Optical Absorption in N-Dimensional Colloidal Quantum Dot Arrays: Influence of Stoichiometry and Applications in Intermediate Band Solar Cells.

We present a theoretical atomistic study of the optical properties of non-toxic InX (X = P, As, Sb) colloidal quantum dot arrays for application in photovoltaics. We focus on the electronic structure and optical absorption and on their dependence on array dimensionality and surface stoichiometry motivated by the rapid development of experimental techniques to achieve high periodicity and colloidal quantum dot characteristics. The homogeneous response of colloidal quantum dot arrays to different light polarizations is also investigated.

Band-like transport in "green" quantum dot films: The effect of composition and stoichiometry.

Two-dimensional quantum dot (QD) arrays are considered as promising candidates for a wide range of applications that heavily rely on their transport properties. Existing QD films, however, are mainly made of either toxic or heavy-metal-based materials, limiting their applications and the commercialization of devices. In this theoretical study, we provide a detailed analysis of the transport properties of "green" colloidal QD films (In-based and Ga-based), identifying possible alternatives to their currently used toxic counterparts.

Indirect to Direct Band Gap Transformation by Surface Engineering in Semiconductor Nanostructures.

Indirect band gap semiconductor materials are routinely exploited in photonics, optoelectronics, and energy harvesting. However, their optical conversion efficiency is low, due to their poor optical properties, and a wide range of strategies, generally involving doping or alloying, has been explored to increase it, often, however, at the cost of changing their material properties and their band gap energy, which, in essence, amounts to changing them into different materials altogether. A key challenge is therefore to identify effective strategies to substantially enhance optical transitions at the band gap in these materials without sacrificing their intrinsic nature.

Decoupling Radiative and Auger Processes in Semiconductor Nanocrystals by Shape Engineering.

One of the most challenging aspects of semiconductor nanotechnology is the presence of extremely efficient nonradiative decay pathways (known as Auger processes) that hinder any attempt at creating population inversion and obtaining gain in nanocrystals. What is even more frustrating is that, in most cases, the strategies adopted to slow down Auger in these nanostructures also lead to a comparable increase in the radiative recombination times, so that there is no overall improvement from the point of view of their applicability as emissive media. Here we present a comprehensive theoretical characterization of CdTe tetrapods and show that in these versatile nanostructures it is possible to achieve a complete decoupling between radiative and Auger processes, where the latter can be strongly suppressed compared to spherical structures, by careful shape engineering, without affecting the efficiency of radiative recombination.

Inverse-designed semiconductor nanocatalysts for targeted CO reduction in water.

The most commonly used photocatalyst for CO reduction is TiO. However, this semiconductor material is far from being ideally suited for this purpose, owing to its inefficient energy harvesting (it absorbs in the UV), low reduction rates (it exhibits short carrier lifetimes), and lack of selectivity with respect to competing reactions (such as the nearly isoenergetic and kinetically more favourable water reduction). In this work we compile a wish-list of properties for the ideal photocatalyst (including high reaction selectivity, availability of multiple redox equivalents at one time, large contact area for CO adsorption with independently tunable band gap, and availability of electrons and holes at different locations on the surface for the two redox reactions to take place), and, using the principles of inverse design, we engineer a semiconductor nanostructure that not only meets all the necessary fundamental criteria to act as a catalyst for CO reduction, but also exhibits all the wish-list properties, as confirmed by our state-of-the-art atomistic semi-empirical pseudopotential modelling.

Tuning the Radiative Lifetime in InP Colloidal Quantum Dots by Controlling the Surface Stoichiometry.

InP nanocrystals exhibit a low photoluminescence quantum yield. As in the case of CdS, this is commonly attributed to their poor surface quality and difficult passivation, which give rise to trap states and negatively affect emission. Hence, the strategies adopted to improve their quantum yield have focused on the growth of shells, to improve passivation and get rid of the surface states.

Charge Dynamics in Quantum-Dot-Acceptor Complexes in the Presence of Confining and Deconfining Ligands.

Nanocrystal surface functionalization is becoming widespread for applications exploiting fast charge extraction or ultrasensitive redox reactions. A variety of molecular acceptors are being linked to the dot surface via a new generation of organic ligands, ranging from neutral linkers to charge delocalizers. Understanding how core states interact with these molecular orbitals, localized outside the dot, is paramount for optimizing the design of efficient nanocrystal-acceptor conjugates.

Optical properties of nanocrystal films: blue shifted transitions as signature of strong coupling.

We present a theoretical study at the atomistic level of the optical properties of semiconductor nanocrystal films. We investigate the dependence of the absorption coefficient on size, inter-dot separation, surface stoichiometry and morphology, temperature, position of the Fermi level and light polarization. Our results show that, counter-intuitively, huge shifts are expected in some intra-band transitions for strongly coupled arrays, in contrast with the predicted and observed shift of the band gap absorption in such systems.

New strategies for colloidal-quantum-dot-based intermediate-band solar cells.

The intermediate-band solar cell (IBSC) concept promises to increase the efficiency limit in a single-junction solar cell through the absorption of below-bandgap-energy photons. Despite their operating principle having been proposed over 20 years ago, IBSCs have not delivered on this promise yet, and the devices fabricated so far, mainly based on embedded epitaxial quantum dots, have instead operated with lower efficiency than conventional solar cells. A new paradigm, based on the exploitation as the intermediate band of the intragap states naturally occurring in the density functional theory description of colloidal (i.

Theoretical Characterization of GaSb Colloidal Quantum Dots and Their Application to Photocatalytic CO Reduction with Water.

With a large exciton Bohr radius and a high hole mobility in the bulk, GaSb is an important semiconductor material for technological applications. Here, we present a theoretical investigation into the evolution of some of its most fundamental characteristics at the nanoscale. GaSb emerges as a widely tunable, potentially disruptive new colloidal material with huge potential for application in a wide range of fields.

Efficient, non-stochastic, Monte-Carlo-like-accurate method for the calculation of the temperature-dependent mobility in nanocrystal films.

We present a new non-stochastic framework for the calculation of the temperature dependence of the mobility in nanocrystal films, that enables speed-ups of several orders of magnitude compared to conventional Monte Carlo approaches, while maintaining a similar accuracy. Our model identifies a new contribution to the reduction of the mobility with increasing temperature in these systems (conventionally attributed to interactions with phonons), that alone is sufficient to explain the observed experimental trend up to room temperature. Comparison of our results with the theoretical predictions of the hopping model and the observed temperature dependence of recent field-effect mobility measurements in nanocrystal films, provides the means to discriminate between band-like and hopping transport and a definitive answer to whether the former has been achieved in quantum dot films.

Suppression of Auger Recombination in Nanocrystals via Ligand-Assisted Wave Function Engineering in Reciprocal Space.

A limiting factor to the technological application of conventional semiconductor nanostructures is their fast Auger recombination time. Strategies to increase it have so far mostly focused on decreasing the electron-hole wave function overlap in real space through structural modifications involving either elongation or shell growth. Here we propose an alternative mechanism for Auger recombination suppression: a decrease in the overlap of electron and hole wave functions in reciprocal space.

Exciton Dynamics in InSb Colloidal Quantum Dots.

Extraordinarily fast biexciton decay times and unexpectedly large optical gaps are two striking features observed in InSb colloidal quantum dots that have remained so far unexplained. The former, should its origin be identified as an Auger recombination process, would have important implications regarding carrier multiplication efficiency, suggesting these nanostructures as potentially ideal active materials in photovoltaic devices. The latter could offer new insights into the factors that influence the electronic structure and consequently the optical properties of systems with reduced dimensionality and provide additional means to fine-tune them.

Origins of photoluminescence decay kinetics in CdTe colloidal quantum dots.

Recent experimental studies have identified at least two nonradiative components in the fluorescence decay of solutions of CdTe colloidal quantum dots (CQDs). The lifetimes reported by different groups, however, differed by orders of magnitude, raising the question of whether different types of traps were at play in the different samples and experimental conditions and even whether different types of charge carriers were involved in the different trapping processes. Considering that the use of these nanomaterials in biology, optoelectronics, photonics, and photovoltaics is becoming widespread, such a gap in our understanding of carrier dynamics in these systems needs addressing.

Effect of Chloride Passivation on Recombination Dynamics in CdTe Colloidal Quantum Dots.

Colloidal quantum dots (CQDs) can be used in conjunction with organic charge-transporting layers to produce light-emitting diodes, solar cells and other devices. The efficacy of CQDs in these applications is reduced by the non-radiative recombination associated with surface traps. Here we investigate the effect on the recombination dynamics in CdTe CQDs of the passivation of these surface traps by chloride ions.

Origins of improved carrier multiplication efficiency in elongated semiconductor nanostructures.

Nanorod solar cells have been attracting a lot of attention recently, as they have been shown to exhibit a lower carrier multiplication onset and a higher quantum efficiency than quantum dots with similar bandgaps. The underpinning theory for this phenomenon is not yet completely understood, and is still the subject of ongoing study. Here we conduct a theoretical investigation into CM efficiency in elongated semiconductor nanostructures with square cross section made of different materials (GaAs, GaSb, InAs, InP, InSb, CdSe, Ge, Si and PbSe), using a single-band effective mass model.

Auger-assisted electron transfer from photoexcited semiconductor quantum dots.

Although quantum confined nanomaterials, such as quantum dots (QDs) have emerged as a new class of light harvesting and charge separation materials for solar energy conversion, theoretical models for describing photoinduced charge transfer from these materials remain unclear. In this paper, we show that the rate of photoinduced electron transfer from QDs (CdS, CdSe, and CdTe) to molecular acceptors (anthraquinone, methylviologen, and methylene blue) increases at decreasing QD size (and increasing driving force), showing a lack of Marcus inverted regime behavior over an apparent driving force range of ∼0-1.3 V.

Universal trapping mechanism in semiconductor nanocrystals.

Size tunability of the optical properties and inexpensive synthesis make semiconductor nanocrystals one of the most promising and versatile building blocks for many modern applications such as lasers, single-electron transistors, solar cells, and biological labels. The performance of these nanocrystal-based devices is however compromised by efficient trapping of the charge carriers. This process exhibits different features depending on the nanocrystal material, surface termination, size, and trap location, leading to the assumption that different mechanisms are at play in each situation.

Hole surface trapping in CdSe nanocrystals: dynamics, rate fluctuations, and implications for blinking.

Carrier trapping is one of the main sources of performance degradation in nanocrystal-based devices. Yet the dynamics of this process is still unclear. We present a comprehensive investigation into the efficiency of hole transfer to a variety of trap sites located on the surface of the core or the shell or at the core/shell interface in CdSe nanocrystals with both organic and inorganic passivation, using the atomistic semiempirical pseudopotential approach.

Size-dependent valence and conduction band-edge energies of semiconductor nanocrystals.

Through the use of photoelectron spectroscopy in air (PESA), we investigate the size-dependent valence and conduction band-edge energies of CdSe, CdTe, PbS, and PbSe semiconductor quantum dots (QDs). The results are compared to those of previous studies, based on differing experimental methods, and to theoretical calculations based on k·p theory and state-of-the-art atomistic semiempirical pseudopotential modeling. To accurately map out the energy level landscapes of QDs as a function of size, the QDs must be passivated by comparable surface chemistries.

Photoinduced surface trapping and the observed carrier multiplication yields in static CdSe nanocrystal samples.

Photocharging has been suggested recently as the explanation for the spread of carrier multiplication yields reported by different groups. If this hypothesis can be plausible in the case of PbSe, it is inconsistent with the reported experimental data relative to CdSe nanocrystals and cannot therefore explain the large discrepancies found in that material system between static and stirred samples. An alternative explanation, photoinduced surface trapping, is suggested here, based on the results of atomistic semiempirical pseudopotential calculations of the Auger recombination rates in a number of excitonic configurations including a variety of surface traps, which show that the photoinduced surface trapping of the hole, which leaves the core negatively charged (but the nanocrystal neutral overall), can lead to recombination rates that are indistinguishable from those of a conventional biexciton with four core-delocalized carriers and therefore result in exaggerated CM yields in static samples.

Model-independent determination of the carrier multiplication time constant in CdSe nanocrystals.

The experimental determination of the carrier multiplication (CM) time constant is complicated by the fact that this process occurs within the initial few hundreds of femtoseconds after excitation and, in transient-absorption experiments, cannot be separated from the buildup time of the 1p-state population. This work provides an accurate theoretical determination of the electron relaxation lifetime during the last stage of the p-state buildup, in CdSe nanocrystals, in the presence of a single photogenerated hole (no CM) and of a hole plus an additional electron-hole pair (following CM). From the invariance of the 1p buildup time observed experimentally for excitations above and below the CM threshold producing hot carriers with the same average per-exciton excess energy, and the calculated corresponding variations in the electron decay time in the two cases, an estimate is obtained for the carrier multiplication time constant.

Direct and inverse auger processes in InAs nanocrystals: can the decay signature of a trion be mistaken for carrier multiplication?

A complete and detailed theoretical investigation of the main processes involved in the controversial detection and quantification of carrier multiplication (CM) is presented, providing a coherent and comprehensive picture of excited state relaxation in InAs nanocrystals (NCs). The observed rise and decay times of the 1S transient bleach are reproduced, in the framework of the Auger model, using an atomistic semiempirical pseudopotential method, achieving excellent agreement with experiment. The CM time constants for small core-only and core/shell nanocrystals are obtained as a function of the excitation energy, assuming an impact-ionization-like process.

The effect of small elongations on the electronic and optical signatures in InAs nanocrystal quantum dots.

We present a detailed theoretical investigation of the electronic structure and optical properties of InAs nanocrystals at the transition from spheres to rods. Using a semiempirical pseudopotential approach, we predict that, despite the qualitative similarity of both intra- and inter-band optical spectra, for NCs with R>15 Å even slight elongations should result in shifts of the order of hundreds of meV in the spacings between STM peaks measured in the positive bias regime, in the position of the intra-band absorption peaks associated with transitions within the conduction band and in the separation between the first and the fifth peak in PLE experiments. Our results show that, based on the spectroscopic data, it should be possible to discriminate between spherical and elongated NCs with aspect ratios of length over diameter as small as 1.

Excited-state relaxation in PbSe quantum dots.

In solids the phonon-assisted, nonradiative decay from high-energy electronic excited states to low-energy electronic excited states is picosecond fast. It was hoped that electron and hole relaxation could be slowed down in quantum dots, due to the unavailability of phonons energy matched to the large energy-level spacings ("phonon-bottleneck"). However, excited-state relaxation was observed to be rather fast (< or =1 ps) in InP, CdSe, and ZnO dots, and explained by an efficient Auger mechanism, whereby the excess energy of electrons is nonradiatively transferred to holes, which can then rapidly decay by phonon emission, by virtue of the densely spaced valence-band levels.