Anomalous Structural Evolution and Glassy Lattice in Mixed-Halide Hybrid Perovskites.

Hybrid halide perovskites have emerged as highly promising photovoltaic materials because of their exceptional optoelectronic properties, which are often optimized via compositional engineering like mixing halides. It is well established that hybrid perovskites undergo a series of structural phase transitions as temperature varies. In this work, the authors find that phase transitions are substantially suppressed in mixed-halide hybrid perovskite single crystals of MAPbI3-x Brx (MA = CH3 NH3 + and x = 1 or 2) using a complementary suite of diffraction and spectroscopic techniques. Furthermore, as a general behavior, multiple crystallographic phases coexist in mixed-halide perovskites over a wide temperature range, and a slightly distorted monoclinic phase, hitherto unreported for hybrid perovskites, is dominant at temperatures above 100 K. The anomalous structural evolution is correlated with the glassy behavior of organic cations and optical phonons in mixed-halide perovskites. This work demonstrates the complex interplay between composition engineering and lattice dynamics in hybrid perovskites, shedding new light on their unique properties.

Effects of thermal annealing on the distribution of boron and phosphorus in p-i-n structured silicon nanocrystals embedded in silicon dioxide.

Thermal annealing temperature and time dictate the microstructure of semiconductor materials such as silicon nanocrystals (Si NCs). Herein, atom probe tomography (APT) and density functional theory (DFT) calculations are used to understand the thermal annealing temperature effects on Si NCs grown in a SiO2matrix and the distribution behaviour of boron (B) and phosphorus (P) dopant atoms. The APT results demonstrate that raising the annealing temperature promotes growth and increased P concentration of the Si NCs. The data also shows that the thermal annealing does not promote the incorporation of B atoms into Si NCs. Instead, B atoms tend to locate at the interface between the Si NCs and SiO2matrix. The DFT calculations support the APT data and reveal that oxygen vacancies regulate Si NC growth and dopant distribution. This study provides the detailed microstructure of p-type, intrinsic, and n-type Si NCs with changing annealing temperature and highlights how B and P dopants preferentially locate with respect to the Si NCs embedded in the SiO2matrix with the aid of oxygen vacancies. These findings will be useful towards future optoelectronic applications.

MgCl2 passivated ZnO electron transporting layer to improve PbS quantum dot solar cells.

The unique tunable bandgaps and straightforward synthesis of colloidal quantum dots make them promising low-cost materials for photovoltaics. High-performance colloidal quantum dot solar cells rely on good-quality electron transporting layers (ETLs) to make carrier selective contacts. Despite extensive use of n-type oxides as ETLs, a detailed understanding of their surface and interface states as well as mechanisms to improve their optical properties are still under development. Here, we report a simple procedure to produce MgCl2 passivated ZnO nanoparticles ETLs that show improved device performance. The MgCl2 treated ZnO electron transporting layers boost the PbS colloidal quantum dot cell efficiency from 6.3% to 8.2%. The cell exhibits reduced defects leading to significant improvements of both FF and J sc. This low-temperature MgCl2 treated ZnO electron transporting layer may be applied in solution processed tandem cells as a promising strategy to further increase cell efficiencies.

Single-Mode Near-Infrared Lasing in a GaAsSb-Based Nanowire Superlattice at Room Temperature.

Semiconductor nanowire lasers can produce guided coherent light emission with miniaturized geometry, bringing about new possibilities for a variety of applications including nanophotonic circuits, optical sensing, and on-chip and chip-to-chip optical communications. Here, we report on the realization of single-mode and room-temperature lasing from 890 to 990 nm, utilizing a novel design of single nanowires with GaAsSb-based multiple axial superlattices as a gain medium under optical pumping. The control of lasing wavelength via compositional tuning with excellent room-temperature lasing performance is shown to result from the unique nanowire structure with efficient gain material, which delivers a low lasing threshold of ∼6 kW/cm2 (75 µJ/cm2 per pulse), a lasing quality factor as high as 1250, and a high characteristic temperature of ∼129 K. These results present a major advancement for the design and synthesis of nanowire laser structures, which can pave the way toward future nanoscale integrated optoelectronic systems with superior performance.

Bipolar Photothermoelectric Effect Across Energy Filters in Single Nanowires.

The photothermoelectric (PTE) effect uses nonuniform absorption of light to produce a voltage via the Seebeck effect and is of interest for optical sensing and solar-to-electric energy conversion. However, the utility of PTE devices reported to date has been limited by the need to use a tightly focused laser spot to achieve the required, nonuniform illumination and by their dependence upon the Seebeck coefficients of the constituent materials, which exhibit limited tunability and, generally, low values. Here, we use InAs/InP heterostructure nanowires to overcome these limitations: first, we use naturally occurring absorption "hot spots" at wave mode maxima within the nanowire to achieve sharp boundaries between heated and unheated subwavelength regions of high and low absorption, allowing us to use global illumination; second, we employ carrier energy-filtering heterostructures to achieve a high Seebeck coefficient that is tunable by heterostructure design. Using these methods, we demonstrate PTE voltages of hundreds of millivolts at room temperature from a globally illuminated nanowire device. Furthermore, we find PTE currents and voltages that change polarity as a function of the wavelength of illumination due to spatial shifting of subwavelength absorption hot spots. These results indicate the feasibility of designing new types of PTE-based photodetectors, photothermoelectrics, and hot-carrier solar cells using nanowires.

Single-nanowire, low-bandgap hot carrier solar cells with tunable open-circuit voltage.

Compared to traditional pn-junction photovoltaics, hot carrier solar cells offer potentially higher efficiency by extracting work from the kinetic energy of photogenerated 'hot carriers' before they cool to the lattice temperature. Hot carrier solar cells have been demonstrated in high-bandgap ferroelectric insulators and GaAs/AlGaAs heterostructures, but so far not in low-bandgap materials, where the potential efficiency gain is highest. Recently, a high open-circuit voltage was demonstrated in an illuminated wurtzite InAs nanowire with a low bandgap of 0.39 eV, and was interpreted in terms of a photothermoelectric effect. Here, we point out that this device is a hot carrier solar cell and discuss its performance in those terms. In the demonstrated devices, InP heterostructures are used as energy filters in order to thermoelectrically harvest the energy of hot electrons photogenerated in InAs absorber segments. The obtained photovoltage depends on the heterostructure design of the energy filter and is therefore tunable. By using a high-resistance, thermionic barrier, an open-circuit voltage is obtained that is in excess of the Shockley-Queisser limit. These results provide generalizable insight into how to realize high voltage hot carrier solar cells in low-bandgap materials, and therefore are a step towards the demonstration of higher efficiency hot carrier solar cells.

Vertically Oriented Growth of GaN Nanorods on Si Using Graphene as an Atomically Thin Buffer Layer.

The monolithic integration of wurtzite GaN on Si via metal-organic vapor phase epitaxy is strongly hampered by lattice and thermal mismatch as well as meltback etching. This study presents single-layer graphene as an atomically thin buffer layer for c-axis-oriented growth of vertically aligned GaN nanorods mediated by nanometer-sized AlGaN nucleation islands. Nanostructures of similar morphology are demonstrated on graphene-covered Si(111) as well as Si(100). High crystal and optical quality of the nanorods are evidenced through scanning transmission electron microscopy, micro-Raman, and cathodoluminescence measurements supported by finite-difference time-domain simulations. Current-voltage characteristics revealed high vertical conduction of the as-grown GaN nanorods through the Si substrates. These findings are substantial to advance the integration of GaN-based devices on any substrates of choice that sustains the GaN growth temperatures, thereby permitting novel designs of GaN-based heterojunction device concepts.

Study of the mechanisms of the phonon bottleneck effect in CdSe/CdS core/shell quantum dots and nanoplatelets and their application in hot carrier multi-junction solar cells.

The hot carrier multi-junction solar cell (HCMJSC) is one of the promising advanced conceptual solar cells with theoretical efficiency greater than 65%, consisting of a thin top junction with a wide bandgap and a thicker junction at the bottom with a medium bandgap for absorption of high and low energy photons. The wide bandgap CdSe/CdS low-dimensional systems (e.g. quantum dots, QDs and nanoplatelets, NPLs) widely used in optoelectrical devices are expected to be an appropriate candidate for the top junction. However, the mechanisms underlying the carrier relaxation rate reduction (or phonon bottleneck effect, PBE) for HCMJSC in these material systems are not well understood so far. In this work, the carrier relaxation mechanisms in CdSe/CdS core/shell QDs and NPLs are quantitatively analyzed by calculating the thermalization coefficient (Qth) through steady state photoluminescence (SSPL) and picosecond-time resolved photoluminescence (ps-TRPL). A significantly extended carrier relaxation time of more than 20 ns was observed in the TRPL of QDs. This could be attributed to both the Auger reheating (AR) at the initial fast decay stage and acoustic phonon folding at the slow decay stage. For SSPL, the Qth value of QDs is much lower due to a 1 order of magnitude higher AR rate. A strong coupling may exist between AR and Qth with a high probability of PBE, where a lower Qth gives a higher AR rate. The AR may dominate carrier thermalization if the PBE level is high. Meanwhile, other mechanisms like acoustic phonon folding will also affect the carrier relaxation if the PBE is at a much lower level.

Investigating Electronic, Optical, and Phononic Properties of Bulk γ-M2ON2 and ß-M7O8N4 (M = Hf and Zr) Insulators Using Density Functional Theory.

Hafnium and zirconium oxynitrides have similar properties, yet a consolidated investigation of their intrinsic properties has not been carried out. In this paper, we perform first-principles density functional theory calculations of γ- and ß-phase hafnium and zirconium oxynitrides, which show that the γ-M2ON2 (M = Hf and Zr) is an indirect band-gap (E g) insulator, while the ß-M7O8N4 has a "pseudo-direct" type of E g. ß-phase has higher E g than γ-phase, with concomitant disappearance of the conduction band tail. Optical properties in γ-M2ON2 show that the anisotropy is negligible, and the optical constant values are in the range of other superhard materials. Phonon calculations present peculiar characteristics such as a small phonon band gap in γ-Hf2ON2 and imaginary phonon frequencies in ß-phases relating to lattice instability. The phononic properties are unfavorable for their potential use as an absorber material of the hot carrier solar cell-an emerging photovoltaic concept.

Enhanced light management and optimization of perovskite solar cells incorporating wavelength dependent reflectance modeling.

Perovskite Solar Cells (PSCs) are the most promising candidates for low-cost and high-efficiency devices in the future photovoltaic market. PSCs are also used as the top cell in tandem devices with silicon bottom cells. However, research in PSCs is still at an early stage while racing towards a promising future. Along with experimental research, numerous simulation studies are conducted with PSCs aiming to analyze new materials and optimize their performance. Here, a wavelength-dependent model is implemented to account for the reflected part of irradiance from the cells, which is ignored in most SCAPS-1D based PSC simulated models. This model optimizes the MgF2 anti-reflective coating in SCAPS-1D simulation to allow maximum photons to pass inside the device. A simple structured PSC (MgF2/Glass/ITO/ZnO/CH3NH3PbI3/Spiro-OMeTAD/Au) is simulated and optimized optically as well as electrically with this model's modified spectrum. The device was optimized for layer thickness, defects, and doping. Moreover, the effects of temperature and device resistances are discussed. The optimized device yields 21.62% power conversion efficiency, which can be further improved to reach over 25% through better processing schemes. Finally, the optimized device was compared with other devices having different ETL/absorber/HTL combinations and the pathway to achieving higher efficiencies was discussed. This article aims at improving the credibility of simulated devices by incorporating top surface reflection with electrical optimization.

Slow-light-enhanced upconversion for photovoltaic applications in one-dimensional photonic crystals.

We present an approach to realizing enhanced upconversion efficiency in erbium (Er)-doped photonic crystals. Slow-light-mode pumping of the first Er excited state transition can result in enhanced emission from higher-energy levels that may lead to finite subbandgap external quantum efficiency in crystalline silicon solar cells. Using a straightforward electromagnetic model, we calculate potential field enhancements of more than 18× within he slow-light mode of a one-dimensional photonic crystal and discuss design trade-offs and considerations for photovoltaics.

Simultaneous Fe3O4 Nanoparticle Formation and Catalyst-Driven Hydrothermal Cellulose Degradation.

Breakdown and utilization of cellulose are critical for the bioenergy sector; however, current cellulose-to-energy conversion schemes often consume large quantities of unrecoverable chemicals, or are expensive, due to the need for enzymes or high temperatures. In this paper, we demonstrate a new method for converting cellulose into soluble compounds using a mixture of Fe2+ and Fe3+ as catalytic centers for the breakdown, yielding Fe3O4 nanoparticles during the hydrothermal process. Iron precursors transformed more than 61% of microcrystalline cellulose into solutes, with the composition of the solute changing with the initial Fe3+ concentration. The primary products of the breakdown of cellulose were a range of aldaric acids with different molecular weights. The nanoparticles have concentration-dependent tuneable sizes between 6.7 and 15.8 nm in diameter. The production of value-added nanomaterials at low temperatures improves upon the economics of traditional cellulose-to-energy conversion schemes with the precursor value increasing rather than deteriorating over time.

Passivating Quantum Dot Carrier Transport Layer with Metal Salts.

Quantum dots (QDs) have a wide range of applications in the field of optoelectronics. They have been playing multiple roles within the configuration of a device, by serving as the building blocks for both the active layer and the carrier transport layer. While the performance of various optoelectronic devices has been steadily improving via developments in passivating the QD active layer, the possible improvement via passivation of the QD-based carrier transport layer has been largely overlooked. Here, with lead sulfide QD photovoltaics as the platform of study, we demonstrate that the device performance can be significantly improved by passivating the QD hole transport layer (HTL) with zinc salt post-treatments. The power conversion efficiency is improved from 8.7% of the reference device to 10.2% and 9.5% for devices with zinc acetate (ZnAc)- and zinc iodide (ZnI2)-treated HTLs, respectively. Transient absorption spectroscopy confirms that both treatments effectively reduce band-tail states and increase carrier lifetime of the HTLs. Further elemental analysis shows that ZnAc provides a higher amount of Zn2+ for passivation while maintaining the function of HTL by allowing essential p-doping oxidation. In contrast, the additional I- passivation from ZnI2 inhibits p-doping oxidation and limits the function of HTL. This work demonstrates the potential of improving device performance by passivating the QD-based HTLs, and the method developed is likely applicable to other optoelectronic devices.

Enhancing PbS Colloidal Quantum Dot Tandem Solar Cell Performance by Graded Band Alignment.

Colloidal quantum dot solids are attractive candidates for tandem solar cells because of their widely tunable bandgaps. However, the development of the quantum dot tandem solar cell has lagged far behind that of its single-junction counterpart. One of the fundamental problems with colloidal quantum dot solar cells is the relatively small diffusion length, which limits the quantum dot absorbing layer thickness and hence the power conversion efficiency. In this research, guided by optical modeling and utilizing a graded band alignment strategy, a two-terminal monolithic solution-processed quantum dot tandem solar cell has been successfully fabricated and a power conversion efficiency of 6.8% has been achieved. The band grading approach utilized the complementary tuning of work functions and band alignment through judicious choices of the nanoparticle surface chemistry and quantum dot confined size. This work demonstrates a general approach to improving the efficiency for tandem thin-film solar cells.

Free charges versus excitons: photoluminescence investigation of InGaN/GaN multiple quantum well nanorods and their planar counterparts.

InGaN/GaN multiple quantum well (MQW) nanorods have demonstrated significantly improved optical and electronic properties compared to their planar counterparts. However, the exact nature of the processes whereby nanorod structures impact the optical properties of quantum wells is not well understood, even though a variety of mechanisms have been proposed. We performed nanoscale spatially resolved, steady-state, and time-resolved photoluminescence (PL) experiments confirming that photoexcited electrons and holes are strongly bound by Coulomb interactions (i.e., excitons) in planar MQWs due to the large exciton binding energy in InGaN quantum wells. In contrast, free electron-hole recombination becomes the dominant mechanism in nanorods, which is ascribed to efficient exciton dissociation. The nanorod sidewall provides an effective pathway for exciton dissociation that significantly improves the optical performance of InGaN/GaN MQWs. We also confirm that surface treatment of nanorod sidewalls has an impact on exciton dissociation. Our results provide new insights into excitonic and charge carrier dynamics of quantum confined materials as well as the influence of surface states.

Role of Surface Recombination in Halide Perovskite Nanoplatelets.

Halide perovskites are an extremely promising material platform for solar cells and photonic devices. The role of surface carrier recombination-well known to detrimentally affect the performance of devices-is still not well understood for thin samples where the thickness is comparable to or less than the carrier diffusion length. Here, using time-resolved microspectroscopy along with modeling, we investigate charge-carrier recombination dynamics in halide perovskite CH3NH3PbI3 nanoplatelets with thicknesses from ∼20 to 200 nm, ranging from much lesser than to comparable to the carrier diffusion length. We show that surface recombination plays a stronger role in thin perovskite nanoplatelets, significantly decreasing photoluminescence (PL) efficiency, PL decay lifetime, and photostability. Interestingly, we find that both thick and thin nanoplatelets exhibit a similar increase in PL efficiency with increasing excitation fluence, well described by our excitation saturation model. We also find that the excited carrier distribution along the depth impacts the surface recombination. Using the diffusion-surface recombination model, we determine the surface recombination velocity. This work provides a comprehensive understanding of the role of surface recombination and charge-carrier dynamics in thin perovskite platelets and reveals valuable insights useful for applications in photovoltaics and photonics.

Investigation of anti-solvent induced optical properties change of cesium lead bromide iodide mixed perovskite (CsPbBr3-xIx) quantum dots.

Cesium lead halide (CsPbX3, X=Cl, Br, I) perovskites are a new material system that has attracted a lot of research focus. Its tunable band gap and better thermal stability than organic lead halide perovskite give it the potential for applications in optoelectronic devices such as light-emitting diodes and solar cells. Here we have synthesized CsPbBr3-xIx perovskite quantum dots (QDs) via a solution process, and then have selected three different anti-solvents to purify the product. A significant effect on optical properties of CsPbBr3-xIx was found after the centrifugation process. Up to a ∼40nm shift was observed in mixed halide CsPbBr3-xIx QDs in both absorbance and PL spectra after purification while there was no obvious change in pure CsPbBr3 when it was subjected to the same purification steps. XPS analysis shows that the Br:I ratio of the CsPbBr3-xIx QDs had changed as a result of exposure to the anti-solvent, causing the change of the band gap and shift of the spectra. It is also shown that iodine can be removed more easily than bromine during the anti-solvent purification. Ab-initio simulations of small CsPbBr3-xIx atomic clusters suggest that exposed Cs ions on Cs-terminated facets are the first species to be attacked by hydrophilic molecules, likely dragging halide ions into solution with them to maintain overall charge neutrality in the material. Charge carrier recombination rates were found to be unchanged and all samples maintained a good PL quantum yield which was more than 44%.

Increased methane production in cyanobacteria and methanogenic microbe co-cultures.

A novel light-to-bioenergy system produced 3.5 times the baseline methane output using a co-culture of cyanobacteria (Oscillatoria sp.) and a methanogenic microbial community. Analysis of micronutrients in the system during the growth phase indicated that cobalt, iron, nickel and zinc were not appreciably consumed. The stable consumption and return of macronutrients calcium and magnesium were also observed. Essential macronutrients nitrogen, in the form of nitrate, and phosphorus showed no cycling during the growth phase and were depleted at rates of 0.35mg/L/day and 0.40µg/L/day, respectively. Biofilm formation increased the resilience of biomass to bacterial degradation in an anaerobic digester, as shown by viability assays of cyanobacterial biofilms in the co-culture.

A New Passivation Route Leading to Over 8% Efficient PbSe Quantum-Dot Solar Cells via Direct Ion Exchange with Perovskite Nanocrystals.

Colloidal quantum dots (QDs) are promising candidate materials for photovoltaics (PV) owing to the tunable bandgap and low-cost solution processability. Lead selenide (PbSe) QDs are particularly attractive to PV applications due to the efficient multiple-exciton generation and carrier transportation. However, surface defects arising from the oxidation of the PbSe QDs have been the major limitation for their development in PV. Here, a new passivation method for chlorinated PbSe QDs via ion exchange with cesium lead halide (Br, I) perovskite nanocrystals is reported. The surface chloride ions on the as-synthesized QDs can be partially exchanged with bromide or iodide ions from the perovskite nanocrystals, hence forming a hybrid halide passivation. Consistent with the improved photoluminescence quantum yield, the champion PV device fabricated with these PbSe QDs achieves a PCE of 8.2%, compared to 7.3% of that fabricated with the untreated QDs. This new method also leads to devices with excellent air-stability, retaining at least 93% of their initial PCEs after being stored in ambient conditions for 57 d. This is considered as the first reported PbSe QD solar cell with a PCE of over 8% to date.

Difference in hot carrier cooling rate between Langmuir-Blodgett and drop cast PbS QD films due to strong electron-phonon coupling.

The carrier dynamics of lead sulphide quantum dot (PbS QD) drop cast films and closely packed ordered Langmuir-Blodgett films are studied with ultra-fast femtosecond transient absorption spectroscopy. The photo-induced carrier temperature is extracted from transient absorption spectra and monitored as a function of time delay. The cooling dynamics of carriers in PbS QDs suggest a reduction of the carrier energy loss rate at longer time delays through the retardation of the longitudinal optical (LO) phonon decay due to partial heating of acoustic phonon modes. A slowed hot carrier cooling time up to 116 ps is observed in the drop cast film. A faster cooling rate was also observed in the highly compact Langmuir-Blodgett film due to the enhanced carrier-LO phonon coupling strength arising from the Coulombic interaction in neighboring QDs, which is verified by temperature dependent steady state PL measurements.