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Understanding the origins of the excessive Stokes shift in the lead chalcogenides family of colloidal quantum dots (CQDs) is of great importance at both the fundamental and applied levels; however, our current understanding is far from satisfactory. Here, utilizing a combination of ab initio computations and UV-vis and photoluminescence measurements, we investigated the contributions to the Stokes shift from polydispersity, ligands, and defects in PbS CQDs. The key results are as follows: (1) The size and energetic disorder of a polydisperse CQD film increase the Stokes shift by 20 to 50 meV compared to that of an isolated CQD; (2) Franck-Condon (FC) shifts increase as the electronegativities of the ligands increase, but the variations are small (<15 meV). (3) Unlike the aforementioned two minor factors, the presence of certain intrinsic defects such as V Cl + (in Cl-passivated CQDs) can cause substantial electron density localization of the band edge states and consequent large FC shifts (100s of meV). This effect arising from defects can explain the excessive Stokes shifts in PbS CQDs and improve our understanding of the optical properties of PbS CQDs.

Solar thermal fuels (STFs) harvest and store solar energy in a closed cycle system through conformational change of molecules and can release the energy in the form of heat on demand. With the aim of developing tunable and optimized STFs for solid-state applications, we designed three azobenzene derivatives functionalized with bulky aromatic groups (phenyl, biphenyl, and tert-butyl phenyl groups). In contrast to pristine azobenzene, which crystallizes and makes nonuniform films, the bulky azobenzene derivatives formed uniform amorphous films that can be charged and discharged with light and heat for many cycles. Thermal stability of the films, a critical metric for thermally triggerable STFs, was greatly increased by the bulky functionalization (up to 180 °C), and we were able to achieve record high energy density of 135 J/g for solid-state STFs, over a 30% improvement compared to previous solid-state reports. Furthermore, the chargeability in the solid state was improved, up to 80% charged from 40% charged in previous solid-state reports. Our results point toward molecular engineering as an effective method to increase energy storage in STFs, improve chargeability, and improve the thermal stability of the thin film.

There is tremendous growth in fields where small functional molecules and colloidal nanomaterials are integrated into thin films for solid-state device applications. Many of these materials are synthesized in solution and there often exists a significant barrier to transition them into the solid state in an efficient manner. Here, we develop a methodology employing an electrodepositable copolymer consisting of small functional molecules for applications in solar energy harvesting and storage. We employ azobenzene solar thermal fuel polymers and functionalize them to enable deposition from low concentration solutions in methanol, resulting in uniform and large-area thin films. This approach enables conformal deposition on a variety of conducting substrates that can be either flat or structured depending on the application. Our approach further enables control over film growth via electrodepsition conditions and results in highly uniform films of hundreds of nanometers to microns in thickness. We demonstrate that this method enables superior retention of solar thermal fuel properties, with energy densities of ∼90 J/g, chargeability in the solid state, and exceptional materials utilization compared to other solid-state processing approaches. This novel approach is applicable to systems such as photon upconversion, photovoltaics, photosensing, light emission, and beyond, where small functional molecules enable solid-state applications.

Colloidal quantum dots (CQDs) are highly versatile nanoscale optoelectronic building blocks, but despite their materials engineering flexibility, there is a considerable lack of fundamental understanding of their electronic structure as they couple within thin films. By employing a joint experimental-theoretical study, we reveal the impact of connectivity in CQD assemblies, going beyond the single CQD picture. High-resolution transmission electron microscopy (HR-TEM) demonstrates connectivity motifs across different CQD sizes and length scales and provides the necessary perspective to build robust computational models to systematically study the achievable degree of connectivity in these materials. We focused on state-of-the-art surface ligand treatments, taking into account both the degree of connectivity and nanocrystal orientation, and performed ab initio simulations within the phonon-assisted hopping regime. Importantly, both the TEM studies and our simulation results revealed morphological and electronic defects that could dramatically reduce optoelectronic performance, and yet would not have been captured within a single CQD model that neglects connectivity. We calculate carrier mobility in the presence of such defect states and conclude that the best-achievable CQD assemblies for optoelectronics will require a modest degree of fusing via the {001} facet, followed by atomic ligand passivation to generate a clean band gap and unprecedentedly high charge transport.

A solution-based passivation scheme is developed featuring the use of molecular iodine and PbS colloidal quantum dots (CQDs). The improved passivation translates into a longer carrier diffusion length in the solid film. This allows thicker solar-cell devices to be built while preserving efficient charge collection, leading to a certified power conversion efficiency of 9.9%, which is a new record in CQD solar cells., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Centrifugal casting of composites and ceramics has been widely employed to improve the mechanical and thermal properties of functional materials. This powerful method has yet to be deployed in the context of nanoparticles--yet size-effect tuning of quantum dots is among their most distinctive and application-relevant features. Here we report the first gradient nanoparticle films to be constructed in a single step. By creating a stable colloid of nanoparticles that are capped with electronic-conduction-compatible ligands we were able to leverage centrifugal casting for thin-films devices. This new method, termed centrifugal colloidal casting, is demonstrated to form films in a bandgap-ordered manner with efficient carrier funnelling towards the lowest energy layer. We constructed the first quantum-gradient photodiode to be formed in a single deposition step and, as a result of the gradient-enhanced electric field, experimentally measured the highest normalized detectivity of any colloidal quantum dot photodetector.

Colloidal quantum dots (CQD) are an attractive thin-film material for photovoltaic applications due to low material costs, ease of fabrication, and size-tunable band gap. Unfortunately, today they suffer from a compromise between light absorption and photocarrier extraction, a fact that currently prevents the complete harvest of incoming above-band-gap solar photons. We have investigated the use of structured substrates and/or electrodes to increase the effective light path through the active material and found that these designs require highly conformal application of the light-absorbing films to achieve the greatest enhancement. This conformality requirement derives from the need for maximal absorption enhancement combined with shortest-distance charge transport. Here we report on a means of processing highly conformal layer-by-layer deposited CQD absorber films onto microstructured, light-recycling electrodes. Specifically, we engineer surface hydrophilicity to achieve conformal deposition of upper layers atop underlying ones. We show that only with the application of conformal coating can we achieve optimal quantum efficiency and enhanced power conversion efficiency in structured-electrode CQD cells.

The spatial location of the predominant source of performance-limiting recombination in today's best colloidal quantum dot (CQD) cells is identified, pinpointing the TiO2:CQD junction; then, a highly n-doped PCBM layer is introduced at the CQD:TiO2 heterointerface. An n-doped PCBM layer is essential to maintain the depletion region and allow for efficient current extraction, thereby producing a record 8.9% in overall power conversion efficiency., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A colloidal quantum dot solar cell is fabricated by spray-coating under ambient conditions. By developing a room-temperature spray-coating technique and implementing a fully automated process with near monolayer control-an approach termed as sprayLD-an electronic defect is eliminated resulting in solar cell performance and statistical distribution superior to prior batch-processed methods along with a hero performance of 8.1%., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidal quantum dots are attractive materials for efficient, low-cost and facile implementation of solution-processed optoelectronic devices. Despite impressive mobilities (1-30 cm2 V(-1) s(-1)) reported for new classes of quantum dot solids, it is--surprisingly--the much lower-mobility (10(-3)-10(-2) cm2 V(-1) s(-1)) solids that have produced the best photovoltaic performance. Here we show that it is not mobility, but instead the average spacing among recombination centres that governs the diffusion length of charges in today's quantum dot solids. In this regime, colloidal quantum dot films do not benefit from further improvements in charge carrier mobility. We develop a device model that accurately predicts the thickness dependence and diffusion length dependence of devices. Direct diffusion length measurements suggest the solid-state ligand exchange procedure as a potential origin of the detrimental recombination centres. We then present a novel avenue for in-solution passivation with tightly bound chlorothiols that retain passivation from solution to film, achieving an 8.5% power conversion efficiency.

We develop a photovoltaic colloidal quantum dot ink that allows for lossless, single-step coating of large areas in a manufacturing-compatible process. Our materials strategy involves a solution-phase ligand exchange to transport compatible linkers that yield 1-thioglycerol-capped PbS quantum dots in dimethyl sulfoxide with a photoluminescence quantum yield of 24%. A proof-of-principle solar cell made from the ink exhibits 2.1% power conversion efficiency., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A means to control the net doping of a CQD solid is identified via the design of the bidentate ligand crosslinking the material. The strategy does not rely on implementing different atmospheres at different steps in device processing, but instead is a robust strategy implemented in a single processing ambient. We achieve an order of magnitude difference in doping that allows us to build a graded photovoltaic device and maintain high current and voltage at maximum power-point conditions., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidal quantum dot (CQD) optoelectronics offers a compelling combination of low-cost, large-area solution processing, and spectral tunability through the quantum size effect. Since early reports of size-tunable light emission from solution-synthesized CQDs over 25 years ago, tremendous progress has been made in synthesis and assembly, optical and electrical properties, materials processing, and optoelectronic applications of these materials. Here some of the major developments in this field are reviewed, touching on key milestones as well as future opportunities., (© 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Colloidal quantum dots (CQDs) are attractive materials for inexpensive, room-temperature-, and solution-processed optoelectronic devices. A high carrier diffusion length is desirable for many CQD device applications. In this work we develop two new experimental methods to investigate charge carrier diffusion in coupled CQD solids under charge-neutral, i.e., undepleted, conditions. The methods take advantage of the quantum-size-effect tunability of our materials, utilizing a smaller-bandgap population of quantum dots as a reporter system. We develop analytical models of diffusion in 1D and 3D structures that allow direct extraction of diffusion length from convenient parametric plots and purely optical measurements. We measure several CQD solids fabricated using a number of distinct methods and having significantly different doping and surface ligand treatments. We find that CQD materials recently reported to achieve a certified power conversion efficiency of 7% with hybrid organic-inorganic passivation have a diffusion length of 80 ± 10 nm. The model further allows us to extract the lifetime, trap density, mobility, and diffusion coefficient independently in each material system. This work will facilitate further progress in extending the diffusion length, ultimately leading to high-quality CQD solid semiconducting materials and improved CQD optoelectronic devices, including CQD solar cells.

A novel approach to improving all-inorganic colloidal quantum dot (CQD) homojunction solar cells by engineering the doping spatial profile to produce a doping gradient within the n-type absorber is presented. The doping gradient greatly improves carrier collection and enhances the voltages attainable by the device, leading to a 1 power point power conversion efficiency (PCE) improvement over previous inorganic CQD solar cells., (Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A new solution-phase halide passivation strategy to improve the electronic properties of colloidal quantum dot films is reported. We prove experimentally that the approach leads to an order-of-magnitude increase in mobility and a notable reduction in trap state density. We build solar cells having the highest efficiency (6.6%) reported using all-inorganic colloidal quantum dots. The improved photocurrent results from increased efficiency of collection of infrared-generated photocarriers., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

N-type PbS colloidal-quantum-dot (CQD) films are fabricated using a controlled halide chemical treatment, applied in an inert processing ambient environment. The new materials exhibit a mobility of 0.1 cm(2) V(-1) s(-1) . The halogen ions serve both as a passivating agent and n-dope the films via substitution at surface chalcogen sites. The majority electron concentration across the range 10(16) to 10(18) cm(-3) is varied systematically., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We present a framework--validated using both modeling and experiment--to predict doping in CQD films. In the ionic semiconductors widely deployed in CQD films, the framework reduces to a simple accounting of the contributions of the oxidation state of each constituent, including both inorganic species and organic ligands. We use density functional theory simulations to confirm that the type of doping can be reliably predicted based on the overall stoichiometry of the CQDs, largely independent of microscopic geometrical bonding configurations. Studies employing field-effect transistors constructed from CQDs that have undergone various chemical treatments, coupled with Rutherford backscattering and X-ray photoelectron spectroscopy to provide compositional analysis, allow us to test and confirm the proposed model in an experimental framework. We investigate both p- and n-type electronic doping spanning a wide range of carrier concentrations from 10(16) cm(-3) to over 10(18) cm(-3), and demonstrate reversible switching between p- and n-type doping by changing the CQD stoichiometry. We show that the summation of the contributions from all cations and anions within the film can be used to predict accurately the majority carrier type. The findings enable predictable control over majority carrier concentration via tuning of the overall stoichiometry.

Colloidal quantum dot solids combine convenient solution-processing with quantum size effect tuning, offering avenues to high-efficiency multijunction cells based on a single materials synthesis and processing platform. The highest-performing colloidal quantum dot rectifying devices reported to date have relied on a junction between a quantum-tuned absorber and a bulk material (e.g., TiO(2)); however, quantum tuning of the absorber then requires complete redesign of the bulk acceptor, compromising the benefits of facile quantum tuning. Here we report rectifying junctions constructed entirely using inherently band-aligned quantum-tuned materials. Realizing these quantum junction diodes relied upon the creation of an n-type quantum dot solid having a clean bandgap. We combine stable, chemically compatible, high-performance n-type and p-type materials to create the first quantum junction solar cells. We present a family of photovoltaic devices having widely tuned bandgaps of 0.6-1.6 eV that excel where conventional quantum-to-bulk devices fail to perform. Devices having optimal single-junction bandgaps exhibit certified AM1.5 solar power conversion efficiencies of 5.4%. Control over doping in quantum solids, and the successful integration of these materials to form stable quantum junctions, offers a powerful new degree of freedom to colloidal quantum dot optoelectronics.

Colloidal quantum dot (CQD) films allow large-area solution processing and bandgap tuning through the quantum size effect. However, the high ratio of surface area to volume makes CQD films prone to high trap state densities if surfaces are imperfectly passivated, promoting recombination of charge carriers that is detrimental to device performance. Recent advances have replaced the long insulating ligands that enable colloidal stability following synthesis with shorter organic linkers or halide anions, leading to improved passivation and higher packing densities. Although this substitution has been performed using solid-state ligand exchange, a solution-based approach is preferable because it enables increased control over the balance of charges on the surface of the quantum dot, which is essential for eliminating midgap trap states. Furthermore, the solution-based approach leverages recent progress in metal:chalcogen chemistry in the liquid phase. Here, we quantify the density of midgap trap states in CQD solids and show that the performance of CQD-based photovoltaics is now limited by electron-hole recombination due to these states. Next, using density functional theory and optoelectronic device modelling, we show that to improve this performance it is essential to bind a suitable ligand to each potential trap site on the surface of the quantum dot. We then develop a robust hybrid passivation scheme that involves introducing halide anions during the end stages of the synthesis process, which can passivate trap sites that are inaccessible to much larger organic ligands. An organic crosslinking strategy is then used to form the film. Finally, we use our hybrid passivated CQD solid to fabricate a solar cell with a certified efficiency of 7.0%, which is a record for a CQD photovoltaic device.

A bulk heterojunction of ordered titania nanopillars and PbS colloidal quantum dots is developed. By using a pre-patterned template, an ordered titania nanopillar matrix with nearest neighbours 275 nm apart and height of 300 nm is fabricated and subsequently filled in with PbS colloidal quantum dots to form an ordered depleted bulk heterojunction exhibiting power conversion efficiency of 5.6%., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The size-effect tunability of colloidal quantum dots enables facile engineering of the bandgap at the time of nanoparticle synthesis. The dependence of effective bandgap on nanoparticle size also presents a challenge if the size dispersion, hence bandgap variability, is not well-controlled within a given quantum dot solid. The impact of this polydispersity is well-studied in luminescent devices as well as in unipolar electronic transport; however, the requirements on monodispersity have yet to be quantified in photovoltaics. Here we carry out a series of combined experimental and model-based studies aimed at clarifying, and quantifying, the importance of quantum dot monodispersity in photovoltaics. We successfully predict, using a simple model, the dependence of both open-circuit voltage and photoluminescence behavior on the density of small-bandgap (large-diameter) quantum dot inclusions. The model requires inclusion of trap states to explain the experimental data quantitatively. We then explore using this same experimentally tested model the implications of a broadened quantum dot population on device performance. We report that present-day colloidal quantum dot photovoltaic devices with typical inhomogeneous linewidths of 100-150 meV are dominated by surface traps, and it is for this reason that they see marginal benefit from reduction in polydispersity. Upon eliminating surface traps, achieving inhomogeneous broadening of 50 meV or less will lead to device performance that sees very little deleterious impact from polydispersity., (© 2012 American Chemical Society)

Colloidal quantum dots offer broad tuning of semiconductor bandstructure via the quantum size effect. Devices involving a sequence of layers comprised of quantum dots selected to have different diameters, and therefore bandgaps, offer the possibility of funneling energy toward an acceptor. Here we report a quantum funnel that efficiently conveys photoelectrons from their point of generation toward an intended electron acceptor. Using this concept we build a solar cell that benefits from enhanced fill factor as a result of this quantum funnel. This concept addresses limitations on transport in soft condensed matter systems and leverages their advantages in large-area optoelectronic devices and systems.

Over the past two decades, there has been an increasing trend towards miniaturization of both biological and chemical sensors and their integration with miniaturized sample pre-processing and analysis systems. These miniaturized lab-on-chip devices have several functional advantages including low cost, their ability to analyze smaller samples, faster analysis time, suitability for automation, and increased reliability and repeatability. Electrical based sensing methods that transduce biological or chemical signals into the electrical domain are a dominant part of the lab-on-chip devices. A vital part of any electrochemical sensing system is the reference electrode, which is a probe that is capable of measuring the potential on the solution side of an electrochemical interface. Research on miniaturization of this crucial component and analysis of the parameters that affect its performance, stability and lifetime, is sparse. In this paper, we present the basic electrochemistry and thermodynamics of these reference electrodes and illustrate the uses of reference electrodes in electrochemical and biological measurements. Different electrochemical systems that are used as reference electrodes will be presented, and an overview of some contemporary advances in electrode miniaturization and their performance will be provided.

Histone deacetylases (HDACs) execute biological regulation through post-translational modification of chromatin and other cellular substrates. In humans, there are eleven HDACs, organized into three distinct subfamilies. This large number of HDACs raises questions about functional overlap and division of labor among paralogs. In vivo roles are simpler to address in Drosophila, where there are only five HDAC family members and only two are implicated in transcriptional control. Of these two, HDAC1 has been characterized genetically, but its most closely related paralog, HDAC3, has not. Here we describe the isolation and phenotypic characterization of hdac3 mutations. We find that both hdac3 and hdac1 mutations are dominant suppressors of position effect variegation, suggesting functional overlap in heterochromatin regulation. However, all five hdac3 loss-of-function alleles are recessive lethal during larval/pupal stages, indicating that HDAC3 is essential on its own for Drosophila development. The mutant larvae display small imaginal discs, which result from abnormally elevated levels of apoptosis. This cell death occurs as a cell-autonomous response to HDAC3 loss and is accompanied by increased expression of the pro-apoptotic gene, hid. In contrast, although HDAC1 mutants also display small imaginal discs, this appears to result from reduced proliferation rather than from elevated apoptosis. The connection between HDAC loss and apoptosis is important since HDAC inhibitors show anticancer activities in animal models through mechanisms involving apoptotic induction. However, the specific HDACs implicated in tumor cell killing have not been identified. Our results indicate that protein deacetylation by HDAC3 plays a key role in suppression of apoptosis in Drosophila imaginal tissue., Competing Interests: The authors have declared that no competing interests exist.