Negative Trions Research Articles

Carrier-doping as a tool to probe the electronic structure and multi-carrier recombination dynamics in heterostructured colloidal nanocrystals.

Heterostructured colloidal nanocrystals, such as core/shells and dot-in-rods, enable new spectral and dynamic properties otherwise unachievable with single-component nanocrystals or quantum dots (QDs). For example, the electron and hole wavefunctions can be engineered such that they are either both confined in the same domain or (partially) separated over different domains in the heterostructures, which are the so-called type I or (quasi-) type II localization regimes, respectively. A critical factor dictating the carrier localization regime is the band alignment or electronic structure of the heterostructure, which, however, is difficult to measure and hence is often ambiguous. In this work, using CdSe@CdS dot-in-rods (DIRs) as a model system, we show that band edge carrier-doping is a simple-yet-powerful tool to probe the electronic structure of heterostructures. By doping an electron into the CdSe core and then observing whether the doped electron bleaches band edge absorption of only the core or those of both the core and shell, we can easily differentiate the type I and quasi-type II structures. A systematic study of DIRs with various dimensions shows that the extent of electron wavefunction delocalization can be tuned by the core sizes and rod diameters. Comparison with the electronic structure determined from transient absorption measurements also reveals the important role of electron-hole binding in affecting the delocalization of electron wavefunction. In addition to probing the electronic structure, the doped electron allows for studying multi-carrier recombination dynamics in these heterostructures which plays a vital role in their many optical and optoelectronic applications. Specifically, by comparing the band edge exciton recombination kinetics of the doped and neutral DIRs, we can extract the negative trion lifetime, which can be further used to derive the positive trion lifetime when combined with biexciton lifetime measurements. These lifetimes also depend sensitively on the core sizes and rod diameters of the DIRs.

Diversity of trion states and substrate effects in the optical properties of an MoS2 monolayer

Almost all experiments and future applications of transition metal dichalcogenide monolayers rely on a substrate for mechanical stability, which can significantly modify the optical spectra of the monolayer. Doping from the substrate might lead to the domination of the spectra by trions. Here we show by ab initio many-body theory that the negative trion (A−) splits into three excitations, with both inter- and intra-valley character, while the positive counterpart (A+) consists of only one inter-valley excitation. Furthermore, the substrate enhances the screening, which renormalizes both band gap and exciton as well as the trion-binding energies. We verify that these two effects do not perfectly cancel each other, but lead to red-shifts of the excitation energies for three different substrates ranging from a wide-bandgap semiconductor up to a metal. Our results explain recently found experimental splittings of the lowest trion line as well as excitation red-shifts on substrates.

Dielectric environment and/or random disorder effects on free, charged and localized excitonic states in monolayer WS2

Excitonic effects play an important role on the optoelectronic behavior of atomically thin two-dimensional (2D) crystals of the WS2 transition metal dichalcogenide. In this paper, neutral and charged exciton behaviors in monolayer WS2 are handled within effective-mass approximation for which the critical parameters are ensured from our ab initio calculations. Firstly, we reveal an exciton series with a novel energy dependence on the orbital angular momentum. Considerable control of the dielectric environment on neutral and charged excitons binding energies is elucidated. We demonstrate that for accepted values of effective masses, the negative and positive trion binding energies should be identical. Secondly, localization of neutral exciton center of mass motion by random potential arising from monolayer defects is also studied. The results obtained are in agreement with available experimental work.

Radiative Decay of a Trion in a Quantum Well of a Semiconductor Heterostructure

A quasi-classical model for the decay of a negative trion (exciton + electron) in a single crystalline quantum well (QW) into a c-band electron and the exciton followed by recombination of the electron and hole constituting the exciton was developed. It was shown that the trion binding energy increased if the QW quantum-sized energy levels were populated by electrons from a semiconductor matrix selectively doped with donors. Calculations established that the trion emission line width was slightly larger than that for a single exciton. The results as a whole agreed with known experimental data on the low-temperature radiative decay of trions in a QW. It was pointed out that the population of the trion quantum-sized energy levels could be changed by the application an external longitudinal (along the QW) electric field. A scheme for a stationary light-emitting device based on radiative transitions of trions (not leading to their decay) between quantum-sized energy levels was proposed.

Superposition Principle in Auger Recombination of Charged and Neutral Multicarrier States in Semiconductor Quantum Dots

Application of colloidal semiconductor quantum dots (QDs) in optical and optoelectronic devices is often complicated by unintentional generation of extra charges, which opens fast nonradiative Auger recombination pathways whereby the recombination energy of an exciton is quickly transferred to the extra carrier(s) and ultimately dissipated as heat. Previous studies of Auger recombination have primarily focused on neutral and, more recently, negatively charged multicarrier states. Auger dynamics of positively charged species remains more poorly explored due to difficulties in creating, stabilizing, and detecting excess holes in the QDs. Here we apply photochemical doping to prepare both negatively and positively charged CdSe/CdS QDs with two distinct core/shell interfacial profiles ("sharp" versus "smooth"). Using neutral and charged QD samples we evaluate Auger lifetimes of biexcitons, negative and positive trions (an exciton with an extra electron or a hole, respectively), and multiply negatively charged excitons. Using these measurements, we demonstrate that Auger decay of both neutral and charged multicarrier states can be presented as a superposition of independent elementary three-particle Auger events. As one of the manifestations of the superposition principle, we observe that the biexciton Auger decay rate can be presented as a sum of the Auger rates for independent negative and positive trion pathways. By comparing the measurements on the QDs with the "sharp" versus "smooth" interfaces, we also find that while affecting the absolute values of Auger lifetimes, manipulation of the shape of the confinement potential does not lead to violation of the superposition principle, which still allows us to accurately predict the biexciton Auger lifetimes based on the measured negative and positive trion dynamics. These findings indicate considerable robustness of the superposition principle as applied to Auger decay of charged and neutral multicarrier states, suggesting its generality to quantum-confined nanocrystals of arbitrary compositions and complexities.

Excitons and trions in single and vertically coupled quantum dots under an electric field

We present a theoretical study of the exciton (X0), the positive and negative trions (X+ and X−) in single and vertically coupled configurations of self-assembled InGaAs quantum dots under an electric field. The quantum states of X0, X+ and X− have been investigated using a quasi-one-dimensional (Q1D) model within the effective-mass approximation. For the single quantum dots, the electric-field dependent energy levels and the average inter-particle distances for the exciton and trions have been calculated. For the coupled quantum dots, the ground and the excited states for X0, X+ and X− have also been calculated and discussed. It is found that either the hole or the electron can be tuned into resonance states by the electric field and that the transition energy spectra for both trions consequently show crossing and anticrossing patterns. The recombination probabilities of the exciton and trion optical transitions are also calculated. The theoretical results have been compared with previously reported photoluminescence data and qualitative agreement is obtained. The trion conditional wave functions are also plotted under different electric field intensities, and it is found that a molecular orbital can be formed at a critical electric field intensity. The evolution of the energy levels of the trions in coupled quantum dots can be explained by the interplay of particle transfer and the electric field.

Large‐Area 2D/3D MoS2–MoO2 Heterostructures with Thermally Stable Exciton and Intriguing Electrical Transport Behaviors

To date, scale‐up fabrication of transition metal dichalcogenide (TMD‐) based 2D/2D or 2D/3D heterostructures with specific functionalities is still a great challenge. This study, for the first time, reports on the controllable synthesis of large‐area and continuous 2D/3D semiconductor/metal heterostructures consisting of monolayer MoS2 and bulk MoO2 with unique electrical and optical properties via one‐step, vapor‐transport‐assisted rapid thermal processing. The temperature‐dependent electrical transport measurements reveal that the 2D/3D MoS2–MoO2 heterostructure grown on SiO2/Si substrates exhibits metallic phase, while this heterostructure becomes a low‐resistance semiconductor when it is grown on fused silica, which is attributed to the different degrees of sulfurization on different substrates, as being confirmed by surface potential analyses. Photoluminescence measurements taken on the MoS2–MoO2 heterostructures reveal the simultaneous presence of both negative trions and neutral excitons, while only neutral excitons are observed in the monolayer MoS2. The trion‐binding energy is determined to be ≈27 meV, and the trion signal persists up to 330 K, indicating significant stability at room temperature. This work not only provides a new platform for understanding the intriguing physics in TMD‐based heterostructures but also enables the design of more complicated devices with potential applications in nanoelectronics and nanophotonics.

Excitation energy dependence of initial phase shift in Kerr rotation of resident electron spin polarization in a CdTe single quantum well

AbstractThe generation dynamics of a resident electron spin polarization involve the formation and transformation of the associated optically excited states depending on the excitation photon energy. Initial phase shift in the precession of a resident electron spin polarization gives the important clues to reveal the interplay between the associated excited states and resident electrons. In this work, the excitation energy dependence of the initial phase shift in Kerr rotation of a resident electron spin polarization is investigated in a CdTe/CdMgTe single quantum well under a low magnetic field. Through the careful analysis of the spin precession, the excited electron–heavy‐hole pairs show unique spin dynamics when the excitation energy is increasing past the neutral exciton resonance. Meanwhile, the negative initial phase shift becomes significantly large in magnitude. The larger initial phase shift and the unique precession traces are caused by the transformation from neutral excitons to negative trions with accompanying the hole spin‐flip. The exciton‐to‐trion transformation time is estimated experimentally to be 160 ps.

Excitonic fine structure and binding energies of excitonic complexes in single InAs quantum dashes

The fundamental electronic and optical properties of elongated InAs nanostructures embedded in quaternary InGaAlAs barrier are investigated by means of high-resolution optical spectroscopy and many-body atomistic tight-binding theory. These wire-like shaped, self-assembled nanostructures are known as quantum dashes and are typically formed during the molecular beam epitaxial growth on InP substrates. In this paper, we study properties of excitonic complexes confined in quantum dashes emitting in a broad spectral range from below 1.2 to 1.55 \ensuremath{\mu}m. We find peculiar trends for the biexciton and negative trion binding energies, with pronounced trion binding in smaller size quantum dashes. These experimental findings are then compared and qualitatively explained by atomistic theory. The theoretical analysis shows a fundamental role of correlation effects for the absolute values of excitonic binding energies. Eventually, we determine the bright exciton fine structure splitting (FSS), where both the experiment and theory predict a broad distribution of the splitting varying from below 50 to almost 180 \ensuremath{\mu}eV. We identify several key factors determining the FSS values in such nanostructures, including quantum dash size variation and composition fluctuations.

Simultaneous Hosting of Positive and Negative Trions and the Enhanced Direct Band Emission in MoSe2/MoS2 Heterostacked Multilayers.

Heterostacking of layered transition-metal dichalcogenide (LTMD) monolayers (1Ls) offers a convenient way of designing two-dimensional exciton systems. Here we demonstrate the simultaneous hosting of positive trions and negative trions in heterobilayers made by vertically stacking 1L MoSe2 and 1L MoS2. The charge transfer occurring between the 1Ls of MoSe2 and MoS2 converted the polarity of trions in 1L MoSe2 from negative to positive, resulting in the presence of positive trions in the 1L MoSe2 and negative trions in the 1L MoS2 of the same heterostacked bilayer. Significantly enhanced MoSe2 photoluminescence (PL) in the heterostacked bilayers compared to the PL of 1L MoSe2 alone suggests that, unlike other previously reported heterostacked bilayers, direct band transition of 1L MoSe2 in heterobilayer was enhanced after the vertical heterostacking. Moreover, by inserting hexagonal BN monolayers between 1L MoSe2 and 1L MoS2, we were able to adjust the charge transfer to maximize the MoSe2 PL of the heteromultilayers and have achieved a 9-fold increase of the PL emission. The enhanced optical properties of our heterostacked LTMDs suggest the exciting possibility of designing LTMD structures that exploit the superior optical properties of 1L LTMDs.

Magnetic field induced trions in a Telluride-based II–VI material

Effects of geometrical confinement and magnetic field strength on the binding energies of trions (positive trion and negative trion) in a CdTe/ZnTe parabolic dot are investigated. Coulomb interaction energy is obtained by employing Hartree potential and the results are found numerically. The modified Chandrasekhar wavefunctions are employed to obtain the respective energies. The confined energies and the respective binding energies of charged trions are investigated by the self-consistent method. The Poisson equation is used to find the electron and hole potentials. The dielectric mismatch is included throughout the calculations. Magneto-optical transition energies for charged trions in the presence of magnetic field are observed. The effective Landé factor is brought out. Raman shift and the Raman intensity of positive and negative trions for various magnetic field strengths in the CdTe/ZnTe nanostructures are investigated. The dependence of Raman resonance on the magnetic field and the geometrical confinement effect is brought out.

Biexciton Auger Recombination in CdSe/CdS Core/Shell Semiconductor Nanocrystals.

A theoretical study of the positive and negative trion channels in the nonradiative Auger recombination of band-edge biexcitons (BXs) in CdSe/CdS core/shell nanocrystals (NCs) is presented. The theory takes into account the BX fine-structure produced by NC asymmetry and hole-hole exchange interaction. The calculations show that growth of CdS shell upon CdSe core suppresses the rate of the Auger recombination via negative trion channel, while the more efficient Auger recombination via positive trion channel shows much weaker dependence on the shell thickness. The demonstrated oscillatory dependence of the BX Auger rate on the core and shell sizes is explained qualitatively in terms of overlap of the ground and excited carrier wave functions. The calculations show that raise of temperature accelerates the Auger recombination in CdSe/CdS NCs due to reduction of the bulk energy gaps of CdSe and CdS.

Light- and heavy-hole trions bound to isoelectronic centers

Optical control strategies in semiconductor nanostructures have almost exclusively relied on heavy-hole exciton and trion states. Interestingly, optical access to both light- and heavy-hole trions may provide the missing resource for consolidating all single qubit operations in a single magnetic field configuration. In this work, we describe the conditions in which nearly degenerate light- and heavy-hole trions can be exploited for implementing electron spin initialization, control, and single-shot readout in systems of ${C}_{s}$ or higher symmetry. Then, we experimentally demonstrate that a previously unidentified nitrogen pair configuration in GaAs exhibiting ${C}_{s}$ symmetry binds both light- and heavy-hole excitons and negative trions. A detailed analysis of the energy and polarization of the emission allows determining the crystal-field and exchange coefficients, the electron, hole, and exciton Zeeman coefficients, and the light- and heavy-hole character of all states. This analysis also reveals that light- and heavy-hole trion states provide the $\mathrm{\ensuremath{\Lambda}}$ level structure necessary for initialization and control along with an energetically protected cycling transition compatible with single-shot readout.

Multistate Blinking and Scaling of Recombination Rates in Individual Silica-Coated CdSe/CdS Nanocrystals

Nonradiative Auger recombination is the primary exciton loss mechanism in colloidal nanocrystals and an impediment for prospective optoelectronic applications. Recent development of new core/shell nanocrystals with suppressed Auger recombination rates has opened the possibility for studying multicarrier states using time-resolved photoluminescence (PL) spectroscopy. An important aspect not addressed in previous works is the scaling of radiative and nonradiative decay rates with the increasing number and type of excitons in individual nanocrystals. Here we conduct extensive single-dot PL spectroscopy of emissive states in PL blinking trajectories of giant silica-coated CdSe/CdS nanocrystals. At low fluences, we observe the appearance of neutral and charged exciton (trion) states. Both negative and positive trions show strongly suppressed Auger recombination rates resulting in PL quantum yields close to 50%. At higher excitation powers, we observe consecutive emergence of lower efficiency states, indicative...

Excited Biexcitons in Transition Metal Dichalcogenides.

The Stochastic Variational Method (SVM) is used to show that the effective mass model correctly estimates the binding energies of excitons and trions but fails to predict the experimental binding energy of the biexciton. Using high-accuracy variational calculations, it is demonstrated that the biexciton binding energy in transition metal dichalcogenides is smaller than the trion binding energy, contradicting experimental findings. It is also shown that the biexciton has bound excited states and that the binding energy of the L = 0 excited state is in very good agreement with experimental data. This excited state corresponds to a hole attached to a negative trion and may be a possible resolution of the discrepancy between theory and experiment.

Observation of two distinct negative trions in tungsten disulfide monolayers

We report on the observation of two distinct photogenerated negative trion states TA and TB in two-dimensional tungsten disulfide (2D-WS2) monolayers. These trions are postulated to emerge from their parent excitons XA and XB, which originate from spin-orbit-split (SOS) levels in the conduction band (CB) and valence band (VB). Time-resolved spectroscopy measurements suggests that Pauli blocking controls a competition process between TA and TB photoformation, following dissociation of XA and XB through hole trapping at internal or substrate defect sites. While TA arises directly from its parent XA, TB emerges through a different transition accessible only after XB dissociates through a hole trapping channel. This discovery of additional optically-active band-edge transitions in atomically-thin metal dichalcogenides may revolutionize optoelectronic applications and fundamental research opportunities for many-body interaction physics. Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2D-WS2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ~2.02 eV (T1) and ~1.98 eV (T2). The dynamics measurements indicate that trion formation by the probe is enabled by photodoped electrons that remain after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics ofmore » the excitons XA and XB’s characteristic absorption bands, at ~2.03 and ~2.40 eV, respectively, were separately monitored and compared with the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump 2.4 eV, which is just sufficient to excite exciton XB. The dynamics of trion T2 formation are found to correlate with the disappearance of the bleach of XB exciton, which indicates the involvement of holes participating in the bleach dynamics of exciton XB. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T2. Since the proposed trion formation process here involves exciton dissociation through hole-trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role that defects have in defining the optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technology applications.« less

Electronic and optical properties of exciton, trions and biexciton in II–VI parabolic quantum dot

Binding energies of exciton, trions and biexciton and their interband optical transition energies are studied in a CdTe/ZnTe quantum dot nanostructure taking into consideration the geometrical confinement effect. The radial spread of the wavefunctions, binding energies, optical transition energies, oscillator strength, radiative life time and the absorption coefficients of exciton, positively and negatively charged excitons and biexciton are carried out. It is found that the ratio of the radiative life time of exciton with the trions and biexciton enhances with the reduction of geometrical confinement. The results show that (i) the binding energies of exciton, positive and negative trions and the biexciton have strong influence on the reduction of geometrical confinement effect, (ii) the binding energy is found to decrease from the binding energies of exciton to positive trion through biexciton and negative trion binding energies, (iii) the oscillator strength of trions is found to be lesser than exciton and the biexciton and (iv) the electronic and optical properties of exciton, trions and the biexciton are considerably dependent on the spatial confinement, incident photon energy and the radiative life time. The obtained results are in good agreement with the other existing literature.

Reversed oxygen sensing using colloidal quantum wells towards highly emissive photoresponsive varnishes.

Colloidal quantum wells combine the advantages of size-tunable electronic properties with vast reactive surfaces that could allow one to realize highly emissive luminescent-sensing varnishes capable of detecting chemical agents through their reversible emission response, with great potential impact on life sciences, environmental monitoring, defence and aerospace engineering. Here we combine spectroelectrochemical measurements and spectroscopic studies in a controlled atmosphere to demonstrate the ‘reversed oxygen-sensing’ capability of CdSe colloidal quantum wells, that is, the exposure to oxygen reversibly increases their luminescence efficiency. Spectroelectrochemical experiments allow us to directly relate the sensing response to the occupancy of surface states. Magneto-optical measurements demonstrate that, under vacuum, heterostructured CdSe/CdS colloidal quantum wells stabilize in their negative trion state. The high starting emission efficiency provides a possible means to enhance the oxygen sensitivity by partially de-passivating the particle surfaces, thereby enhancing the density of unsaturated sites with a minimal cost in term of luminescence losses.

Size dependence of electron spin dephasing in InGaAs quantum dots

We investigate ensemble electron spin dephasing in self-assembled InGaAs/GaAs quantum dots (QDs) of different lateral sizes by employing optical Hanle measurements. Using low excitation power, we are able to obtain a spin dephasing time T2* (in the order of ns) of the resident electron after recombination of negative trions in the QDs. We show that T2* is determined by the hyperfine field arising from the frozen fluctuation of nuclear spins, which scales with the size of QDs following the Merkulov-Efros-Rosen model. This scaling no longer holds in large QDs, most likely due to a breakdown in the lateral electron confinement.

Optical detection of anisotropic g-factor and nuclear spin polarization in a single CdTe quantum well

Longitudinal and in-plane electron g-factors, and a nuclear spin polarization (NSP) have been evaluated precisely in a CdTe/Cd0.85Mg0.15Te single quantum well by using the time-resolved Kerr rotation and double lock-in detection techniques. Resident electron spin polarization (RESP) was formed via the negative trion formation and recombination, and RESP gave rise to NSP in an oblique magnetic field configuration. We observed the effective nuclear field of a few mT which was weak compared with that in III–V semiconductor nanostructures as expected, but the nuclear field can be converted to the maximal NSP of 12% in Faraday geometry.