Showing papers on "Band gap published in 2009"
TL;DR: In this article, first-principles electronic structure calculations of the layered, stoichiometric crystals Sb2Te3, Bi2Se3, SbSe3 and BiSe3 were performed.
Abstract: Topological insulators are new states of quantum matter in which surface states residing in the bulk insulating gap of such systems are protected by time-reversal symmetry. The study of such states was originally inspired by the robustness to scattering of conducting edge states in quantum Hall systems. Recently, such analogies have resulted in the discovery of topologically protected states in two-dimensional and three-dimensional band insulators with large spin–orbit coupling. So far, the only known three-dimensional topological insulator is BixSb1−x, which is an alloy with complex surface states. Here, we present the results of first-principles electronic structure calculations of the layered, stoichiometric crystals Sb2Te3, Sb2Se3, Bi2Te3 and Bi2Se3. Our calculations predict that Sb2Te3, Bi2Te3 and Bi2Se3 are topological insulators, whereas Sb2Se3 is not. These topological insulators have robust and simple surface states consisting of a single Dirac cone at the Γ point. In addition, we predict that Bi2Se3 has a topologically non-trivial energy gap of 0.3 eV, which is larger than the energy scale of room temperature. We further present a simple and unified continuum model that captures the salient topological features of this class of materials. First-principles calculations predict that Bi2Se3, Bi2Te3 and Sb2Te3 are topological insulators—three-dimensional semiconductors with unusual surface states generated by spin–orbit coupling—whose surface states are described by a single gapless Dirac cone. The calculations further predict that Bi2Se3 has a non-trivial energy gap larger than the energy scale kBT at room temperature.
4,982 citations
TL;DR: This semilocal exchange potential, which recovers the local-density approximation for a constant electron density, mimics very well the behavior of orbital-dependent potentials and leads to calculations which are barely more expensive than LDA calculations, which can be applied to very large systems in an efficient way.
Abstract: A modified version of the exchange potential proposed by Becke and Johnson [J Chem Phys 124, 221101 (2006)101063/12213970] is tested on solids for the calculation of band gaps The agreement with experiment is very good for all types of solids we considered (eg, wide band gap insulators, sp semiconductors, and strongly correlated 3d transition-metal oxides) and is of the same order as the agreement obtained with the hybrid functionals or the GW methods This semilocal exchange potential, which recovers the local-density approximation (LDA) for a constant electron density, mimics very well the behavior of orbital-dependent potentials and leads to calculations which are barely more expensive than LDA calculations Therefore, it can be applied to very large systems in an efficient way
4,169 citations
TL;DR: This work demonstrates a gate-controlled, continuously tunable bandgap of up to 250 meV and suggests novel nanoelectronic and nanophotonic device applications based on graphene that have eluded previous attempts.
Abstract: The electronic bandgap is an intrinsic property of semiconductors and insulators that largely determines their transport and optical properties. As such, it has a central role in modern device physics and technology and governs the operation of semiconductor devices such as p-n junctions, transistors, photodiodes and lasers. A tunable bandgap would be highly desirable because it would allow great flexibility in design and optimization of such devices, in particular if it could be tuned by applying a variable external electric field. However, in conventional materials, the bandgap is fixed by their crystalline structure, preventing such bandgap control. Here we demonstrate the realization of a widely tunable electronic bandgap in electrically gated bilayer graphene. Using a dual-gate bilayer graphene field-effect transistor (FET) and infrared microspectroscopy, we demonstrate a gate-controlled, continuously tunable bandgap of up to 250 meV. Our technique avoids uncontrolled chemical doping and provides direct evidence of a widely tunable bandgap-spanning a spectral range from zero to mid-infrared-that has eluded previous attempts. Combined with the remarkable electrical transport properties of such systems, this electrostatic bandgap control suggests novel nanoelectronic and nanophotonic device applications based on graphene.
3,268 citations
TL;DR: The results establish that Bi2Te3 is a simple model system for the three-dimensional topological insulator with a single Dirac cone on the surface, and points to promising potential for high-temperature spintronics applications.
Abstract: Three-dimensional topological insulators are a new state of quantum matter with a bulk gap and odd number of relativistic Dirac fermions on the surface. By investigating the surface state of Bi2Te3 with angle-resolved photoemission spectroscopy, we demonstrate that the surface state consists of a single nondegenerate Dirac cone. Furthermore, with appropriate hole doping, the Fermi level can be tuned to intersect only the surface states, indicating a full energy gap for the bulk states. Our results establish that Bi2Te3 is a simple model system for the three-dimensional topological insulator with a single Dirac cone on the surface. The large bulk gap of Bi2Te3 also points to promising potential for high-temperature spintronics applications.
2,823 citations
TL;DR: In this paper, the elastic constants of 2D honeycomb structures from the strain energy and calculate the Poisson's ratio as well as in-plane stiffness values were revealed, and the properties of these honeycomb materials were compared to those of three-dimensional Group IV and Group III-V compounds.
Abstract: Using first-principles plane wave calculations, we investigate two dimensional honeycomb structure of Group IV elements and their binary compounds, as well as the compounds of Group III-V elements. Based on structure optimization and phonon mode calculations, we determine that 22 different honeycomb materials are stable and correspond to local minima on the Born-Oppenheimer surface. We also find that all the binary compounds containing one of the first row elements, B, C or N have planar stable structures. On the other hand, in the honeycomb structures of Si, Ge and other binary compounds the alternating atoms of hexagons are buckled, since the stability is maintained by puckering. For those honeycomb materials which were found stable, we calculated optimized structures, cohesive energies, phonon modes, electronic band structures, effective cation and anion charges, and some elastic constants. The band gaps calculated within Density Functional Theory using Local Density Approximation are corrected by GW0 method. Si and Ge in honeycomb structure are semimetal and have linear band crossing at the Fermi level which attributes massless Fermion character to charge carriers as in graphene. However, all binary compounds are found to be semiconductor with band gaps depending on the constituent atoms. We present a method to reveal elastic constants of 2D honeycomb structures from the strain energy and calculate the Poisson’s ratio as well as in-plane stiffness values. Preliminary results show that the nearly lattice matched heterostructures of these compounds can offer new alternatives for nanoscale electronic devices. Similar to those of the three-dimensional Group IV and Group III-V compound semiconductors, one deduces interesting correlations among the calculated properties of present honeycomb structures. PACS numbers: 73.22.-f, 61.48.De, 63.22.-m, 62.23.Kn
1,686 citations
TL;DR: The fabrication of a-Si:H nanowires and nanocones function as both absorber and antireflection layers, which offer a promising approach to enhance the solar cell energy conversion efficiency.
Abstract: Hydrogenated amorphous Si (a-Si:H) is an important solar cell material. Here we demonstrate the fabrication of a-Si:H nanowires (NWs) and nanocones (NCs), using an easily scalable and IC-compatible process. We also investigate the optical properties of these nanostructures. These a-Si:H nanostructures display greatly enhanced absorption over a large range of wavelengths and angles of incidence, due to suppressed reflection. The enhancement effect is particularly strong for a-Si:H NC arrays, which provide nearly perfect impedance matching between a-Si:H and air through a gradual reduction of the effective refractive index. More than 90% of light is absorbed at angles of incidence up to 60° for a-Si:H NC arrays, which is significantly better than NW arrays (70%) and thin films (45%). In addition, the absorption of NC arrays is 88% at the band gap edge of a-Si:H, which is much higher than NW arrays (70%) and thin films (53%). Our experimental data agree very well with simulation. The a-Si:H nanocones functio...
1,238 citations
TL;DR: In this paper, the electronic structure of GNRs and GQDs with 2-20 nm lateral dimensions was verified by tunnelling spectroscopy, and it was shown that GNRs with a higher fraction of zigzag edges exhibit a smaller energy gap than a predominantly armchair-edge ribbon of similar width, and the magnitudes of measured GNR energy gaps agree with recent theoretical calculations.
Abstract: Graphene shows promise as a future material for nanoelectronics owing to its compatibility with industry-standard lithographic processing, electron mobilities up to 150 times greater than Si and a thermal conductivity twice that of diamond. The electronic structure of graphene nanoribbons (GNRs) and quantum dots (GQDs) has been predicted to depend sensitively on the crystallographic orientation of their edges; however, the influence of edge structure has not been verified experimentally. Here, we use tunnelling spectroscopy to show that the electronic structure of GNRs and GQDs with 2-20 nm lateral dimensions varies on the basis of the graphene edge lattice symmetry. Predominantly zigzag-edge GQDs with 7-8 nm average dimensions are metallic owing to the presence of zigzag edge states. GNRs with a higher fraction of zigzag edges exhibit a smaller energy gap than a predominantly armchair-edge ribbon of similar width, and the magnitudes of the measured GNR energy gaps agree with recent theoretical calculations.
1,199 citations
TL;DR: In this paper, the adsorption of graphene on metal substrates using first-principles calculations at the level of density-functional theory was studied, and a simple analytical model was developed that describes the Fermi-level shift in graphene in terms of the metal substrate work function.
Abstract: Measuring the transport of electrons through a graphene sheet necessarily involves contacting it with metal electrodes. We study the adsorption of graphene on metal substrates using first-principles calculations at the level of density-functional theory. The bonding of graphene to Al, Ag, Cu, Au, and Pt (111) surfaces is so weak that its unique “ultrarelativistic” electronic structure is preserved. The interaction does, however, lead to a charge transfer that shifts the Fermi level by up to 0.5 eV with respect to the conical points. The crossover from p-type to n-type doping occurs for a metal with a work function ~5.4 eV, a value much larger than the work function of free-standing graphene, 4.5 eV. We develop a simple analytical model that describes the Fermi-level shift in graphene in terms of the metal substrate work function. Graphene interacts with and binds more strongly to Co, Ni, Pd, and Ti. This chemisorption involves hybridization between graphene pz states and metal d states that opens a band gap in graphene, and reduces its work function considerably. The supported graphene is effectively n-type doped because in a current-in-plane device geometry the work-function lowering will lead to electrons being transferred to the unsupported part of the graphene sheet.
1,086 citations
TL;DR: At high energies, the molar extinction coefficient epsilon increases with the Qdot volume d(3) and agrees with theoretical calculations using the Maxwell-Garnett effective medium theory and bulk values for the Q dot dielectric function.
Abstract: We quantitatively investigate the size-dependent optical properties of colloidal PbS nanocrystals or quantum dots (Qdots), by combining the Qdot absorbance spectra with detailed elemental analysis of the Qdot suspensions. At high energies, the molar extinction coefficient epsilon increases with the Qdot volume d(3) and agrees with theoretical calculations using the Maxwell-Garnett effective medium theory and bulk values for the Qdot dielectric function. This demonstrates that quantum confinement has no influence on epsilon in this spectral range, and it provides an accurate method to calculate the Qdot concentration. Around the band gap, epsilon only increases with d(1.3), and values are comparable to the epsilon of PbSe Qdots. The data are related to the oscillator strength f(if) of the band gap transition and results agree well with theoretical tight-binding calculations, predicting a linear dependence of f(if) on d. For both PbS and PbSe Qdots, the exciton lifetime tau is calculated from f(if). We find values ranging between 1 and 3 mus, in agreement with experimental literature data from time-resolved luminescence spectroscopy. Our results provide a thorough general framework to calculate and understand the optical properties of suspended colloidal quantum dots. Most importantly, it highlights the significance of the local field factor in these systems.
1,022 citations
TL;DR: In this article, a review of work on graphene monolayers adsorbed on metal surfaces is presented, with a focus on the metal/graphene interaction. But the authors do not consider the effect of the metal-graphenes interaction on the electronic structure.
927 citations
TL;DR: In this article, a general experimental method to determine the energy ECT of intermolecular charge transfer (CT) states in electron donor-acceptor (D-A) blends from ground state absorption and electrochemical measurements is proposed.
Abstract: Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor–acceptor (D–A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D–A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D–A blends via eVoc = ECT − 0.5 eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1 → CT) occurs when Eg − ECT > 0.1 eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT → T1) can occur when ECT − ET > 0.1 eV. From these relations, it is concluded that in D–A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc = Eg − 0.6 eV) and ii) the singlet–triplet energy gap should be ΔEST < 0.2 eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area.
TL;DR: In this article, the basic principles of x-ray diffraction of thin films and areas of special current interest, such as analysis of non-polar, semipolar and cubic III-nitrides, are reviewed, along with the basic principle of X-ray diffusion of thin thin films, and some useful values needed in calculations, including elastic constants and lattice parameters.
Abstract: The III-nitrides include the semiconductors AlN, GaN and InN, which have band gaps spanning the entire UV and visible ranges. Thin films of III-nitrides are used to make UV, violet, blue and green light-emitting diodes and lasers, as well as solar cells, high-electron mobility transistors (HEMTs) and other devices. However, the film growth process gives rise to unusually high strain and high defect densities, which can affect the device performance. X-ray diffraction is a popular, non-destructive technique used to characterize films and device structures, allowing improvements in device efficiencies to be made. It provides information on crystalline lattice parameters (from which strain and composition are determined), misorientation (from which defect types and densities may be deduced), crystallite size and microstrain, wafer bowing, residual stress, alloy ordering, phase separation (if present) along with film thicknesses and superlattice (quantum well) thicknesses, compositions and non-uniformities. These topics are reviewed, along with the basic principles of x-ray diffraction of thin films and areas of special current interest, such as analysis of non-polar, semipolar and cubic III-nitrides. A summary of useful values needed in calculations, including elastic constants and lattice parameters, is also given. Such topics are also likely to be relevant to other highly lattice-mismatched wurtzite-structure materials such as heteroepitaxial ZnO and ZnSe.
TL;DR: A new low band gap semiconducting polymer, PTB1, was synthesized and found promising for solar energy harvesting, and an external quantum efficiency of 67% and fill-factor of 65% are achieved, both of which are among the highest values reported for a solar cell system based on a lowBand gap polymer.
Abstract: A new low band gap semiconducting polymer, PTB1, was synthesized and found promising for solar energy harvesting. Simple polymer solar cells based on PTB1 and methanofullerene [6,6]-phenyl-C71-butyric acid methyl esters (PC71BM) exhibit a solar conversion efficiency of 5.6%. An external quantum efficiency of 67% and fill-factor of 65% are achieved, both of which are among the highest values reported for a solar cell system based on a low band gap polymer.
TL;DR: In this paper, the authors summarized recent research on and development of semiconductor-based photocatalyst materials that are applicable to environmental remediation and/or chemical synthesis purposes, including the incorporation of noble metal nanoclusters onto the surface of semiconducted particles.
Abstract: This feature article summarizes recent research on and development of semiconductor-based photocatalyst materials that are applicable to environmental remediation and/or chemical synthesis purposes. A wide variety of TiO2 particles and/or films have been studied during the past 30 years because they are the most stable and powerful photocatalysts leading to the degradation of various organic pollutants. The photocatalytic performance of other semiconductor materials such as ZnO, SnO2, WO3, Fe2O3 and CdS has also been intensively investigated. A general limitation in the efficiency of any photocatalytic process is the recombination of the photogenerated charge carriers, i.e., of electrons and holes, following bandgap illumination. Considerable efforts have been made to suppress this recombination and hence to enhance the charge carrier separation and the overall efficiency by means of coupling of different semiconductors with desirable matching of their electronic band structures, or incorporation of noble metal nanoclusters onto the surface of semiconductor photocatalyst particles. Modification of the physicochemical properties, such as particle size, surface area, porosity and/or crystallinity of the semiconductor materials, and optimization of the experimental conditions, such as pH, illumination conditions and/or catalyst loading, during photocatalytic reactions have also been carefully addressed to achieve high reaction rates or yields. To utilize solar energy more efficiently, i.e., to extend the optical absorption of the mostly UV-sensitive photocatalysts into the visible light range, numerous research groups have contributed to the development of novel visible light active photocatalysts. With the application of semiconductors with narrower bandgaps such as CdS, Fe2O3 and WO3 being straightforward choices, doping of wide bandgap semiconductors like TiO2 has been the most popular technique to enhance the catalysts' optical absorption abilities. Research on mixed-oxide-based semiconductor photocatalysts with deliberately modulated band structures has also attracted tremendous attention in the past decade, concentrating on, for example, the generation of H2 and/or O2 from H2O splitting, and the degradation of organic pollutants under visible light irradiation. Both theoretical calculations and experimental results have convincingly shown that the developed materials can serve as highly efficient photocatalysts that are both environmentally and economically significant.
Book•
17 Feb 2009
TL;DR: Theoretical studies on ZnO-based Dilute Magnetic Semiconductors 5.8 as mentioned in this paper Theoretical Studies on DMS 5.7 Magnetic Interactions in DMS 4.2 p-Type Doping 4.1 Doping with Transition Metals 5.4 A Brief Theory of Magnetization 5.6 Measurements Techniques for Identification of Ferromagnetism
Abstract: Preface 1 General Properties of ZnO 1.1 Crystal Structure 1.2 Lattice Parameters 1.3 Electronic Band Structure 1.4 Mechanical Properties 1.5 Vibrational Properties 1.6 Thermal Properties 1.7 Electrical Properties of Undoped ZnO 2 ZnO Growth 2.1 Bulk Growth 2.2 Substrates 2.3 Epitaxial Growth Techniques 3 Optical Properties 3.1 Optical Processes in Semiconductors 3.2 Optical Transitions in ZnO 3.3 Defects in ZnO 3.4 Refractive Index of ZnO and MgZnO 3.5 Stimulated Emission in ZnO 3.6 Recombination Dynamics in ZnO 3.7 Nonlinear Optical Properties 4 Doping of ZnO 4.1 n-Type Doping 4.2 p-Type Doping 5 ZnO-Based Dilute Magnetic Semiconductors 5.1 Doping with Transition Metals 5.2 General Remarks about Dilute Magnetic Semiconductors 5.3 Classification of Magnetic Materials 5.4 A Brief Theory of Magnetization 5.5 Dilute Magnetic Semiconductor Theoretical Aspects 5.6 Measurements Techniques for Identification of Ferromagnetism 5.7 Magnetic Interactions in DMS 5.8 Theoretical Studies on ZnO-Based Magnetic Semiconductors 5.9 Experimental Results on ZnO-Based Dilute Magnetic Semiconductors 6 Bandgap Engineering 6.1 MgxZn1-xO Alloy 6.2 BexZn1-xO Alloy 6.3 CdyZn1-yO Alloy 7 ZnO Nanostructures 7.1 Synthesis of ZnO Nanostructures 7.2 Applications of ZnO Nanostructures 8 Processing, Devices, and Heterostructures 8.1 A Primer to Semiconductor-Metal Contacts 8.2 Ohmic Contacts to ZnO 8.3 Schottky Contacts to ZnO 8.4 Etching of ZnO 8.5 Heterostructure Devices 8.6 Piezoelectric Devices 8.7 Sensors and Solar Cells Based on ZnO Nanostructures 8.8 Concluding Remarks
TL;DR: The progress and developments made so far through these techniques in the visible light photocatalysis with TiO2 and ZnO are encompassed.
TL;DR: It is found that the ionicity of the phase affects its electronic bandgap, infrared adsorption and dielectric constants, and that it arises from the different electronic properties of the B2 pairs and B12 clusters and the resultant charge transfer between them.
Abstract: Boron is an element of fascinating chemical complexity. This arises from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons that could in principle favour metallicity, yet they are sufficiently localized to give rise to an insulating state. This delicately balanced electronic structure is easily modified by pressure, temperature and impurities, making it difficult to establish boron's structure and properties. Oganov et al. have now explored the high-pressure behaviour of boron and uncovered a previously unknown ionic phase consisting of negatively charged icosahedral B12 clusters and positively charged B2 pairs. The ionicity of the new phase strongly affects many of its properties, and arises from the different electronic properties of the B12 clusters and B2 pairs and the resultant charge transfer between them. This paper has explored the high-pressure behaviour of boron and uncovered a new phase that consists of negatively charged icosahedral B12 clusters and positively charged B2 pairs. The ionicity of the new phase strongly affects many of its properties, and arises from the different electronic properties of the B12 clusters and B2 pairs and the resultant charge transfer between them. Boron is an element of fascinating chemical complexity. Controversies have shrouded this element since its discovery was announced in 1808: the new ‘element’ turned out to be a compound containing less than 60–70% of boron, and it was not until 1909 that 99% pure boron was obtained1. And although we now know of at least 16 polymorphs2, the stable phase of boron is not yet experimentally established even at ambient conditions3. Boron’s complexities arise from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons, which would favour metallicity, but they are sufficiently localized that insulating states emerge. However, this subtle balance between metallic and insulating states is easily shifted by pressure, temperature and impurities. Here we report the results of high-pressure experiments and ab initio evolutionary crystal structure predictions4,5 that explore the structural stability of boron under pressure and, strikingly, reveal a partially ionic high-pressure boron phase. This new phase is stable between 19 and 89 GPa, can be quenched to ambient conditions, and has a hitherto unknown structure (space group Pnnm, 28 atoms in the unit cell) consisting of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement. We find that the ionicity of the phase affects its electronic bandgap, infrared adsorption and dielectric constants, and that it arises from the different electronic properties of the B2 pairs and B12 clusters and the resultant charge transfer between them.
TL;DR: A new semiconducting polymer, PDPP3T, with alternating diketopyrrolopyrrole and terthiophene units is presented and the efficiency of the photovoltaic cells was found to be strongly dependent on the molecular weight of PDPp3T and the use of diiodooctane as a processing agent.
Abstract: A new semiconducting polymer, PDPP3T, with alternating diketopyrrolopyrrole and terthiophene units is presented. PDPP3T has a small band gap of 1.3 eV and exhibits nearly balanced hole and electron mobilities of 0.04 and 0.01 cm2 V−1 s−1, respectively, in field-effect transistors (FETs). By the combination of two identical ambipolar transistors, an inverter was constructed that exhibits a gain of ∼30. When PDPP3T was combined with [60]PCBM or [70]PCBM in a 1:2 weight ratio, photovoltaic cells were made that provide a photoresponse up to 900 nm and an AM1.5 power conversion efficiency of 3.8 or 4.7%, respectively. In contrast to the almost constant FET mobility, the efficiency of the photovoltaic cells was found to be strongly dependent on the molecular weight of PDPP3T and the use of diiodooctane as a processing agent.
TL;DR: In this paper, the photocatalytic activity of mesoporous TiO 2 nanorods has been investigated by using an impregnating-calcination method using the hydrothermally prepared titanate nanotubes.
Abstract: Fe-doped TiO 2 (Fe-TiO 2 ) nanorods were prepared by an impregnating-calcination method using the hydrothermally prepared titanate nanotubes as precursors and Fe(NO 3 ) 3 as dopant. The as-prepared samples were characterized by scanning electron microscope, transmission electron microscope, X-ray diffraction, X-ray photoelectron spectroscopy, N 2 adsorption–desorption isotherms and UV–vis spectroscopy. The photocatalytic activity was evaluated by the photocatalytic oxidation of acetone in air under visible-light irradiation. The results show that Fe-doping greatly enhance the visible-light photocatalytic activity of mesoporous TiO 2 nanorods, and when the atomic ratio of Fe/Ti ( R Fe ) is in the range of 0.1–1.0%, the photocatalytic activity of the samples is higher than that of Degussa P25 and pure TiO 2 nanorods. At R Fe = 0.5%, the photocatalytic activity of Fe-TiO 2 nanorods exceeds that of Degussa P25 by a factor of more than two times. This is ascribed to the fact that the one-dimensional nanostructure can enhance the transfer and transport of charge carrier, the Fe-doping induces the shift of the absorption edge into the visible-light range with the narrowing of the band gap and reduces the recombination of photo-generated electrons and holes. Furthermore, the first-principle density functional theory (DFT) calculation further confirms the red shift of absorption edges and the narrowing of band gap of Fe-TiO 2 nanorods.
TL;DR: PBDTTT-C has the potential to be successfully applied in the large-scale manufacturing of polymer solar cells because of its highly efficient photovoltaic performance and more feasible synthesis approach.
Abstract: HOMO level of the PBDTTT-based polymer was successfully reduced by introducing an keton group in place of the ester group. The average PCE of the PBDTTT-based devices reached 6.3% with a champion PCE result of 6.58%. Due to its highly efficient photovoltaic performance and more feasible synthesis approach, PBDTTT-C has the potential to be successfully applied in the large-scale manufacturing of polymer solar cells.
TL;DR: By selectively tuning the crystal structure, this work fabricates highly reproducible polytypic and twin-plane superlattices within single nanowires, which could lead to bandgap engineering and novel electronic behaviour.
Abstract: Semiconductor nanowires show promise for use in nanoelectronics, fundamental electron transport studies, quantum optics and biological sensing. Such applications require a high degree of nanowire growth control, right down to the atomic level. However, many binary semiconductor nanowires exhibit a high density of randomly distributed twin defects and stacking faults, which results in an uncontrolled, or polytypic, crystal structure. Here, we demonstrate full control of the crystal structure of InAs nanowires by varying nanowire diameter and growth temperature. By selectively tuning the crystal structure, we fabricate highly reproducible polytypic and twin-plane superlattices within single nanowires. In addition to reducing defect densities, this level of control could lead to bandgap engineering and novel electronic behaviour.
TL;DR: In this paper, the structural and electronic properties of Cu2ZnSnS4 and Cu2znSnSe4 were studied using first-principles calculations and it was shown that the low energy crystal structure obeys the octet rule and is the kesterite structure.
Abstract: The structural and electronic properties of Cu2ZnSnS4 and Cu2ZnSnSe4 are studied using first-principles calculations. We find that the low energy crystal structure obeys the octet rule and is the kesterite (KS) structure. However, the stannite or partially disordered KS structures can also exist in synthesized samples due to the small energy cost. We find that the dependence of the band structure on the (Cu,Zn) cation ordering is weak and predict that the band gap of Cu2ZnSnSe4 should be on the order of 1.0 eV and not 1.5 eV as was reported in previous absorption measurements.
TL;DR: Experimental observations of a pressure-induced transformation of Na into an optically transparent phase at ∼200 GPa are reported, attributing the emergence of this dense insulating state not to atom pairing, but to p–d hybridizations of valence electrons and their repulsion by core electrons into the lattice interstices.
Abstract: Under pressure, metals exhibit increasingly shorter interatomic distances. Intuitively, this response is expected to be accompanied by an increase in the widths of the valence and conduction bands and hence a more pronounced free-electron-like behaviour. But at the densities that can now be achieved experimentally, compression can be so substantial that core electrons overlap. This effect dramatically alters electronic properties from those typically associated with simple free-electron metals such as lithium (Li; refs 1-3) and sodium (Na; refs 4, 5), leading in turn to structurally complex phases and superconductivity with a high critical temperature. But the most intriguing prediction-that the seemingly simple metals Li (ref. 1) and Na (ref. 4) will transform under pressure into insulating states, owing to pairing of alkali atoms-has yet to be experimentally confirmed. Here we report experimental observations of a pressure-induced transformation of Na into an optically transparent phase at approximately 200 GPa (corresponding to approximately 5.0-fold compression). Experimental and computational data identify the new phase as a wide bandgap dielectric with a six-coordinated, highly distorted double-hexagonal close-packed structure. We attribute the emergence of this dense insulating state not to atom pairing, but to p-d hybridizations of valence electrons and their repulsion by core electrons into the lattice interstices. We expect that such insulating states may also form in other elements and compounds when compression is sufficiently strong that atomic cores start to overlap strongly.
TL;DR: In this paper, carbon nanoparticles were prepared by refluxing the combustion soot of natural gas in nitric acid and the resulting particles exhibited an average diameter of 4.8 ± 0.6 nm, and the crystalline lattices were consistent with graphitic carbons.
Abstract: Carbon nanoparticles were prepared by refluxing the combustion soot of natural gas in nitric acid. Transmission Electron Microscopy measurements showed that the resulting particles exhibited an average diameter of 4.8 ± 0.6 nm, and the crystalline lattices were consistent with graphitic carbons. 13C NMR and FTIR spectroscopic measurements further confirmed the presence of sp2 carbons in the form of aryl and carboxylic/carbonyl moieties. The resulting carbon nanoparticles were found to emit photoluminescence with a quantum yield of approximately 0.43%. Additionally, the emission band energy of the carbon nanoparticle was very similar to that of much smaller carbon nanoparticles obtained from candle soot, suggesting that the photoluminescence might arise from particle surface states, analogous to the behaviors of semiconductor quantum dots with an indirect bandgap. In electrochemical measurements, two pairs of well-defined voltammetric waves were observed, which might be ascribed to the peripheral functiona...
TL;DR: In this paper, the first principles of the electronic structure of BiVO4, a promising photocatalyst for hydrogen generation, were reported, which is a direct band gap semiconductor, despite having band extrema away from the Brillouin zone center.
Abstract: We report the first-principles electronic structure of BiVO4, a promising photocatalyst for hydrogen generation. BiVO4 is found to be a direct band gap semiconductor, despite having band extrema away from the Brillouin zone center. Coupling between Bi 6s and O 2p forces an upward dispersion of the valence band at the zone boundary; however, a direct gap is maintained via coupling between V 3d, O 2p, and Bi 6p, which lowers the conduction band minimum. These interactions result in symmetric hole and electron masses. Implications for the design of ambipolar metal oxides are discussed.
TL;DR: In-depth characterization indicated that pure stoichiometric CZTS nanocrystals with an average particle size of 12.8 +/- 1.8 nm were formed, and optical measurements showed a band gap of 1.5 eV, which is optimal for a single-junction solar device.
Abstract: Recent advances have been made in thin-film solar cells using CdTe and CuIn1−xGaxSe2 (CIGS) nanoparticles, which have achieved impressive efficiencies. Despite these efficiencies, CdTe and CIGS are not amenable to large-scale production because of the cost and scarcity of Te, In, and Ga. Cu2ZnSnS4 (CZTS), however, is an emerging solar cell material that contains only earth-abundant elements and has a near-optimal direct band gap of 1.45−1.65 eV and a large absorption coefficient. Here we report the direct synthesis of CZTS nanocrystals using the hot-injection method. In-depth characterization indicated that pure stoichiometric CZTS nanocrystals with an average particle size of 12.8 ± 1.8 nm were formed. Optical measurements showed a band gap of 1.5 eV, which is optimal for a single-junction solar device.
TL;DR: In this article, the authors presented a systematic study of two-and one-dimensional honeycomb structures of boron nitride (BN) using first-principles plane-wave method.
Abstract: This paper presents a systematic study of two- and one-dimensional honeycomb structures of boron nitride (BN) using first-principles plane-wave method. In order to reveal dimensionality effects, a brief study of all allotropic forms of three-dimensional (3D) BN crystals and truly one-dimensional atomic BN chains are also included. Two-dimensional (2D) graphenelike BN is a wide band-gap semiconductor with ionic bonding through significant charge transfer from B to N. Phonon-dispersion curves demonstrate the stability of 2D BN flakes. Quasi-one-dimensional (1D) armchair BN nanoribbons are nonmagnetic semiconductors with edge states. Upon passivation of B and N with hydrogen atoms these edge states disappear and the band gap increases. Bare zigzag BN nanoribbons are metallic but become a ferromagnetic semiconductor when both their edges are passivated with hydrogen. However, their magnetic ground state, electronic band structure, and band gap are found to be strongly dependent on whether B or N edge of the ribbon is saturated with hydrogen. Vacancy defects in armchair and zigzag nanoribbons affect also the magnetic state and electronic structure. Harmonic, anharmonic, and plastic regions are deduced in the variation in the total energy of armchair and zigzag nanoribbons as a function of strain. The calculated force constants display a Hookian behavior. In the plastic region the nanoribbon is stretched, whereby the honeycomb structure of hexagons change into different polygons through sequential structural transformations. In order to reveal dimensionality effects these properties are contrasted with those of various 3D BN crystals and 1D BN atomic chain.
TL;DR: The optical conductivity of bilayer graphene with an efficient electrolyte top gate for a photon energy range of 0.2-0.7 eV is measured and the emergence of new transitions as a band gap opens is seen.
Abstract: It has been predicted that application of a strong electric field perpendicular to the plane of bilayer graphene can induce a significant band gap. We have measured the optical conductivity of bilayer graphene with an efficient electrolyte top gate for a photon energy range of 0.2-0.7 eV. We see the emergence of new transitions as a band gap opens. A band gap approaching 200 meV is observed when an electric field approximately 1 V/nm is applied, inducing a carrier density of about 10(13) cm(-2)}. The magnitude of the band gap and the features observed in the infrared conductivity spectra are broadly compatible with calculations within a tight-binding model.
TL;DR: In this paper, the authors report broadband visible photoluminescence from solid graphene oxide, and modifications of the emission spectrum by progressive chemical reduction, suggesting a gapping of the two-dimensional electronic system by removal of π-electrons.
Abstract: We report broadband visible photoluminescence from solid graphene oxide, and modifications of the emission spectrum by progressive chemical reduction. The data suggest a gapping of the two-dimensional electronic system by removal of π-electrons. We discuss possible gapping mechanisms, and propose that a Kekule pattern of bond distortions may account for the observed behavior.
TL;DR: The results suggest the possibility of creating and tuning the band gap in graphene by varying the oxidation level and the relative amount of epoxide and hydroxyl functional groups on the surface.
Abstract: We have systematically investigated the effect of oxidation on the structural and electronic properties of graphene based on first-principles calculations. Energetically favorable atomic configurations and building blocks are identified, which contain epoxide and hydroxyl groups in close proximity with each other. Different arrangements of these units yield a local-density approximation band gap over a range of a few eV. These results suggest the possibility of creating and tuning the band gap in graphene by varying the oxidation level and the relative amount of epoxide and hydroxyl functional groups on the surface.