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Heterogeneous photocatalysis is an important research problem relevant to a variety of sustainable energy technologies. However, obtaining high photocatalytic efficiency from visible light absorbing semiconductors is challenging due to a combination of weak absorption, transport losses, and low activity. Aspects of this problem have been addressed by multilayer approaches, which provide a general scheme for engineering surface reactivity and stability independent of electronic considerations. However, an analogous broad framework for optimizing light–matter interactions has not yet been demonstrated. Here, we establish a photonic approach using semiconductor metasurfaces that is highly effective in enhancing the photocatalytic activity of GaAs, a high-performance semiconductor with a near-infrared bandgap. Our engineered pillar arrays with heights of ∼150 nm exhibit Mie resonances near 700 nm that result in near-unity absorption and exhibit a field profile that maximizes charge carrier generation near the solid–liquid interface, enabling short transport distances. Our hybrid metasurface photoanodes facilitate oxygen evolution and exhibit enhanced incident photon-to-current efficiencies that are ∼22× larger than a corresponding thin film for resonant excitation and 3× larger for white light illumination. Key to these improvements is the preferential generation of photogenerated carriers near the semiconductor interface that results from the field enhancement profile of magnetic dipolar-type modes. [ABSTRACT FROM AUTHOR]

Material architectures that balance optical transparency and electrical conductivity are highly sought after for thin-film device applications. However, these are competing properties, since the electronic structure that gives rise to conductivity typically also leads to optical opacity. Nanostructured metal films that exhibit extraordinary optical transmission, while at the same time being electrically continuous, offer considerable flexibility in the design of their transparency and resistivity. Here, we present design guidelines for metal films perforated with arrays of nanometer-scale holes, discussing the consequences of the choice of nanostructure dimensions, of the type of metal, and of the underlying substrate on their electrical, optical, and interfacial properties. We experimentally demonstrate that such films can be designed to have broad-band optical transparency while being an order of magnitude more conductive than indium tin oxide. Prototypical photovoltaic devices constructed with perforated metal contacts convert ~18% of the incident photons, compared to <1% for identical devices having contacts without the hole array. [ABSTRACT FROM AUTHOR]

Rayleigh scattering spectra were obtained from individual single-walled carbon nanotubes with the use of a laser-generated visible and near-infrared supercontinuum. This diagnostic method is noninvasive and general for nanoscale objects. The approach permits clear identification of excited states in arbitrary metallic and semiconducting nanotubes. We analyzed spectral lineshapes in relation to the role of excitonic effects and correlated the results with Raman scattering data on individual tubes. The nanotube structure remained the same over distances of tens of micrometers. Small nanotube bundles retained distinct Rayleigh spectroscopic signatures of their component nanotubes, thus allowing the probing of nanotube-nanotube interactions. [ABSTRACT FROM AUTHOR]

We simultaneously determined the physical structure and optical transition energies of individual single-walled carbon nanotubes by combining electron diffraction with Rayleigh scattering spectroscopy. These results test fundamental features of the excited electronic states of carbon nanotubes. We directly verified the systematic changes in transition energies of semiconducting nanotubes as a function of their chirality and observed predicted energy splittings of optical transitions in metallic nanotubes. [ABSTRACT FROM AUTHOR]

Photodetectors operating across the short‐, mid‐, and long‐wave infrared (SWIR–LWIR, λ = 1–14 µm) underpin modern science, technology, and society in profound ways. Narrow bandgap semiconductors that form the basis for these devices require complex manufacturing, high costs, cooling, and lack compatibility with silicon electronics, attributes that remain prohibitive for their widespread usage and the development of emerging technologies. Here, a photoconductive detector, fabricated using a solution‐processed narrow bandgap conjugated polymer is demonstrated that enables charge carrier generation in the infrared and ultrasensitive SWIR–LWIR photodetection at room temperature. Devices demonstrate an ultralow electronic noise that enables outstanding performance from a simple, monolithic device enabling a high detectivity (D*, the figure of merit for detector sensitivity) >2.44 × 109 Jones (cm Hz1/2 W−1) using the ultralow flux of a blackbody that mirrors the background emission of objects. These attributes, ease of fabrication, low dark current characteristics, and highly sensitive operation overcome major limitations inherent within modern narrow–bandgap semiconductors, demonstrate practical utility, and suggest that uncooled detectivities superior to many inorganic devices can be achieved at high operating temperatures. [ABSTRACT FROM AUTHOR]

Metal halide perovskites have witnessed great success in green, red, and near‐infrared light‐emitting diodes (LEDs), yet blue LEDs still lag behind. Reducing undesired energetic disorders – broad n‐phases and halide segregation – is considered as the most critical strategy to further improve the performances. Here, the study reports a newly designed and synthesized di‐ammonium ligand with rigid π‐conjugated rings and additional methyl groups to construct Dion–Jacobson (DJ) structure. Augmented coordination from the extra ammonium site and increased effective bulkiness from methyl groups lead to better distribution control over conventional mono‐ammonium ligands. This enhances the radiative recombination of blue emissions in the film with homogeneous energy landscape and improved surface morphology, as evidenced by a series of imaging and mapping techniques. As a result, it demonstrates DJ perovskite LEDs (PeLEDs) with peak external quantum efficiencies of ≈4% at 484 nm and ≈11% at 494 nm, which are among the top reported for pure DJ phase‐based PeLEDs in the corresponding wavelength regions. The results deepen the understanding of regulating energetic disorders in perovskite materials via molecular engineering. [ABSTRACT FROM AUTHOR]

A major limitation of transient optical spectroscopy is that relatively high laser fluences are required to enable broadband, multichannel detection with acceptable signal-to-noise levels. Under typical experimental conditions, many condensed phase and nanoscale materials exhibit fluence-dependent dynamics, including higher order effects such as carrier–carrier annihilation. With the proliferation of commercial laser systems, offering both high repetition rates and high pulse energies, have come new opportunities for high sensitivity pump-probe measurements at low pump fluences. However, experimental considerations needed to fully leverage the statistical advantage of these laser systems have not been fully described. Here, we demonstrate a high repetition rate, broadband transient spectrometer capable of multichannel shot-to-shot detection at 90 kHz. Importantly, we find that several high-speed cameras exhibit a time-domain fixed pattern noise resulting from interleaved analog-to-digital converters, which is particularly detrimental to the conventional "ON/OFF" modulation scheme used in pump-probe spectroscopy. Using a modified modulation and data processing scheme, we achieve a noise level of 10−5 in 4 s for differential transmission, an order of magnitude lower than for commercial 1 kHz transient spectrometers for the same acquisition time. We leverage the high sensitivity of this system to measure the differential transmission of monolayer graphene at low pump fluence. We show that signals on the order of 10−6 OD can be measured, enabling a new data acquisition regime for low-dimensional materials. [ABSTRACT FROM AUTHOR]

Polymers are desirable optoelectronic materials, stemming from their solution processability, tunable electronic properties, and large absorption coefficients. An exciting development is the recent discovery that singlet fission (SF), the conversion of a singlet exciton to a pair of triplet states, can occur along the backbone of an individual conjugated polymer chain. Compared to other intramolecular SF compounds, the nature of the triplet pair state in SF polymers remains poorly understood, hampering the development of new materials with optimized excited state dynamics. Here, we investigate the effect of solvent polarity on the triplet pair dynamics in the SF polymer polybenzodithiophene-thiophene-1,1-dioxide. We use transient emission measurements to study isolated polymer chains in solution and use the change in the solvent polarity to investigate the role of charge transfer character in both the singlet exciton and the triplet pair multiexciton. We identify both singlet fluorescence and direct triplet pair emission, indicating significant symmetry breaking. Surprisingly, the singlet emission peak is relatively insensitive to solvent polarity despite its nominal "charge-transfer" nature. In contrast, the redshift of the triplet pair energy with increasing solvent polarity indicates significant charge transfer character. While the energy separation between singlet and triplet pair states increases with solvent polarity, the overall SF rate constant depends on both the energetic driving force and additional environmental factors. The triplet pair lifetime is directly determined by the solvent effect on its overall energy. The dominant recombination channel is a concerted, radiationless decay process that scales as predicted by a simple energy gap law. [ABSTRACT FROM AUTHOR]

We demonstrate that a nonperturbative framework for the treatment of the excitations of single-walled carbon nanotubes based upon a field theoretic reduction is able to accurately describe experiment observations of the absolute values of excitonic energies. This theoretical framework yields a simple scaling function from which the excitonic energies can be read off. This scaling function is primarily determined by a single parameter, the charge Luttinger parameter of the tube, which is in turn a function of the tube chirality, dielectric environment, and the tube's dimensions, thus expressing disparate influences on the excitonic energies in a unified fashion. We test this theory explicitly on the data reported by Dukovic et al. [Nano Lett. 5, 2314 (2005)] and Sfeir et al. [Phys. Rev. B 82, 195424 (2010)] and so demonstrate the method works over a wide range of reported excitonic spectra. [ABSTRACT FROM AUTHOR]

We synthesized a new class of heterostructures by depositing CdS, CdSe, or CdTe quantum dots (QDs) onto α-V2O5 nanowires (NWs) via either successive ionic layer adsorption and reaction (SILAR) or linker-assisted assembly (LAA). SILAR yielded the highest loadings of QDs per NW, whereas LAA enabled better control over the size and properties of QDs. Soft and hard x-ray photoelectron spectroscopy in conjunction with density functional theory calculations revealed that all α-V2O5/QD heterostructures exhibited Type-II band offset energetics, with a staggered gap where the conduction- and valence-band edges of α-V2O5 NWs lie at lower energies (relative to the vacuum level) than their QD counterparts. Transient absorption spectroscopy measurements revealed that the Type-II energetic offsets promoted the ultrafast (10−12–10−11 s) separation of photogenerated electrons and holes across the NW/QD interface to yield long-lived (10−6 s) charge-separated states. Charge-transfer dynamics and charge-recombination time scales varied subtly with the composition of heterostructures and the nature of the NW/QD interface, with both charge separation and recombination occurring more rapidly within SILAR-derived heterostructures. LAA-derived α-V2O5/CdSe heterostructures promoted the photocatalytic reduction of aqueous protons to H2 with a 20-fold or greater enhancement relative to isolated colloidal CdSe QDs or dispersed α-V2O5 NWs. The separation of photoexcited electrons and holes across the NW/QD interface could thus be exploited in redox photocatalysis. In light of their programmable compositions and properties and their Type-II energetics that drive ultrafast charge separation, the α-V2O5/QD heterostructures are a promising new class of photocatalyst architectures ripe for continued exploration. [ABSTRACT FROM AUTHOR]

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. Little is known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. Here, we reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons to one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm-1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The observed electron localization phenomenon provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion. [ABSTRACT FROM AUTHOR]

Controlling how electromagnetic waves interact with complex media is critical for applications in imaging and focusing. Such lightwave interactions with complex media can lead to dramatic optical effects like lasing. While much work in random lasing focus on understanding how gain and scattering co‐operatively generate lasing, little work has focused on how to manipulate the lasing threshold without modifying the structural disorder. Here, a simple, mostly unexplored, strategy is demonstrated that employs atomic layer deposition (ALD) to tune the local near‐field environment while preserving the underpinning disorder—controlling lasing in a nanoscale complex medium on a large scale (>cm2). The nanoscale complex medium is a quasi‐2D system of coupled zinc oxide nanospheres with overall thickness deep in the sub‐wavelength regime (≈λ/4). Near‐ultraviolet femtosecond spectroscopy probes the broadband response of the gain nanomaterial, details how ALD process fundamentally modifies the fast‐picosecond and slow‐nanosecond carrier dynamics, and informs on the relevant timescales critical for lasing. Full‐field electromagnetic simulations provide critical insights about how near‐field dielectric environment modifies the nanostructure's scattering cross‐section, which ultimately results in enhanced lasing. These results highlight a simple path to control how electromagnetic waves interact in a complex medium, a key step toward large‐scale implementation of complex lasers. [ABSTRACT FROM AUTHOR]

As wide bandgap materials are nanostructured for optoelectronics and energy technologies, understanding how size and defects modify the carrier dynamics becomes critical. Here, we examine broadband ultraviolet-visible subpicosecond emission dynamics of prototypical ZnO in bulk, nanowire and nanosphere geometries. Using a high-sensitivity transient emission Kerr-based spectrometer, we probe exciton dynamics in the low fluence regime to determine how defects states impact thermalization and recombination rates. In contrast to steady-state measurements, we transiently identify low-energy emission features that originate from localized excitonic states rather than mid-gap states, characterized by distinct recombination kinetics, and correlate to longer thermalization times. These states are critical for understanding the overall excited state lifetime of materials in this size regime, where crystallinity rather than dimensionality plays a primary role in dictating recombination dynamics. [ABSTRACT FROM AUTHOR]

The synthesis and structure of atomically precise Au130−xAgx (average x=98) alloy nanoclusters protected by 55 ligands of 4‐tert‐butylbenzenethiolate are reported. This large alloy structure has a decahedral M54 (M=Au/Ag) core. The Au atoms are localized in the truncated Marks decahedron. In the core, a drum of Ag‐rich sites is found, which is enclosed by a Marks decahedral cage of Au‐rich sites. The surface is exclusively Ag−SR; X‐ray absorption fine structure analysis supports the absence of Au−S bonds. The optical absorption spectrum shows a strong peak at 523 nm, seemingly a plasmon peak, but fs spectroscopic analysis indicates its non‐plasmon nature. The non‐metallicity of the Au130−xAgx nanocluster has set up a benchmark to study the transition to metallic state in the size evolution of bimetallic nanoclusters. The localized Au/Ag binary architecture in such a large alloy nanocluster provides atomic‐level insights into the Au−Ag bonds in bimetallic nanoclusters. [ABSTRACT FROM AUTHOR]

The synthesis and structure of atomically precise Au130−xAgx (average x=98) alloy nanoclusters protected by 55 ligands of 4‐tert‐butylbenzenethiolate are reported. This large alloy structure has a decahedral M54 (M=Au/Ag) core. The Au atoms are localized in the truncated Marks decahedron. In the core, a drum of Ag‐rich sites is found, which is enclosed by a Marks decahedral cage of Au‐rich sites. The surface is exclusively Ag−SR; X‐ray absorption fine structure analysis supports the absence of Au−S bonds. The optical absorption spectrum shows a strong peak at 523 nm, seemingly a plasmon peak, but fs spectroscopic analysis indicates its non‐plasmon nature. The non‐metallicity of the Au130−xAgx nanocluster has set up a benchmark to study the transition to metallic state in the size evolution of bimetallic nanoclusters. The localized Au/Ag binary architecture in such a large alloy nanocluster provides atomic‐level insights into the Au−Ag bonds in bimetallic nanoclusters. [ABSTRACT FROM AUTHOR]

Research on plasmons of gold nanoparticles has gained broad interest in nanoscience. However, ultrasmall sizes near the metal-to-nonmetal transition regime have not been explored until recently due to major synthetic difficulties. Herein, intriguing electron dynamics in this size regime is observed in atomically precise Au333(SR)79 nanoparticles. Femtosecond transient-absorption spectroscopy reveals an unprecedented relaxation process of 4-5 ps--a fast phonon-phonon relaxation process, together with electron-phonon coupling (~1 ps) and normal phonon-phonon coupling (>100 ps) processes. Three types of -R capped Au333(SR)79 all exhibit two plasmon-bleaching signals independent of the -R group as well as solvent, indicating plasmon splitting and quantum effect in the ultrasmall core of Au333(SR)79. This work is expected to stimulate future work on the transition-size regime of nanometals and discovery of behavior of nascent plasmons. [ABSTRACT FROM AUTHOR]

We report a three-orders-of-magnitude variation of carrier lifetimes in exotic crystalline phases of gold nanoclusters (NCs) in addition to the well-known face-centered cubic structure, including hexagonal close-packed (hcp) Au30 and body-centered cubic (bcc) Au38 NCs protected by the same type of capping ligand. The bcc Au38 NC had an exceptionally long carrier lifetime (4.7 microseconds) comparable to that of bulk silicon, whereas the hcp Au30 NC had a very short lifetime (1 nanosecond). Although the presence of ligands may, in general, affect carrier lifetimes, experimental and theoretical results showed that the drastically different recombination lifetimes originate in the different overlaps of wave functions between the tetrahedral Au4 building blocks in the hierarchical structures of these NCs. [ABSTRACT FROM AUTHOR]

The optical properties of metal nanoparticles have attracted wide interest. Recent progress in controlling nanoparticles with atomic precision (often called nanoclusters) provide new opportunities for investigating many fundamental questions, such as the transition from excitonic to plasmonic state, which is a central question in metal nanoparticle research because it provides insights into the origin of surface plasmon resonance (SPR) as well as the formation of metallic bond. However, this question still remains elusive because of the extreme difficulty in preparing atomically precise nanoparticles larger than 2 nm. Here we report the synthesis and optical properties of an atomically precise Au279(SR)84 nanocluster. Femtosecond transient absorption spectroscopic analysis reveals that the Au279 nanocluster shows a laser power dependence in its excited state lifetime, indicating metallic state of the particle, in contrast with the nonmetallic electronic structure of the Au246(SR)80 nanocluster. Steady-state absorption spectra reveal that the nascent plasmon band of Au279 at 506 nm shows no peak shift even down to 60 K, consistent with plasmon behavior. The sharp transition from nonmetallic Au246 to metallic Au279 is surprising and will stimulate future theoretical work on the transition and many other relevant issues. [ABSTRACT FROM AUTHOR]

Abstract: Infrared organic photodetector materials are investigated using transient absorption spectroscopy, demonstrating that ultrafast charge generation assisted by polymer aggregation is essential to compensate for the energy gap law, which dictates that excited state lifetimes decrease as the band gap narrows. Short sub‐picosecond singlet exciton lifetimes are measured in a structurally related series of infrared‐absorbing copolymers that consist of alternating cyclopentadithiophene electron‐rich “push” units and strong electron‐deficient “pull” units, including benzothiadiazole, benzoselenadiazole, pyridalselenadiazole, or thiadiazoloquinoxaline. While the ultrafast lifetimes of excitons localized on individual polymer chains suggest that charge carrier generation will be inefficient, high detectivity for polymer:PC71BM infrared photodetectors is measured in the 0.6 < λ < 1.5 µm range. The photophysical processes leading to charge generation are investigated by performing a global analysis on transient absorption data of blended polymer:PC71BM films. In these blends, charge carriers form primarily at polymer aggregate sites on the ultrafast time scale (within our instrument response), leaving quickly decaying single‐chain excitons unquenched. The results have important implications for the further development of organic infrared optoelectronic devices, where targeting processes such as excited state delocalization over aggregates may be necessary to mitigate losses to ultrafast exciton decay as materials with even lower band gaps are developed. [ABSTRACT FROM AUTHOR]

The transition from molecular to plasmonic behaviour in metal nanoparticles with increasing size remains a central question in nanoscience. We report that the giant 246-gold-atom nanocluster (2.2 nm in gold core diameter) protected by 80 thiolate ligands is surprisingly non-metallic based on UV/Vis and femtosecond transient absorption spectroscopy as well as electrochemical measurements. Specifically, the Au246 nanocluster exhibits multiple excitonic peaks in transient absorption spectra and electron dynamics independent of the pump power, which are in contrast to the behaviour of metallic gold nanoparticles. Moreover, a prominent oscillatory feature with frequency of 0.5 THz can be observed in almost all the probe wavelengths. The phase and amplitude analysis of the oscillation suggests that it arises from the wavepacket motion on the ground state potential energy surface, which also indicates the presence of a small band-gap and thus non-metallic or molecular-like behaviour. [ABSTRACT FROM AUTHOR]

The transition from molecular to plasmonic behaviour in metal nanoparticles with increasing size remains a central question in nanoscience. We report that the giant 246-gold-atom nanocluster (2.2 nm in gold core diameter) protected by 80 thiolate ligands is surprisingly non-metallic based on UV/Vis and femtosecond transient absorption spectroscopy as well as electrochemical measurements. Specifically, the Au246 nanocluster exhibits multiple excitonic peaks in transient absorption spectra and electron dynamics independent of the pump power, which are in contrast to the behaviour of metallic gold nanoparticles. Moreover, a prominent oscillatory feature with frequency of 0.5 THz can be observed in almost all the probe wavelengths. The phase and amplitude analysis of the oscillation suggests that it arises from the wavepacket motion on the ground state potential energy surface, which also indicates the presence of a small band-gap and thus non-metallic or molecular-like behaviour. [ABSTRACT FROM AUTHOR]

We have designed a series of pentacene dimers separated by homoconjugated or nonconjugated bridges that exhibit fast and efficient intramolecular singlet exciton fission (iSF). These materials are distinctive among reported iSF compounds because they exist in the unexplored regime of close spatial proximity but weak electronic coupling between the singlet exciton and triplet pair states. Using transient absorption spectroscopy to investigate photophysics in these molecules, we find that homoconjugated dimers display desirable excited-state dynamics, with significantly reduced recombination rates as compared to conjugated dimers with similar singlet fission rates. In addition, unlike conjugated dimers, the time constants for singlet fission are relatively insensitive to the interplanar angle between chromophores, since rotation about σ bonds negligibly affects the orbital overlap within the p-bonding network. In the nonconjugated dimer, where the iSF occurs with a time constant >10 ns, comparable to the fluorescence lifetime, we used electron spin resonance spectroscopy to unequivocally establish the formation of triplet-triplet multiexcitons and uncoupled triplet excitons through singlet fission. Together, these studies enable us to articulate the role of the conjugation motif in iSF. [ABSTRACT FROM AUTHOR]

The article reports that singlet fission may increase the solar energy conversion efficiency beyond the Shockley-Queisser limit. The nature of the triplet pair state and its spectroscopic signature is said to remain actively debated. An end-connected pentacene dimer (BP0) is used as a model system and show evidence for a tightly bound state.

Semiconductor photoelectrodes for photoelectrochemical (PEC) water splitting require efficient carrier generation, separation, and transport at and beyond the space charge region (SCR) formed at the aqueous interface. The trade-off between photon collection and minority carrier delivery governs the photoelectrode design and implies maximum water splitting efficiency at an electrode thickness equivalent to the light absorption depth. Here, using planar ZnO thin films as a model system, we identify the photocarriers beyond the SCR as another significant source to substantially enhance the PEC performance. The high-quality ZnO films synthesized by pulsed laser deposition feature very few deep trap states and support a long photocarrier lifetime. Combined with photoelectrochemical characterization, ultrafast spectroscopy, and numerical calculations, it is revealed that engineering the exciton concentration gradient by film thickness facilitates the inward diffusion of photocarriers from the neighboring illuminated region to the SCR and, therefore, achieves a record high quantum efficiency over 80% at a thickness far beyond its light absorption depth and the SCR width. These results elucidate the important role of the photocarriers beyond SCR for the PEC process and provide new insight into exploring the full potential for efficient photoelectrode materials with large exciton diffusivity. [ABSTRACT FROM AUTHOR]

One measure of exciton mobility in an aggregate is the efficiency of exciton-exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH-PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. The wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly. [ABSTRACT FROM AUTHOR]

We report a tunable library of N,N,N'-trisubstituted selenourea precursors and their reaction with lead oleate at 60-150 °C to form carboxylate-terminated PbSe nanocrystals in quantitative yields. Single exponential conversion kinetics can be tailored over 4 orders of magnitude by adjusting the selenourea structure. The wide range of conversion reactivity allows the extent of nucleation ([nanocrystal] = 4.6-56.7 μM) and the size following complete precursor conversion (d = 1.7-6.6 nm) to be controlled. Narrow size distributions (σ = 0.5-2%) are obtained whose spectral line widths are dominated (73-83%) by the intrinsic single particle spectral broadening, as observed using spectral hole burning measurements. The intrinsic broadening decreases with increasing size (fwhm = 320-65 meV, d = 1.6-4.4 nm) that derives from exciton fine structure and exciton-phonon coupling rather than broadening caused by the size distribution. [ABSTRACT FROM AUTHOR]

The incorporation of multiple donors into the bulk-heterojunction layer of organic polymer solar cells (PSCs) has been demonstrated as a practical and elegant strategy to improve photovoltaics performance. However, it is challenging to successfully design and blend multiple donors, while minimizing unfavorable interactions (e.g., morphological traps, recombination centers, etc.). Here, a new Förster resonance energy transfer-based design is shown utilizing the synergistic nature of three light active donors (two small molecules and a high-performance donor-acceptor polymer) with a fullerene acceptor to create highly efficient quaternary PSCs with power conversion efficiencies (PCEs) of up to 10.7%. Within this quaternary architecture, it is revealed that the addition of small molecules in low concentrations broadens the absorption bandwidth, induces cocrystalline molecular conformations, and promotes rapid (picosecond) energy transfer processes. These results provide guidance for the design of multiple-donor systems using simple processing techniques to realize single-junction PSC designs with unprecedented PCEs. [ABSTRACT FROM AUTHOR]

The article reports on the observation that graphitic carbon, sheets as well as tubes, can be prepared from solution at temperatures as low as 100 degrees Celsius. Energy dispersive spectroscopy shows primarily carbon with smaller amounts of iron and oxygen. Transmission electron microscopy also shows sheets and micrometer long tubes in addition to nanoparticles of magnetite.

We have synthesized a series of asymmetric pentacene--tetracene heterodimers with a variable-length conjugated bridge that undergo fast and efficient intramolecular singlet fission (iSF). These compounds have distinct singlet and triplet energies, which allow us to study the spatial dynamics of excitons during the iSF process, including the significant role of exciton correlations in promoting triplet pair generation and recombination. We demonstrate that the primary photoexcitations in conjugated dimers are delocalized singlets that enable fast and efficient iSF. However, in these asymmetric dimers, the singlet becomes more localized on the lower energy unit as the length of the bridge is increased, slowing down iSF relative to analogous symmetric dimers. We resolve the recombination kinetics of the inequivalent triplets produced via iSF, and find that they primarily decay via concerted processes. By identifying different decay channels, including delayed fluorescence via triplet--triplet annihilation, we can separate transient species corresponding to both correlated triplet pairs and uncorrelated triplets. Recombination of the triplet pair proceeds rapidly despite our experimental and theoretical demonstration that individual triplets are highly localized and unable to be transported across the conjugated linker. In this class of compounds, the rate of formation and yield of uncorrelated triplets increases with bridge length. Overall, these constrained, asymmetric systems provide a unique platform to isolate and study transient species essential for singlet fission, which are otherwise difficult to observe in symmetric dimers or condensed phases. [ABSTRACT FROM AUTHOR]

Solution-processed organometallic perovskites have rapidly developed into a top candidate for the active layer of photovoltaic devices. Despite the remarkable progress associated with perovskite materials, many questions about the fundamental photophysical processes taking place in these devices, remain open. High on the list of unexplained phenomena are very modest mobilities despite low charge carrier effective masses. Moreover, experiments elucidate unique degradation of photocurrent affecting stable operation of perovskite solar cells. These puzzles suggest that, while ionic hybrid perovskite devices may have efficiencies on par with conventional Si and GaAs devices, they exhibit more complicated charge transport phenomena. Here we report the results from an in-depth computational study of small polaron formation, electronic structure, charge density, and reorganization energies using both periodic boundary conditions and isolated structures. Using the hybrid density functional theory, we found that volumetric strain in a CsPbI3 cluster creates a polaron with binding energy of around 300 and 900 meV for holes and electrons, respectively. In the MAPbI3 (MA = CH3NH3) cluster, both volumetric strain and MA reorientation effects lead to larger binding energies at around 600 and 1300 meV for holes and electrons, respectively. Such large reorganization energies suggest appearance of small polarons in organometallic perovskite materials. The fact that both volumetric lattice strain and MA molecular rotational degrees of freedom can cooperate to create and stabilize polarons indicates that in order to mitigate this problem, formamidinium (FA = HC(NH2)2) and cesium (Cs) based crystals and alloys, are potentially better materials for solar cell and other optoelectronic applications. [ABSTRACT FROM AUTHOR]

Lasing in solution-processed nanomaterials has gained significant interest because of the potential for low-cost integrated photonic devices. Still, a key challenge is to utilize a comprehensive knowledge of the system's spectral and temporal dynamics to design low-threshold lasing devices. Here, we demonstrate intrinsic lasing (without external cavity) at low-threshold in an ultrathin film of coupled, highly crystalline nanospheres with overall thickness on the order of ~λ/4. The cavity-free geometry consists of ~35 nm zinc oxide nanospheres that collectively localize the in-plane emissive light fields while minimizing scattering losses, resulting in excitonic lasing with fluence thresholds at least an order of magnitude lower than previous UV-blue random and quantum-dot lasers (<75 µJ/cm²). Fluence-dependent effects, as quantified by subpicosecond transient spectroscopy, highlight the role of phonon-mediated processes in excitonic lasing. Subpicosecond evolution of distinct lasing modes, together with three-dimensional electromagnetic simulations, indicate a random lasing process, which is in violation of the commonly cited criteria of strong scattering from individual nanostructures and an optically thick sample. Subsequently, an electron-hole plasma mechanism is observed with increased fluence. These results suggest that coupled nanostructures with high crystallinity, fabricated by low-cost solution-processing methods, can function as viable building blocks for high-performance optoelectronics devices. [ABSTRACT FROM AUTHOR]

We investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower-energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. The ability to tune the energies of these materials provides a key strategy to study and design new SF materials-an important process for third-generation photovoltaics. [ABSTRACT FROM AUTHOR]

We investigate singlet fission (SF) in heterodimers comprising a pentacene unit covalently bonded to another acene as we systematically vary the singlet and triplet pair energies. We find that these energies control the SF process, where dimers undergo SF provided that the resulting triplet pair energy is similar or lower in energy than the singlet state. In these systems the singlet energy is determined by the lower-energy chromophore, and the rate of SF is found to be relatively independent of the driving force. However, triplet pair recombination in these heterodimers follows the energy gap law. The ability to tune the energies of these materials provides a key strategy to study and design new SF materials-an important process for third-generation photovoltaics. [ABSTRACT FROM AUTHOR]

We describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki-Miyaura cross-coupling reactions. Because this synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entire visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV-vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. This effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics. [ABSTRACT FROM AUTHOR]

We describe a facile route to well-defined, solution-processable pentacene oligomers (2 to 7) and homopolymer using Suzuki-Miyaura cross-coupling reactions. Because this synthetic strategy leads to regioisomers, regiopure syn- and anti-trimers were also synthesized, revealing minimal changes in solution properties but significant changes in the solid state arising from differing levels of crystallinity. The materials were characterized by steady state absorption spectroscopy and cyclic voltammetry to study their electronic structure. The steady state absorption spectra exhibit a new high-energy transition in the oligomers, which intensifies as a function of oligomer length, thus increasing the range of absorption to include the entire visible spectrum. Density functional theory calculations indicate that the new peak results directly from the oligomerization. Solid state UV-vis suggests that while the monomer is amorphous, bricklayer packing in the higher oligomers significantly alters the solid state absorption relative to solution. This effect of oligomerization on packing was corroborated by GIWAXS analysis, which revealed crystalline domains in the oligomers. These domains, which are most evident in anti-trimer, become more pronounced upon thermal annealing. Photodegradation studies revealed considerable stability enhancement of oligomers toward oxygen and cycloaddition reactions relative to monomer. The synthesis and characterization of the first higher oligomers and homopolymer of pentacene should pave the way to applications in singlet fission, organic field-effect transistors, and organic photovoltaics. [ABSTRACT FROM AUTHOR]

Singlet fission (SF) has the potential to significantly enhance the photocurrent in single-junction solar cells and thus raise the power conversion efficiency from the Shockley--Queisser limit of 33% to 44%. Until now, quantitative SF yield at room temperature has been observed only in crystalline solids or aggregates of oligoacenes. Here, we employ transient absorption spectroscopy, ultrafast photoluminescence spectroscopy, and triplet photosensitization to demonstrate intramolecular singlet fission (iSF) with triplet yields approaching 200% per absorbed photon in a series of bipentacenes. Crucially, in dilute solution of these systems, SF does not depend on intermolecular interactions. Instead, SF is an intrinsic property of the molecules, with both the fission rate and resulting triplet lifetime determined by the degree of electronic coupling between covalently linked pentacene molecules. We found that the triplet pair lifetime can be as short as 0.5 ns but can be extended up to 270 ns. [ABSTRACT FROM AUTHOR]

The ability to advance our understanding of multiple exciton generation (MEG) in organic materials has been restricted by the limited number of materials capable of singlet fission. A particular challenge is the development of materials that undergo efficient intramolecular fission, such that local order and strong nearest-neighbour coupling is no longer a design constraint. Here we address these challenges by demonstrating that strong intrachain donor-acceptor interactions are a key design feature for organic materials capable of intramolecular singlet fission. By conjugating strong-acceptor and strong-donor building blocks, small molecules and polymers with charge-transfer states that mediate population transfer between singlet excitons and triplet excitons are synthesized. Using transient optical techniques, we show that triplet populations can be generated with yields up to 170%. These guidelines are widely applicable to similar families of polymers and small molecules, and can lead to the development of new fission-capable materials with tunable electronic structure, as well as a deeper fundamental understanding of MEG. [ABSTRACT FROM AUTHOR]

A quantitative description of recombinationprocesses in nanostructuredsemiconductor photocatalystsone that distinguishes betweenbulk (charge transport) and surface (chemical reaction) lossesiscritical for advancing solar-to-fuel technologies. Here we presentan in situ experimental framework that determines the bias-dependentquantum yield for ultrafast carrier transport to the reactive interface.This is achieved by simultaneously measuring the electrical characteristicsand the subpicosecond charge dynamics of a heterostructured photoanodein a working photoelectrochemical cell. Together with direct measurementsof the overall incident-photon-to-current efficiency, we illustratehow subtle structural modifications that are not perceivable by conventionalX-ray diffraction can drastically affect the overall photocatalyticquantum yield. We reveal how charge carrier recombination losses occurringon ultrafast time scales can limit the overall efficiency even innanostructures with dimensions smaller than the minority carrier diffusionlength. This is particularly true for materials with high carrierconcentration, where losses as high as 37% are observed. Our methodologyprovides a means of evaluating the efficacy of multifunctional designswhere high overall efficiency is achieved by maximizing surface transportyield to near unity and utilizing surface layers with enhanced activity. [ABSTRACT FROM AUTHOR]

In this report, we synthesize andcharacterize the structural andoptical properties of novel heterostructures composed of (i) semiconductingnanocrystalline CdSe quantum dots (QDs) coupled with (ii) both one-and zero-dimensional (1D and 0D) motifs of self-activated luminescentCaWO4metal oxides. Specifically, ∼4 nm CdSe QDshave been anchored onto (i) high-aspect ratio 1D nanowires, measuring∼230 nm in diameter and ∼3 μm in length, as wellas onto (ii) crystalline 0D nanoparticles (possessing an average diameterof ∼80 nm) of CaWO4through the mediation of 3-mercaptopropionicacid (MPA) as a connecting linker. Composite formation was confirmedby complementary electron microscopy and spectroscopy (i.e., IR andRaman) data. In terms of luminescent properties, our results showthat our 1D and 0D heterostructures evince photoluminescence (PL)quenching and shortened PL lifetimes of CaWO4as comparedwith unbound CaWO4. We propose that a photoinduced electrontransfer process occurs from CaWO4to CdSe QDs, a scenariowhich has been confirmed by NEXAFS measurements and which highlightsa decrease in the number of unoccupied orbitals in the conductionbands of CdSe QDs. By contrast, the PL signature and lifetimes ofMPA-capped CdSe QDs within these heterostructures do not exhibit noticeablechanges as compared with unbound MPA-capped CdSe QDs. The strikingdifference in optical behavior between CaWO4nanostructuresand CdSe QDs within our heterostructures can be correlated with therelative positions of their conduction and valence energy band levels.In addition, the PL quenching behaviors for CaWO4withinthe heterostructure configuration were examined by systematicallyvarying (i) the quantities and coverage densities of immobilized CdSeQDs as well as (ii) the intrinsic morphology (and by extension, theinherent crystallite size) of CaWO4itself. [ABSTRACT FROM AUTHOR]

We present a methodology for probing light-matter interactions in prototype photovoltaic devices consisting of an organic semiconductor active layer with a semitransparent metal electrical contact exhibiting surface plasmon-based enhanced optical transmission. We achieve high-spectral irradiance in a spot size of less than 100 μm using a high-brightness laser-driven light source and appropriate coupling optics. Spatially resolved Fourier transform photocurrent spectroscopy in the visible and near-infrared spectral regions allows us to measure external quantum efficiency with high sensitivity in small-area devices (<1 mm2). This allows for rapid fabrication of variable-pitch sub-wavelength hole arrays in metal films for use as transparent electrical contacts, and evaluation of the evanescent and propagating mode coupling to resonances in the active layer. [ABSTRACT FROM AUTHOR]

We report an efficiency of 6.1% for a solution-processed non-fullerene solar cell using a helical perylene diimide (PDI) dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor—acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current—voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions. [ABSTRACT FROM AUTHOR]

Bridgehead imine-substituted cyclopentadithiophene structural units, in combination with highly electronegative acceptors that exhibit progressively delocalized π-systems, afford donor-acceptor (DA) conjugated polymers with broad absorption profiles that span technologically relevant wavelength (λ) ranges from 0.7 < λ < 3.2 μm. A joint theoretical and experimental study demonstrates that the presence of the cross-conjugated substituent at the donor bridgehead position results in the capability to fine-tune structural and electronic properties so as to achieve very narrow optical bandgaps ( Egopt < 0.5 eV). This strategy affords modular DA copolymers with broad- and long-wavelength light absorption in the infrared and materials with some of the narrowest bandgaps reported to date. [ABSTRACT FROM AUTHOR]

Singlet fission, the conversion of a singlet excitation into two triplet excitations, is a viable route to improved solar-cell efficiency. Despite active efforts to understand the singlet fission mechanism, which would aid in the rational design of new materials, a comprehensive understanding of mechanistic principles is still lacking. Here, we present the first study of singlet fission in crystalline hexacene which, together with tetracene and pentacene, enables the elucidation of mechanistic trends. We characterize the static and transient optical absorption and combine our findings with a theoretical analysis of the relevant electronic couplings and rates. We find a singlet fission time scale of 530 fs, which is orders of magnitude faster than tetracene (10— 100 ps) but significantly slower than pentacene (80—110 fs). We interpret this increased time scale as a multiphonon relaxation effect originating from a large exothermicity and present a microscopic theory that quantitatively reproduces the rates in the acene family. [ABSTRACT FROM AUTHOR]

Exciton fission is a process that occurs in certain organic materials whereby one singlet exciton splits into two independent triplets. In photovoltaic devices these two triplet excitons can each generate an electron, producing quantum yields per photon of >100% and potentially enabling single-junction power efficiencies above 40%. Here, we measure fission dynamics using ultrafast photoinduced absorption and present a first-principles expression that successfully reproduces the fission rate in materials with vastly different structures. Fission is non-adiabatic and Marcus-like in weakly interacting systems, becoming adiabatic and coupling-independent at larger interaction strengths. In neat films, we demonstrate fission yields near unity even when monomers are separated by >5 Å. For efficient solar cells, however, we show that fission must outcompete charge generation from the singlet exciton. This work lays the foundation for tailoring molecular properties like solubility and energy level alignment while maintaining the high fission yield required for photovoltaic applications. [ABSTRACT FROM AUTHOR]

Double-walled carbon nanotube (DWNT)-CdSe heterostructures with the individual nanoscale building blocks linked together by 4-aminothiophenol (4-ATP) have been successfully synthesized using two different and complementary routes, i.e. covalent attachment and non-covalent π-π stacking. Specifically, using a number of characterization methods, we have probed the effects of these differential synthetic coupling approaches on the resulting CdSe quantum dot (QD) coverage on the underlying nanotube template as well as the degree of charge transfer between the CdSe QDs and the DWNTs. In general, based on microscopy and spectroscopy data collectively, we noted that heterostructures generated by noncovalent π-π stacking interactions evinced not only higher QD coverage density but also possibly more efficient charge transfer behavior as compared with their counterparts produced using covalent linkermediated protocols. [ABSTRACT FROM AUTHOR]

There are two crucial tasks for realizing high-efficiency polymer solar cells (PSCs): increasing the range of the spectral absorption of light and efficiently harvesting photogenerated excitons. Here, we describe Förster resonance energy transfer-based heterojunction polymer solar cells that incorporate squaraine dye. The high absorbance of squaraine in the near-infrared region broadens the spectral absorption of the solar cells and assists in developing an ordered nanomorphology for enhanced charge transport. Femtosecond spectroscopic studies reveal highly efficient (up to 96%) excitation energy transfer from poly(3-hexylthiophene) to squaraine occurring on a picosecond timescale. We demonstrate a 38% increase in power conversion efficiency to reach 4.5%, and suggest that this system has improved exciton migration over long distances. This architecture transcends traditional multiblend systems, allowing multiple donor materials with separate spectral responses to work synergistically, thereby enabling an improvement in light absorption and conversion. This opens up a new avenue for the development of high-efficiency polymer solar cells. [ABSTRACT FROM AUTHOR]

We report a simple but powerful method for engineering multi-walled carbon nanotubes (MWNTs) by using manipulation by an atomic-force microscope. The successive shell-by-shell extraction process of ultralong MWNTs allows the exposure of the innermost single-walled carbon nanotubes (SWNTs), which have diameters as small as ≈0.4 nm. The inner-shell extraction process changes the electrical characteristics of the MWNTs. Whereas the outer hollowed-out nanotubes show either metallic or semiconducting character, the innermost SWNTs of small diameter exhibit predominantly metallic transport properties. [ABSTRACT FROM AUTHOR]

A central challenge for both the science and the technology of carbon nanotubes is the controlled assembly of devices. Here, we report a technique that allows us to place a nanotube with the desired properties in a predetermined location by direct mechanical transfer. We demonstrate single-tube and multiple-tube transfer and electrical characterization of an optically characterized nanotube. The ability to rationally design nanotube devices and circuits will enable more detailed study of the physics and chemistry of nanotubes and provide a stepping stone toward implementation of a wide spectrum of applications. [ABSTRACT FROM AUTHOR]

Connecting the complex electronic excitations of hybrid perovskites to their intricate organic-inorganic lattice structure has critical implications for energy conversion and optoelectronic technologies. Here we detail the multiband, multivalley electronic structure of a halide hybrid perovskite by measuring the absorption transients of a millimeter-scale-grain thin film as it undergoes a thermally controlled reversible tetragonal-to-orthogonal phase transition. Probing nearly single grains of this hybrid perovskite, we observe an unreported energy splitting (degeneracy lifting) of the high-energy 2.6 eV band in the tetragonal phase that further splits as the rotational degrees of freedom of the disordered CH3NH3+ molecules are reduced when the sample is cooled. This energy splitting drastically increases during an extended phase-transition coexistence region that persists from 160 to 120 K, becoming more pronounced in the orthorhombic phase. By tracking the temperature-dependent optical transition energies and using symmetry analysis that describes the evolution of electronic states from the tetragonal phase to the orthorhombic phase, we assign this energy splitting to the nearly degenerate transitions in the tetragonal phase from both the R- and M-point-derived states. Importantly, these assignments explain how momentum conservation effects lead to long hot-carrier lifetimes in the room-temperature tetragonal phase, with faster hot-carrier relaxation when the hybrid perovskite structurally transitions to the orthorhombic phase due to enhanced scattering at the Γ point. [ABSTRACT FROM AUTHOR]

The first highly efficient single junction quaternary blend solar cells that break efficiency above 10% with complementary squaraine small molecules and low band‐gap polymer combinations are reported by Nilay Hazari, André D. Taylor and co‐workers in article number 1600660. The quaternary design demonstrates several advantages: (i) broader light absorption, (ii) improved surface morphology, (iii) enhanced co‐crystallization packing, (iv) multiple energy and charge transfer pathways to reduce recombination, and (v) increased charge mobility. [ABSTRACT FROM AUTHOR]