ABSTRACT
The dynamics of strongly coupled polariton systems integrated with 2D transition metal dichalcogenides (TMDs) is key to enabling efficient coherent processes and achieving high-performance TMD-based polaritonic devices, such as ultralow-threshold polariton lasers and ultrafast optical switches. However, there has been a lack of a comprehensive understanding of the excited state dynamics in TMD-based polariton systems. In this work, ultrafast pump-probe optical spectroscopy is used to investigate the room temperature dynamics of the polariton systems consisting of TMD monolayer excitons strongly coupled with Bloch surface waves (BSWs) supported by all-dielectric photonic structures. The transient response is found for both above-exciton energy pumping and polariton-resonant pumping. The excited state population and ultrafast coherent coupling of the exciton reservoir and lower polariton (LP) branch are observed for resonant pumping. Moreover, it is found that the transient response of the LP first decays on a short-time scale of 0.15-0.25 ps compared to the calculated intrinsic lifetime of 0.11-0.20 ps, and is followed by a longer decay (>100 ps) due to the dynamical evolution of the exciton reservoir. The results provide a fundamental understanding of the dynamics of TMD-based polariton systems while showing the potential for achieving efficient coherent optical processes for device applications.
ABSTRACT
Phosphorescent organic light-emitting diodes (PHOLEDs) feature high efficiency1,2, brightness and colour tunability suitable for both display and lighting applications3. However, overcoming the short operational lifetime of blue PHOLEDs remains one of the most challenging high-value problems in the field of organic electronics. Their short lifetimes originate from the annihilation of high-energy, long-lived blue triplets that leads to molecular dissociation4-7. The Purcell effect, the enhancement of the radiative decay rate in a microcavity, can reduce the triplet density and, hence, the probability of destructive high-energy triplet-polaron annihilation (TPA)5,6 and triplet-triplet annihilation (TTA) events4,5,7,8. Here we introduce the polariton-enhanced Purcell effect in blue PHOLEDs. We find that plasmon-exciton polaritons9 (PEPs) substantially increase the strength of the Purcell effect and achieve an average Purcell factor (PF) of 2.4 ± 0.2 over a 50-nm-thick emission layer (EML) in a blue PHOLED. A 5.3-fold improvement in LT90 (the time for the PHOLED luminance to decay to 90% of its initial value) of a cyan-emitting Ir-complex device is achieved compared with its use in a conventional PHOLED. Shifting the chromaticity coordinates to (0.14, 0.14) and (0.15, 0.20) into the deep blue, the Purcell-enhanced devices achieve 10-14 times improvement over similarly deep-blue PHOLEDs, with one structure reaching the longest Ir-complex device lifetime of LT90 = 140 ± 20 h reported so far10-21. The polariton-enhanced Purcell effect and microcavity engineering provide new possibilities for extending deep-blue PHOLED lifetimes.
ABSTRACT
A series of bimetallic carbene-metal-amide (cMa) complexes have been prepared with bridging biscarbene ligands to serve as a model for the design of luminescent materials with large oscillator strengths and small energy differences between the singlet and triplet states (ΔEST). The complexes have a general structure (R2N)Au(:carbeneâcarbene:)Au(NR2). The bimetallic complexes show solvation-dependent absorption and emission that is analyzed in detail. It is found that the molar absorptivity of the bimetallic complexes is correlated with the energy barrier to rotation of the metal-ligand bond. The bimetallic cMa complexes also exhibit short emission lifetimes (τ = 200-300 ns) with high photoluminescence efficiencies (ΦPL > 95%). The radiative rates of bimetallic cMa complexes are 3-4 times faster than that of the corresponding monometallic complexes. Analysis of temperature-dependent luminescence data indicates that the lifetime for the singlet state (τS1) of bimetallic cMa complexes is near 12 ns with a ΔEST of 40-50 meV. The presented compounds provide a general design for cMa complexes to achieve small values for ΔEST while retaining high radiative rates. Solution-processed organic light-emitting devices (OLEDs) made using two of the complexes as luminescent dopants show high efficiency and low roll-off at high luminance.
ABSTRACT
We derive the thermodynamic limit for organic light-emitting diodes (OLEDs), and show that strong exciton binding in these devices requires a higher voltage to achieve the same luminance as a comparable inorganic LED. The OLED overpotential, which does not reduce the power conversion efficiency, is minimized by having a small exciton binding energy, a long exciton lifetime, and a large Langevin coefficient for electron-hole recombination. Based on these results, it seems likely that the best phosphorescent and thermally activated delayed fluorescence OLEDs reported to date approach their thermodynamic limit. The framework developed here is broadly applicable to other excitonic materials, and should therefore help guide the development of low voltage LEDs for display and solid-state lighting applications.
Subject(s)
Electrons , ThermodynamicsABSTRACT
Atomically thin transition metal dichalcogenides (TMDs), a subclass of two-dimensional (2D) layered materials, have numerous fascinating properties that make them a promising platform for photonic and optoelectronic devices. In particular, excited state transport by TMDs is important in energy harvesting and photonic switching; however, long-range transport in TMDs is challenging due to the lack of availability of large area films. Whereas most previous studies have focused on small, exfoliated monolayer flakes, in this work we demonstrate metal-organic chemical vapor deposition grown centimeter-scale monolayers of WS2 that support polariton propagation lengths of up to 60 µm. The polaritons form through the strong coupling of excitons with Bloch surface waves (BSWs) supported by all-dielectric photonic structures. We observe that the propagation length increases with the number of dielectric pairs due to the increased quality factor of the supporting distributed Bragg reflector. Furthermore, a longer propagation length is observed as the guided or BSW content of the polariton is increased. Our results provide a practical approach for the systematic engineering of long-range energy transport mediated by exciton-polaritons in TMD layers. Along with the accessibility of large area TMDs, our work enables applications for practical TMD-based polaritonic devices that operate at room temperature.
ABSTRACT
For organic photovoltaic (OPV) devices to achieve consistent performance and long operational lifetimes, organic semiconductors must be processed with precise control over their purity, composition, and structure. This is particularly important for high volume solar cell manufacturing where control of materials quality has a direct impact on yield and cost. Ternary-blend OPVs containing two acceptor-donor-acceptor (A-D-A)-type nonfullerene acceptors (NFAs) and a donor have proven to be an effective strategy to improve solar spectral coverage and reduce energy losses beyond that of binary-blend OPVs. Here, we show that the purity of such a ternary is compromised during blending to form a homogeneously mixed bulk heterojunction thin film. We find that the impurities originate from end-capping C=C/C=C exchange reactions of A-D-A-type NFAs, and that their presence influences both device reproducibility and long-term reliability. The end-capping exchange results in generation of up to four impurity constituents with strong dipolar character that interfere with the photoinduced charge transfer process, leading to reduced charge generation efficiency, morphological instabilities, and an increased vulnerability to photodegradation. As a consequence, the OPV efficiency falls to less than 65% of its initial value within 265 h when exposed to up to 10 suns intensity illumination. We propose potential molecular design strategies critical to enhancing the reproducibility as well as reliability of ternary OPVs by avoiding end-capping reactions.
ABSTRACT
Mixing a sterically bulky, electron-transporting host material into a conventional single host-guest emissive layer is demonstrated to suppress phase separation of the host matrix while increasing the efficiency and operational lifetime of deep-blue phosphorescent organic light-emitting diodes (PHOLEDs) with chromaticity coordinates of (0.14, 0.15). The bulky host enables homogenous mixing of the molecules comprising the emissive layer while suppressing single host aggregation; a significant loss channel of nonradiative recombination. By controlling the amorphous phase of the host-matrix morphology, the mixed-host device achieves a significant reduction in nonradiative exciton decay, resulting in 120 ± 6% increase in external quantum efficiency relative to an analogous, single-host device. In contrast to single host PHOLEDs where electrons are transported by the host and holes by the dopants, both charge carriers are conducted by the mixed host, reducing the probability of exciton annihilation, thereby doubling of the deep-blue PHOLED operational lifetime. These findings demonstrate that the host matrix morphology affects almost every aspect of PHOLED performance.
ABSTRACT
Tension control is critical for maintaining good product quality in most roll-to-roll (R2R) production systems. Previous work has primarily focused on improving the disturbance rejection performance of tension controllers. Here, a robust linear parameter-varying model predictive control (LPV-MPC) scheme is designed to enhance the tension tracking performance of a pilot R2R system for deposition of materials used in flexible thin film applications. The performance of a tension controller may degrade due to disturbances associated with model uncertainties and the slowly-changing dynamics in R2R systems. We introduce a method that separately treats these two sources of disturbance. The controller utilizes an incremental model to eliminate the errors caused by the mismatch between the nominal model and the actual system. A tube-based MPC formulation combined with scheduled parameters adequately updates models and corrects for the time-varying dynamics. Constraints on the rated motor torque are incorporated in the MPC to maintain the controller reliability and avoid machine failures. We illustrate the operation of our control algorithm through simulation of an actual R2R system. The controller outperforms the benchmarks in terms of fast transient response and offset-free tension tracking. It also demonstrates immunity from variations due to parametric uncertainties.
ABSTRACT
Recent advances in thermophotovoltaic (TPV) power generation have produced notable gains in efficiency, particularly at very high emitter temperatures. However, there remains substantial room for improving TPV conversion of waste, solar, and nuclear heat streams at temperatures below 1,100°C. Here, we demonstrate the concept of transmissive spectral control that enables efficient recuperation of below-bandgap photons by allowing them to transmit through the cell to be absorbed by a secondary emitter. We fabricate a semitransparent TPV cell consisting of a thin InGaAs-InP heterojunction membrane supported by an infrared-transparent heat-conducting substrate. The device absorbs less than 1% of below-bandgap radiation, resulting in a TPV efficiency of 32.5% at an emitter temperature of 1,036°C. To our knowledge, this represents an 8% absolute improvement (~33% relative) in efficiency relative to the best TPV devices at such low temperatures. By enabling near-zero photon loss, the semitransparent architecture facilitates high TPV efficiencies over a wide range of applications.
Subject(s)
Cold Temperature , Hot Temperature , TemperatureABSTRACT
The thermal stability of inverted, halogen-rich non-fullerene acceptor (NFA)-based organic photovoltaics with MoOx as the hole transporting layer is studied at temperatures up to 80 °C. Over time, the power conversion efficiency shows a "check-mark" shaped thermal aging pattern, featuring an early decrease, followed by a long-term recovery. A high Cl concentration at the bulk heterojunction (BHJ)/MoOx interface in the thermally aged device is found using energy dispersive X-ray spectroscopy. X-ray photoelectron spectroscopy shows that the MoOx is chlorinated after thermal aging. With bulk quantum efficiency analysis, we propose an explanation to the check-mark shaped pattern. Inserting a thin C70 layer between the BHJ and MoOx suppresses the thermal degradation mechanisms, resulting in three orders of magnitude increase in device lifetime at 80 °C.
ABSTRACT
Organic photovoltaic cells (OPVs) have the potential of becoming a productive renewable energy technology if the requirements of low cost, high efficiency and prolonged lifetime are simultaneously fulfilled. So far, the remaining unfulfilled promise of this technology is its inadequate operational lifetime. Here, we demonstrate that the instability of NFA solar cells arises primarily from chemical changes at organic/inorganic interfaces bounding the bulk heterojunction active region. Encapsulated devices stabilized by additional protective buffer layers as well as the integration of a simple solution processed ultraviolet filtering layer, maintain 94% of their initial efficiency under simulated, 1 sun intensity, AM1.5 G irradiation for 1900 hours at 55 °C. Accelerated aging is also induced by exposure of light illumination intensities up to 27 suns, and operation temperatures as high as 65 °C. An extrapolated intrinsic lifetime of > 5.6 × 104 h is obtained, which is equivalent to 30 years outdoor exposure.
ABSTRACT
We report a method to neutralize the mid-gap defect states in MoS2 monolayers using laser soaking of an organic/transition metal oxide (TMO) blend thin film. The treated MoS2 monolayer shows negligible emission from defect states as compared to the as-exfoliated MoS2, accompanied by a photoluminescence quantum yield improvement from 0.018 to 4.5% at excitation power densities of 10 W/cm2. The effectiveness of the method toward defect neutralization is governed by the polaron pair generated at the organic/TMO interface, the diffusion of free electrons, and the subsequent formation of TMO radicals at the MoS2 monolayer. The treated monolayers are stable in air, vacuum, and acetone environments, potentially enabling the fabrication of defect-free optoelectronic devices based on 2D materials and 2D/organic heterojunctions.
ABSTRACT
Thermophotovoltaic approaches that take advantage of near-field evanescent modes are being actively explored due to their potential for high-power density and high-efficiency energy conversion. However, progress towards functional near-field thermophotovoltaic devices has been limited by challenges in creating thermally robust planar emitters and photovoltaic cells designed for near-field thermal radiation. Here, we demonstrate record power densities of ~5 kW/m2 at an efficiency of 6.8%, where the efficiency of the system is defined as the ratio of the electrical power output of the PV cell to the radiative heat transfer from the emitter to the PV cell. This was accomplished by developing novel emitter devices that can sustain temperatures as high as 1270 K and positioning them into the near-field (<100 nm) of custom-fabricated InGaAs-based thin film photovoltaic cells. In addition to demonstrating efficient heat-to-electricity conversion at high power density, we report the performance of thermophotovoltaic devices across a range of emitter temperatures (~800 K-1270 K) and gap sizes (70 nm-7 µm). The methods and insights achieved in this work represent a critical step towards understanding the fundamental principles of harvesting thermal energy in the near-field.
ABSTRACT
The orientation of facial (fac) tris-cyclometalated iridium complexes in doped films prepared by vacuum deposition is investigated by altering the physical shape and electronic asymmetry in the molecular structure. Angle-dependent photoluminescence spectroscopy and Fourier-plane imaging microscopy show that the orientation of roughly spherical fac-tris(2-phenylpyridyl)iridium (Ir(ppy)3 ) is isotropic, whereas complexes that are oblate spheroids, fac-tris(mesityl-2-phenyl-1H-imidazole)iridium (Ir(mi)3 ) and fac-tris((3,5-dimethyl-[1,1'-biphenyl]-4-yl)-2-phenyl-1H-imidazole)iridium (Ir(mip)3 ), have a net horizontal alignment of their transition dipole moments. Optical anisotropy factors of 0.26 and 0.15, respectively, are obtained from the latter complexes when doped into tris(4-(9H-carbazol-9-yl)phenyl)amine host thin films. The horizontal alignment is attributed to the favorable van der Waals interaction between the oblate Ir complexes and host material. Trifluoromethyl groups substituted on one polar face of the Ir(ppy)3 and Ir(mi)3 complexes introduce chemical asymmetries in the molecules at the expense of their oblate shapes. The anisotropy factors of films doped with these substituted derivatives are lower relative to the parent complexes, indicating that the fluorinated patches reinforce horizontal alignment during deposition. High efficiencies obtained from organic light emitting diodes prepared using the Ir dopants is attributed, in part, to improved outcoupling of electroluminescence brought about by molecular alignment.
ABSTRACT
Organic photovoltaics (OPVs) based on nonfullerene acceptors are now approaching commercially viable efficiencies. One key to their success is efficient charge separation with low potential loss at the donor-acceptor heterojunction. Due to the lack of spectroscopic probes, open questions remain about the mechanisms of charge separation. Here, we study charge separation of a model system composed of the donor, poly[(2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione) (PBDB-T), and the nonfullerene acceptor, 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC), using multidimensional spectroscopy spanning the visible to the mid-infrared. We find that bound polaron pairs (BPPs) generated within ITIC domains play a dominant role in efficient hole transfer, transitioning to delocalized polarons within 100 fs. The weak electron-hole binding within the BPPs and the resulting polaron delocalization are key factors for efficient charge separation at nearly zero driving force. Our work provides useful insight into how to further improve the power conversion efficiency in OPVs.
ABSTRACT
Controlling matter-light interactions with cavities is of fundamental importance in modern science and technology1. This is exemplified in the strong-coupling regime, where matter-light hybrid modes form, with properties that are controllable by optical-wavelength photons2,3. By contrast, matter excitations on the nanometre scale are harder to access. In two-dimensional van der Waals heterostructures, a tunable moiré lattice potential for electronic excitations may form4, enabling the generation of correlated electron gases in the lattice potentials5-9. Excitons confined in moiré lattices have also been reported10,11, but no cooperative effects have been observed and interactions with light have remained perturbative12-15. Here, by integrating MoSe2-WS2 heterobilayers in a microcavity, we establish cooperative coupling between moiré-lattice excitons and microcavity photons up to the temperature of liquid nitrogen, thereby integrating versatile control of both matter and light into one platform. The density dependence of the moiré polaritons reveals strong nonlinearity due to exciton blockade, suppressed exciton energy shift and suppressed excitation-induced dephasing, all of which are consistent with the quantum confined nature of the moiré excitons. Such a moiré polariton system combines strong nonlinearity and microscopic-scale tuning of matter excitations using cavity engineering and long-range light coherence, providing a platform with which to study collective phenomena from tunable arrays of quantum emitters.
ABSTRACT
Over the past 3 decades, there has been a vast expansion of research in both tissue engineering and organic electronics. Although the two fields have interacted little, the materials and fabrication technologies which have accompanied the rise of organic electronics offer the potential for innovation and translation if appropriately adapted to pattern biological materials for tissue engineering. In this work, we use two organic electronic materials as adhesion points on a biocompatible poly(p-xylylene) surface. The organic electronic materials are precisely deposited via vacuum thermal evaporation and organic vapor jet printing, the proven, scalable processes used in the manufacture of organic electronic devices. The small molecular-weight organics prevent the subsequent growth of antifouling polyethylene glycol methacrylate polymer brushes that grow within the interstices between the molecular patches, rendering these background areas both protein and cell resistant. Last, fibronectin attaches to the molecular patches, allowing for the selective adhesion of fibroblasts. The process is simple, reproducible, and promotes a high yield of cell attachment to the targeted sites, demonstrating that biocompatible organic small-molecule materials can pattern cells at the microscale, utilizing techniques widely used in electronic device fabrication.
Subject(s)
Biocompatible Materials , Electronics , Biocompatible Materials/toxicity , Tissue EngineeringABSTRACT
Moiré lattices formed in twisted van der Waals bilayers provide a unique, tunable platform to realize coupled electron or exciton lattices unavailable before. While twist angle between the bilayer has been shown to be a critical parameter in engineering the moiré potential and enabling novel phenomena in electronic moiré systems, a systematic experimental study as a function of twist angle is still missing. Here we show that not only are moiré excitons robust in bilayers of even large twist angles, but also properties of the moiré excitons are dependant on, and controllable by, the moiré reciprocal lattice period via twist-angle tuning. From the twist-angle dependence, we furthermore obtain the effective mass of the interlayer excitons and the electron inter-layer tunneling strength, which are difficult to measure experimentally otherwise. These findings pave the way for understanding and engineering rich moiré-lattice induced phenomena in angle-twisted semiconductor van der Waals heterostructures.
ABSTRACT
We determine precise nanoscale information about the morphologies of several organic thin film structures using Fourier plane imaging microscopy (FIM). We used FIM microscopy to detect the orientation of molecular transition dipole moments from an extremely low density of luminescent dye molecules, which we call "morphology sensors". The orientation of the sensor molecules is driven by the local film structure and thus can be used to determine details of the host morphology without influencing it. We use symmetric planar phosphorescent dye molecules as the sensors that are deposited into the bulk of organic film hosts during the growth. We demonstrate morphological mapping with a depth resolution to a few Ångstroms that is limited by the ability to determine thickness during deposition, along with an in-plane resolution limited by optical diffraction. Furthermore, we monitor morphological changes arising from thermal annealing of metastable organic films that are commonly employed in photonic devices.