Structure-transport correlation reveals anisotropic charge transport in coupled PbS nanocrystal superlattices
Andre Maier, Dmitry Lapkin, Nastasia Mukharamova, Philipp Frech, Dameli Assalauova, Alexandr Ignatenko, Ruslan Khubbutdinov, Sergey Lazarev, Michael Sprung, Flo… 展开作者
Andre Maier, Dmitry Lapkin, Nastasia Mukharamova, Philipp Frech, Dameli Assalauova, Alexandr Ignatenko, Ruslan Khubbutdinov, Sergey Lazarev, Michael Sprung, Florian Laible, Ronny Loeffler, Nicolas Previdi, Thomas Guenkel, Monika Fleischer, Frank Schreiber, Ivan A. Vartanyants, Marcus Scheele
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 structures of coupled PbS NC SLs, which are directly correlated with the electronic properties of the same SL microdomains. We find strong evidence for the effect of SL crystallinity on charge transport and reveal anisotropic charge transport in highly ordered monocrystalline hexagonal close-packed PbS NC SLs, caused by the dominant effect of shortest interparticle distance. This implies that transport anisotropy should be a general feature of weakly coupled NC SLs.
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.
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, howev…
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…
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…
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.
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…
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…
Moire superlattices are twisted bilayer materials, in which the tunable interlayer quantum confinement offers access to new physics and novel device functionalities. Previously, moire superlattices were built exclusively using materials with weak van der Waals interactions and synthesizing moire superlattices with strong interlayer chemical bonding was considered to be impractical. Here using lead sulfide (PbS) as an example, we report a strategy for synthesizing of moire superlattices coupled by strong chemical bonding. We use water-soluble ligands as a removable template to obtain free-stand…
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…
X-ray nanodiffraction is applied to study the formation and correlation of domain boundaries in mesocrystalline superlattices of PbS nanocrystals with face-centered cubic structure. Each domain of the superlattice can be described with one of two mesocrystalline polymorphs with different orientational order. Close to a grain boundary, the lattice constant decreases and the superlattice undergoes an out-of-plane rotation, while the orientation of the nanocrystals with respect to the superlattice remains unchanged. These findings are explained with the release of stress on the expense of specifi…
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 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…
The annealing-induced formation of (Mn,Ga)As nanocrystals in (Ga,Mn)As/GaAs superlattices was studied by X-ray diffraction, transmission electron microscopy and magnetometry. The superlattice structures with 50 A thick (Ga,Mn)As layers separated by 25, 50 and 100 A thick GaAs spacers were grown by molecular beam epitaxy at low temperature (250 C), and then annealed at high temperatures of: 400, 560 and 630 C. The high temperature annealing causes decomposition to GaMnAs ternary alloy and formation of (Mn,Ga)As nanocrystals inside the GaAs matrix. The nanocrystals are confined in the planes tha…
Diffraction from a lattice of periodically spaced crystals is a topic of current interest because of the great development of self-organised superlattices (SL) of nanocrystals (NC). The self-organisation of NC into SL has theoretical interest, but especially a rich application prospect, as the coherent organisation has large effects on a wide range of material properties. Diffraction is a key method to understand the type and quality of SL ordering. Hereby the characteristic diffraction signature of a SL of NC - together with the characteristic types of disorder - are theoretically explored.
Probing Plasmonic Oscillations in 2D Moiré Nanocrystal Superlattices by Low-Loss EELS
University of Pennsylvania（宾夕法尼亚大学）；University of Washington（华盛顿大学）；SuperSTEM, SciTech Daresbury Science and Innovation Campus（超级扫描透射电子显微镜，科学技术达尔斯伯里科学与创新园区）；University of Leeds（利兹大学）
Over the past thirty years, it has been consistently observed that surface engineering of colloidal nanocrystals (NC) is key to their performance parameters. In the case of lead chalcogenide NCs, for example, replacing thiols with halide anion surface termination has been shown to increase power conversion efficiency in NC-based solar cells. To gain insight into the origins of these improvements, we perform ab initio molecular dynamics (AIMD) on experimentally-relevant sized lead sulfide (PbS) NCs constructed with thiol or Cl, Br, and I anion surfaces. The surface of both the thiol- and halide…
The interlayer spin correlations in the magnetic/non-magnetic semiconductor superlattices are reviewed. The experimental evidences of interlayer exchange coupling in different all-semiconductor structures, based on neutronographic and magnetic studies, are presented. A tight-binding model is used to explain interaction transfer across the non-magnetic block without the assistance of carriers in ferromagnetic EuS/PbS and antiferromagnetic EuTe/PbTe systems.
Sinusoidal Displacement Describes Disorder in CsPbBr3 Nanocrystal Superlattices
Istituto Italiano di Tecnologia（意大利理工大学）；Università Cattolica del Sacro Cuore（天主教大学）；Lund University（隆德大学）；Massachusetts Institute of Technology（麻省理工学院）；Istituto di Cristallografia (CNR-IC)（晶体学研究所（国家研究委员会））；MAX IV Laboratory（MAX IV 实验室）
We show that the combination of X-ray scattering with a nanofocused beam and X-ray cross correlation analysis is an efficient means for the full structural characterization of mesocrystalline nanoparticle assemblies with a single experiment. We analyze several hundred diffraction patterns of individual sample locations, i.e. individual grains, to obtain a meaningful statistical distribution of the superlattice and atomic lattice ordering. Simultaneous small- and wide-angle X-ray scattering of the same sample location allows us to determine the structure and orientation of the superlattice as w…
The interlayer coupling between (Ga,Mn)As ferromagnetic layers in all-semiconductor superlattices is studied theoretically within a tight-binding model, which takes into account the crystal, band and magnetic structure of the constituent superlattice components. It is shown that the mechanism originally introduced to describe the spin correlations in antiferromagnetic EuTe/PbTe superlattices, explains the experimental results observed in ferromagnetic semiconductor structures, i.e., both the antiferromagnetic coupling between ferromagnetic layers in IV-VI (EuS/PbS and EuS/YbSe) superlattices a…
The nucleation and growth kinetics of highly ordered nanocrystal superlattices during the evaporation of nanocrystal colloidal droplets was elucidated by in situ time resolved small-angle x-ray scattering. We demonstrated for the first time that evaporation kinetics can affect the dimensionality of the superlattices. The formation of two-dimensional nanocrystal superlattices at the liquid-air interface of the droplet has an exponential growth kinetics that originates from interface "crushing".
Colloidal dispersions of sterically and electrostatically stabilized PbS quantum dots: the effect of stabilization mechanism on structure factors, second virial coefficients, and film-forming properties
We report measurements of low-frequency electronic noise in ordered superlattice, weakly-ordered and random-packed thin films of 6.5 nm PbSe quantum dots prepared using several different ligand chemistries. For all samples, the normalized noise spectral density of the dark current revealed a Lorentzian component, reminiscent of the generation-recombination noise, superimposed on the 1/f background (f is the frequency). An activation energy of 0.3 eV was extracted from the temperature dependence of the noise spectra. The noise level in the ordered films was lower than that in the weakly-ordered…
Semiconducting, core-shell nanocrystals (NCs) are promising building blocks for the construction of higher dimensional artificial nanostructures using oriented attachment. However, the assembly and epitaxial attachment steps critical to this construction introduce disorder and defects which inhibit the observation of desirable emergent electronic phenomena. Consequently, understanding defect formation and remediation in these systems as a function of dimensionality is a crucial step to perfecting their synthesis. In this work, we use in situ high resolution transmission electron microscopy to …
A large-scale nanocrystal database with aligned synthesis and properties enabling generative inverse design
MIIT Key Laboratory for Low-Dimensional Quantum Structure and Devices, School of Materials Sciences & Engineering, Beijing Institute of Technology（信息产业部低维量子结构与器件重点实验室，材料科学与工程学院，北京理工大学）；School of Computer Science and Technology, Beijing Institute of Technology（计算机科学与技术学院，北京理工大学）
In the framework of four-band envelope-function formalism, developed earlier for spherical semiconductor nanocrystals, we study the electronic structure and optical properties of quantum-confined lead-salt (PbSe and PbS) nanowires (NWs) with a strong coupling between the conduction and the valence bands. We derive spatial quantization equations, and calculate numerically energy levels of spatially quantized states of a transverse electron motion in the plane perpendicular to the NW axis, and electronic subbands developed due to a free longitudinal motion along the NW axis. Using explicit expre…
Mesocrystals are nanostructured materials consisting of individual nanocrystals having a preferred crystallographic orientation. On mesoscopic length scales, the properties of mesocrystals are strongly affected by structural heterogeneity. Here, we report the detailed structural characterization of a faceted mesocrystal grain self-assembled from 60 nm sized gold nanocubes. Using coherent X-ray diffraction imaging, we determined the structure of the mesocrystal with the resolution sufficient to resolve each gold nanoparticle. The reconstructed electron density of the gold mesocrystal reveals it…
