[Show abstract][Hide abstract] ABSTRACT: We fabricate the thinnest (1.3 μm) and lightest (3.6 g/m2) solar cells yet demonstrated, with weight-specific power exceeding 6 W/g, in order to illustrate the lower limits of substrate thickness and materials use achievable with a new processing paradigm. Our fabrication process uniquely starts with growth of an ultra-thin flexible polymer substrate in vacuum, followed by deposition of electrodes and photoactive layers in situ. With this process sequence, the entire cell—from transparent substrate to active layers to encapsulation—can be fabricated at room temperature without solvents and without breaking vacuum, avoiding exposure to dust and other contaminants, and minimizing damage risk associated with handling of thin substrates. We use in situ vapor-phase growth of smooth, transparent, and flexible parylene-C films to produce ultra-thin, lightweight molecular organic solar cells as thin as 2.3 μm including encapsulation with a second parylene-C film. These parylene-based devices exhibit power conversion efficiencies and fabrication yields comparable to glass-based cells. Flexible solar cells on parylene membranes can be seamlessly adhered to a variety of solid surfaces to provide additive solar power.
[Show abstract][Hide abstract] ABSTRACT: We report the use of isobenzofulvene–C60 adducts in bulk heterojunction organic solar cells, synthesized via the [4 + 2] cycloaddition of C60 with an in situ generated isobenzofulvene intermediate. The LUMO energy levels of these adducts are 20–180 meV higher than that of PCBM ([6,6]-phenyl-C61-butyric acid methyl ester). This large increase of the LUMO level is attributed to cofacial π-orbital interactions between the fullerene surface and the isobenzofulvene π–system (aromatic ring and double bond). Raised LUMO levels of fullerenes, together with their desirably slow recombination dynamics, led to higher open-circuit voltages (VOC) in bulk heterojunction polymer solar cells (up to 0.75 V for bisadducts) relative to cells tested in parallel using the well-known PCBM as the fullerene acceptor. In addition to enhanced VOC, the short-circuit current densities (JSC) were improved in the devices containing the epoxide analogs of the isobenzofulvene–C60. Notably the epoxide derivative of the monoadduct (IBF–Ep) exhibited ∼20% enhancement of power conversion efficiency (PCE) compared to reference P3HT:PCBM solar cells. A combination of optical and electronic methods was used to investigate the origin of the PCE enhancement observed with these new fullerene acceptors with particular attention to the increased VOCs.
[Show abstract][Hide abstract] ABSTRACT: Optical upconversion via sensitized triplet–triplet exciton annihilation converts incoherent low-energy photons to shorter wavelengths under modest excitation intensities. Here, we report a solid-state thin film for infrared-to-visible upconversion that employs lead sulphide colloidal nanocrystals as a sensitizer. Upconversion is achieved from pump wavelengths beyond λ = 1 μm to emission at λ = 612 nm. When excited at λ = 808 nm, two excitons in the sensitizer are converted to one higher-energy state in the emitter at a yield of 1.2 ± 0.2%. Peak efficiency is attained at an absorbed intensity equivalent to less than one sun. We demonstrate that colloidal nanocrystals are an attractive alternative to existing molecular sensitizers, given their small exchange splitting, wide wavelength tunability, broadband infrared absorption, and our transient observations of efficient energy transfer. This solid-state architecture for upconversion may prove useful for enhancing the capabilities of solar cells and photodetectors.
No preview · Article · Nov 2015 · Nature Photonics
[Show abstract][Hide abstract] ABSTRACT: Thermally activated delayed fluorescence (TADF) is becoming an increasingly important OLED technology that extracts light from nonemissive triplet states via reverse intersystem crossing (RISC) to the bright singlet state. Here we present the rather surprising finding that in TADF materials that contain a mixture of donor and acceptor molecules the electron-hole separation fluctuates as a function of time. By performing time-resolved photoluminescence experiments, both with and without a magnetic field, we observe that at short times the TADF dynamics are insensitive to magnetic field, but a large magnetic field effect (MFE) occurs at longer times. We explain these observations by constructing a quantum mechanical rate model in which the electron and hole cycle between a near-neighbor exciplex state that shows no MFE and a separated polaron-pair state that is not emissive but does show magnetic field dependent dynamics. Interestingly, the model suggests that only a portion of TADF in these blends comes from direct RISC from triplet to singlet exciplex. A substantial contribution comes from an indirect path, where the electron and hole separate, undergo RISC from hyperfine interactions, and then recombine to form a bright singlet exciplex. These observations have a significant impact on the design rules for TADF materials, as they imply a separate set of electronic parameters that can influence efficiency.
No preview · Article · Oct 2015 · The Journal of Physical Chemistry C
[Show abstract][Hide abstract] ABSTRACT: Charge-transfer (CT) states, bound combinations of an electron and a hole on separate molecules, play a crucial role in organic optoelectronic devices. We report direct nanoscale imaging of the transport of long-lived CT states in molecular organic donor-acceptor blends, which demonstrates that the bound electron-hole pairs that form the CT states move geminately over distances of 5-10 nm, driven by energetic disorder and diffusion to lower energy sites. Magnetic field dependence reveals a fluctuating exchange splitting, indicative of a variation in electron-hole spacing during diffusion. The results suggest that the electron-hole pair of the CT state undergoes a stretching transport mechanism analogous to an 'inchworm' motion, in contrast to conventional transport of Frenkel excitons. Given the short exciton lifetimes characteristic of bulk heterojunction organic solar cells, this work confirms the potential importance of CT state transport, suggesting that CT states are likely to diffuse farther than Frenkel excitons in many donor-acceptor blends.
No preview · Article · Sep 2015 · Nature Materials
[Show abstract][Hide abstract] ABSTRACT: Plexcitons are polaritonic modes that result from the strong coupling between
excitons and plasmons. We consider plexcitons emerging from the interaction of
excitons in an organic molecular layer with surface plasmons in a metallic
film. We predict the emergence of Dirac cones in the two-dimensional
bandstructure of plexcitons due to the inherent alignment of the excitonic
transitions in the organic layer. These Dirac cones may open up in energy by
simultaneously interfacing the metal with a magneto-optical layer and
subjecting the whole system to a perpendicular magnetic field. The resulting
energy gap becomes populated with topologically protected one-way modes which
travel at the interface of this plexcitonic system. Our theoretical proposal
suggests that plexcitons are a convenient and simple platform for the
exploration of exotic phases of matter as well as of novel ways to direct
energy flow at the nanoscale.
[Show abstract][Hide abstract] ABSTRACT: Abrupt switching behavior and near-zero leakage current of nanoelectromechanical (NEM) switches are advantageous properties through which NEMs can outperform conventional semiconductor electrical switches. To date, however, typical NEMs structures require high actuation voltages and can prematurely fail through permanent adhesion (defined as stiction) of device components. To overcome these challenges, in the present work we propose a NEM switch, termed a "squitch," which is designed to electromechanically modulate the tunneling current through a nanometer-scale gap defined by an organic molecular film sandwiched between two electrodes. When voltage is applied across the electrodes, the generated electrostatic force compresses the sandwiched molecular layer, thereby reducing the tunneling gap and causing an exponential increase in the current through the device. The presence of the molecular layer avoids direct contact of the electrodes during the switching process. Furthermore, as the layer is compressed, the increasing surface adhesion forces are balanced by the elastic restoring force of the deformed molecules which can promote zero net stiction and recoverable switching. Through numerical analysis, we demonstrate the potential of optimizing squitch design to enable large on-off ratios beyond 6 orders of magnitude with operation in the sub-1 V regime and with nanoseconds switching times. Our preliminary experimental results based on metal-molecule-graphene devices suggest the feasibility of the proposed tunneling switching mechanism. With optimization of device design and material engineering, squitches can give rise to a broad range of low-power electronic applications.
[Show abstract][Hide abstract] ABSTRACT: Abstract Polyselenophene (PSe) donor layers are successfully integrated into organic photovoltaic devices (OPV) for the first time. Thin, patterned films of this insoluble semiconductor were fabricated using a vacuum-based vapor-printing technique, oxidative chemical vapor deposition (oCVD) combined with in-situ shadow masking. The vapor-printed PSe exhibits a reduced optical bandgap of 1.76 eV and enhanced photo-responsivity in the red compared to its sulfur containing analog, polythiophene. These relative advantages are most likely explained by selenium's enhanced electron-donating character compared to sulfur. The HOMO level of PSe was determined to be at -4.85 eV. The maximum power conversion efficiency achieved was 0.4% using a bilayer heterojunction device architecture with C60 as the donor.
No preview · Article · Jul 2015 · Organic Electronics
[Show abstract][Hide abstract] ABSTRACT: We report an ultra-bright, highly efficient, low roll-off, inverted quantum dot-based red light emitting device (QLED) using solution-processed zinc oxide nanoparticles and cesium carbonate films as the electron injection and hole blocking layers, respectively. Record luminance of 165,000 Cd/m2 has been obtained at a current density of 1000 mA/cm2 with a low driving voltage of 5.8 V for deep red device with CIE coordinates of (0.69, 0.31).
[Show abstract][Hide abstract] ABSTRACT: Using solvent-free composite membrane transfer, we demonstrate an electrically tunable organic visible light-emitting laser with reversible tuning range of 10 nm under 6 V actuation. Large-area scalability of utilized fabrication methods suggests potential use in alloptical pressure-sensing surfaces.
[Show abstract][Hide abstract] ABSTRACT: 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.
[Show abstract][Hide abstract] ABSTRACT: Direct modification of exciton energy has been previously used to optimize the operation of organic optoelectronic devices. One demonstrated method for exciton energy modification is through the use of the solvent dielectric effects in doped molecular films. To gain a deeper appreciation of the underlying physical mechanisms, in this work we test the solid-state solvation effect in molecular thin films under applied external pressure. We observe that external mechanical pressure increases dipole-dipole interactions, leading to shifts in the Frenkel exciton energy and enhancement of the time-resolved spectral red shift associated with the energy-transfer-mediated exciton diffusion. Measurements are performed on host:dopant molecular thin films, which show bathochromic shifts in photoluminescence (PL) under increasing pressure. This is in agreement with a simple solvation theory model of exciton energetics with a fitting parameter based on the mechanical properties of the host matrix material. We measure no significant change in exciton lifetime with increasing pressure, consistent with unchanged aggregation in molecular films under compression. However, we do observe an increase in exciton spectral thermalization rate for compressed molecular films, indicating enhanced exciton diffusion for increased dipole-dipole interactions under pressure. The results highlight the contrast between molecular energy landscapes obtained when dipole-dipole interactions are increased by the pressure technique vs. the conventional dopant concentration variation methods, which can lead to extraneous effects such as aggregation at higher doping concentrations. The present work demonstrates the use of pressure-probing techniques in studying energy disorder and exciton dynamics in amorphous molecular thin films.
[Show abstract][Hide abstract] ABSTRACT: Charge transfer states play a crucial role in organic photovoltaics, mediating both photocurrent generation and recombination losses. In this work, we examine recombination losses as a function of the electron-hole spacing in fluorescent charge transfer states, including direct monitoring of both singlet and triplet charge transfer state dynamics. Here we demonstrate that large donor-acceptor separations minimize back transfer from the charge transfer state to a low-lying triplet exciton 'drain' or the ground state by utilizing external pressure to modulate molecular spacing. The triplet drain quenches triplet charge transfer states that would otherwise be spin protected against recombination, and switches the most efficient origin of the photocurrent from triplet to singlet charge transfer states. Future organic solar cell designs should focus on raising the energy of triplet excitons to better utilize triplet charge transfer mediated photocurrent generation or increasing the donor-acceptor spacing to minimize recombination losses.
No preview · Article · Mar 2015 · Nature Communications
[Show abstract][Hide abstract] ABSTRACT: 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.
Full-text · Article · Feb 2015 · Energy & Environmental Science
[Show abstract][Hide abstract] ABSTRACT: Utilizing stiction, a common failure mode in micro/nano electromechanical systems (M/NEMS), we propose a method for the controlled fabrication of nanometer-thin gaps between electrodes. In this approach, a single lithography step is used to pattern cantilevers that undergo lateral motion towards opposing stationary electrodes separated by a defined gap. Upon wet developing of the pattern, capillary forces induce cantilever deflection and collapse leading to permanent adhesion between the tip and an opposing support structure. The deflection consequently reduces the separation gap between the cantilever and the electrodes neighboring the point of stiction to dimensions smaller than originally patterned. Through nanoscale force control achieved by altering device design, we demonstrate the fabrication of nanogaps having controlled widths smaller than 15 nm. We further discuss optimization of these nanoscale gaps for applications in NEM and molecular devices.
No preview · Article · Feb 2015 · Proceedings of the IEEE International Conference on Micro Electro Mechanical Systems (MEMS)
[Show abstract][Hide abstract] ABSTRACT: We study the dielectric constant of lead sulfide quantum dot (QD) films as a function of the volume fraction of QDs by varying the QD size and keeping the ligand constant. We create a reliable QD sizing curve using small-angle X-ray scattering (SAXS), thin-film SAXS to extract a pair-distribution function for QD spacing, and a stacked-capacitor geometry to measure the capacitance of the thin film. Our data support a reduced dielectric constant in nanoparticles.Keywords: Dielectric constant; quantum dot; PbS; SAXS; capacitance
[Show abstract][Hide abstract] ABSTRACT: Triplet excitons are ubiquitous in organic optoelectronics, but they are often an undesirable energy sink because they are spin-forbidden from emitting light and their high binding energy hinders the generation of free electron-hole pairs. Harvesting their energy is consequently an important technological challenge. Here, we demonstrate direct excitonic energy transfer from 'dark' triplets in the organic semiconductor tetracene to colloidal PbS nanocrystals, thereby successfully harnessing molecular triplet excitons in the near infrared. Steady-state excitation spectra, supported by transient photoluminescence studies, demonstrate that the transfer efficiency is at least (90 ± 13)%. The mechanism is a Dexter hopping process consisting of the simultaneous exchange of two electrons. Triplet exciton transfer to nanocrystals is expected to be broadly applicable in solar and near-infrared light-emitting applications, where effective molecular phosphors are lacking at present. In particular, this route to 'brighten' low-energy molecular triplet excitons may permit singlet exciton fission sensitization of conventional silicon solar cells.
No preview · Article · Oct 2014 · Nature Materials
[Show abstract][Hide abstract] ABSTRACT: We report an ultracompact low-threshold laser with an Alq3:DCM host:guest molecular organic thin film gain layer. The device uses a photonic crystal nanobeam cavity which provides a high quality factor to mode volume (Q/V) ratio and increased spontaneous emission factor along with a small footprint. Lasing is observed with a threshold of 4.2 μJ/cm(2) when pumped by femtosecond pulses of λ = 400 nm wavelength light. We also model the dynamics of the laser and show good agreement with the experimental data. The inherent waveguide geometry of the structure enables easy on-chip integration with potential applications in biochemical sensing, inertial sensors, and data communication.