Study of Exciton Hopping Transport in PbS Colloidal Quantum Dot Thin Films Using Frequency- and Temperature-Scanned Photocarrier Radiometry (original) (raw)
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Enhanced Mobility-Lifetime Products in PbS Colloidal Quantum Dot Photovoltaics
ACS Nano, 2012
Colloidal quantum dot (CQD) photovoltaics offer a promising approach to harvest the near-IR region of the solar spectrum, where half of the sun's power reaching the earth resides. High external quantum efficiencies have been obtained in the visible region in lead chalcogenide CQD photovoltaics. However, the corresponding efficiencies for band gap radiation in the near-infrared lag behind because the thickness of CQD photovoltaic layers from which charge carriers can be extracted is limited by short carrier diffusion lengths. Here, we investigate, using a combination of electrical and optical characterization techniques, ligand passivation strategies aimed at tuning the density and energetic distribution of charge trap states at PbS nanocrystal surfaces. Electrical and optical measurements reveal a more than 7-fold enhancement of the mobility-lifetime product of PbS CQD films treated with 3-mercaptopropionic acid (MPA) in comparison to traditional organic passivation strategies that have been examined in the literature. We show by direct head-to-head comparison that the greater mobility-lifetime products of MPA-treated devices enable markedly greater short-circuit current and higher power conversion efficiency under AM1.5 illumination. Our findings highlight the importance of selecting ligand treatment strategies capable of passivating a diversity of surface states to enable shallower and lower density trap distributions for better transport and more efficient CQD solar cells.
Solar Energy Materials and Solar Cells, 2017
Solution-processed colloidal quantum dots (CQDs) are promising candidates for large-scale, low-cost, and lightweight photovoltaic and electronic devices. Carrier transport dynamics has a substantial impact on device efficiency optimization. Coupled with photocarrier radiometry (PCR)a dynamic spectrally integrated frequency-domain photoluminescence (PL) modality, we report the derivation of a trap-state-mediated carrier hopping transport model for the extraction of multiple carrier transport parameters in PbS CQD thin films. These parameters, including effective carrier lifetime τ E , hopping diffusivity D h , trap-state-dependent carrier trapping rate R T , diffusion length L h , and carrier thermal emission rate e i , were obtained for CQD thin films with different dot size and capping ligands: tetrabutylammonium iodide (TBAI), 1,2-ethanedithiol (EDT), and methylammonium lead triiodide perovskite (MAPbI 3). Consistent with the framework of phonon-assisted carrier hopping mechanism, τ E , D h , and L h have demonstrated a monotonic dependence on temperature in the range from 100 K to 300 K. Perovskite-passivated PbS CQD thin films, especially those with larger dot sizes which are free of apparent defect induced PL emission and have higher τ E and D h at room temperature (ca. 0.51 μs and 1.80×10 −2 cm 2 /s, respectively) than their counterparts, demonstrate better photovoltaic material properties. Dot-size-dependent exciton binding energies (35.21-53.20 meV) were characterized using a dynamic PCR photo-thermal spectroscopy that also characterized the trap-state-mediated carrier hopping activation energies in the range from 100 meV to 280 meV. To test the reliability of the best-fitted results, computational fitting uniqueness was examined using a parametric theory.
Carrier Transport in PbS and PbSe QD Films Measured by Photoluminescence Quenching
The Journal of Physical Chemistry C, 2014
The temperature-dependent quantum yield of photoluminescence (PL) has been measured in films of various sizes of PbS and PbSe quantum dots (QDs) capped with alkanedithiol ligands with lengths varying from 4 to 20 Å. We demonstrate that PL within QD films can provide information about transport in a regime that is relevant to solar photoconversion. The ligand-length dependent PL quenching reveals behavior similar to that of ligand-length dependent carrier mobility determined from field-effect transistor (FET) measurements in the dark. The data are described by a model in which band tail luminescence is quenched upon thermal activation by charge separation and hopping followed by nonradiative recombination. We extract the tunneling parameter β and find values of 1.1 ± 0.2 Å −1 except for a value of 0.7 for the smallest QD sample. Changes in the transport mechanism may be due to unique surface faceting or QD-ligand coupling that occurs in small QDs. Furthermore, we compare all-organic capped PbS QD films with those infilled by Al 2 O 3 , discovering a surprisingly small value of β less than 0.3 for the latter, which may be related to a graded potential barrier because of amorphous Al 2 O 3 at the QD surface or interfacial chemistry inherent in the atomic layer deposition process.
Electrochimica Acta, 2016
Lead sulfide (PbS) quantum dot (QD) photovoltaics have reached impressive efficiencies of 12%, making them particularly promising for future applications. Like many other types of emerging photovoltaic devices, their environmental instability remains the Achilles heel of this technology. In this work, we demonstrate that the degradation processes in PbS QDs which are exposed to oxygenated environments are tightly related to the choice of ligands, rather than their intrinsic properties. In particular, we demonstrate that while 1,2-ethanedithiol (EDT) ligands result in significant oxidation of PbS, lead iodide/lead bromide (PbX 2) coated PbS QDs show no signs of oxidation or degradation. Consequently, since the former is ubiquitously used as a hole extraction layer in QD solar cells, it is predominantly responsible for the device performance evolution. The oxidation of EDT-PbS QDs results in a significantly reduced effective QD size, which triggers two competing processes: improved energetic alignment that enhances electron blocking, but reduced charge transport through the layer. At early times, the former process dominates, resulting in the commonly reported, but so far not fully explained initial increase in performance, while the latter governs the onset of degradation and deterioration of the photovoltaic performance. Our work highlights that the stability of PbS quantum dot solar cells can be significantly enhanced by an appropriate choice of ligands for all device components.
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...
Small, 2017
The power conversion efficiency of colloidal PbS quantum dot based solar cells is significantly hampered by lower than expected open circuit voltage (VOC). The VOC deficit is considerably higher in QD based solar cells compared to other types of existing solar cells due to in-gap trap induced bulk recombination of photogenerated carriers. Here, we report ligand exchange procedure based on a mixture of zinc iodide and 3-mercaptopropyonic acid to reduce the VOC deficit without compromising the high current density. This layer-by-layer solid state ligand exchange treatment enhanced the photovoltaic performance from 6.62% to 9.92% with a significant improvement in VOC from 0.58V to 0.66V. We further employed opto-electronic characterization, XPS and PL spectroscopy to understand the origin of VOC improvement. The mixed ligand treatment reduces the sub bandgap traps and significantly reduces the bulk recombination in the devices.
ACS Energy Letters, 2017
Surface passivation of PbS colloidal quantum dots (QDs) with iodide has been used in highly efficient solar cells. Iodide passivation is typically achieved by ligand exchange processes on QD films. Complementary to this approach, herein we present a non-intrusive solution-based strategy for doping QDs with iodide to further optimize solar cell performance. The doping step is applied in-situ at the end of the synthesis of the QDs. The optimum precursor I/Pb ratio is found to be in the 1.5-3% range at which iodide substitutes S without excessively altering the dots´ surface chemistry. This allows for band engineering and decreasing the density of deep trap states of the QDs which taken together lead to PbS QD solar cells with efficiency in excess of 10%.
The Journal of Physical Chemistry C, 2016
We fabricated the long term air stable PbSe colloidal quantum dots (CQDs) based planar heterojunction solar cells (FTO/TiO 2 /PbSe/Au) with relatively larger active area (0.25 cm) using tetrabutylammonium iodide (TBAI, I-) as ligand in solid state ligand-exchange process. For the first time, we have achieved the whole preparation process of the device in the ambient atmosphere from PbSe CQDs collection to PbSe colloidal quantum dot solar cells (CQDSCs) fabrication, then storage and in their following measurements. Especially, TBAI-treated PbSe CQDSCs exhibited a power conversion efficiency (PCE) of 3.53% under AM 1.5 G in air, and also a remarkable long term stability (more than 90 days) of their storage in ambient atmosphere has been identified. By contrast, 1,2-ethanedithiol (EDT), 3-mercaptopropionic acid (MPA) and cetyltrimethylammonium bromide (CTAB, Br-) treated PbSe CQDSCs were further studied. The ligand-dependent exciton dissociation, recombination, energy level shift and air stability of PbSe CQDs treated with these different ligands were systematically investigated. It was noted that TBAI-treated PbSe CQDSCs exhibited suppressed recombination, faster charge transfer rate, and longer carrier lifetimes, which resulted in a higher power conversation efficiency (PCE) and long term air stability.