Growth temperature induced changes of luminescence in epitaxial BN: from colour centres to donor-acceptor recombination.

Defects play a very important role in semiconductors and only the control over the defect properties allows the implementation of materials in dedicated applications. We present an investigation of the UV luminescence of defects in hexagonal boron nitride (h-BN) grown by Metal Organic Vapor Phase Epitaxy (MOVPE). Such intentionally introduced defects are important for applications like deep UV emission and quantum information. In this work, we performed photoluminescence and cathodoluminescence experiments on a set of h-BN layers grown by MOVPE at different growth temperatures (tgr). The obtained defect-related spectra in the ultraviolet range include well-known lines at about 230 nm (X230, hν = 5.4 eV) and 300 nm (C300 - the brightest one, hν = 4.14 eV) as well as a rarely observed band with a zero-phonon line at 380 nm (C380, hν = 3.24 eV). The C300 and C380 bands have the characteristic of a color centre showing sharp lines (0.6 nm width) at 5 K. These lines are most probably an internal transition of carbon-related defects. We show that for samples grown at high temperatures (tgr > 1200 °C), the lines related to the color centres C are replaced by broad bands at 330 nm and 400 nm, which we marked as D330 and D400, respectively. The D bands have similar central energies to the C bands but extend over a large energy range, so we propose that the D emission is due to a shallow donor to deep acceptor recombination. Time-resolved photoluminescence analysis determined the lifetimes of the individual lines in the range from 0.9 ns (C300), 1.8 ns (C380) to 4 ns (D400). The C300 and C380 color centre bands are composed of a series of characteristic lines that are due to the interaction with phonons. The E1u (198 meV) and A2u (93 meV) phonon replicas have been identified.

Temperature induced giant shift of phonon energy in epitaxial boron nitride layers.

The recent progress in the growth of large-area boron nitride epilayers opens up new possibilities for future applications. However, it remains largely unclear how weakly attached two-dimensional BN layers interact with their substrate and how their properties are influenced by defects. In this work, we investigate hBN layers grown by metal organic vapor phase epitaxy using Fourier-transform infrared spectroscopy in the temperature range of 160-540 K. Our measurements reveal strong differences in the character of layer-substrate interaction for as-grown and delaminated epitaxial layers. A much weaker interaction of as-grown layers is explained by wrinkles formation that reduces strain at the layer-substrate interface, which for layers transferred to other substrates occurs only in a limited temperature range. The most striking result is the observation of a giant increase in theE1uphonon energy of up to ∼6 cm-1in a narrow temperature range. We show that the amplitude and temperature range of the anomaly is strongly modified by UV light illumination. The observed giant effect is explained in terms of strain generation resulting from charge redistribution between shallow traps and different defects, which can be interpreted as a result of strong electron-phonon coupling in hBN. The observed narrow temperature range of the anomaly indicates that the effect may be further enhanced for example by electrostrictive effects, expected for sp2boron nitride.

Towards practical applications of quantum emitters in boron nitride.

We demonstrate quantum emission capabilities from boron nitride structures which are relevant for practical applications and can be seamlessly integrated into a variety of heterostructures and devices. First, the optical properties of polycrystalline BN films grown by metalorganic vapour-phase epitaxy are inspected. We observe that these specimens display an antibunching in the second-order correlation functions, if the broadband background luminescence is properly controlled. Furthermore, the feasibility to use flexible and transparent substrates to support hBN crystals that host quantum emitters is explored. We characterise hBN powders deposited onto polydimethylsiloxane films, which display quantum emission characteristics in ambient environmental conditions.

Upconverted electroluminescence via Auger scattering of interlayer excitons in van der Waals heterostructures.

The intriguing physics of carrier-carrier interactions, which likewise affect the operation of light emitting devices, stimulate the research on semiconductor structures at high densities of excited carriers, a limit reachable at large pumping rates or in systems with long-lived electron-hole pairs. By electrically injecting carriers into WSe2/MoS2 type-II heterostructures which are indirect in real and k-space, we establish a large population of typical optically silent interlayer excitons. Here, we reveal their emission spectra and show that the emission energy is tunable by an applied electric field. When the population is further increased by suppressing the radiative recombination rate with the introduction of an hBN spacer between WSe2 and MoS2, Auger-type and exciton-exciton annihilation processes become important. These processes are traced by the observation of an up-converted emission demonstrating that excitons gaining energy in non-radiative Auger processes can be recovered and recombine radiatively.

Raman scattering from the bulk inactive out-of-plane [Formula: see text] mode in few-layer MoTe2.

We report a study of Raman scattering in few-layer MoTe2 focused on high-frequency out-of-plane vibrational modes near 291 cm-1 which are associated with the bulk-inactive [Formula: see text] mode. Our temperature-dependent measurements reveal a double peak structure of the feature related to these modes in the Raman scattering spectra of 4- and 5-layer MoTe2. In accordance with literature data, the doublet's lower- and higher-energy components are ascribed to the Raman-active A1g/[Formula: see text] vibrations involving, respectively, only the inner and surface layers. We demonstrate a strong enhancement of the inner mode's intensity at low temperature for 1.91 eV and 1.96 eV laser light excitation which suggests a resonant character of the Raman scattering processes probed under such conditions. A resonance of the laser light with a singularity of the electronic density of states at the M point of the MoTe2 Brillouin zone is proposed to be responsible for the observed effects.

In situ Raman spectroscopy of the graphene/water interface of a solution-gated field-effect transistor: electron-phonon coupling and spectroelectrochemistry.

We present a novel measurement approach which combines the electrical characterization of solution-gated field-effect transistors based on epitaxial bilayer graphene on 4H-SiC (0001) with simultaneous Raman spectroscopy. By changing the gate voltage, we observed Raman signatures related to the resonant electron-phonon coupling. An analysis of these Raman bands enabled the extraction of the geometrical capacitance of the system and an accurate calculation of the Fermi levels for bilayer graphene. An intentional application of higher gate voltages allowed us to trigger electrochemical reactions, which we followed in situ by Raman spectroscopy. The reactions showed a partially reversible character, as indicated by an emergence/disappearance of peaks assigned to C-H and Si-H vibration modes as well as an increase/decrease of the defect-related Raman D band intensity. Our setup provides a highly interesting platform for future spectroelectrochemical research on electrically-induced sorption processes of graphene on the micrometer scale.

Carrier scattering from dynamical magnetoconductivity in quasineutral epitaxial graphene.

The energy dependence of the electronic scattering time is probed by Landau level spectroscopy in quasineutral multilayer epitaxial graphene. From the broadening of overlapping Landau levels we find that the scattering rate 1/τ increases linearly with energy ϵ. This implies a surprising property of the Landau level spectrum in graphene-the number of resolved Landau levels remains constant with the applied magnetic field. Insights are given about possible scattering mechanisms and carrier mobilities in the graphene system investigated.

Graphene epitaxy by chemical vapor deposition on SiC.

We demonstrate the growth of high quality graphene layers by chemical vapor deposition (CVD) on insulating and conductive SiC substrates. This method provides key advantages over the well-developed epitaxial graphene growth by Si sublimation that has been known for decades. (1) CVD growth is much less sensitive to SiC surface defects resulting in high electron mobilities of ∼1800 cm(2)/(V s) and enables the controlled synthesis of a determined number of graphene layers with a defined doping level. The high quality of graphene is evidenced by a unique combination of angle-resolved photoemission spectroscopy, Raman spectroscopy, transport measurements, scanning tunneling microscopy and ellipsometry. Our measurements indicate that CVD grown graphene is under less compressive strain than its epitaxial counterpart and confirms the existence of an electronic energy band gap. These features are essential for future applications of graphene electronics based on wafer scale graphene growth.

Fine structure of effective mass acceptors in gallium nitride.

Magnetoluminescence of the exciton bound to a neutral acceptor was measured to investigate the electronic structure of a shallow acceptor center in GaN. The application of magnetic fields along different directions with respect to the crystal c axis allowed us to determine the symmetry of the ground (Gamma(9)) and the first excited state (Gamma(7)) of the acceptor. The observed Zeeman splitting pattern has axial symmetry but can be explained well only by assuming a significant reduction of the spin-orbit interaction for this acceptor state. Because of this reduction, the energy structure of the neutral acceptor is found to be very sensitive to any local, axial perturbation.