We report here an assessment of carrier multiplication (CM) yields in PbSe and PbS nanocrystals (NCs) by a quantitative analysis of biexciton and exciton dynamics in transient photoluminescence decays. Interest in CM, the generation of more than one electron and hole in a semiconductor after absorption of one photon, has renewed in recent years because of reports suggesting greatly increased efficiencies in nanocrystalline materials compared to the bulk form, in which CM was otherwise too weak to be of consequence in photovoltaic energy conversion devices. In our PbSe and PbS NC samples, however, we estimate using transient photoluminescence that at most 0.25 additional e-h pairs are generated per photon even at energies hv > 5Eg, instead of the much higher values reported in the literature. We argue by comparing NC CM estimates and reported bulk values on an absolute energy basis, which we justify as appropriate on physical grounds, that the data reported thus far are inconclusive with respect to the importance of nanoscale-specific phenomena in the CM process.
The bulk moduli of PbS$_{x}$Se$_{1-x}$, PbS$_{x}$Te$_{1-x}$, and PbSe$_{x}$Te$_{1-x}$ have been recently determined [E. Skordas, Materials Science in Semiconductor Processing 43 (2016) 65-68] by employing a thermodynamical model, the so called $cBΩ$ model, which has been found to give successful results in several applications of defects in solids. Here, we suggest an alternative procedure for this determination which combines the $cBΩ$ model with the modified Born theory. The results are in satisfactory agreement with those deduced independently by the generalized gradient approximation appro…
Very recently, first-principle technique of full-potential linearized augmented plane-wave method, by using for exchange-correlation potential the generalized gradient approximation (GGA), was employed for the study of the lead chalcogenide semiconductors' alloys PbS$_{x}$Se$_{1-x}$, PbS$_{x}$Te$_{1-x}$ and PbSe$_{x}$Te$_{1-x}$. These density functional calculations led to the determination of structural, electronic and optical properties, including the values of lattice constants and bulk moduli as a function of composition. Here, we investigate the latter properties, but by employing a therm…
While each atom species in PbSe corresponds to a single crystallographic site and transport measurements reveal a single carrier density, $^{207}$Pb NMR reveals a more complicated picture than previously thought comprising three discrete homogeneous carrier components, each associated with $n$- or $p$-type carrier fractions. The origins of these fractions are discussed in terms of electronic heterogeneity of the native semiconductor. The interaction mechanism between nuclear spins and lattice vibrations via fluctuating spin-rotation interaction, applicable to heavy spin-1/2 nuclei [Phys. Rev. …
The fabrication of nanocrystal (NC) films, starting from colloidal dispersion, is a very attractive topic in condensed matter physics community. NC films can be employed for transistors, light emitting diodes, laser, and solar cells. For this reason the understanding of the film conductivity is of major importance. In this paper we describe a probabilistic model that allow to predict the conductivity of the NC films, in this case of a cubic lattice of Lead Selenide NCs. The model is based on the hopping probability between NCs show a comparison with experimental data reported in literature.
Rock-salt lead selenide nanocrystals can be used as building blocks for large scale square superlattices via two-dimensional assembly of nanocrystals at a liquid-air interface followed by oriented attachment. Here we report measurements of the local density of states of an atomically coherent superlattice with square geometry made from PbSe nanocrystals. Controlled annealing of the sample permits the imaging of a clean structure and to reproducibly probe the band gap and the valence hole and conduction electron states. The measured band gap and peak positions are compared to the results of opt…
Optical materials with semiconductor nanoparticles within dielectric matrices are of interest for construction of non-linear optical elements, selective filters, spectral converters, etc. In the present work, we concern the glasses with PbS and PbSe fabricated by the two-step technique on the basis of silicate glass matrix and report the recent studied using the small-angle neutron scattering (SANS) technique. A proper understanding the structure of material, size of particles and spectral features need to control optical functionality of glasses. SANS is efficient non-destructive technique al…
The lead chalcogenides represent an important family of functional materials, in particular due to the benchmark high-temperature thermoelectric performance of PbTe. A number of recent investigations, experimental and theoretical, have aimed to gather insight into their unique lattice dynamics and electronic structure. However, the majority of first-principles modelling has been performed at fixed temperatures, and there has been no comprehensive and systematic computational study of the effect of temperature on the material properties. We report a comparative lattice-dynamics study of the tem…
Positron annihilation lifetime spectroscopy (PALS) and positron-electron momentum density (PEMD) studies on multilayers of PbSe nanocrystals (NCs), supported by transmission electron microscopy (TEM), show that positrons are strongly trapped at NC surfaces, where they provide insight into the surface composition and electronic structure of PbSe NCs. Our analysis indicates abundant annihilation of positrons with Se electrons at the NC surfaces and with O electrons of the oleic ligands bound to Pb ad-atoms at the NC surfaces, which demonstrates that positrons can be used as a sensitive probe to …
We report on photoluminescence in the 3-7 $μ$m mid-wave infrared (MWIR) range from sub-100 nm strained thin films of rocksalt PbSe(001) grown on GaAs(001) substrates by molecular beam epitaxy. These bare films, grown epitaxially at temperatures below 400 °C, luminesce brightly at room temperature and have minority carrier lifetimes as long as 172 ns. The relatively long lifetimes in PbSe thin films are achievable despite threading dislocation densities exceeding $10^9$ $cm^{-2}$ arising from island growth on the nearly 8% lattice- and crystal-structure-mismatched GaAs substrate. Using quasi-co…
We demonstrate for the first time that impact ionization (II) [the inverse of Auger recombination (AR)] occurs with very high efficiency in semiconductor nanocrystals (NCs). Interband optical excitation of PbSe NCs at low pump intensities, for which less than one exciton is initially generated per NC on average, results in the formation of two or more excitons (carrier multiplication) when pump photon energies are more than three times the NC band gap energy. Generation of multiexcitons from a single photon absorption event is observed to take place on an ultrafast (picosecond) timescale and o…
We measure the photoluminescence (PL) lifetime, $τ$, of excitons in colloidal PbSe nanocrystals (NCs) at low temperatures to 270~mK and in high magnetic fields to 15~T. For all NCs (1.3-2.3~nm radii), $τ$ increases sharply below 10~K but saturates by 500~mK. In contrast to the usual picture of well-separated ``bright" and ``dark" exciton states (found, e.g., in CdSe NCs), these dynamics fit remarkably well to a system having two exciton states with comparable - but small - oscillator strengths that are separated by only 300-900 $μ$eV. Importantly, magnetic fields reduce $τ$ below 10~K, consist…
High-throughput ab-initio calculations, cluster expansion techniques and thermodynamic modeling have been synergistically combined to characterize the binodal and the spinodal decompositions features in the pseudo-binary lead chalcogenides PbSe-PbTe, PbS-PbTe, and PbS-PbSe. While our results agree with the available experimental data, our consolute temperatures substantially improve with respect to previous computational modeling. The computed phase diagrams corroborate that the formation of spinodal nanostructures causes low thermal conductivities in these alloys. The presented approach, maki…
Strong photoluminescent emission has been obtained from 3 nm PbS nanocrystals in aqueous colloidal solution, following treatment with CdS precursors. The observed emission can extend across the entire visible spectrum and usually includes a peak near 1.95 eV. We show that much of the visible emission results from absorption by higher-lying excited states above 3.0 eV with subsequent relaxation to and emission from states lying above the observed band-edge of the PbS nanocrystals. The fluorescent lifetimes for this emission are in the nanosecond regime, characteristic of exciton recombination.
Effective surface-passivation of PbS nanocrystals in aqueous colloidal solution has been achieved following treatment with CdS precursors. The resultant photoluminescent emission displays two distinct components, one originating from the absorption band-edge and the other from above the absorption band-edge. We show that both of these components are strongly polarised but display distinctly different behaviours. The polarisation arising from the band-edge shows little dependence on the excitation energy while the polarisation of the above-band-edge component is strongly dependent on the excita…
Small-angle neutron and X-ray scattering, neutron backscattering and neutron time-of-flight spectroscopy are applied to reveal the structure of the ligand shell, the temperature-dependent diffusion properties and the phonon spectrum of PbS nanocrystals functionalized with oleic acid in deuterated hexane. The nanocrystals decorated with oleic acid as well as the desorbed ligand molecules exhibit simple Brownian diffusion with a Stokes-Einstein temperature-dependence and inhibited freezing. Ligand molecules desorbed from the surface show strong spatial confinement. The phonon spectrum of oleic a…
Colloidal nanocrystals (NCs), especially lead sulfide NCs, are promising candidates for solution-processed next-generation photodetectors with high-speed operation frequencies. However, the intrinsic response time of PbS-NC photodetectors, which is the material-specific physical limit, is still elusive, as the reported response times are typically limited by the device geometry. Here, we use the two-pulse coincidence photoresponse technique to identify the intrinsic response time of 1,2-ethanedithiol-functionalized PbS-NC photodetectors after fs-pulsed 1560 nm excitation. We obtain an intrinsi…
Semiconductive nanocrystals (NCs) can be self-assembled into ordered superlattices (SLs) to create artificial solids with emerging collective properties. Computational studies have predicted that properties such as electronic coupling or charge transport are determined not only by the individual NCs but also by the degree of their organization and structure. However, experimental proof for a correlation between structure and charge transport in NC SLs is still pending. Here, we perform X-ray nano-diffraction and apply Angular X-ray Cross-Correlation Analysis (AXCCA) to characterize the structu…
We bring fresh insight into the ensemble properties of PbS colloidal quantum dots with a critical review of the literature on semiconductors followed by systematic comparisons between steady-state photocurrent and photoluminescence measurements. Our experiments, performed with sufficiently low powers to neglect nonlinear effects, indicate that the photoluminescence spectra have no other noticeable contribution beside the radiative recombination of thermalized photocarriers (i.e. photocarriers in thermodynamic quasi-equilibrium). A phenomenological model based on the local Kirchhoff law is prop…
Controlling anisotropy is a key concept to generate complex functionality in advanced materials. For this, oriented attachment of nanocrystal building blocks, a self assembly of particles into larger single crystalline objects, is one of the most promising approaches in nanotechnology. We report here the 2D oriented attachment of PbS nanocrystals into ultra-thin single crystal sheets with dimensions on the micrometer scale. We found that this process is initiated by co-solvents which alter nucleation and growth rates during the primary nanocrystal formation and finally driven by dense packing …
In this paper we report the first measurements of carrier mobilities in an inorganic nanocrystal: conducting polymer composite. The composite material in question (lead sulphide nanocrystals in the conducting polymer MEH-PPV was made using a new single-pot, surfactant-free synthesis. Mobilties were measured using time of flight (ToF) and steady-state techniques. We have found that the inclusion of PbS nanocrystals in MEH-PPV both balances and markedly increases the hole and electron mobilities - the hole mobility is increased by a factor of ~105 and the electron mobility increased by ~107 unde…
Twelve two-dimensional group-IV monochalcogenide monolayers (SiS, SiSe, SiTe, GeS, GeSe, GeTe, SnS, SnSe, SnTe, PbS, PbSe, and PbTe) with a buckled honeycomb atomistic structure--belonging to symmetry group P3m1--and an out-of-plane intrinsic electric polarization are shown to be metastable by three independendent methods. First, we uncover a coordination-preserving structural transformation from the low-buckled honeycomb structure onto the lower-energy Pnm2$_1$ (or Pmmn for PbS, PbSe, and PbTe) phase to estimate {\em energy barriers} $E_B$ that must be overcome during such structural transfor…
A novel one pot process has been developed for the preparation of PbS nanocrystals in the conjugated polymer poly 2-methoxy,5-(2 -ethyl-hexyloxy-p-phenylenevinylene) (MEH-PPV). Current techniques for making such composite materials rely upon synthesizing the nanocrystals and conducting polymer separately, and subsequently mixing them. This multi-step technique has two serious drawbacks: templating surfactant must be removed before mixing, and co-solvent incompatibility causes aggregation. In our method, we eliminate the need for an initial surfactant by using the conducting polymer to terminat…
We report a simple one pot process for the preparation of lead sulphide (PbS) nanocrystals in the conjugated polymer MEH-PPV, and we demonstrate electronic coupling between the two components.
We study the role of the effective mass, band mixing and phonon emission on multiexciton generation in IV-VI nanocrystals. A 4-band k dot p effective mass model, which allows for an independent variation of these parameters, is adopted to describe the electronic structure of the nanocrystals. Multiexciton generation efficiencies are calculated using a Green's function formalism, providing results that are numerically similar to impact excitation. We find that multiexciton generation efficiencies are maximized when the effective mass of the electron and hole are small and similar. Contact with …
In this paper we report photovoltaic devices fabricated from PbS nanocrystals and the conducting polymer poly MEH-PPV. This composite material was produced via a new single-pot synthesis which solves many of the issues associated with existing methods. Our devices have white light power conversion efficiencies under AM1.5 illumination of 0.7% and single wavelength conversion efficiencies of 1.1%. Additionally, they exhibit remarkably good ideality factors (n=1.15). Our measurements show that these composites have significant potential as soft optoelectronic materials.
We present a physics based multiscale materials-to-systems model for polycrystalline $PbSe$ photodetectors that connects fundamental material properties to circuit level performance metrics. From experimentally observed film structures and electrical characterization, we first develop a bandstructure model that explains carrier-type inversion and large carrier lifetimes in sensitized films. The unique bandstructure of the photosensitive film causes separation of generated carriers with holes migrating to the inverted $PbSe|PbI_2$ interface, while electrons are trapped in the bulk of the film i…
In conventional solar cell semiconductor materials (predominantly Si) photons with energy higher than the band gap initially generate hot electrons and holes, which subsequently cool down to the band edge by phonon emission. Due to the latter process, the energy of the charge carriers in excess of the band gap is lost as heat and does not contribute to the conversion of solar to electrical power. If the excess energy is more than the band gap it can in principle be utilized through a process known as carrier multiplication (CM) in which a single absorbed photon generates two (or more) pairs of…
