The electronic properties of colloidal quantum dots (QDs) are critically dependent on both QD size and surface chemistry. Modification of quantum confinement provides control of the QD bandgap, while ...ligand-induced surface dipoles present a hitherto underutilized means of control over the absolute energy levels of QDs within electronic devices. Here, we show that the energy levels of lead sulfide QDs, measured by ultraviolet photoelectron spectroscopy, shift by up to 0.9 eV between different chemical ligand treatments. The directions of these energy shifts match the results of atomistic density functional theory simulations and scale with the ligand dipole moment. Trends in the performance of photovoltaic devices employing ligand-modified QD films are consistent with the measured energy level shifts. These results identify surface-chemistry-mediated energy level shifts as a means of predictably controlling the electronic properties of colloidal QD films and as a versatile adjustable parameter in the performance optimization of QD optoelectronic devices.
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.
The presence of surface and grain boundary defects in organic–inorganic halide perovskite films can be detrimental to both the performance and operational stability of perovskite solar cells (PSCs). ...Here, the effect of chloride additives is studied on the bulk and surface defects of the mixed cation and halide PSCs. It is found that using an antisolvent technique, the perovskite film is divided into two layers, i.e., a bottom layer with large grains and a thin capping layer with small grains. The addition of formamidinium chloride (FACl) into the precursor solution removes the small‐grained perovskite capping layer and suppresses the formation of bulk and surface defects, providing a perovskite film with enhanced crystallinity and large grain size of over 1 µm. Time‐resolved photoluminescence measurements show longer lifetimes for perovskite films modified by FACl and subsequently passivated by 1‐adamantylamine hydrochloride as compared to the reference sample. Impedance spectroscopy measurements show that these treatments reduce the recombination in the PSCs, leading to a champion device with power conversion efficiency (PCE) of 21.2%, an open circuit voltage of 1152 mV and negligible hysteresis. The Cl treated PSC also shows improved operational stability with only 12% PCE loss after 700 h under continuous illumination.
Molecular additive engineering using chlorine‐based compounds such as formamidinium chloride reduces the bulk and surface carrier recombination and improves the crystallinity of the perovskite film, resulting in solar cell devices with high efficiency exceeding 21% and great stability.
Quantum dots show great promise for fabrication of hybrid bulk heterojunction solar cells with enhanced power conversion efficiency, yet controlling the morphology and interface structure on the ...nanometer length scale is challenging. Here, we demonstrate quantum dot-based hybrid solar cells with improved electronic interaction between donor and acceptor components, resulting in significant improvement in short-circuit current and open-circuit voltage. CdS quantum dots were bound onto crystalline P3HT nanowires through solvent-assisted grafting and ligand exchange, leading to controlled organic–inorganic phase separation and an improved maximum power conversion efficiency of 4.1% under AM 1.5 solar illumination. Our approach can be applied to a wide range of quantum dots and polymer hybrids and is compatible with solution processing, thereby offering a general scheme for improving the efficiency of nanocrystal hybrid solar cells.
Hybrid interfaces combining inorganic and organic materials underpin the operation of many optoelectronic and photocatalytic systems and allow for innovative approaches to photon up- and ...down-conversion. However, the mechanism of exchange-mediated energy transfer of spin-triplet excitons across these interfaces remains obscure, particularly when both the macroscopic donor and acceptor are composed of many separately interacting nanoscopic moieties. Here, we study the transfer of excitons from colloidal lead sulfide (PbS) nanocrystals to the spin-triplet state of rubrene molecules. By reducing the length of the carboxylic acid ligands on the nanocrystal surface from 18 to 4 carbon atoms, thinning the effective ligand shell from 13 to 6 Å, we are able to increase the characteristic transfer rate by an order of magnitude. However, we observe that the energy transfer rate asymptotes for shorter separation distances (≤10 Å) which we attribute to the reduced Dexter coupling brought on by the increased effective dielectric constant of these solid-state devices when the aliphatic ligands are short. This implies that the shortest ligands, which hinder long-term colloidal stability, offer little advantage for energy transfer. Indeed, we find that hexanoic acid ligands are already sufficient for near-unity transfer efficiency. Using nanocrystals with these optimal-length ligands in an improved solid-state device structure, we obtain an upconversion efficiency of (7 ± 1)% with excitation at λ = 808 nm.
Biomolecular monitoring in the gastrointestinal tract could offer rapid, precise disease detection and management but is impeded by access to the remote and complex environment. Here, we present an ...ingestible micro-bio-electronic device (IMBED) for in situ biomolecular detection based on environmentally resilient biosensor bacteria and miniaturized luminescence readout electronics that wirelessly communicate with an external device. As a proof of concept, we engineer heme-sensitive probiotic biosensors and demonstrate accurate diagnosis of gastrointestinal bleeding in swine. Additionally, we integrate alternative biosensors to demonstrate modularity and extensibility of the detection platform. IMBEDs enable new opportunities for gastrointestinal biomarker discovery and could transform the management and diagnosis of gastrointestinal disease.
Pathways for solar photovoltaics Jean, Joel; Brown, Patrick R; Jaffe, Robert L ...
Energy & environmental science,
01/2015, Letnik:
8, Številka:
4
Journal Article
Recenzirano
Solar energy is one of the few renewable, low-carbon resources with both the scalability and the technological maturity to meet ever-growing global demand for electricity. Among solar power ...technologies, solar photovoltaics (PV) are the most widely deployed, providing 0.87% of the world's electricity in 2013 and sustaining a compound annual growth rate in cumulative installed capacity of 43% since 2000. Given the massive scale of deployment needed, this article examines potential limits to PV deployment at the terawatt scale, emphasizing constraints on the use of commodity and PV-critical materials. We propose material complexity as a guiding framework for classifying PV technologies, and we analyze three core themes that focus future research and development: efficiency, materials use, and manufacturing complexity and cost.
Infrared-to-visible photon upconversion could benefit applications such as photovoltaics, infrared sensing, and bioimaging. Solid-state upconversion based on triplet exciton annihilation sensitized ...by nanocrystals is one of the most promising approaches, albeit limited by relatively weak optical absorption. Here, we integrate the upconverting layers into a Fabry–Pérot microcavity with quality factor Q = 75. At the resonant wavelength λ = 980 nm, absorption increases 74-fold and we observe a 227-fold increase in the intensity of upconverted emission. The threshold excitation intensity is reduced by 2 orders of magnitude to a subsolar flux of 13 mW/cm2. We measure an external quantum efficiency of 0.06 ± 0.01% and a 2.2-fold increase in the generation yield of upconverted photons. Our work highlights the potential of triplet–triplet annihilation-based upconversion in low-intensity sensing applications and demonstrates the importance of photonic designs in addition to materials engineering to improve the efficiency of solid-state upconversion.
Metal halide perovskites are exceptional candidates for inexpensive yet high‐performing optoelectronic devices. Nevertheless, polycrystalline perovskite films are still limited by nonradiative losses ...due to charge carrier trap states that can be affected by illumination. Here, in situ microphotoluminescence measurements are used to elucidate the impact of light‐soaking individual methylammonium lead iodide grains in high‐quality polycrystalline films while immersing them with different atmospheric environments. It is shown that emission from each grain depends sensitively on both the environment and the nature of the specific grain, i.e., whether it shows good (bright grain) or poor (dark grain) luminescence properties. It is found that the dark grains show substantial rises in emission, while the bright grain emission is steady when illuminated in the presence of oxygen and/or water molecules. The results are explained using density functional theory calculations, which reveal strong adsorption energies of the molecules to the perovskite surfaces. It is also found that oxygen molecules bind particularly strongly to surface iodide vacancies which, in the presence of photoexcited electrons, lead to efficient passivation of the carrier trap states that arise from these vacancies. The work reveals a unique insight into the nature of nonradiative decay and the impact of atmospheric passivation on the microscale properties of perovskite films.
Metal halide perovskites are an exciting class of materials for low‐cost optoelectronics but their performance remains limited by nonradiative losses. The surface adsorption of different atmospheric molecules to different types of grains in perovskite films can have a profound impact on the local luminescence of that grain under continual illumination depending on whether the grain has few (bright grain) or many (dark grain) defects. Oxygen molecules are shown to bind particularly strongly to iodide vacancies which, in the presence of photoexcited electrons, leads to passivation of the carrier trap states that arise from these vacancies.
PDF
