We introduce the 2D counterpart of layered black phosphorus, which we call phosphorene, as an unexplored p-type semiconducting material. Same as graphene and MoS2, single-layer phosphorene is flexible and can be mechanically exfoliated. We find phosphorene to be stable and, unlike graphene, to have an inherent, direct, and appreciable band gap. Our ab initio calculations indicate that the band gap is direct, depends on the number of layers and the in-layer strain, and is significantly larger than the bulk value of 0.31-036 eV. The observed photoluminescence peak of single-layer phosphorene in the visible optical range confirms that the band gap is larger than that of the bulk system. Our transport studies indicate a hole mobility that reflects the structural anisotropy of phosphorene and complements n-type MoS2. At room temperature, our few-layer phosphorene field-effect transistors with 1.0 mu m channel length display a high on-current of 194 mA/mm, a high hole field-effect mobility of 286 cm(2) N.s, and an on/off ratio of up to 10(4). We demonstrate the possibility of phosphorene integration by constructing a 2D CMOS inverter consisting of phosphorene PMOS and MoS2 NMOS transistors.
The isolation of graphene in 2004 from graphite was a defining moment for the "birth" of a field: two-dimensional (20) materials. In recent years, there has been a rapidly increasing number of papers focusing on non-graphene layered materials, including transition-metal dichalcogenides (TMDs), because of the new properties and applications that emerge upon 2D confinement. Here, we review significant recent advances and important new developments in 2D materials "beyond graphene". We provide insight into the theoretical modeling and understanding of the van der Waals (vdW) forces that hold together the 20 layers in bulk solids, as well as their excitonic properties and growth morphologies. Additionally, we highlight recent breakthroughs in TMD synthesis and characterization and discuss the newest families of 2D materials, including monoelement 20 materials (i.e., silicene, phosphorene, etc.) and transition metal carbide- and carbon nitride-based MXenes. We then discuss the doping and functionalization of 2D materials beyond graphene that enable device applications, followed by advances in electronic, optoelectronic, and magnetic devices and theory. Finally, we provide perspectives on the future of 20 materials beyond graphene.
The past decade has witnessed an extraordinary increase in research progress on ultrathin two-dimensional (2D) nanomaterials in the fields of condensed matter physics, materials science, and chemistry after the exfoliation of graphene from graphite in 2004. This unique class of nanomaterials has shown many unprecedented properties and thus is being explored for numerous promising applications. In this Perspective, I briefly review the state of the art in the development of ultrathin 2D nanomaterials and highlight their unique advantages. Then, I discuss the typical synthetic methods and some promising applications of ultrathin 2D nanomaterials together with some personal insights on the challenges in this research area. Finally, on the basis of the current achievement on ultrathin 2D nanomaterials, I give some personal perspectives on potential future research directions.
Organometal halide perovskites are inexpensive materials with desirable characteristics of color-tunable and narrow-band emissions for lighting and display technology, but they suffer from low photoluminescence quantum yields at low excitation fluencies. Here we developed a ligand-assisted reprecipitation strategy to luminescent and color-tunable colloidal CH3NH3PbX3 (X = Br, I, Cl) quantum dots with absolute quantum yield up to 70% at room temperature and low excitation fluencies. To illustrate the photoluminescence enhancements in these quantum dots, we conducted comprehensive composition and surface characterizations and determined the time- and temperature-dependent photoluminescence spectra. Comparisons between small-sized CH3NH3PbBr3 quantum dots (average diameter 3.3 nm) and corresponding micrometer-sized bulk particles (2-8 mu m) suggest that the intense increased photoluminescence quantum yield originates from the increase of exciton binding energy due to size reduction as well as proper chemical passivations of the Br-rich surface. We further demonstrated wide-color gamut white-light-emitting diodes using green emissive CH3NH3PbBr3 quantum dots and red emissive K2SiF6:Mn4+ as color converters, providing enhanced color quality for display technology. Moreover, colloidal CH3NH3PbBX3 quantum dots are expected to exhibit interesting nanoscale excitonic properties and also have other potential applications in lasers, electroluminescence devices, and optical sensors.
A new phototransistor based on the mechanically exfoliated single-layer MoS2 nanosheet is fabricated, and Its light-induced electric properties are investigated in detail. Photocurrent generated from the phototransistor is solely determined by the illuminated optical power at a constant drain or gate voltage. The switching behavior of photocurrent generation and annihilation can be completely finished within ca. 50 ms, and it shows good stability. Especially, the single-layer MoS2 phototransistor exhibits a better photoresponsivity as compared with the graphene-based device. The unique characteristics of Incident-light control, prompt photoswitching, and good photoresponsivity from the MoS2 phototransistor pave an avenue to develop the single-layer semiconducting materials for multifunctional optoelectronic device applications in the future.
Carbon dots (CDs) with tunable photoluminescence (PL) and a quantum yield of up to 35% in water were hydrothermally synthesized in one pot and separated via silica column chromatography. These separated CDs emitted bright and stable luminescence in gradient colors from blue to red under a single-wavelength UV light. They exhibited high optical uniformity; that is, every sample showed only one peak in the PL excitation spectrum, only one peak in the excitation-independent PL emission spectrum, and similar monoexponential fluorescence lifetimes. Although these samples had similar distributions of particle size and graphite structure in their carbon cores, the surface state gradually varied among the samples, especially the degree of oxidation. Therefore, the observed red shift in their emission peaks from 440 to 625 nm was ascribed to a gradual reduction in their band gaps with the increasing incorporation of oxygen species into their surface structures. These energy bands were found to depend on the surface groups and structures but not on the particle size, not as in traditional semiconductor quantum dots. In addition, because of their excellent PL properties and low cytotoxicity, these CDs could be used to image cells in different colors under a single-wavelength light source, and the red-emitting CDs could be used to image live mice because of the strong penetration capability of their fluorescence.
With advances in exfoliation and synthetic techniques, atomically thin films of semiconducting transition metal dichalcogenides have recently been isolated and characterized. Their two-dimensional structure, coupled with a direct band gap in the visible portion of the electromagnetic spectrum, suggests suitability for digital electronics and optoelectronics. Toward that end, several classes of high-performance devices have been reported along with significant progress in understanding their physical properties. Here, we present a review of the architecture, operating principles, and physics of electronic and optoelectronic devices based on ultrathin transition metal dichalcogenide semiconductors. By critically assessing and comparing the performance of these devices with competing technologies, the merits and shortcomings of this emerging class of electronic materials are identified, thereby providing a roadmap for future development.
Hierarchical porous nitrogen-doped carbon (HPNC) nanosheets (NS) have been prepared via simultaneous activation and graphitization of biomass-derived natural silk. The as-obtained HPNC-NS show favorable features for electrochemical energy storage such as high specific surface area (S-BET: 2494 m(2)/g), high volume of hierarchical pores (2.28 cm(3)/g), nanosheet structures, rich N-doping (4.7%), and defects. With respect to the multiple synergistic effects of these features, a lithium-ion battery anode and a two-electrode-based supercapacitor have been prepared. A reversible lithium storage capacity of 1865 mA h/g has been reported, which is the highest for N-doped carbon anode materials to the best of our knowledge. The HPNC-NS supercapacitor's electrode in ionic liquid,electrolytes exhibit a capacitane of 242 F/g and energy density of 102 W h/kg (48W h/L), with high cycling life stability (9% loss after 10 000 cycles). Thus, a high-performance Li-ion battery and supercapacitors were successfully assembled for the same electrode material, which was obtained through a one-step and facile large-scale synthesis route. It is promising for next-generation hybrid energy storage and renewable delivery devices.
Perovskite compounds have attracted recently great attention in photovoltaic research. The devices are typically fabricated using condensed or mesoporous TiO2 as the electron transport layer and 2,2'7,7'-tetrakis-(N,N-dip-methoxyphenylamine)9,9'-spirobifluorene as the hole transport layer. However, the high-temperature processing (450 degrees C) requirement of the TiO2 layer could hinder the widespread adoption of the technology. In this report, we adopted a low-temperature processing technique to attain high-efficiency devices in both rigid and flexible substrates, using device structure substrate/ITO/PEDOT:PSS/CH(3)NH(3)Pbl(3-x)Cl(x)/PCBM/Al, where PEDOT:PSS and PCBM are used as hole and electron transport layers, respectively. Mixed halide perovskite, CH(3)NH(3)Pbl(3-x)Cl(x) was used due to its long carrier lifetime and good electrical properties. All of these layers are solution-processed under 120 degrees C. Based on the proposed device structure, power conversion efficiency (PCE) of 11.5% is obtained in rigid substrates (glass/ITO), and a 9.2% PCE is achieved for a polyethylene terephthalate/ITO flexible substrate.
The demand for flexible and wearable electronic devices is increasing due to their facile interaction with human body. Flexible, stretchable and wearable sensors can be easily mounted on clothing or directly attached onto the body. Especially, highly stretchable and sensitive strain sensors are needed for the human motion detection. Here, we report highly flexible, stretchable and sensitive strain sensors based on the nanocomposite of silver nanowire (AgNW) network and PDMS elastomer in the form of the sandwich structure (i.e., AgNW thin film embedded between two layers of PDMS). The AgNW network-elastomer nanocomposite based strain sensors show strong piezoresistivity with tunable gauge factors in the ranges of 2 to 14 and a high stretchability up to 70%. We demonstrate the applicability of our high performance strain sensors by fabricating a glove Integrated with five strain sensors for the motion detection of fingers and control of an avatar in the virtual environment.
Perovskite solar cells have rapidly advanced to the forefront of solution-processable photovoltaic devices, but the CH3NH3PbI3 semiconductor decomposes rapidly in moist air, limiting their commercial utility. In this work, we report a quantitative and systematic investigation of perovskite degradation processes. By carefully controlling the relative humidity of an environmental chamber and using in situ absorption spectroscopy and in situ grazing incidence X-ray diffraction to monitor phase changes in perovskite degradation process, we demonstrate the formation of a hydrated intermediate containing isolated PbI64- octahedra as the first step of the degradation mechanism. We also show that the identity of the hole transport layer can have a dramatic impact on the stability of the underlying perovskite film, suggesting a route toward perovskite solar cells with long device lifetimes and a resistance to humidity.
Phosphorene, a elemental 2D material, which is the monolayer of black phosphorus, has been mechanically exfoliated recently. In its bulk form, black phosphorus shows high carrier mobility (similar to 10000 cm(2)/V.s) and a similar to 0.3 eV direct band gap. Well-behaved p-type field-effect transistors with mobilities of up to 1000 cm(2)/V.s, as well as phototransistors, have been demonstrated on few-layer black phosphorus, showing its promise for electronics and optoelectronics applications due to its high hole mobility and thickness dependent direct band gap. However, p-n junctions, the basic building blocks of modem electronic and optoelectronic devices, have not yet been realized based on black phosphorus. In this paper, we demonstrate a gate-tunable p-n diode based on a p-type black phosphorus/n-type monolayer MoS2 van der Waals p-n heterojunction. Upon illumination, these ultrathin p-n diodes show a maximum photodetection responsivity of 418 mA/W at the wavelength of 633 nm and photovoltaic energy conversion with an external quantum efficiency of 0.3%. These p-n diodes show promise for broad-band photodetection and solar energy harvesting.
Organic-inorganic metal halide perovskites have recently emerged as a top contender to be used as an absorber material in highly efficient, low-cost photovoltaic devices. Solution-processed semiconductors tend to have a high density of defect states and exhibit a large degree of electronic disorder. Perovskites appear to go against this trend, and despite relatively little knowledge of the impact of electronic defects, certified solar-to-electrical power conversion efficiencies of up to 17.9% have been achieved. Here, through treatment of the crystal surfaces with the Lewis bases thiophene and pyridine, we demonstrate significantly reduced nonradiative electron-hole recombination within the CH3NH3PbI3-xClx perovskite, achieving photoluminescence lifetimes which are enhanced by nearly an order of magnitude, up to 2 mu s. We propose that this is due to the electronic passivation of under-coordinated Pb atoms within the crystal. Through this method of Lewis base passivation, we achieve power conversion efficiencies for solution-processed planar heterojunction solar cells enhanced from 13% for the untreated solar cells to 15.3% and 16.5% for the thiophene and pyridine-treated solar cells, respectively.
Triboelectrification is an effect that is known to each and every one probably since ancient Greek time, but it is usually taken as a negative effect and is avoided in many technologies. We have recently invented a triboelectric nanogenerator (TENG) that is used to convert mechanical energy into electricity by a conjunction of triboelectrification and electrostatic induction. As for this power generation unit, in the inner circuit, a potential is created by the triboelectric effect due to the charge transfer between two thin organic/inorganic films that exhibit opposite tribo-polarity; in the outer circuit, electrons are driven to flow between two electrodes attached on the back sides of the films in order to balance the potential. Since the most useful materials for TENG are organic, it is also named organic nanogenerator, which is the first using organic materials for harvesting mechanical energy. In this paper, we review the fundamentals of the TENG in the three basic operation modes: vertical contact-separation mode, in-plane sliding mode, and single-electrode mode. Ever since the first report of the TENG in January 2012, the output power density of TENG has been improved 5 orders of magnitude within 12 months. The area power density reaches 313 W/m(2), volume density reaches 490 kW/m(3), and a conversion efficiency of similar to 60% has been demonstrated. The TENG can be applied to harvest all kinds of mechanical energy that is available but wasted in our daily life, such as human motion, walking, vibration, mechanical triggering, rotating tire, wind, flowing water, and more. Alternatively, TENG can also be used as a self-powered sensor for actively detecting the static and dynamic processes arising from mechanical agitation using the voltage and current output signals of the TENG, respectively, with potential applications for touch pad and smart skin technologies. To enhance the performance of the TENG, besides the vast choices of materials in the triboelectric series, from polymer to metal and to fabric, the morphologies of their surfaces can be modified by physical techniques with the creation of pyramid-, square-, or hemisphere-based micro- or nanopatterns, which are effective for enhancing the contact area and possibly the triboelectrification. The surfaces of the materials can be functionalized chemically using various molecules, nanotubes, nanowires, or nanoparticles, in order to enhance the triboelectric effect. The contact materials can be composites, such as embedding nanoparticles in a polymer matrix, which may change not only the surface electrification but also the permittivity of the materials so that they can be effective for electrostatic induction. Therefore, there are numerous ways to enhance the performance of the TENG from the materials point of view. This gives an excellent opportunity for chemists and materials scientists to do extensive study both in the basic science and in practical applications. We anticipate that a better enhancement of the output power density will be achieved in the next few years. The TENG is possible not only for self-powered portable electronics but also as a new energy technology with potential to contribute to the world energy in the near future.
Nanoporous carbon and nanoporous cobalt oxide (Co3O4) materials have been selectively prepared from a single metal organic framework (MOF) (zeolitic imidazolate framework, ZIF-67) by optimizing the annealing conditions. The resulting ZIF-derived carbon possesses highly graphitic walls and a high specific surface area of 350 m(2) g(-1), while the resulting ZIF-derived nanoporous Co3O4 possesses a high specific surface area of 148 m(2).g(-1) with much less carbon content (1.7 at%). When nanoporous carbon and nanoporous Co3O4 were tested as electrode materials for supercapacitor application, they showed high capacitance values (272 and 504 F.g(-1), respectively, at a scan rate of 5 mV.s(-1)). To further demonstrate the advantages of our ZIF-derived nanoporous materials, symmetric (SSCs) and asymmetric supercapacitors (ASCs) were also fabricated using nanoporous carbon and nanoporous Co3O4 electrodes. Improved capacitance performance was successfully realized for the AS( (Co3O4/carbon), better than those of the SSCs based on nanoporous carbon and nanoporous Co3O4 materials (i.e., carbon//carbon and Co3O4//Co3O4). The developed AS( with an optimal mass loading can be operated within a wide potential window of 0.0-1.6 V, which leads to a high specific energy of 36 W. h. kg(-1). More interestingly, this ASC also exhibits excellent rate capability (with the highest specific power of 8000 W. kg-1 at a specific energy of 15 W.h.kg(-1)) combined with long-term stability up to 2000 cycles.
Due to the recent expanding Interest in two-dimensional layered materials, molybdenum disulfide (MoS2) has been receiving much research attention. Having an ultrathin layered structure and an appreciable direct band gap of 1.9 eV in the monolayer regime, few-layer MoS2 has good potential applications in nanoelectronics, optoelectronics, and flexible devices. In addition, the capability of controlling spin and valley degrees of freedom makes it a promising material for spintronic and valleytronic devices. In this review, we attempt to provide an overview of the research relevant to the structural and physical properties, fabrication methods, and electronic devices of few-layer MoS2. Recent developments and advances in studying the material are highlighted.
Delamination of layer materials into two-dimensional single atom sheets has induced exceptional physical properties, including large surface area, ultrahigh intrinsic carrier mobility, pronounced changes in the energy band structure, and other properties. Here, atomically thin mesoporous nanomesh of graphitic carbon nitride (g-C3N4) is fabricated by solvothermal exfoliation of mesoporous g-C3N4 bulk made from thermal polymerization of freeze-drying assembled Dicyandiamide nanostructure precursor. With the unique structural advantages for aligned energy levels, electron transfer, light harvesting, and the richly available reaction sites, the as-prepared monolayer of mesoporous g-C3N4 nanomesh exhibits a superior photocatalytic hydrogen evolution rate of 8510 mu mol h(-1) g(-1) under lambda > 420 nm and an apparent quantum efficiency of 5.1% at 420 nm, the highest of all the metal-free g-C3N4 nanosheets photocatalysts.
The abundant reserve and low cost of sodium have provoked tremendous evolution of Na-ion batteries (SIBs) in the past few years, but their performances are still limited by either the specific capacity or rate capability. Attempts to pursue high rate ability with maintained high capacity in a single electrode remains even more challenging. Here, an elaborate self-branched 2D SnS2 (B-SnS2) nanoarray electrode is designed by a facile hot bath method for Na storage. This interesting electrode exhibits areal reversible capacity of ca. 3.7 mAh cm(-2) (900 mAh g(-1)) and rate capability of 1.6 mAh cm(-2) (400 mAh g(-1)) at 40 mA cm(-2) (10 A g(-1)). Improved extrinsic pseudocapacitive contribution is demonstrated as the origin of fast kinetics of an alloying-based SnS2 electrode. Sodiation dynamics analysis based on first-principles calculations, ex-situ HRTEM, in situ impedance, and in situ Raman technologies verify the S-edge effect on the fast Na+ migration and reversible and sensitive structure evolution during high-rate charge/discharge. The excellent alloying-based pseudocapacitance and unsaturated edge effect enabled by self-branched surface nano engineering could be a promising strategy for promoting development of SIBs with both high response.
Lead halide perovskite materials have attracted significant attention in the context of photovoltaics and other optoelectronic applications, and recently, research efforts have been directed to nanostructured lead halide perovskites. Collodial nanocrystals (NCs) of cesium lead halides (CsPbX3, X = Cl, Br, I) exhibit bright photoluminescence, with emission tunable over the entire visible spectral region. However, previous studies on CsPbX3 NCs did not address key aspects of their chemistry and photophysics such as surface chemistry and quantitative light absorption. Here, we elaborate on the synthesis of CsPbBr3 NCs and their surface chemistry. In addition, the intrinsic absorption coefficient was determined experimentally by combining elemental analysis with accurate optical absorption measurements. H-1 solution nuclear magnetic resonance spectroscopy was used to characterize sample purity, elucidate the surface chemistry, and evaluate the influence of purification methods on the surface composition. We find that ligand binding to the NC surface is highly dynamic, and therefore, ligands are easily lost during the isolation and purification procedures. However, when a small amount of both oleic acid and oleylamine is added, the NCs can be purified, maintaining optical, colloidal, and material integrity. In addition, we find that a high amine content in the ligand shell increases the quantum yield due to the improved binding of the carboxylic acid.