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As scaling down the size of metal oxide semiconductor field-effect transistors (FETs), power dissipation has become a major challenge. Lowering down the sub-threshold swing (SS) is known as an effective technique to decrease the operating voltage of FETs and hence lower down the power consumption. However, the Boltzmann distribution of electrons (so-called 'Boltzmann tyranny') implements a physical limit to the SS value. Use of negative capacitance (NC) effect has enabled a new path to achieve a low SS below the Boltzmann limit (60 mV dec-1at room temperature). In this work, we have demonstrated a NC-FET from an all two-dimensional (2D) metal ferroelectric semiconductor (MFS) vertical heterostructure: Graphene/CuInP2S6/MoS2. The negative capacitance from the ferroelectric CuInP2S6has enabled the breaking of the 'Boltzmann tyranny'. The heterostructure based device has shown steep slopes switching below 60 mV dec-1(lowest to < 10 mV dec-1) over 3 orders of source-drain current, which provides an avenue for all 2D material based steep slope FETs.
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Two-dimensional (2D) MoS2, which has great potential for optoelectronic and other applications, is thermodynamically stable and hence easily synthesized in its semiconducting 2H phase. In contrast, growth of its metastable 1T and 1T' phases is hampered by their higher formation energy. Here we use theoretical calculations to design a potassium (K)-assisted chemical vapour deposition method for the phase-selective growth of 1T' MoS2 monolayers and 1T'/2H heterophase bilayers. This is realized by tuning the concentration of K in the growth products to invert the stability of the 1T' and 2H phases. The synthesis of 1T' MoS2 monolayers with high phase purity allows us to characterize their intrinsic optical and electrical properties, revealing a characteristic in-plane anisotropy. This phase-controlled bottom-up synthesis offers a simple and efficient way of manipulating the relevant device structures, and provides a general approach for producing other metastable-phase 2D materials with unique properties.
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Corrugation is a ubiquitous phenomenon for graphene grown on metal substrates by chemical vapor deposition, which greatly affects the electrical, mechanical, and chemical properties. Recent years have witnessed great progress in controlled growth of large graphene single crystals; however, the issue of surface roughness is far from being addressed. Here, the corrugation at the interface of copper (Cu) and graphene, including Cu step bunches (CuSB) and graphene wrinkles, are investigated and ascribed to the anisotropic strain relaxation. It is found that the corrugation is strongly dependent on Cu crystallographic orientations, specifically, the packed density and anisotropic atomic configuration. Dense Cu step bunches are prone to form on loose packed faces due to the instability of surface dynamics. On an anisotropic Cu crystal surface, Cu step bunches and graphene wrinkles are formed in two perpendicular directions to release the anisotropic interfacial stress, as revealed by morphology imaging and vibrational analysis. Cu(111) is a suitable crystal face for growth of ultraflat graphene with roughness as low as 0.20 nm. It is believed the findings will contribute to clarifying the interplay between graphene and Cu crystal faces, and reducing surface roughness of graphene by engineering the crystallographic orientation of Cu substrates.
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Identification of the crystalline axis of anisotropic black phosphorus (BP) is important for investigating its physical properties, as well as for optical and electronic applications. Herein, it is showed that by applying in-plane uniaxial strain and measuring the changes of the Raman shifts, the crystalline axis of BP can be reliably determined. The strain effects on the Raman shifts are angle-dependent, and they can be expressed as a combination of the Raman responses under zigzag and armchair strain. Differing from previous polarized optical spectroscopic methods where the Raman intensity is analyzed, the proposed method uses the Raman frequency shift, which is less affected by laser polarization, excitation wavelength, the sample thickness, and the substrate. The effective strain applied on BP from the stretched substrate is estimated, and the results show that only 20 to 40% of the strain can be effectively transferred to BP flakes from a polyethylene terephthalate substrate. Our method provides not only an effective and robust approach to identify the crystalline orientation of layered BP, but it is also a model to extract additional information in strain-related studies. It can also be extended to other 2D anisotropic materials.
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The striking in-plane anisotropy remains one of the most intriguing properties for the newly rediscovered black phosphorus (BP) 2D crystals. However, because of its rather low-energy band gap, the optical anisotropy of few-layer BP has been primarily investigated in the near-infrared (NIR) regime. Moreover, the essential physics that determine the intrinsic anisotropic optical property of few-layer BP, which is of great importance for practical applications in optical and optoelectronic devices, are still in the fancy of theory. Herein, we report the direct observation of the optical anisotropy of few-layer BP in the visible regime simply by using polarized optical microscopy. On the basis of the Fresnel equation, the intrinsic anisotropic complex refractive indices (n-iκ) in the visible regime (480-650 nm) were experimentally obtained for the first time using the anisotropic optical contrast spectra. Our findings not only provide a convenient approach to measure the optical constants of 2D layered materials but also suggest a possibility to design novel BP-based photonic devices such as atom-thick light modulators, including linear polarizer, phase plate, and optical compensator in a broad spectral range extending to the visible window.
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The incident and scattered light engaged in the Raman scattering process of low symmetry crystals always suffer from the birefringence-induced depolarization. Therefore, for anisotropic crystals, the classical Raman selection rules should be corrected by taking the birefringence effect into consideration. The appearance of the 2D anisotropic materials provides an excellent platform to explore the birefringence-directed Raman selection rules, due to its controllable thickness at the nanoscale that greatly simplifies the situation comparing with bulk materials. Herein, a theoretical and experimental investigation on the birefringence-directed Raman selection rules in the anisotropic black phosphorus (BP) crystals is presented. The abnormal angle-dependent polarized Raman scattering of the Ag modes in thin BP crystal, which deviates from the normal Raman selection rules, is successfully interpreted by the theoretical model based on birefringence. It is further confirmed by the examination of different Raman modes using different laser lines and BP samples of different thicknesses.
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For the application of single-walled carbon nanotubes (SWNTs) in nanoelectronic devices, techniques to obtain horizontally aligned semiconducting SWNTs (s-SWNTs) with higher densities are still in their infancy. We reported herein a rational approach for the preferential growth of densely packed and well-aligned s-SWNTs arrays using oxygen-deficient TiO2 nanoparticles as catalysts. Using this approach, a suitable concentration of oxygen vacancies in TiO2 nanoparticles could form by optimizing the flow rate of hydrogen and carbon sources during the process of SWNT growth, and then horizontally aligned SWNTs with the density of â¼ 10 tubes/µm and the s-SWNT percentage above 95% were successfully obtained on ST-cut quartz substrates. Theoretical calculations indicated that TiO2 nanoparticles with a certain concentration of oxygen vacancies have a lower formation energy between s-SWNT than metallic SWNT (m-SWNT), thus realizing the preferential growth of s-SWNT arrays. Furthermore, this method can also be extended to other semiconductor oxide nanoparticles (i.e., ZnO, ZrO2 and Cr2O3) for the selective growth of s-SWNTs, showing clear potential to the future applications in nanoelectronics.
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For the application of single-walled carbon nanotubes (SWNTs) to electronic and optoelectronic devices, techniques to obtain semiconducting SWNT (s-SWNT) arrays are still in their infancy. We have developed herein a rational approach for the preferential growth of horizontally aligned s-SWNT arrays on a ST-cut quartz surface through the selective scission of C-O and C-C bonds of ethanol using bimetal catalysts, such as Cu/Ru, Cu/Pd, and Au/Pd. For a common carbon source, ethanol, a reforming reaction occurs on Cu or Au upon C-C bond breakage and produces C(ads) and CO, while a deoxygenating reaction occurs on Ru or Pd through C-O bond breaking resulting in the production of O(ads) and C2H4. The produced C2H4 by Ru or Pd can weaken the oxidative environment through decomposition and the neutralization of O(ads). When the bimetal catalysts with an appropriate ratio were used, the produced C(ads) and C2H4 can be used as carbon source for SWNT growth, and O(ads) promotes a suitable and durable oxidative environment to inhibit the formation of metallic SWNTs (m-SWNTs). Finally, we successfully obtained horizontally aligned SWNTs on a ST-cut quartz surface with a density of 4-8 tubes/µm and an s-SWNT ratio of about 93% using an Au/Pd (1:1) catalyst. The synergistic effects in bimetallic catalysts provide a new mechanism to control the growth of s-SWNTs.
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An optical anisotropic nature of black phosphorus (BP) is revealed by angle-resolved polarized Raman spectroscopy (ARPRS), and for the first time, an all-optical method was realized to identify the crystal orientation of BP sheets, that is, the zigzag and armchair directions. We found that Raman intensities of Ag(1), B2g, and Ag(2) modes of BP not only depend on the polarization angle α, but also relate to the sample rotation angle θ. Furthermore, their intensities reach the local maximum or minimum values when the crystalline orientation is along with the polarization direction of scattered light (es). Combining with the angle-resolved conductance, it is confirmed that Ag(2) mode intensity achieves a relative larger (or smaller) local maximum under parallel polarization configuration when armchair (or zigzag) direction is parallel to es. Therefore, ARPRS can be used as a rapid, precise, and nondestructive method to identify the crystalline orientation of BP layers.
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A 2D atomic-layer-thickness phototransistor based on a graphene-MoS2 bybrid device is constructed with a photoresponse much larger than that of individual graphene or MoS2 based phototransistors. Strong and selective light absorption in the MoS2 layer creates electric charges that are transferred to graphene layers derived by a build-in electrical field, where they recirculate many times due to the high carrier mobility of graphene. Gate tunable Fermi level in graphene layer allows the responsivity of this hybrid phototransistor to be continuously tuned from 0 to about 10(4) mA/W by the gate voltage. Furthermore, large scale, flexible, and transparent 2D phototransistors with high responsivity are constructed from the CVD-grown graphene and MoS2 flakes. The high responsivity, gate-tunable sensitivity, wavelength selectivity, and compatibility with current circuit technologies of this type device give it great potential for future application in integrated nano-optoelectronic systems.
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Supramolecular hydrogels (SMHs) are three-dimensional networks filled with a large amount of water. The crosslinking force in the 3D network is always constructed by relatively weak and dynamic non-covalent interactions, and thus SMHs usually possess extremely high susceptibility to external environment and can show extraordinary stimuli-responsive, self-healing or other attractive properties. However, the overall crosslinking force in hydrogel networks is difficult to flexibly modulate, and this leads to limited functions of the SMHs. In this regard, hierarchical hydrogen bonds, that is, the mixture of relatively strong and relatively weak hydrogen bonds, are used herein as crosslinking force for the hydrogel preparation. The ratio of strong and weak hydrogen bonds can be finely tuned to tailor the properties of resultant gels. Thus, by delicate manipulation of the overall crosslinking force in the system, a hydrogel with multiple (thermal, pH and NIR light) responsiveness, autonomous self-healing property and interesting temperature dependent, reversible adhesion behavior is obtained. This kind of hierarchical hydrogen bond manipulation is proved to be a general method for multiple-functionality hydrogel preparation, and the resultant material shows potential for a range of applications.
Assuntos
Hidrogéis/química , Nanotubos de Carbono/química , Adesividade , Hidrogéis/síntese química , Ligação de Hidrogênio , Concentração de Íons de Hidrogênio , Poliaminas/síntese química , Poliaminas/química , Polietilenos/síntese química , Polietilenos/química , Espectroscopia de Luz Próxima ao Infravermelho , TemperaturaRESUMO
The discovery of intrinsic 2D magnetic materials has opened up new opportunities for exploring magnetic properties at atomic layer thicknesses, presenting potential applications in spintronic devices. Here a new 2D ferrimagnetic crystal of nonlayered FeCr2S4 is synthesized with high phase purity using chemical vapor deposition. The obtained 2D FeCr2S4 exhibits perpendicular magnetic anisotropy, as evidenced by the out-of-plane/in-plane Hall effect and anisotropic magnetoresistance. Theoretical calculations further elucidate that the observed magnetic anisotropy can be attributed to its surface termination structure. By combining temperature-dependent magneto-transport and polarized Raman spectroscopy characterizations, it is discovered that both the measured Curie temperature and the critical temperature at which a low energy magnon peak disappeared remains constant, regardless of its thickness. Magnetic force microscopy measurements show the flipping process of magnetic domains. The exceptional air-stability of the 2D FeCr2S4 is also confirmed via Raman spectroscopy and Hall hysteresis loops. The robust anisotropic ferrimagnetism, the thickness-independent of Curie temperature, coupled with excellent air-stability, make 2D FeCr2S4 crystals highly attractive for future spintronic devices.
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In-memory computing is a highly efficient approach for breaking the bottleneck of von Neumann architectures, i.e., reducing redundant latency and energy consumption during the data transfer between the physically separated memory and processing units. Herein we have designed a in-memory computing device, a van der Waals ferroelectric semiconductor (InSe) based metal-oxide-ferroelectric semiconductor field-effect transistor (MOfeS-FET). This MOfeS-FET integrates memory and logic functions in the same material, in which the out-of-plane (OOP) ferroelectric polarization in InSe is used for data storage and the semiconducting property is used for the logic computation. The MOfeS-FET shows a long retention time with high on/off ratios (>106), high program/erase (P/E) ratios (103), and stable cyclic endurance. Moreover, inverter, programmable NAND, and NOR Boolean logic operations with nonvolatile storage of the results have all been demonstrated using our approach. These findings highlight the potential of van der Waals ferroelectric semiconductor-based MOfeS-FETs in the in-memory computing and their potential of achieving size scaling beyond Moore's law.
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A rational approach to investigate the effect of molecular orientation on the intensity of chemical enhancement using graphene-enhanced Raman spectroscopy (GERS) is developed. A planar molecule, copper phthalocyanine (CuPc), is used as probe molecule. Annealing allows the CuPc molecule in a Langmuir-Blodgett film to change orientation from upstanding to lying down. The UV-visible absorption spectra prove the change of the molecular orientation, as well as the variation of the interaction between the CuPc molecule and graphene. The Raman spectra of the molecule in the two different orientations are compared and analyzed. The results show that chemical enhancement is highly sensitive to the molecular orientation. The different molecular orientations induce different magnitudes of the interaction between the molecule and graphene. The stronger the interaction, the more the Raman signal is enhanced. Furthermore, the sensitivity of GERS to molecular orientation is promising to determine the orientation of the molecule on graphene. Based on this molecular orientation sensitive Raman enhancement, quantitative calculation of the magnitude of the chemical enhancement is implemented for a series of Pc derivatives. It shows that the magnitude of the chemical enhancement can be used to evaluate the degree of interaction between the molecules and graphene. Moreover, an understanding of the chemical enhancement in GERS is promoted and the effect of molecular orientation on the intensity of chemical enhancement is explained.
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Constructing 2D heterojunctions with high performance is the critical solution for the optoelectronic applications of 2D materials. This work reports on the studies on the preparation of high-quality van der Waals SiAs single crystals and high-performance photodetectors based on the 2D SiAs/SnS2 heterojunction. The crystals are grown using the chemical vapor transport (CVT) method and then the bulk crystals are exfoliated to a few layers. Raman spectroscopic characterization shows that the low wavenumber peaks from interlayer vibrations shift significantly along with SiAs' thickness. In addition, when van der Waals heterojunctions of p-type SiAs/n-type SnS2 are fabricated, under the source-drain voltage of -1 V-1 V, they exhibit prominent rectification characteristics, and the ratio of forwarding conduction current to reverse shutdown current is close to 102, showing a muted response of 1 A/W under excitation light of 550 nm. The light responsivity and external quantum efficiency are increased by 100 times those of SiAs photodetectors. Our experimental results enrich the research on the IVA-VA group p-type layered semiconductors.
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Recently, ultrathin two-dimensional (2D) metallic vanadium dichalcogenides have attracted widespread attention because of the charge density wave (CDW) phase transition and possible ferromagnetism. Herein, we report the synthesis and temperature-dependent Raman characterization of the 2D vanadium ditelluride (VTe2). The synthesis is done by atmospheric pressure chemical vapor deposition (APCVD) using vanadium chloride (VCl3) precursor on fluorphlogopite mica, sapphire, and h-BN substrates. A large area of the thin film with thickness â¼10 nm is grown on the hexagonal boron nitride (h-BN) substrate. Temperature-dependent Raman characterization of VTe2 is conducted from room temperature to 513 K. Remarkable changes of Raman modes at around 413 K are observed, indicating the structural phase transition.
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The recent discovery of van der Waals magnetic materials has attracted great attention in materials science and spintronics. The preparation of ultrathin magnetic layers down to atomic thickness is challenging and is mostly by mechanical exfoliation. Here, we report vapor deposition of magnetic van der Waals NiI2 crystals. Two-dimensional (2D) NiI2 flakes are grown on SiO2/Si substrates with a thickness of 5-40 nm and on hexagonal boron nitride (h-BN) down to monolayer thickness. Temperature-dependent Raman spectroscopy reveals robust magnetic phase transitions in the as-grown 2D NiI2 crystals down to trilayer. Electrical measurements show a semiconducting transport behavior with a high on/off ratio of 106 for the NiI2 flakes. Lastly, density functional theory calculation shows an intralayer ferromagnetic and interlayer antiferromagnetic ordering in 2D NiI2. This work provides a feasible approach to epitaxy 2D magnetic transition metal halides and also offers atomically thin materials for spintronic devices.
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Layered materials with phase transitions, such as charge density wave (CDW) and magnetic and dipole ordering, have potential to be exfoliated into monolayers and few-layers and then become a large and important subfamily of two-dimensional (2D) materials. Benefitting from enriched physical properties from the collective interactions, long-range ordering, and related phase transitions, as well as the atomic thickness yet having nondangling bonds on the surface, 2D phase-transition materials have vast potential for use in new-concept and functional devices. Here, potential 2D phase-transition materials with CDWs and magnetic and dipole ordering, including transition metal dichalcogenides, transition metal halides, metal thio/selenophosphates, chromium silicon/germanium tellurides, and more, are introduced. The structures and experimental phase-transition properties are summarized for the bulk materials and some of the obtained monolayers. In addition, recent experimental progress on the synthesis and measurement of monolayers, such as 1T-TaS2 , CrI3 , and Cr2 Ge2 Te6 , is reviewed.
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Ultrathin two-dimensional (2D) charge density wave (CDW) materials, with sharp resistance change at the phase-transition temperature, yet with ultrathin thickness, hold great potential for electrical device applications. However, chemical synthesis of high-quality samples and observation of the CDW states down to the monolayer limit is still of great challenge. Chemical vapor deposition of 1T-TaS2 sheets on hexagonal boron nitride (h-BN) with robust CDW states even down to the monolayer extreme is reported here. Further, based on the near commensurate CDW to incommensurate CDW phase transition with a high temperature coefficient of resistance (TCR), highly responsive room-temperature bolometers are fabricated by suspending the as-grown 1T-TaS2 sheets.