Probing 2D black phosphorus by quantum capacitance measurements

Two-dimensional materials and their heterostructures have emerged as a new class of materials, not only for fundamental physics but also for electronic and optoelectronic applications. Black phosphorus (BP) is a relatively new addition to this class of materials. Its strong in-plane anisotropy makes BP a unique material for making conceptually new types of electronic devices. However, the global density of states (DOS) of BP in device geometry has not been measured experimentally. Here, we report the quantum capacitance measurements together with the conductance measurements on an hBN-protected few-layer BP (similar to six layers) in a dual-gated field effect transistor (FET) geometry. The measured DOS from our quantum capacitance is compared with density functional theory (DFT). Our results reveal that the transport gap for quantum capacitance is smaller than that in conductance measurements due to the presence of localized states near the band edge. The presence of localized states is confirmed by the variable range hopping seen in our temperature dependence conductivity. A large asymmetry is observed between the electron and hole side. This asymmetric nature is attributed to the anisotropic band dispersion of BP. Our measurements establish the uniqueness of quantum capacitance in probing the localized states near the band edge, hitherto not seen in conductance measurements.

Efficient density matrix renormalization group algorithm to study Y junctions with integer and half-integer spin

An efficient density matrix renormalization group (DMRG) algorithm is presented and applied to Y junctions, systems with three arms of n sites that meet at a central site. The accuracy is comparable to DMRG of chains. As in chains, new sites are always bonded to the most recently added sites and the superblock Hamiltonian contains only new or once renormalized operators. Junctions of up to N = 3n + 1 approximate to 500 sites are studied with antiferromagnetic (AF) Heisenberg exchange J between nearest-neighbor spins S or electron transfer t between nearest neighbors in half-filled Hubbard models. Exchange or electron transfer is exclusively between sites in two sublattices with N-A not equal N-B. The ground state (GS) and spin densities rho(r) = < S-r(z)> at site r are quite different for junctions with S = 1/2, 1, 3/2, and 2. The GS has finite total spin S-G = 2S(S) for even (odd) N and for M-G = S-G in the S-G spin manifold, rho(r) > 0(< 0) at sites of the larger (smaller) sublattice. S = 1/2 junctions have delocalized states and decreasing spin densities with increasing N. S = 1 junctions have four localized S-z = 1/2 states at the end of each arm and centered on the junction, consistent with localized states in S = 1 chains with finite Haldane gap. The GS of S = 3/2 or 2 junctions of up to 500 spins is a spin density wave with increased amplitude at the ends of arms or near the junction. Quantum fluctuations completely suppress AF order in S = 1/2 or 1 junctions, as well as in half-filled Hubbard junctions, but reduce rather than suppress AF order in S = 3/2 or 2 junctions.

Electronic properties of graphene grain boundaries

Grain boundaries and defect lines in graphene are intensively studied for their novel electronic and magnetic properties. However, there is not a complete comprehension of the appearance of localized states along these defects. Graphene grain boundaries are herein seen as the outcome of matching two semi-infinite graphene sheets with different edges. We classify the energy spectra of grain boundaries into three different types, directly related to the combination of the four basic classes of spectra of graphene edges. From the specific geometry of the grains, we are able to obtain the band structure and the number of localized states close to the Fermi energy. This provides a new understanding of states localized at grain boundaries, showing that they are derived from the edge states of graphene. Such knowledge is crucial for the ultimate tailoring of electronic and optoelectronic applications.

Optical study of lateral carrier transfer in (In,Ga)As/GaAs quantum-dot chains

We have studied the lateral carrier transfer in a specially designed quantum dot chain structure by means of time-resolved photoluminescence (PL) and polarization PL. The PL decay time increases with temperature, following the T-1/2 law for the typical one-dimensional quantum system. The decay time depends strongly on the emission energy: it decreases as the photon energy increases. Moreover, a strong polarization anisotropy is observed. These results are attributed to the efficient lateral transfer of carriers along the chain direction. (c) 2008 American Institute of Physics.

Temperature-induced switching-over of the luminescence transitions in GaInNAs/GaAs quantum wells

Photoluminescence (PL) spectra of the GaInNAs/GaAs single quantum well (SQW) with different N compositions are carefully studied in a range of temperatures and excitation power densities. The anomalous S-shape temperature dependence of the PL peak is analysed based on the competition and switching-over between the peaks related to N-induced localized states and the peak related to interband excitonic recombination. It is found that with increasing N composition, the localized energy increases and the turning point of the S-shape temperature dependence occurs at higher temperature, where the localized carriers in the bandtail states obtain enough thermal activation energy to be dissociated and delocalized. The rapid thermal annealing (RTA) effectively reduces the localized energy and causes a decrease of the switching-over temperature.

Optical properties and exciton localization in GaNas/GaAs

GaNAs/GaAs single quantum wells (SQWs) and dilute GaNAs bulk grown by molecular beam epitaxy(MBE) were studied by photoluminescence (PL), selectively-excited PL, and time-resolved PL. Exciton localization and delocalization were investigated in detail. Under short pulse laser excitation, the delocalization exciton emission was revealed in GaNAs/GaAs SQWs. It exhibits quite different optical properties from N-related localized states. In dilute GaNAs bulk, a transition of alloy band related recombination was observed by measuring the PL dependence on temperature and excitation intensity and time-resolved PL, as well. This alloy-related transition presents intrinsic optical properties. These results are very important for realizing the abnomal features of III-V-N semiconductors.

Recombination kinetics of Te isoelectronic centers in ZnSTe

The recombination kinetics of Te isoelectronic centers in ZnS1-xTex (0.0065 less than or equal to x less than or equal to 0.85) alloys is studied by time-resolved photoluminescence (TRPL) at low temperature. The measured radiative recombination lifetimes of different Te bound exciton states are quite different, varying from a few nanoseconds to tens of nanosecond. As the bound exciton state evolves from a single Te impurity (Te-1) to larger Te clusters (Te-n, n=2,3,4), the recombination lifetime increases. It reaches maximum (similar to40 ns) for the Te-4 bound states at x=0.155. The increase of the exciton lifetime is attributed to the increasing exciton localization effect caused by larger localization potential. In the large Te composition range (x > 0.155), the exciton recombination lifetime decreases monotonically with Te composition. It is mainly due to the hybridization between the Te localized states and the host valence band states. The composition dependences of the exciton binding energy and the photoluminescence (PL) line width show the similar tendency that further support the localization picture obtained from the TRPL measurement. (C) 2005 American Institute of Physics.

A study of the growth and optical properties of AlInGaN alloys

We have studied the growth and optical properties of AlInGaN alloys in this article. By the measurement of three samples, we found that the incorporation of In decreases with the increase of temperature, while there is nearly no change for the incorporation of Al. The sample grown at the lowest temperature had the best material and optical properties, which owes to the high In component, because the In component can reduce defects and improve the material quality. We also used the time-resolved photoluminescence(PL) to study the mechanism of recombination of carriers, and found that the time dependence of PL intensity was not in exponential decay, but in stretched-exponential decay. Through the study of the character of this decay, we come to the conclusion that the emission comes from the recombination of localized excitons. Once more, this localization exhibites the character of quantum dots, and the stretched, exponential decay results from the hopping of carriers between different localized states. In addition, we have used the relation of emission energy dependence of carrier's lifetime and the character of radiative recombination and non-radiative combination to confirm our conclusion.

Structural and optical properties of InAlGaN films grown directly on low-temperature buffer layer with (0001)sapphire substrate

Quaternary InAlGaN film has been grown directly on top of low-temperature-deposited GaN buffer layer by low-pressure metalorganic vapor phase epitaxy. High-resolution X-ray diffraction and photoluminescence (PL) results show that the film has good crystal quality and optical property. Temperature-dependent PL and time-resolved PL (TRPL) have been employed to study the carriers recombination dynamics in the film. The TRPL signals can be well fitted as a stretched exponential function exp[-(t/tau)(beta)] from 14 to 250 K, indicating that the emission is attributed to the radiative recombination of excitons localized in disorder quantum nanostructures such as quantum disks originating from indium (In) clusters or In composition fluctuation. The cross-sectional high-resolution electron microscopy measurement further proves that there exist the disorder quantum nanostructures in the quaternary. By investigating the dependence of the exponential parameter beta on the temperature, it is shown that the multiple trapping-detrapping mechanism dominates the diffusion among the localized states. The localized states are considered to have two-dimensional density of states (DOS) at 250 K, since radiative recombination lifetime tau(r) increases linearly with increasing temperature. (C) 2002 Elsevier Science B.V. All rights reserved.

Photoluminescence study of multilayer In0.55Al0.45As/Al0.5Ga0.5As quantum dot at various temperature

The photoluminescence of self-assembled multilayer In0.55Al0.45As/Al0.5Ga0.5As quantum dot (QD) was measured at various temperatures. Strong photoluminescence of wetting layer (WL) and quantum dots were observed at the same time. Furthermore, direct excitons thermal transfer process between the wetting layer and quantum dots was observed. In the study of temperature dependence of PL intensity it was found that the PL peak of wetting layer contains two quenching processes: at low temperature, excitons are thermally activated from localized states to extended two-dimensional states and then trapped by QDs; at high temperature excitons quench through the X valley of barriers. Using rate equation excitons thermal transfer and quenching processes were analyzed quantitatively.

First principles study of N-N split interstitial in GaN nanowires

Atomic and electronic properties of N-N split interstitial in GaN nanowires have been investigated using first principles calculations. The formation energy calculations show that the N-N interstitial favors substituting an N atom at the surface of the nanowires. The interstitial induces localized states in the band gap of GaN nanowires.

Optical properties of AIInGaN quaternary alloys

Carrier recombination dynamics in AlInGaN alloy has been studied by photoluminescence (PL) and time-resolved photoluminescence (TRPL). The fast redshift of PL peak energy is observed and well fitted by a physical model considering the thermal activation and transfer processes. This result provides evidence for the exciton localization in the quantum dot (QD)-like potentials in our AlInGaN alloy. The TRPL signals are found to be described by a stretched exponential function of exp[(-t/tau)(beta)], indicating the presence of a significant disorder in the material. The disorder is attributed to a randomly distributed quantum dots or clusters caused by indium fluctuations. By studying the dependence of the dispersive exponent 8 on the temperature and emission energy, we suggest that the exciton hopping dominate the diffusion of carriers localized in the disordered quantum dots. Furthermore, the localized states are found to have OD density of states up to 250 K, since the radiative lifetime remains almost unchanged with increasing temperature.

Unusual photoresponse of indium doped ZnO/organic thin film heterojunction

Photoresponse of n-type indium-doped ZnO and a p-type polymer (PEDOT:PSS) heterojunction devices are studied, juxtaposed with the photoluminescence of the In-ZnO samples. In addition to the expected photoresponse in the ultraviolet, the heterojunctions exhibit significant photoresponse to the visible (532 nm). However, neither the doped ZnO nor PEDOT: PSS individually show any photoresponse to visible light. The sub-bandgap photoresponse of the heterojunction originates from visible photon mediated e-h generation between the In-ZnO valence band and localized states lying within the band gap. Though increased doping of In-ZnO has limited effect on the photoluminescence, it significantly diminishes the photoresponse. The study indicates that optimally doped devices are promising for the detection of wavelengths in selected windows in the visible. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4704655]

Propriétés optiques dans l'infrarouge des nanotubes de carbone et du graphène

Les nanotubes de carbone et le graphène sont des nanostructures de carbone hybridé en sp2 dont les propriétés électriques et optiques soulèvent un intérêt considérable pour la conception d’une nouvelle génération de dispositifs électroniques et de matériaux actifs optiquement. Or, de nombreux défis demeurent avant leur mise en œuvre dans des procédés industriels à grande échelle. La chimie des matériaux, et spécialement la fonctionnalisation covalente, est une avenue privilégiée afin de résoudre les difficultés reliées à la mise en œuvre de ces nanostructures. La fonctionnalisation covalente a néanmoins pour effet de perturber la structure cristalline des nanostructures de carbone sp2 et, par conséquent, d’affecter non seulement lesdites propriétés électriques, mais aussi les propriétés optiques en émanant. Il est donc primordial de caractériser les effets des défauts et du désordre dans le but d’en comprendre les conséquences, mais aussi potentiellement d’en exploiter les retombées. Cette thèse traite des propriétés optiques dans l’infrarouge des nanotubes de carbone et du graphène, avec pour but de comprendre et d’expliquer les mécanismes fondamentaux à l’origine de la réponse optique dans l’infrarouge des nanostructures de carbone sp2. Soumise à des règles de sélection strictes, la spectroscopie infrarouge permet de mesurer la conductivité en courant alternatif à haute fréquence des matériaux, dans une gamme d’énergie correspondant aux vibrations moléculaires, aux modes de phonons et aux excitations électroniques de faible énergie. Notre méthode expérimentale consiste donc à explorer un espace de paramètres défini par les trois axes que sont i. la dimensionnalité du matériau, ii. le potentiel chimique et iii. le niveau de désordre, ce qui nous permet de dégager les diverses contributions aux propriétés optiques dans l’infrarouge des nanostructures de carbone sp2. Dans un premier temps, nous nous intéressons à la spectroscopie infrarouge des nanotubes de carbone monoparois sous l’effet tout d’abord du dopage et ensuite du niveau de désordre. Premièrement, nous amendons l’origine couramment acceptée du spectre vibrationnel des nanotubes de carbone monoparois. Par des expériences de dopage chimique contrôlé, nous démontrons en effet que les anomalies dans lespectre apparaissent grâce à des interactions électron-phonon. Le modèle de la résonance de Fano procure une explication phénoménologique aux observations. Ensuite, nous établissons l’existence d’états localisés induits par la fonctionnalisation covalente, ce qui se traduit optiquement par l’apparition d’une bande de résonance de polaritons plasmons de surface (nanoantenne) participant au pic de conductivité dans le térahertz. Le dosage du désordre dans des films de nanotubes de carbone permet d’observer l’évolution de la résonance des nanoantennes. Nous concluons donc à une segmentation effective des nanotubes par les greffons. Enfin, nous montrons que le désordre active des modes de phonons normalement interdits par les règles de sélection de la spectroscopie infrarouge. Les collisions élastiques sur les défauts donnent ainsi accès à des modes ayant des vecteurs d’onde non nuls. Dans une deuxième partie, nous focalisons sur les propriétés du graphène. Tout d’abord, nous démontrons une méthode d’électrogreffage qui permet de fonctionnaliser rapidement et à haute densité le graphène sans égard au substrat. Par la suite, nous utilisons l’électrogreffage pour faire la preuve que le désordre active aussi des anomalies dépendantes du potentiel chimique dans le spectre vibrationnel du graphène monocouche, des attributs absents du spectre d’un échantillon non fonctionnalisé. Afin d’expliquer le phénomène, nous présentons une théorie basée sur l’interaction de transitions optiques intrabandes, de modes de phonons et de collisions élastiques. Nous terminons par l’étude du spectre infrarouge du graphène comportant des îlots de bicouches, pour lequel nous proposons de revoir la nature du mécanisme de couplage à l’œuvre à la lumière de nos découvertes concernant le graphène monocouche.

Étude de dispositifs électroniques moléculaires à l'aide de modèles simples

Cette thèse en électronique moléculaire porte essentiellement sur le développement d’une méthode pour le calcul de la transmission de dispositifs électroniques moléculaires (DEMs), c’est-à-dire des molécules branchées à des contacts qui forment un dispositif électronique de taille moléculaire. D’une part, la méthode développée vise à apporter un point de vue différent de celui provenant des méthodes déjà existantes pour ce type de calculs. D’autre part, elle permet d’intégrer de manière rigoureuse des outils théoriques déjà développés dans le but d’augmenter la qualité des calculs. Les exemples simples présentés dans ce travail permettent de mettre en lumière certains phénomènes, tel que l’interférence destructive dans les dispositifs électroniques moléculaires. Les chapitres proviennent d’articles publiés dans la littérature. Au chapitre 2, nous étudions à l’aide d’un modèle fini avec la méthode de la théorie de la fonctionnelle de la densité de Kohn-Sham un point quantique moléculaire. De plus, nous calculons la conductance du point quantique moléculaire avec une implémentation de la formule de Landauer. Nous trouvons que la structure électronique et la conductance moléculaire dépendent fortement de la fonctionnelle d’échange et de corrélation employée. Au chapitre 3, nous discutons de l’effet de l’ajout d’une chaîne ramifiée à des molécules conductrices sur la probabilité de transmission de dispositifs électroniques moléculaires. Nous trouvons que des interférences destructives apparaissent aux valeurs propres de l’énergie des chaînes ramifiées isolées, si ces valeurs ne correspondent pas à des états localisés éloignés du conducteur moléculaire. Au chapitre 4, nous montrons que les dispositifs électroniques moléculaires contenant une molécule aromatique présentent généralement des courants circulaires qui sont associés aux phénomènes d’interférence destructive dans ces systèmes. Au chapitre 5, nous employons l’approche « source-sink potential » (SSP) pour étudier la transmission de dispositifs électroniques moléculaires. Au lieu de considérer les potentiels de sources et de drains exactement, nous utilisons la théorie des perturbations pour trouver une expression de la probabilité de transmission, T(E) = 1 − |r(E)|2, où r(E) est le coefficient de réflexion qui dépend de l’énergie. Cette expression dépend des propriétés de la molécule isolée, en effet nous montrons que c’est la densité orbitalaire sur les atomes de la molécule qui sont connectés aux contacts qui détermine principalement la transmission du dispositif à une énergie de l’électron incident donnée. Au chapitre 6, nous présentons une extension de l’approche SSP à un canal pour des dispositifs électroniques moléculaires à plusieurs canaux. La méthode à multiples canaux proposée repose sur une description des canaux propres des états conducteurs du dispositif électronique moléculaire (DEM) qui sont obtenus par un algorithme auto-cohérent. Finalement, nous utilisons le modèle développé afin d’étudier la transmission du 1-phényl-1,3-butadiène branché à deux rangées d’atomes couplées agissant comme contacts à gauche et à la droite.