Minority Carrier Transport in Lead Sulfide Quantum Dot Photovoltaics.

Lead sulfide quantum dots (PbS QDs) are an attractive material system for the development of low-cost photovoltaics (PV) due to their ease of processing and stability in air, with certified power conversion efficiencies exceeding 11%. However, even the best PbS QD PV devices are limited by diffusive transport, as the optical absorption length exceeds the minority carrier diffusion length. Understanding minority carrier transport in these devices will therefore be critical for future efficiency improvement. We utilize cross-sectional electron beam-induced current (EBIC) microscopy and develop methodology to quantify minority carrier diffusion length in PbS QD PV devices. We show that holes are the minority carriers in tetrabutylammonium iodide (TBAI)-treated PbS QD films due to the formation of a p-n junction with an ethanedithiol (EDT)-treated QD layer, whereas a heterojunction with n-type ZnO forms a weaker n+-n junction. This indicates that modifying the standard device architecture to include a p-type window layer would further boost the performance of PbS QD PV devices. Furthermore, quantitative EBIC measurements yield a lower bound of 110 nm for the hole diffusion length in TBAI-treated PbS QD films, which informs design rules for planar and ordered bulk heterojunction PV devices. Finally, the low-energy EBIC approach developed in our work is generally applicable to other emerging thin-film PV absorber materials with nanoscale diffusion lengths.

Identifying and Eliminating Emissive Sub-bandgap States in Thin Films of PbS Nanocrystals.

Chemical oxidation of under-charged Pb atoms reduces the density of trap states by a factor of 40 in films of colloidal PbS quantum dots for devices. These emissive sub-bandgap states are a byproduct of several standard ligand-exchange procedures. X-ray photoelectron spectro-scopy measurements and density function theory simulations demonstrate that they are associated with under-charged Pb.

Open-circuit voltage deficit, radiative sub-bandgap states, and prospects in quantum dot solar cells.

Quantum dot photovoltaics (QDPV) offer the potential for low-cost solar cells. To develop strategies for continued improvement in QDPVs, a better understanding of the factors that limit their performance is essential. Here, we study carrier recombination processes that limit the power conversion efficiency of PbS QDPVs. We demonstrate the presence of radiative sub-bandgap states and sub-bandgap state filling in operating devices by using photoluminescence (PL) and electroluminescence (EL) spectroscopy. These sub-bandgap states are most likely the origin of the high open-circuit-voltage (VOC) deficit and relatively limited carrier collection that have thus far been observed in QDPVs. Combining these results with our perspectives on recent progress in QDPV, we conclude that eliminating sub-bandgap states in PbS QD films has the potential to show a greater gain than may be attainable by optimization of interfaces between QDs and other materials. We suggest possible future directions that could guide the design of high-performance QDPVs.

Improved performance and stability in quantum dot solar cells through band alignment engineering.

Solution processing is a promising route for the realization of low-cost, large-area, flexible and lightweight photovoltaic devices with short energy payback time and high specific power. However, solar cells based on solution-processed organic, inorganic and hybrid materials reported thus far generally suffer from poor air stability, require an inert-atmosphere processing environment or necessitate high-temperature processing, all of which increase manufacturing complexities and costs. Simultaneously fulfilling the goals of high efficiency, low-temperature fabrication conditions and good atmospheric stability remains a major technical challenge, which may be addressed, as we demonstrate here, with the development of room-temperature solution-processed ZnO/PbS quantum dot solar cells. By engineering the band alignment of the quantum dot layers through the use of different ligand treatments, a certified efficiency of 8.55% has been reached. Furthermore, the performance of unencapsulated devices remains unchanged for over 150 days of storage in air. This material system introduces a new approach towards the goal of high-performance air-stable solar cells compatible with simple solution processes and deposition on flexible substrates.

Interfacial nanostructuring on the performance of polymer/TiO2 nanorod bulk heterojunction solar cells.

This work presents polymer photovoltaic devices based on poly(3-hexylthiophene) (P3HT) and TiO2 nanorod hybrid bulk heterojunctions. Interface modification of a TiO2 nanorod surface is conducted to yield a very promising device performance of 2.20% with a short circuit current density (J(sc)) of 4.33 mA/cm2, an open circuit voltage (V(oc)) of 0.78 V, and a fill factor (FF) of 0.65 under simulated A.M. 1.5 illumination (100 mW/cm2). The suppression of recombination at P3HT/TiO2 nanorod interfaces by the attachment of effective ligand molecules substantially improves device performance. The correlation between surface photovoltage and hybrid morphology is revealed by scanning Kelvin probe microscopy. The proposed method provides a new route for fabricating low-cost, environmentally friendly polymer/inorganic hybrid bulk heterojunction photovoltaic devices.