Selective band gap manipulation of graphene oxide by its reduction with mild reagents, Carbon (2015), doi: http://dx. ABSTRACTGraphene oxide (GO) can be used as an electron acceptor for polymeric solar cells but still band gap matching for electron donor and acceptor demands more study. The generation of the exciton in such materials is intimately related to the optical band gap. However, exciton dissociation is related to transport band gap that controls the device performance, particularly the open circuit voltage and short circuit current. Therefore, the modulation of the optical gap is useful because it results into tuning of the transport gap. The interest of the present work is to study the reduction of graphene oxide (GO) at room temperature, using environmental friendly reagents like glucose, fructose and ascorbic acid for the modulation of a band gap. It has been found that glucose and fructose function effectively only in presence of NH 4 OH. Although ascorbic acid can reduce GO alone, NH 4 OH speeds up the reaction. The optical band gap of GO can be reduced and tuned effectively from 2.7eV to 1.15eV.

The manipulation of individual intrinsic point defects is crucial for boosting the thermoelectric performances of n-Bi2Te3-based thermoelectric films, but was not achieved in previous studies. In this work, we realize the independent manipulation of Te vacancies VTe and antisite defects of TeBi and BiTe in molecular beam epitaxially grown n-Bi2Te3 films, which is directly monitored by a scanning tunneling microscope. By virtue of introducing dominant TeBi antisites, the n-Bi2Te3 film can achieve the state-of-the-art thermoelectric power factor of 5.05 mW m–1 K–2, significantly superior to films containing VTe and BiTe as dominant defects. Angle-resolved photoemission spectroscopy and systematic transport studies have revealed two detrimental effects regarding VTe and BiTe, which have not been discovered before: (1) The presence of BiTe antisites leads to a reduction of the carrier effective mass in the conduction band; and (2) the intrinsic transformation of VTe to BiTe during the film growth results in a built-in electric field along the film thickness direction and thus is not beneficial for the carrier mobility. This research is instructive for further engineering defects and optimizing electronic transport properties of n-Bi2Te3 and other technologically important thermoelectric materials.

Despite the same crystal structure and homologous constituent elements, the chalcopyrite compounds ABTe2 (A = Cu, Ag; B = Ga, In) exhibit distinct electronic and thermal transport properties. The aim of this work is to understand the origin of such discrepancy employing experiments and theoretical calculations. The results of Hall coefficient measurements, absorption spectroscopy, and electronic transport studies suggest the deep‐level in‐gap states induced by the native A‐site vacancies play a key role in the observed intrinsic semiconductor to degenerate semiconductor transition and are the origins of the distinct electrical conductivity among ABTe2 compounds. In addition, the cryogenic heat capacity measurements and calculated phonon dispersion relations show that the acoustic and low‐frequency optical modes of AgGaTe2 and AgInTe2 are governed by the vibrations of AgTe clusters while the counterparts of CuGaTe2 and CuInTe2 compounds are dominated by the vibrations of Te atoms, and the coupling between the acoustic and low‐frequency optical modes is notably different among ABTe2 compounds. Specifically, lower avoided‐crossing frequencies, lower sound velocity together with stronger Umklapp process yield lower thermal conductivities of AgGaTe2 and AgInTe2 than CuGaTe2 and CuInTe2. This work provides new insights into the understanding and improvement of electrical and thermal properties toward higher thermoelectric performance of chalcopyrite compounds.

Interactions among various film growth parameters, such as the substrate temperature (Tsub), film thickness (d), and composition, play a crucial role in controlling the type and density of the intrinsic point defects. In turn, the point defects modulate and control electronic transport properties of Bi2Te3 films. We have grown n-type Bi2Te3 films with different d by molecular beam epitaxy at different Tsub. The formation of point defects was analyzed by a combined use of angle-resolved photoelectron spectroscopy (ARPES) and electronic transport measurements. Two important findings were made: (i) the negatively charged vacancies, VTe··, initially the dominant intrinsic defects, transform gradually during the growth process into positively charged anti-site defects, BiTe′, driven by thermal annealing from a continuously heated substrate; and (ii) from the film's surface into the inner strata of the film, the density of VTe·· decreases while the density of BiTe′ increases, leading to a gradient of vacancies and anti-site defects along the film growth direction. As a result, the electron density in Bi2Te3 films decreases monotonically with increasing d. Moreover, elevating Tsub leads to a more significant in situ annealing effect and an eventual onset of intrinsic excitations that deteriorates electronic transport properties. The thinnest Bi2Te3 film (16 nm) grown at Tsub = 245 °C has the highest electron concentration of 2.03 × 1020 cm−3 and also the maximum room temperature power factor of 1.6 mW m−1 K−2 of all grown epitaxial films. The new insights regarding the defect formation and transformation pave the way for further optimization of electronic transport properties of n-type Bi2Te3-based films.

As a novel class of soft matter, two-dimensional (2D) atomic nanosheet-like crystals have attracted much attention for energy storage devices due to the fact that nearly all of the atoms can be exposed to the electrolyte and involved in redox reactions. Herein, atomically thin γ-FeOOH nanosheets with a thickness of ∼1.5 nm are synthesized in a high yield, and the band and electronic structures of the γ-FeOOH nanosheet are revealed using density-functional theory calculations for the first time. The rationally designed γ-FeOOH@rGO composites with a heterostacking structure are used as an anode material for lithium-ion batteries (LIBs). A high reversible capacity over 850 mAh g(-1) after 100 cycles at 200 mA g(-1) is obtained with excellent rate capability. The remarkable performance is attributed to the ultrathin nature of γ-FeOOH nanosheets and 2D heterostacking structure, which provide the minimized Li(+) diffusion length and buffer zone for volume change. Further investigation on the Li storage electrochemical mechanism of γ-FeOOH@rGO indicates that the charge-discharge processes include both conversion reaction and capacitive behavior. This synergistic effect of conversion reaction and capacitive behavior originating from 2D heterostacking structure casts new light on the development of high-energy anode materials.