Elucidating the Impact of Thin Film Texture on Charge Transport and Collection in Perovskite Solar Cells

Organic–inorganic halide perovskites have emerged as one of the most promising materials for photovoltaic applications. Because of the polycrystalline nature of perovskite thin films, it is crucial to investigate the impact of microstructures on device performance. In this study, we employ ramp-annealing to tailor the texture of perovskite thin films via controlling the nucleation of perovskite grains. Electrochemical impedance spectroscopy studies further suggest that the thin film texture impacts not only the charge collection at the contact but also the carrier transport in the bulk perovskite layer. The combination of the two effects leads to enhanced performance in devices constructed of preferentially oriented perovskite thin films

Efficient, Ordered Bulk Heterojunction Nanocrystalline Solar Cells by Annealing of Ultrathin Squaraine Thin Films

Spin-cast 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl]squaraine (SQ) thin films only 62 Å thick are converted from amorphous to polycrystalline via postannealing at elevated temperatures. The surface roughness of the SQ films increases by a factor of 2, while selected area electron diffraction spectra indicate an increase in the extent of postannealed film crystallinity. Dichloromethane solvent annealing is also demonstrated to increase the exciton diffusion length of SQ by a factor of 3 over thermally annealed SQ films as a result of further enhancement in crystalline order. We find that the roughened surface features have a length scale on the order of the exciton diffusion length. Hence, coating the donor SQ with the acceptor, C60, results in a nearly optimum controlled bulk heterojunction solar cell structure. Optimized SQ/C60 photovoltaic cells have a power conversion efficiency of ηp = 4.6 ± 0.1% (correcting for solar mismatch) at 1 sun (AM1.5G) simulated solar intensity, and a corresponding peak external quantum efficiency of EQE = 43 ± 1% even for the very thin SQ layers employed

Enhanced Lifetime of Cyanine Salts in Dilute Matrix Luminescent Solar Concentrators via Counterion Tuning

Organic luminophores offer great potential for energy harvesting and light emission due to tunable spectral properties, strong luminescence, high solubility, and excellent wavelength selectivity. To realize their full potential, the lifetimes of luminophores must extend to many years under illumination. Many organic luminophores, however, have a tendency to degrade and undergo rapid photobleaching, leading to the perception of intrinsic instability of organic molecules. In this work, we demonstrate that by exchanging the counterion of a heptamethine cyanine salt the photostability and corresponding lifetime of dilute cyanine salts can be enhanced by orders of magnitude from 10 h to an extrapolated lifetime of greater than 65,000 h under illumination. To help correlate and comprehend the underlying mechanism behind this phenomenon, the water contact angle and binding energy of each pairing were measured and calculated. We find that increased water contact angle, and therefore increasing hydrophobicity, generally correlates to improved lifetimes. Similarly, a lower absolute binding energy between cation and anion correlates to increased lifetimes. Utilizing the binding energy formalism, we predict the stability of a new anion and experimentally verify it with good consistency. Moving forward, these factors could be used to rapidly screen and identify highly photostable organic luminophore salt systems for a range of energy harvesting and light-emitting applications

Enhanced Electroluminescence Efficiency in Metal Halide Nanocluster Based Light Emitting Diodes through Apical Halide Exchange

Metal halide nanoclusters represent an attractive class of molecular building blocks for the design of functional materials with superior optical properties that can be utilized in a range of applications. Here, we demonstrate red and near-infrared light emitting diodes with a maximum external quantum efficiency >1%, utilizing phosphorescent octahedral molybdenum iodide nanoclusters. Efficiency improvement in these devices is realized by substituting heavier ligands in the apical nanocluster position that lead to the improvement in photoluminescence and exciton formation efficiencies in the nanoclusters. These results highlight how modulation of nanocluster salts with key terminal ligands has a profound effect on photoluminescence as well as electrical injection

Toward Efficient Carbon Nanotube/P3HT Solar Cells: Active Layer Morphology, Electrical, and Optical Properties

We demonstrate single-walled carbon nanotube (SWCNT)/P3HT polymer bulk heterojunction solar cells with an AM1.5 efficiency of 0.72%, significantly higher than previously reported (0.05%). A key step in achieving high efficiency is the utilization of semiconducting SWCNTs coated with an ordered P3HT layer to enhance the charge separation and transport in the device active layer. Electrical characteristics of devices with SWCNT concentrations up to 40 wt % were measured and are shown to be strongly dependent on the SWCNT loading. A maximum open circuit voltage was measured for SWCNT concentration of 3 wt % with a value of 1.04 V, higher than expected based on the interface band alignment. Modeling of the open-circuit voltage suggests that despite the large carrier mobility in SWCNTs device power conversion efficiency is governed by carrier recombination. Optical characterization shows that only SWCNT with diameter of 1.3–1.4 nm can contribute to the photocurrent with internal quantum efficiency up to 26%. Our results advance the fundamental understanding and improve the design of efficient polymer/SWCNTs solar cells

Energy Level Modification in Lead Sulfide Quantum Dot Thin Films through Ligand Exchange

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

Counterion Tuning of Near-Infrared Organic Salts Dictates Phototoxicity to Inhibit Tumor Growth

Photodynamic therapy (PDT) has the potential to improve cancer treatment by providing dual selectivity through the use of both photoactive agent and light, with the goal of minimal harmful effects from either the agent or light alone. However, current PDT is limited by insufficient photosensitizers (PSs) that can suffer from low tissue penetration, insufficient phototoxicity (toxicity with light irradiation), or undesirable cytotoxicity (toxicity without light irradiation). Recently, we reported a platform for decoupling optical and electronic properties with counterions that modulate frontier molecular orbital levels of a photoactive ion. Here, we demonstrate the utility of this platform in vivo by pairing near-infrared (NIR) photoactive heptamethine cyanine cation (Cy+), which has enhanced optical properties for deep tissue penetration, with counterions that make it cytotoxic, phototoxic, or nontoxic in a mouse model of breast cancer. We find that pairing Cy+ with weakly coordinating anion FPhB– results in a selectively phototoxic PS (CyFPhB) that stops tumor growth in vivo with minimal side effects. This work provides proof of concept that our counterion pairing platform can be used to generate improved cancer PSs that are selectively phototoxic to tumors and nontoxic to normal healthy tissues

Broad Spectral Response Using Carbon Nanotube/Organic Semiconductor/C₆₀ Photodetectors

We demonstrate that photogenerated excitons in semiconducting carbon nanotubes (CNTs) can be efficiently dissociated by forming a planar heterojunction between CNTs wrapped in semiconducting polymers and the electon acceptor, C60. Illumination of the CNTs at their near-infrared optical band gap results in the generation of a short-circuit photocurrent with peak external and internal quantum efficiencies of 2.3% and 44%, respectively. Using soft CNT-hybrid materials systems combining semiconducting small molecules and polymers, we have fabricated broad-band photodetectors with a specific detectivity >1010 cm Hz1/2 W1− from λ = 400 to 1450 nm and a response time of τ = 7.2 ± 0.2 ns

Improved Current Extraction from ZnO/PbS Quantum Dot Heterojunction Photovoltaics Using a MoO₃ Interfacial Layer

The ability to engineer interfacial energy offsets in photovoltaic devices is one of the keys to their optimization. Here, we demonstrate that improvements in power conversion efficiency may be attained for ZnO/PbS heterojunction quantum dot photovoltaics through the incorporation of a MoO3 interlayer between the PbS colloidal quantum dot film and the top-contact anode. Through a combination of current–voltage characterization, circuit modeling, Mott–Schottky analysis, and external quantum efficiency measurements performed with bottom- and top-illumination, these enhancements are shown to stem from the elimination of a reverse-bias Schottky diode present at the PbS/anode interface. The incorporation of the high-work-function MoO3 layer pins the Fermi level of the top contact, effectively decoupling the device performance from the work function of the anode and resulting in a high open-circuit voltage (0.59 ± 0.01 V) for a range of different anode materials. Corresponding increases in short-circuit current and fill factor enable 1.5-fold, 2.3-fold, and 4.5-fold enhancements in photovoltaic device efficiency for gold, silver, and ITO anodes, respectively, and result in a power conversion efficiency of 3.5 ± 0.4% for a device employing a gold anode