalline Phase Transition Temperature of 1T‐TaS2 via Surface Oxidation
2025
Owning various and unique properties, the crystalline phases of transition metal dichalcogenides (TMDs) and the introduced phase engineering have a range of potential applications in future devices. The phase transition temperature, corresponding to the stability of the atomic structural phase, is one of the key parameters in the phase engineering study. However, the reported method for tuning the transition temperature is always complicated and brings impurities, impairing the properties. Here, tuning the phase transition temperature via the surface oxidation of the octahedral phase (1T)‐TaS2 is reported. The surface characterization results reveal that the phase transition would originate from the sulfur surface sublimation and its induced doping. Then the Ta oxide layer, a surface cap, is fabricated using O2 plasma treatment, without affecting the 1T‐TaS2 under the surface. As revealed by the Raman results, the phase transition temperature of 1T‐TaS2 increase significantly, in contrast to the samples without oxidation. The work provides a facile and effective method to tune the phase of the TMDs, toward the fabrication of the nanostructure based on the phase engineering for future applications. The critical temperature of the 1T‐ to 2H‐TaS2 phase transition can be tuned via the surface oxidation process, which originates from the sulfur surface sublimation and its induced doping. This work provides a facile and effective method to tune the phase of the TMDs, toward the fabrication of the nanostructure based on the phase engineering for future applications.
Journal Article