Uncovering forbidden optical transitions in PbSe nanocrystals

The 1S(h,e)-1P(e,h) exciton transition energy of PbSe nanocrystals was determined via two-photon photoluminescence excitation spectroscopy and was found to be in good agreement with predictions from a tight-binding calculation. The two-photon excitation peak occurs at energies very close to a strong feature in the one-photon absorption spectrum and suggests that it should be assigned as a formally forbidden S-P transition. Leading explanations for the unusual strength of the forbidden transition are discussed.     

The peculiar electronic structure of PbSe quantum dots

PbSe is a pseudo-II-VI material distinguished from ordinary II-VI's (e.g., CdSe, ZnSe) by having both its valence band maximum (VBM) and its conduction band minimum (CBM) located at the fourfold-degenerate L-point in the Brillouin zone. It turns out that this feature dramatically affects the properties of the nanosystem. We have calculated the electronic and optical properties of PbSe quantum dots using an atomistic pseudopotential method, finding that the electronic structure is different from that of ordinary II-VI's and, at the same time, is more subtle than what k.p or tight-binding calculations have suggested previously for PbSe. We find the following in PbSe dots: (i) The intraband (valence-to-valence and conduction-to-conduction) as well as interband (valence-to-conduction) excitations involve the massively split L-manifold states. (ii) In contrast to previous suggestions that the spacings between valence band levels will equal those between conduction band levels (because the corresponding effective-masses me approximately mh are similar), we find a densely spaced hole manifold and much sparser electron manifold. This finding reflects the existence of a few valence band maxima in bulk PbSe within approximately 500 meV. This result reverses previous expectations of slow hole cooling in PbSe dots. (iii) The calculated optical absorption spectrum reproduces the measured absorption peak that had previously been attributed to the forbidden 1Sh --> 1Pe or 1Ph --> 1Se transitions on the basis of k.p calculations. However, we find that this transition corresponds to an allowed 1Ph --> 1Pe excitation arising mainly from bulk states near the L valleys on the Gamma-L lines of the Brillouin zone. We discuss this reinterpretation of numerous experimental results.     

Optical investigation of quantum confinement in PbSe nanocrystals at different points in the Brillouin zone

We present detailed investigations on the optical properties of PbSe nanocrystals. The absorption spectra of monodisperse, quasispherical nanocrystals exhibit sharp features as a result of distinct optical transitions. To study the size dependence, absorption spectra of nanocrystals ranging from 3.4 to 10.9 nm in diameter are analysed and a total of 11 distinct optical transitions are identified. The assignment of the various optical transitions is discussed and compared to theoretically calculated transition energies. By plotting all transitions as a function of nanocrystal size (D) we find that the energy (E) changes with the following relationship [Formula: see text] for the lowest energy transitions. The transition energy extrapolates to approximately 0.3 eV for infinite crystal size, in agreement with the bandgap of bulk PbSe at the L-point in the Brillouin zone. In addition, high-energy transitions are observed, which extrapolate to 1.6 eV for infinite crystal size, which is in good agreement with the bulk bandgap of PbSe at the Sigma-point in the Brillouin zone. Tight-binding calculations confirm that the high-energy transitions originate from the Sigma-point in the Brillouin zone. The Sigma-character of the high-energy transitions may be of importance to explain the mechanism behind multiple exciton generation in PbSe nanocrystals.     

Highly efficient multiple exciton generation in colloidal PbSe and PbS quantum dots

We report ultra-efficient multiple exciton generation (MEG) for single photon absorption in colloidal PbSe and PbS quantum dots (QDs). We employ transient absorption spectroscopy and present measurement data acquired for both intraband as well as interband probe energies. Quantum yields of 300% indicate the creation, on average, of three excitons per absorbed photon for PbSe QDs at photon energies that are four times the QD energy gap. Results indicate that the threshold photon energy for MEG in QDs is twice the lowest exciton absorption energy. We find that the biexciton effect, which shifts the transition energy for absorption of a second photon, influences the early time transient absorption data and may contribute to a modulation observed when probing near the lowest interband transition. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs. We present experimental and theoretical values of the size-dependent interband transition energies for PbSe QDs, and we also introduce a new model for MEG based on the coherent superposition of multiple excitonic states.     

PbSe纳米晶的制备及在太阳能电池中的应用

基于简单的溶剂注射工艺制备了PbSe纳米晶，利用平均粒径为5nm的PbSe米晶制备了P3HT／PbSeeh,P3HT／PbSe／PCBM两种结构的纳米晶聚合物太阳能电池，P3HT／PbSe电池的最高光电转换效率为O．19％，而基于三相体系P3HT／PbSe／PCBM池的光电转换效率为2．09％，说明PCBM对提高电池的光电转换效率具有重要的作用。     

Anomalous independence of multiple exciton generation on different group IV-VI quantum dot architectures

Multiple exciton generation (MEG) in PbSe quantum dots (QDs), PbSe(x)S(1-x) alloy QDs, PbSe/PbS core/shell QDs, and PbSe/PbSe(y)S(1-y) core/alloy-shell QDs was studied with time-resolved optical pump and probe spectroscopy. The optical absorption exhibits a red-shift upon the introduction of a shell around a PbSe core, which increases with the thickness of the shell. According to electronic structure calculations this can be attributed to charge delocalization into the shell. Remarkably, the measured quantum yield of MEG, the hot exciton cooling rate, and the Auger recombination rate of biexcitons are similar for pure PbSe QDs and core/shell QDs with the same core size and varying shell thickness. The higher density of states in the alloy and core/shell QDs provide a faster exciton cooling channel that likely competes with the fast MEG process due to a higher biexciton density of states. Calculations reveal only a minor asymmetric delocalization of holes and electrons over the entire core/shell volume, which may partially explain why the Auger recombination rate does not depend on the presence of a shell.     

Nanocrystals of PbSe core, PbSe/PbS, and PbSe/PbSxS(1-x) core/shell as saturable absorbers in passively Q-switched near-infrared lasers

The saturable optical absorption properties of PbSe core nanocrystals (NCs), and their corresponding PbSe/PbScore/shell and PbSe/PbSexS(1-x) core/alloyed-shell NCs, were examined at lambda = 1.54 microm. Saturation intensities of approximately 100 MW/cm2 were obtained. The NCs act as passive Q switches in near-infrared pulsed lasers. Q-switched output pulse energies up to 3 mJ, with a pulse duration of 40-55 ns were demonstrated. Analysis of the optical transmission versus pulse light intensity was carried out according to a model that includes ground-state as well as excited-state absorption. For pulses approximately 10 ns long, the NCs act as fast saturable absorbers. The theoretical fits yield a ground-state absorption cross section of 10-16-10-15 cm2, an excited-state absorption cross section of sigma(es) is congruent to 10(-16) cm2, and an effective lifetime of tau(eff) is congruent to 5 x 10(-12) s.     

纳米Zn1-xFexSe薄膜的制备和结构研究

采用双源热蒸发方法制备了纳米 Zn1-xFexSe稀释磁性半导体薄膜,根据 X 射线衍射谱和Raman散射谱研究了薄膜的晶体结构和声子谱特征。结果表明:Zn1-xFexSe薄膜中纳米晶粒的晶格常数随Fe含量增加而增大;通过 Raman 散射光谱观察到明显的声子限域效应,与 ZnSe体材料相比,Zn1-xFexSe薄膜同光学声子模对应的 Raman 散射峰表现出宽化和红移;纳米晶粒的晶格膨胀导致 Raman散射峰红移随Fe含量增多而相应加大。     

Comparison of carrier multiplication yields in PbS and PbSe nanocrystals: the role of competing energy-loss processes

Infrared band gap semiconductor nanocrystals are promising materials for exploring generation III photovoltaic concepts that rely on carrier multiplication or multiple exciton generation, the process in which a single high-energy photon generates more than one electron-hole pair. In this work, we present measurements of carrier multiplication yields and biexciton lifetimes for a large selection of PbS nanocrystals and compare these results to the well-studied PbSe nanocrystals. The similar bulk properties of PbS and PbSe make this an important comparison for discerning the pertinent properties that determine efficient carrier multiplication. We observe that PbS and PbSe have very similar biexciton lifetimes as a function of confinement energy. Together with the similar bulk properties, this suggests that the rates of multiexciton generation, which is the inverse of Auger recombination, are also similar. The carrier multiplication yields in PbS nanocrystals, however, are strikingly lower than those observed for PbSe nanocrystals. We suggest that this implies the rate of competing processes, such as phonon emission, is higher in PbS nanocrystals than in PbSe nanocrystals. Indeed, our estimations for phonon emission mediated by the polar Fr?hlich-type interaction indicate that the corresponding energy-loss rate is approximately twice as large in PbS than in PbSe.     

Ultrafast supercontinuum spectroscopy of carrier multiplication and biexcitonic effects in excited states of PbS quantum dots

We examine the population dynamics of multiple excitons in PbS quantum dots using spectrally resolved ultrafast supercontinuum transient absorption (SC-TA) measurements. We simultaneously probe the first three excitonic transitions. The transient spectra show the presence of bleaching of absorption for the 1S(h)-1S(e) transition, as well as transients associated with the 1P(h)-1P(e) transition. We examine signatures of carrier multiplication (multiple excitons arising from a single absorbed photon) from analysis of the bleaching features in the limit of low absorbed photon numbers (left angle bracket N(abs) right angle bracket ～ 10(-2)) for pump photon energies from two to four times that of the band gap. The efficiency of multiple-exciton generation is discussed both in terms of the ratio between early- to long-time transient absorption signals and of a broadband global fit to the data. Analysis of the population dynamics shows that bleaching associated with biexciton population is red shifted with respect to the single exciton feature, which is in accordance with a positive binding energy for the biexciton.     

Low-temperature noninjection approach to homogeneously-alloyed PbSe(x)S(1-x) colloidal nanocrystals for photovoltaic applications

Homogeneously alloyed PbSe(x)S(1-x) nanocrystals (NCs) with their excitonic absorption peaks in wavelength shorter than 1200 nm were developed for photovoltaic (PV) applications. Schottky-type solar cells fabricated with our PbSe?.?S?.? NCs as their active materials reached a high power conversion efficiency (PCE) of 3.44%, with an open circuit voltage (V(oc)) of 0.49 V, short circuit photocurrent (J(sc)) of 13.09 mA/cm2, and fill factor (FF) of 0.54 under Air Mass 1.5 global (AM 1.5G) irradiation of 100 mW/cm2. The syntheses of the small-sized colloidal PbSe(x)S(1-x) NCs were carried out at low temperature (60 °C) with long growth periods (such as 45 min) via a one-pot noninjection-based approach in 1-octadecene (ODE), featuring high reaction yield, high product quality, and high synthetic reproducibility. This low-temperature approach employed Pb(oleate)? as a Pb precursor and air-stable low-cost thioacetamide (TAA) as a S source instead of air-sensitive high-cost bis(trimethylsilyl)sulfide ((TMS)?S), with n-tributylphosphine selenide (TBPSe) as a Se precursor instead of n-trioctylphosphine selenide (TOPSe). The reactivity difference of TOPSe made from commercial TOP 90% and TBPSe made from commercial TBP 97% and TBP 99% was addressed with in situ observation of the temporal evolution of NC absorption and with 31P nuclear magnetic resonance (NMR). Furthermore, the addition of a strong reducing/nucleation agent diphenylphosphine (DPP) promoted the reactivity of the Pb precursor through the formation of a Pb-P complex, which is much more reactive than Pb(oleate)?. Thus, the reactivity of TBPSe was increased more than that of TAA. The larger the DPP-to-Pb feed molar ratio, the more the Pb-P complex, the higher the Se amount in the resulting homogeneously alloyed PbSe(x)S(1-x) NCs. Therefore, the use of DPP allowed reactivity match of the Se and S precursors and led to sizable nucleation at low temperature so that long growth periods became feasible. The present study brings insight into the formation mechanism of monomers, nucleation/growth of colloidal composition-tunable NCs, and materials design and synthesis for next-generation low-cost and high-efficiency solar cells.     

In spite of recent doubts carrier multiplication does occur in PbSe nanocrystals

Efficient carrier multiplication has been reported for several semiconductor nanocrystals: PbSe, PbS, PbTe, CdSe, InAs, and Si. Some of these reports have been challenged by studies claiming that carrier multiplication does not occur in CdSe, CdTe, and InAs nanocrystals, thus raising legitimate doubts concerning the occurrence of carrier multiplication in the remaining materials. Here, conclusive evidence is given for its occurrence in PbSe nanocrystals using femtosecond transient photobleaching. In addition, it is shown that a correct determination of carrier-multiplication efficiency requires spectral integration over the photobleach feature. The carrier multiplication efficiency we obtain is significantly lower than what has been reported previously, and it remains an open question whether it is higher in nanocrystals than it is in bulk semiconductors.     

CdTe nanocrystals: synthesis,optical characterization,and pseudopotential calculation of the band gap

CdTe nanocrystals were synthesized in aqueous solution using 1-thioglycerol and 2-mercaptoethanol as surface stabilizers. The nanocrystals were characterized by means of X-ray powder diffraction and UV-vis absorption measurements. The UV-vis absorption spectra exhibit two distinct transition lines. Comparison of the experimental measurements with the results of the empirical pseudopotential calculations of the CdTe nanocrystals showed that the lower energy absorption line can be assigned to the heavy-hole exciton transition, whereas the higher energy absorption line can be attributed to the light-hole exciton transition.     

Interface-induced nucleation, orientational alignment and symmetry transformations in nanocube superlattices

The self-assembly of colloidal nanocrystals into ordered superstructures depends critically on the shape of the nanocrystal building blocks. We investigated the self-assembly of cubic PbSe nanocrystals from colloidal suspensions in real-time using in situ synchrotron-based X-ray scattering. We combined small-angle and wide-angle scattering to investigate the translational ordering of nanocrystals and their orientational ordering in the lattice sites, respectively. We found that cubic PbSe nanocrystals assembled into a face-up (i.e., ?100? normal to the interface) configuration at the liquid/substrate interface whereas nanocubes at the liquid/air interface assume a corner-up (i.e., ?111? normal to the interface) configuration. The latter nanocrystal superlattice displays polymorphism as a function inter-NC separation distance. We explain the observed superlattice structure polymorphs in terms of the interactions directing the self-assembly. Insights into the directed self-assembly of superlattices gained from this study have important implication on the future development of nanocrystals as building blocks in artificial solids.     

Narrow absorption lines induced by electron shelving

Abstract

We investigate the absorption spectrum of a laser-driven V system in which one of the upper levels is metastable. If the Rabi frequency of the laser driving the metastable transition is sufficiently small we find an extremely narrow peak in the stationary absorption spectrum of a weak probe on the strong transition. We give analytical expressions approximating the stationary absorption spectrum. The absorption spectrum of a two-level system is investigated for the case where an upper limit for the time separation of successive emissions is given. The absorption spectrum then exhibits a delta-function-like peak and using this we then show that the origin of the narrow peak in the absorption spectrum can be traced back to electron shelving, i.e. to the existence of light and dark periods in the resonance fluorescence emitted on the strong transition.     

Far-infrared absorption of PbSe nanorods

Measurements of the far-infrared absorption spectra of PbSe nanocrystals and nanorods are presented. As the aspect ratio of the nanorods increases, the Fro?hlich sphere resonance splits into two peaks. We analyze this splitting with a classical electrostatic model, which is based on the dielectric function of bulk PbSe but without any free-carrier contribution. Good agreement between the measured and calculated spectra indicates that resonances in the local field factors underlie the measured spectra.     

Shape control of PbSe nanocrystals using noble metal seed particles

We demonstrate that the shape of PbSe nanocrystals can be controlled systematically by seeding their growth with noble metal nanoparticles (Au, Ag, or Pd) and varying the seed and precursor concentrations. Cylinders (quantum rods), cubes, crosses, stars, and branched structures were produced in high yield at 150 degrees C in reaction times of a few minutes. Although their absorption spectrum does not exhibit sharp features, the quantum rods exhibit significant photogeneration efficiency, enabling infrared sensitization of a polymeric photoconductive nanocomposite.     

Carrier multiplication in semiconductor nanocrystals: theoretical screening of candidate materials based on band-structure effects

Direct carrier multiplication (DCM) occurs when a highly excited electron-hole pair decays by transferring its excess energy to the electrons rather than to the lattice, possibly exciting additional electron-hole pairs. Atomistic electronic structure calculations have shown that DCM can be induced by electron-hole Coulomb interactions, in an impact-ionization-like process whose rate is proportional to the density of biexciton states rho XX. Here we introduce a DCM "figure of merit" R2(E) which is proportional to the ratio between the biexciton density of states rhoXX and the single-exciton density of states rhoX, restricted to single-exciton and biexciton states that are coupled by Coulomb interactions. Using R2(E), we consider GaAs, InAs, InP, GaSb, InSb, CdSe, Ge, Si, and PbSe nanocrystals of different sizes. Although DCM can be affected by both quantum-confinement effects (reflecting the underly electronic structure of the confined dot-interior states) and surface effects, here we are interested to isolate the former. To this end the nanocrystal energy levels are obtained from the corresponding bulk band structure via the truncated crystal approximation. We find that PbSe, Si, GaAs, CdSe, and InP nanocrystals have larger DCM figure of merit than the other nanocrystals. Our calculations suggest that high DCM efficiency requires high degeneracy of the corresponding bulk band-edge states. Interestingly, by considering band structure effects we find that as the dot size increases the DCM critical energy E0 (the energy at which R2(E) becomes >or=1) is reduced, suggesting improved DCM. However, whether the normalized E0/epsilong increases or decreases as the dot size increases depends on dot material.     

Size selective excitonic transition energies in strongly confined CdSe quantum dots

We report on the synthesis of CdSe nanocrystal quantum dots (QDs) of different radii (R). Size dependent optical properties like increase in the confinement energy with decreasing radius for different excitonic transitions are studied. Different excitonic transitions are calculated from the second derivative of UV-vis absorption spectra of as synthesized CdSe QDs. The transitions are assigned to specific states by calculating the transition energies using effective mass approximation. A close matching of the transition energies with the experiment suggesting that the second derivative of the absorption spectra could provide a direct knowledge of the electronic transition for the direct band gap semiconductor quantum dots.