Towards linking lab and field lifetimes of perovskite solar cells.

Metal halide perovskite solar cells (PSCs) represent a promising low-cost thin-film photovoltaic technology, with unprecedented power conversion efficiencies obtained for both single-junction and tandem applications1-8. To push PSCs towards commercialization, it is critical, albeit challenging, to understand device reliability under real-world outdoor conditions where multiple stress factors (for example, light, heat and humidity) coexist, generating complicated degradation behaviours9-13. To quickly guide PSC development, it is necessary to identify accelerated indoor testing protocols that can correlate specific stressors with observed degradation modes in fielded devices. Here we use a state-of-the-art positive-intrinsic-negative (p-i-n) PSC stack (with power conversion efficiencies of up to approximately 25.5%) to show that indoor accelerated stability tests can predict our six-month outdoor ageing tests. Device degradation rates under illumination and at elevated temperatures are most instructive for understanding outdoor device reliability. We also find that the indium tin oxide/self-assembled monolayer-based hole transport layer/perovskite interface most strongly affects our device operation stability. Improving the ion-blocking properties of the self-assembled monolayer hole transport layer increases averaged device operational stability at 50 °C-85 °C by a factor of about 2.8, reaching over 1,000 h at 85 °C and to near 8,200 h at 50 °C, with a projected 20% degradation, which is among the best to date for high-efficiency p-i-n PSCs14-17.

Sustainability pathways for perovskite photovoltaics.

Solar energy is the fastest-growing source of electricity generation globally. As deployment increases, photovoltaic (PV) panels need to be produced sustainably. Therefore, the resource utilization rate and the rate at which those resources become available in the environment must be in equilibrium while maintaining the well-being of people and nature. Metal halide perovskite (MHP) semiconductors could revolutionize PV technology due to high efficiency, readily available/accessible materials and low-cost production. Here we outline how MHP-PV panels could scale a sustainable supply chain while appreciably contributing to a global renewable energy transition. We evaluate the critical material concerns, embodied energy, carbon impacts and circular supply chain processes of MHP-PVs. The research community is in an influential position to prioritize research efforts in reliability, recycling and remanufacturing to make MHP-PVs one of the most sustainable energy sources on the market.

Engineering charge injection and charge transport for high performance PbSe nanocrystal thin film devices and circuits.

We study charge injection and transport in PbSe nanocrystal thin films. By engineering the contact metallurgy and nanocrystal ligand exchange chemistry and surface passivation, we demonstrate partial Fermi-level pinning at the metal-nanocrystal interface and an insulator-to-metal transition with increased coupling and doping, allowing us to design high conductivity and mobility PbSe nanocrystal films. We construct complementary nanocrystal circuits from n-type and p-type transistors realized from a single nanocrystal material by selecting the contact metallurgy.

Designing high-performance PbS and PbSe nanocrystal electronic devices through stepwise, post-synthesis, colloidal atomic layer deposition.

We report a simple, solution-based, postsynthetic colloidal, atomic layer deposition (PS-cALD) process to engineer stepwise the surface stoichiometry and therefore the electronic properties of lead chalcogenide nanocrystal (NC) thin films integrated in devices. We found that unlike chalcogen-enriched NC surfaces that are structurally, optically, and electronically unstable, lead chloride treatment creates a well-passivated shell that stabilizes the NCs. Using PS-cALD of lead chalcogenide NC thin films we demonstrate high electron field-effect mobilities of ∼4.5 cm(2)/(V s).

Surface band bending and carrier dynamics in colloidal quantum dot solids.

Band bending in colloidal quantum dot (CQD) solids has become important in driving charge carriers through devices. This is typically a result of band alignments at junctions in the device. Whether band bending is intrinsic to CQD solids, i.e. is band bending present at the surface-vacuum interface, has previously been unanswered. Here we use photoemission surface photovoltage measurements to show that depletion regions are present at the surface of n and p-type CQD solids with various ligand treatments (EDT, MPA, PbI2, MAI/PbI2). Using laser-pump photoemission-probe time-resolved measurements, we show that the timescale of carrier dynamics in the surface of CQD solids can vary over at least 6 orders of magnitude, with the fastest dynamics on the order of microseconds in PbS-MAI/PbI2 solids and on the order of seconds for PbS-MPA and PbS-PbI2. By investigating the surface chemistry of the solids, we find a correlation between the carrier dynamics timescales and the presence of oxygen contaminants, which we suggest are responsible for the slower dynamics due to deep trap formation.

Methods for tuning plasmonic and photonic optical resonances in high surface area porous electrodes.

Surface plasmons have found a wide range of applications in plasmonic and nanophotonic devices. The combination of plasmonics with three-dimensional photonic crystals has enormous potential for the efficient localization of light in high surface area photoelectrodes. However, the metals traditionally used for plasmonics are difficult to form into three-dimensional periodic structures and have limited optical penetration depth at operational frequencies, which limits their use in nanofabricated photonic crystal devices. The recent decade has seen an expansion of the plasmonic material portfolio into conducting ceramics, driven by their potential for improved stability, and their conformal growth via atomic layer deposition has been established. In this work, we have created three-dimensional photonic crystals with an ultrathin plasmonic titanium nitride coating that preserves photonic activity. Plasmonic titanium nitride enhances optical fields within the photonic electrode while maintaining sufficient light penetration. Additionally, we show that post-growth annealing can tune the plasmonic resonance of titanium nitride to overlap with the photonic resonance, potentially enabling coupled-phenomena applications for these three-dimensional nanophotonic systems. Through characterization of the tuning knobs of bead size, deposition temperature and cycle count, and annealing conditions, we can create an electrically- and plasmonically-active photonic crystal as-desired for a particular application of choice.

Chiral-induced spin selectivity enables a room-temperature spin light-emitting diode.

In traditional optoelectronic approaches, control over spin, charge, and light requires the use of both electrical and magnetic fields. In a spin-polarized light-emitting diode (spin-LED), charges are injected, and circularly polarized light is emitted from spin-polarized carrier pairs. Typically, the injection of carriers occurs with the application of an electric field, whereas spin polarization can be achieved using an applied magnetic field or polarized ferromagnetic contacts. We used chiral-induced spin selectivity (CISS) to produce spin-polarized carriers and demonstrate a spin-LED that operates at room temperature without magnetic fields or ferromagnetic contacts. The CISS layer consists of oriented, self-assembled small chiral molecules within a layered organic-inorganic metal-halide hybrid semiconductor framework. The spin-LED achieves ±2.6% circularly polarized electroluminescence at room temperature.

Strategies to Achieve High Circularly Polarized Luminescence from Colloidal Organic-Inorganic Hybrid Perovskite Nanocrystals.

Colloidal metal halide perovskite nanocrystals (NCs) with chiral ligands are outstanding candidates as a circularly polarized luminescence (CPL) light source due to many advantages such as high photoluminescence quantum efficiency, large spin-orbit coupling, and extensive tunability via composition and choice of organic ligands. However, achieving pronounced and controllable polarized light emission remains challenging. Here, we develop strategies to achieve high CPL responses from colloidal formamidinium lead bromide (FAPbBr3) NCs at room temperature using chiral surface ligands. First, we show that replacing a portion of typical ligands (oleylamine) with short chiral ligands ((R)-2-octylamine) during FAPbBr3 NC synthesis results in small and monodisperse NCs that yield high CPL with average luminescence dissymmetry g-factor, glum = 6.8 × 10-2. To the best of our knowledge, this is the highest among reported perovskite materials at room temperature to date and represents around 10-fold improvement over the previously reported colloidal CsPbClxBryI3-x-y NCs. In order to incorporate NCs into any optoelectronic or spintronic application, the NCs necessitate purification, which removes a substantial amount of the chiral ligands and extinguishes the CPL signals. To circumvent this issue, we also developed a postsynthetic ligand treatment using a different chiral ligand, (R-/S-)methylbenzylammonium bromide, which also induces a CPL with an average glum = ±1.18 × 10-2. This postsynthetic method is also amenable for long-range charge transport since methylbenzylammonium is quite compact in relation to other surface ligands. Our demonstrations of high CPL and glum from both as-synthesized and purified perovskite NCs at room temperature suggest a route to demonstrate colloidal NC-based spintronics.

Conductivity Tuning via Doping with Electron Donating and Withdrawing Molecules in Perovskite CsPbI3 Nanocrystal Films.

Doping of semiconductors enables fine control over the excess charge carriers, and thus the overall electronic properties, crucial to many technologies. Controlled doping in lead-halide perovskite semiconductors has thus far proven to be difficult. However, lower dimensional perovskites such as nanocrystals, with their high surface-area-to-volume ratio, are particularly well-suited for doping via ground-state molecular charge transfer. Here, the tunability of the electronic properties of perovskite nanocrystal arrays is detailed using physically adsorbed molecular dopants. Incorporation of the dopant molecules into electronically coupled CsPbI3 nanocrystal arrays is confirmed via infrared and photoelectron spectroscopies. Untreated CsPbI3 nanocrystal films are found to be slightly p-type with increasing conductivity achieved by incorporating the electron-accepting dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4 TCNQ) and decreasing conductivity for the electron-donating dopant benzyl viologen. Time-resolved spectroscopic measurements reveal the time scales of Auger-mediated recombination in the presence of excess electrons or holes. Microwave conductance and field-effect transistor measurements demonstrate that both the local and long-range hole mobility are improved by F4 TCNQ doping of the nanocrystal arrays. The improved hole mobility in photoexcited p-type arrays leads to a pronounced enhancement in phototransistors.

Very High Refractive Index Transition Metal Dichalcogenide Photonic Conformal Coatings by Conversion of ALD Metal Oxides.

Materials for nanophotonic devices ideally combine ease of deposition, very high refractive index, and facile pattern formation through lithographic templating and/or etching. In this work, we present a scalable method for producing high refractive index WS2 layers by chemical conversion of WO3 synthesized via atomic layer deposition (ALD). These conformal nanocrystalline thin films demonstrate a surprisingly high index of refraction (n > 3.9), and structural fidelity compatible with lithographically defined features down to ~10 nm. Although this process yields highly polycrystalline films, the optical constants are in agreement with those reported for single crystal bulk WS2. Subsequently, we demonstrate three photonic structures - first, a two-dimensional hole array made possible by patterning and etching an ALD WO3 thin film before conversion, second, an analogue of the 2D hole array first patterned into fused silica before conformal coating and conversion, and third, a three-dimensional inverse opal photonic crystal made by conformal coating of a self-assembled polystyrene bead template. These results can be trivially extended to other transition metal dichalcogenides, thus opening new opportunities for photonic devices based on high refractive index materials.

Perovskite Quantum Dot Photovoltaic Materials beyond the Reach of Thin Films: Full-Range Tuning of A-Site Cation Composition.

We present a cation-exchange approach for tunable A-site alloys of cesium (Cs+) and formamidinium (FA+) lead triiodide perovskite nanocrystals that enables the formation of compositions spanning the complete range of Cs1- xFA xPbI3, unlike thin-film alloys or the direct synthesis of alloyed perovskite nanocrystals. These materials show bright and finely tunable emission in the red and near-infrared range between 650 and 800 nm. The activation energy for the miscibility between Cs+ and FA+ is measured (∼0.65 eV) and is shown to be higher than reported for X-site exchange in lead halide perovskites. We use these alloyed colloidal perovskite quantum dots to fabricate photovoltaic devices. In addition to the expanded compositional range for Cs1- xFA xPbI3 materials, the quantum dot solar cells exhibit high open-circuit voltage ( VOC) with a lower loss than the thin-film perovskite devices of similar compositions.

Charge Transport Modulation in PbSe Nanocrystal Solids by Au xAg1- x Nanoparticle Doping.

Nanocrystal (NC) solids are an exciting class of materials, whose physical properties are tunable by choice of the NCs as well as the strength of the interparticle coupling. One can consider these NCs as "artificial atoms" in analogy to the formation of condensed matter from atoms. Akin to atomic doping, the doping of a semiconducting NC solid with impurity NCs can drastically alter its electronic properties. A high degree of complexity is possible in these artificial structures by adjusting the size, shape, and composition of the building blocks, which enables "designer" materials with targeted properties. Here, we present the doping of the PbSe NC solids with a series of Au xAg1- x alloy nanoparticles (NPs). A combination of temperature-dependent electrical conductance and Seebeck coefficient measurements and room-temperature Hall effect measurements demonstrates that the incorporation of metal NPs both modifies the charge carrier density of the NC solids and introduces energy barriers for charge transport. These studies point to charge carrier injection from the metal NPs into the PbSe NC matrix. The charge carrier density and charge transport dynamics in the doped NC solids are adjustable in a wide range by employing the Au xAg1- x NP with different Au:Ag ratio as dopants. This doping strategy could be of great interest for thermoelectric applications taking advantage of the energy filtering effect introduced by the metal NPs.

Coherent Acoustic Phonons in Colloidal Semiconductor Nanocrystal Superlattices.

The phonon properties of films fabricated from colloidal semiconductor nanocrystals play a major role in thermal conductance and electron scattering, which govern the principles for building colloidal-based electronics and optics including thermoelectric devices with a high ZT factor. The key point in understanding the phonon properties is to obtain the strength of the elastic bonds formed by organic ligands connecting the individual nanocrystallites. In the case of very weak bonding, the ligands become the bottleneck for phonon transport between infinitively rigid nanocrystals. In the opposite case of strong bonding, the colloids cannot be considered as infinitively rigid beads and the distortion of the superlattice caused by phonons includes the distortion of the colloids themselves. We use the picosecond acoustics technique to study the acoustic coherent phonons in superlattices of nanometer crystalline CdSe colloids. We observe the quantization of phonons with frequencies up to 30 GHz. The frequencies of quantized phonons depend on the thickness of the colloidal films and possess linear phonon dispersion. The measured speed of sound and corresponding wave modulus in the colloidal films point on the strong elastic coupling provided by organic ligands between colloidal nanocrystals.

Lifetime, mobility, and diffusion of photoexcited carriers in ligand-exchanged lead selenide nanocrystal films measured by time-resolved terahertz spectroscopy.

Colloidal semiconductor nanocrystals have been used as building blocks for electronic and optoelectronic devices ranging from field-effect transistors to solar cells. Properties of the nanocrystal films depend sensitively on the choice of capping ligand to replace the insulating synthesis ligands. Thus far, ligands leading to the best performance in transistors result in poor solar cell performance, and vice versa. To gain insight into the nature of this dichotomy, we used time-resolved terahertz spectroscopy measurements to study the mobility and lifetime of PbSe nanocrystal films prepared with five common ligand-exchange reagents. Noncontact terahertz spectroscopy measurements of conductivity were corroborated by contacted van der Pauw measurements of the same samples. The films treated with different displacing ligands show more than an order of magnitude difference in the peak conductivities and a bifurcation of time dynamics. Inorganic chalcogenide ligand exchanges with sodium sulfide (Na2S) or ammonium thiocyanate (NH4SCN) show high mobilities but nearly complete decay of transient photocurrent in 1.4 ns. In contrast, ligand exchanges with 1,2-ethylenediamine (EDA), 1,2-ethanedithiol (EDT), and tetrabutylammonium iodide (TBAI) show lower mobilities but longer carrier lifetimes, resulting in longer diffusion lengths. This bifurcated behavior may explain the divergent performance of field-effect transistors and photovoltaics constructed from nanocrystal building blocks with different ligand exchanges.

Increased carrier mobility and lifetime in CdSe quantum dot thin films through surface trap passivation and doping.

Passivating surface defects and controlling the carrier concentration and mobility in quantum dot (QD) thin films is prerequisite to designing electronic and optoelectronic devices. We investigate the effect of introducing indium in CdSe QD thin films on the dark mobility and the photogenerated carrier mobility and lifetime using field-effect transistor (FET) and time-resolved microwave conductivity (TRMC) measurements. We evaporate indium films ranging from 1 to 11 nm in thickness on top of approximately 40 nm thick thiocyanate-capped CdSe QD thin films and anneal the QD films at 300 °C to densify and drive diffusion of indium through the films. As the amount of indium increases, the FET and TRMC mobilities and the TRMC lifetime increase. The increase in mobility and lifetime is consistent with increased indium passivating midgap and band-tail trap states and doping the films, shifting the Fermi energy closer to and into the conduction band.

Enhanced energy transfer in quasi-quaternary nanocrystal superlattices.

Quasi-quaternary nanocrystal superlattices are assembled by using exclusively core-shell particles as building blocks. The assemblies show an enhancement of energy-transfer from cadmium selenide-based core-shell quantum dots to gold-iron oxide core-shell nanocrystals compared to random mixtures of the same components.

X-ray mapping of nanoparticle superlattice thin films.

We combine grazing-incidence and transmission small-angle X-ray diffraction with electron microscopy studies to characterize the structure of nanoparticle films with long-range order. Transmission diffraction is used to collect in-plane diffraction data from single grains and locally aligned nanoparticle superlattice films. Systematic mapping of samples can be achieved by translating the sample in front of the X-ray beam with a spot size selected to be on the order of superlattice grain features. This allows a statistical determination of superlattice grain size and size distribution over much larger areas than typically accessible with electron microscopy. Transmission X-ray measurements enables spatial mapping of the grain size, orientation, uniformity, strain, or crystal projections and polymorphs. We expand this methodology to binary nanoparticle superlattice and nanorod superlattice films. This study provides a framework for characterization of nanoparticle superlattices over large areas which complements or expands microstructure information from real-space imaging.

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

Stoichiometric control of lead chalcogenide nanocrystal solids to enhance their electronic and optoelectronic device performance.

We investigate the effects of stoichiometric imbalance on the electronic properties of lead chalcogenide nanocrystal films by introducing excess lead (Pb) or selenium (Se) through thermal evaporation. Hall-effect and capacitance-voltage measurements show that the carrier type, concentration, and Fermi level in nanocrystal solids may be precisely controlled through their stoichiometry. By manipulating only the stoichiometry of the nanocrystal solids, we engineer the characteristics of electronic and optoelectronic devices. Lead chalcogenide nanocrystal field-effect transistors (FETs) are fabricated at room temperature to form ambipolar, unipolar n-type, and unipolar p-type semiconducting channels as-prepared and with excess Pb and Se, respectively. Introducing excess Pb forms nanocrystal FETs with electron mobilities of 10 cm(2)/(V s), which is an order of magnitude higher than previously reported in lead chalcogenide nanocrystal devices. Adding excess Se to semiconductor nanocrystal solids in PbSe Schottky solar cells enhances the power conversion efficiency.