A density functional theory study on multiple exciton generation in lead chalcogenides (original) (raw)
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The effect of electric field on multiple exciton generation in lead chalcogenide nanocrystals
arXiv: Atomic and Molecular Clusters, 2017
Unique properties of lead chalcogenides have enabled multiple exciton generation (MEG) in their nanocrystals that can be beneficial in enhancing the efficiency of the third generation solar cells. Although the intrinsic electric field plays an imperative role in a solar cell, its effect on the multiple exciton generation (MEG) has been overlooked, so far. Using EOM-CCSD as a many-body approach, we show that any electric field can affect the absorptivity spectra of the lead chalcogenide nanocrystals (Pb4Te4, Pb4Se4, and Pb4S4). The same electric field, however, has insignificant effects on the MEG quantum probabilities and the thresholds in these nanocrystals. Furthermore, simulations show that Pb4Te4, among the aforementioned nanocrystals, has the lowest MEG threshold and the strongest absorptivity peak that is located in the multi-excitation window, irrespective of the field strength, making it the most suitable candidate for MEG applications. Simulations also demonstrate that an e...
2010 35th IEEE Photovoltaic Specialists Conference, 2010
We determine the internal quantum efficiency (IQE) of the active layer of PbSe nanocrystal (NC) back-contact Schottky solar cells by combining external quantum efficiency (EQE) and total reflectance measurements with an optical model of the device stack. The model is parametrized with the complex index of refraction of each layer in the stack as calculated from ellipsometry data. Good agreement between the experimental and modeled reflectance spectra permits a quantitative estimate of the fraction of incident light absorbed by the NC films at each wavelength, thereby yielding well-constrained QE spectra for photons absorbed only by the NCs. Using a series of devices fabricated from 5.1 ( 0.4 nm diameter PbSe NCs, we show that thin NC cells achieve an EQE and an active layer IQE as high as 60 ( 5% and 80 ( 7%, respectively, while the QE of devices with NC layers thicker than about 150 nm falls, particularly in the blue, because of progressively greater light absorption in the field-free region of the films and enhanced recombination overall. Our results demonstrate that interference effects must be taken into account in order to calculate accurate optical generation profiles and IQE spectra for these thin film solar cells. The mixed modeling/experimental approach described here is a rigorous and powerful way to determine if multiple exciton generation (MEG) photocurrent is collected by devices with EQE < 100%. On the basis of the magnitudes and shapes of the IQE spectra, we conclude that the 1,2-ethanedithiol treated NC devices studied here do not produce appreciable MEG photocurrent.
The Journal of Physical Chemistry C, 2008
We demonstrate for the first time using a combination of the Hartree-Fock approximation and the symmetry adapted cluster theory with configuration interaction (SAC-CI) that multiple excitons (ME) in PbSe and CdSe quantum dots (QD) can be generated directly upon photoexcitation. At energies 2.5-3 times the lowest excitation, almost all optically excited states in Pb 4 Se 4 become MEs, while both single excitons and MEs are seen in Cd 6 Se 6. We analyze the high-level SAC-CI results of the small clusters based on the band structure and then extend our band structure analysis to Pb 68 Se 68 , Pb 180 Se 180 , Cd 33 Se 33 , and Cd 111 Se 111. Our results explain the ultrafast generation of MEs without the need for a phonon relaxation bottleneck and clarify why PbSe is particularly suitable for generation of MEs. Efficient exciton multiplication can be used to considerably increase the efficiency of QD-based solar cells.
The Journal of Physical Chemistry C, 2009
We demonstrate using symmetry adapted cluster theory with configuration interaction (SAC-CI) that charging of small PbSe nanocrystals (NCs) greatly modifies their electronic states and optical excitations. Conduction and valence band transitions that are not available in neutral NCs dominate low energy electronic excitations and show weak optical activity. At higher energies these transitions mix with both single excitons (SEs) and multiple excitons (MEs) associated with transitions across the band-gap. As a result, both SEs and MEs are significantly blue-shifted, and ME generation is drastically hampered. The overall contribution of MEs to the electronic excitations of the charged NCs is small even at very high energies. The calculations support the recent view that the observed strong dependence of the ME yields on the experimental conditions is likely due to the effects of NC charging.
Chalcogenides-based quantum dots: Optical investigation using first-principles calculations
Materials Science in Semiconductor Processing, 2015
The full potential-linearized augmented plane wave (FP-LAPW) method is implemented in WIEN2K code to calculate the indirect energy gap (Γ-X) using density functional theory (DFT). The Engel-Vosko generalized gradient approximation (EV-GGA) and modified Becke Johnson (mBJ) formalisms are used to optimize the corresponding potential for energetic transition and optical properties calculations of lead chalcogenides (PbS 1 À x Te x) alloys as a function of quantum dot diameter and is used to test the validity of our model of quantum dot potential. The refractive index and optical dielectric constant are investigated to explore best applications for solar cells.
Enhanced Multiple Exciton Generation in PbS|CdS Janus-like Heterostructured Nanocrystals
ACS nano, 2018
Generating multiple excitons by a single high-energy photon is a promising third-generation solar energy conversion strategy. We demonstrate that multiple exciton generation (MEG) in PbS|CdS Janus-like heteronanostructures is enhanced over that of single-component and core/shell nanocrystal architectures, with an onset close to two times the PbS band gap. We attribute the enhanced MEG to the asymmetric nature of the heteronanostructure that results in an increase in the effective Coulomb interaction that drives MEG and a reduction of the competing hot exciton cooling rate. Slowed cooling occurs through effective trapping of hot-holes by a manifold of valence band interfacial states having both PbS and CdS character, as evidenced by photoluminescence studies and ab initio calculations. Using transient photocurrent spectroscopy, we find that the MEG characteristics of the individual nanostructures are maintained in conductive arrays and demonstrate that these quasi-spherical PbS|CdS n...
Physical chemistry chemical physics : PCCP, 2016
The surface chemistry of colloidal quantum dots (QDs) plays an important role in determining the photoelectric properties of QD films and the corresponding quantum dot heterojunction solar cells (QDHSCs). To investigate the effects of the ligand structure on the photovoltaic performance and exciton dynamics of QDHSCs, PbS QDHSCs were fabricated by the solid state ligand exchange method with mercaptoalkanoic acid as the cross-linking ligand. Temperature-dependent photoluminescence and ultrafast transient absorption spectra show that the electronic coupling and charge transfer rate within QD ensembles were monotonically enhanced as the ligand length decreased. However, in practical QDHSCs, the second shortest ligand 3-mercaptopropionic acid (MPA) showed higher power conversion efficiency than the shortest ligand thioglycolic acid (TGA). This could be attributed to the difference in their surface trap states, supported by thermally stimulated current measurements. Moreover, compared wi...
The Synergy of Lead Chalcogenide Nanocrystals in Polymeric Bulk Heterojunction Solar Cells
ACS Omega
Photoactive polymer and quantum dots (QDs)/nanocrystals (NCs)-based bulk heterojunction (BHJ) solar cells have the combined positivity of organic semiconductors and inorganic components, which can enable a high carrier mobility and absorption coefficient. Additionally, the NCs also provide the opportunity to tune the band gap to obtain enhanced absorption in a broad solar spectrum. Among the semiconductors, lead chalcogenide NCs are of particular interest due to their good photosensitivity in the near-infrared (NIR) region of the solar spectrum. These NCs have large exciton Bohr radii (18, 46, and 150 nm for PbS, PbSe, and PbTe, respectively) and tunable sizes depending on the optical bandgaps between 0.3 and 1.5 eV. Independently, lead chalcogenide NCs have been studied extensively for different applications; however, uses in polymer−NCbased bulk heterojunction solar cells are limited. This Review has been structured on the lead chalcogenide NCs incorporated in polymer composite-based bulk heterojunction solar cells covering the material, properties, and solar cell performance to find the issues and explore future opportunities.
ACS Nano
Carrier multiplication is a process in which one absorbed photon excites two or more electrons. This is of great promise to increase the efficiency of photovoltaic devices. Until now, the factors that determine the onset energy of carrier multiplication have not been convincingly explained. We show experimentally that the onset of carrier multiplication in lead chalcogenide quantum confined and bulk crystals is due to asymmetric optical transitions. In such transitions most of the photon energy in excess of the band gap is given to either the hole or the electron. The results are confirmed and explained by theoretical tight-binding calculations of the competition between impact ionization and carrier cooling. These results are a large step forward in understanding carrier multiplication and allow for a screening of materials with an onset of carrier multiplication close to twice the band gap energy. Such materials are of great interest for development of highly efficient photovoltaic devices.
Enhanced Multiple Exciton Generation in Quasi-One-Dimensional Semiconductors
Nano Letters, 2011
The creation of a single electronÀhole pair (i.e., exciton) per incident photon is a fundamental limitation for current optoelectronic devices including photodetectors and photovoltaic cells. The prospect of multiple exciton generation per incident photon is of great interest to fundamental science and the improvement of solar cell technology. Multiple exciton generation is known to occur in semiconductor nanostructures with increased efficiency and reduced threshold energy compared to their bulk counterparts. Here we report a significant enhancement of multiple exciton generation in PbSe quasi-one-dimensional semiconductors (nanorods) over zero-dimensional nanostructures (nanocrystals), characterized by a 2-fold increase in efficiency and reduction of the threshold energy to (2.23 ( 0.03)E g , which approaches the theoretical limit of 2E g . Photovoltaic cells based on PbSe nanorods are capable of improved power conversion efficiencies, in particular when operated in conjunction with solar concentrators.