Charge Injection Rates in Hybrid Nanosilicon–Polythiophene Bulk Heterojunction Solar Cells

The injection time for transfer of an electron from photoexcited dodecathiophene or polythiophene to a silicon nanocrystal (2.2 nm diameter) is calculated by computing the retarded Green’s function for the system from the Hamiltonian and Kohn–Sham states produced by density functional calculations. We found that it can be of the order of 10–100 fs if the thiophene chain lies approximately parallel to the silicon surface. However, the electron injection time is 1–2 orders of magnitude longer if the oligothiophene chain lies perpendicular to the silicon surface. A chemisorption interaction between the thiophene chain and the nanocrystal provides a relatively small improvement (decrease) of injection times, much weaker than that achieved by enforcing the parallel arrangement of the chain with respect to the nanocrystal

Origin of Indirect Optical Transitions in Few-Layer MoS₂, WS₂, and WSe₂

It has been well-established that single layer MX₂ (M = Mo, W and X = S, Se) are direct gap semiconductors with band edges coinciding at the K point in contrast to their indirect gap multilayer counterparts. In few-layer MX₂, there are two valleys along the Γ–K line with similar energy. There is little understanding on which of the two valleys forms the conduction band minimum (CBM) in this thickness regime. We investigate the conduction band valley structure in few-layer MX₂ by examining the temperature-dependent shift of indirect exciton photoluminescence peak. Highly anisotropic thermal expansion of the lattice and the corresponding evolution of the band structure result in a distinct peak shift for indirect transitions involving the K and Λ (midpoint along Γ-K) valleys. We identify the origin of the indirect emission and concurrently determine the relative energy of these valleys

Microsteganography on WS₂ Monolayers Tailored by Direct Laser Painting

We present scanning focused laser beam as a multipurpose tool to engineer the physical and chemical properties of WS₂ microflakes. For monolayers, the laser modification integrates oxygen into the WS₂ microflake, resulting in ∼9 times enhancement in the intensity of the fluorescence emission. This modification does not cause any morphology change, allowing “micro-encryption” of information that is only observable as fluorescence under excitation. The same focused laser also facilitates on demand thinning down of WS₂ multilayers into monolayers, turning them into fluorescence active components. With a scanning focused laser beam, micropatterns are readily created on WS₂ multilayers through selective thinning of specific regions on the flake

Evidence for Fast Interlayer Energy Transfer in MoSe₂/WS₂ Heterostructures

Strongly bound excitons confined in two-dimensional (2D) semiconductors are dipoles with a perfect in-plane orientation. In a vertical stack of semiconducting 2D crystals, such in-plane excitonic dipoles are expected to efficiently couple across van der Waals gap due to strong interlayer Coulomb interaction and exchange their energy. However, previous studies on heterobilayers of group 6 transition metal dichalcogenides (TMDs) found that the exciton decay dynamics is dominated by interlayer charge transfer (CT) processes. Here, we report an experimental observation of fast interlayer energy transfer (ET) in MoSe₂/WS₂ heterostructures using photoluminescence excitation (PLE) spectroscopy. The temperature dependence of the transfer rates suggests that the ET is Förster-type involving excitons in the WS₂ layer resonantly exciting higher-order excitons in the MoSe₂ layer. The estimated ET time of the order of 1 ps is among the fastest compared to those reported for other nanostructure hybrid systems such as carbon nanotube bundles. Efficient ET in these systems offers prospects for optical amplification and energy harvesting through intelligent layer engineering

Atomic Healing of Defects in Transition Metal Dichalcogenides

As-grown transition metal dichalcogenides are usually chalcogen deficient and therefore contain a high density of chalcogen vacancies, deep electron traps which can act as charged scattering centers, reducing the electron mobility. However, we show that chalcogen vacancies can be effectively passivated by oxygen, healing the electronic structure of the material. We proposed that this can be achieved by means of surface laser modification and demonstrate the efficiency of this processing technique, which can enhance the conductivity of monolayer WSe₂ by ∼400 times and its photoconductivity by ∼150 times

Fluorescence Concentric Triangles: A Case of Chemical Heterogeneity in WS₂ Atomic Monolayer

We report a novel optical property in WS₂ monolayer. The monolayer naturally exhibits beautiful in-plane periodical and lateral homojunctions by way of alternate dark and bright band in the fluorescence images of these monolayers. The interface between different fluorescence species within the sample is distinct and sharp. This gives rise to intriguing concentric triangular fluorescence patterns in the monolayer. The novel optical property of this special WS₂ monolayer is facilitated by chemical heterogeneity. The photoluminescence of the bright band is dominated by emissions from trion and biexciton while the emission from defect-bound exciton dominates the photoluminescence at the dark band. The discovery of such concentric fluorescence patterns represents a potentially new form of optoelectronic or photonic functionality

Bandgap Engineering of Phosphorene by Laser Oxidation toward Functional 2D Materials

We demonstrate a straightforward and effective laser pruning approach to reduce multilayer black phosphorus (BP) to few-layer BP under ambient condition. Phosphorene oxides and suboxides are formed and the degree of laser-induced oxidation is controlled by the laser power. Since the band gaps of the phosphorene suboxide depend on the oxygen concentration, this simple technique is able to realize localized band gap engineering of the thin BP. Micropatterns of few-layer phosphorene suboxide flakes with unique optical and fluorescence properties are created. Remarkably, some of these suboxide flakes display long-term (up to 2 weeks) stability in ambient condition. Comparing against the optical properties predicted by first-principle calculations, we develop a “calibration” map in using focused laser power as a handle to tune the band gap of the BP suboxide flake. Moreover, the surface of the laser patterned region is altered to be sensitive to toxic gas by way of fluorescence contrast. Therefore, the multicolored display is further demonstrated as a toxic gas monitor. In addition, the BP suboxide flake is demonstrated to exhibit higher drain current modulation and mobility comparable to that of the pristine BP in the electronic application

Electron Doping of Ultrathin Black Phosphorus with Cu Adatoms

Few-layer black phosphorus is a monatomic two-dimensional crystal with a direct band gap that has high carrier mobility for both holes and electrons. Similarly to other layered atomic crystals, like graphene or layered transition metal dichalcogenides, the transport behavior of few-layer black phosphorus is sensitive to surface impurities, adsorbates, and adatoms. Here we study the effect of Cu adatoms onto few-layer black phosphorus by characterizing few-layer black phosphorus field effect devices and by performing first-principles calculations. We find that the addition of Cu adatoms can be used to controllably n-dope few layer black phosphorus, thereby lowering the threshold voltage for n-type conduction without degrading the transport properties. We demonstrate a scalable 2D material-based complementary inverter which utilizes a boron nitride gate dielectric, a graphite gate, and a single bP crystal for both the p- and n-channels. The inverter operates at matched input and output voltages, exhibits a gain of 46, and does not require different contact metals or local electrostatic gating

Gate-Tunable Giant Stark Effect in Few-Layer Black Phosphorus

Two-dimensional black phosphorus (BP) has sparked enormous research interest due to its high carrier mobility, layer-dependent direct bandgap and outstanding in-plane anisotropic properties. BP is one of the few two-dimensional materials where it is possible to tune the bandgap over a wide energy range from the visible up to the infrared. In this article, we report the observation of a giant Stark effect in electrostatically gated few-layer BP. Using low-temperature scanning tunnelling microscopy, we observed that in few-layer BP, when electrons are injected, a monotonic reduction of the bandgap occurs. The injected electrons compensate the existing defect-induced holes and achieve up to 35.5% bandgap modulation in the light-doping regime. When probed by tunnelling spectroscopy, the local density of states in few-layer BP shows characteristic resonance features arising from layer-dependent sub-band structures due to quantum confinement effects. The demonstration of an electrical gate-controlled giant Stark effect in BP paves the way to designing electro-optic modulators and photodetector devices that can be operated in a wide electromagnetic spectral range

Resolving the Spatial Structures of Bound Hole States in Black Phosphorus

Understanding the local electronic properties of individual defects and dopants in black phosphorus (BP) is of great importance for both fundamental research and technological applications. Here, we employ low-temperature scanning tunnelling microscope (LT-STM) to probe the local electronic structures of single acceptors in BP. We demonstrate that the charge state of individual acceptors can be reversibly switched by controlling the tip-induced band bending. In addition, acceptor-related resonance features in the tunnelling spectra can be attributed to the formation of Rydberg-like bound hole states. The spatial mapping of the quantum bound states shows two distinct shapes evolving from an extended ellipse shape for the 1s ground state to a dumbbell shape for the 2p_<i>x</i> excited state. The wave functions of bound hole states can be well-described using the hydrogen-like model with anisotropic effective mass, corroborated by our theoretical calculations. Our findings not only provide new insight into the many-body interactions around single dopants in this anisotropic two-dimensional material but also pave the way to the design of novel quantum devices